Chemical compositions and precipitation timing of basement carbonate vein from fossil spreading ridge of South China Sea

NASA Astrophysics Data System (ADS)

Ding, W.; Chen, Y.

2016-12-01

Eighteen calcium carbonate veins within the igneous basement recovered close to the fossil spreading ridge of the South China Sea during the Integrated Ocean Drilling Program (IODP) Expedition 349 were investigated. These carbonates are of primarily either calcite or aragonite, or some mixed aragonite and calcite, with rarely ankerite. The chemical (Ca, Mg, Sr, Mn, Fe) contents and isotopic (87Sr/86Sr, δ18O, δ18C) compositions of the veins were determined to study the evolving chemistry of hydrothermal fluids and to constrain the timing of vein formation. The carbonate δ18O values range from -5.0 to -0.2 ‰ PDB, indicating these are typical low temperature basement carbonates. Chemical analyses show distinct Mg/Ca and Sr/Ca ratios for aragonite and calcite. 87Sr/86Sr ratios show negative correlations with both the depth and δ18O-calculated formation temperature, and are independent of mineralogy with both aragonite and calcite, indicating more geochemically evolved carbonated have precipitated from warmer fluids. The hightest 87Sr/86Sr ratios of vein samples at each drill site are believed to reflect the contemporaneous seawater compositions when carbonates precipitated. No unambiguous precipitation ages can be constrained by correlating 87Sr/86Sr ratios with the global seawater Sr isotope evolution. However, based on correlations of vein chemical composition with depth and formation temperature, as well as the Neogene post-spreading magmatism, we hypothesize 10 Ma is a particular time favoring the formation of carbonate veins in our study area.

Constraints on Neogene deformation in the southern Terror Rift from calcite twinning analyses of veins within the ANDRILL MIS core, Victoria Land Basin, Antarctica

NASA Astrophysics Data System (ADS)

Paulsen, T. S.; Demosthenous, C.; Wilson, T. J.; Millan, C.

2009-12-01

The ANDRILL MIS (McMurdo Ice Shelf) Drilling Project obtained over 1200 meters of Neogene sedimentary and volcanic rocks in 2006/2007. Systematic fracture logging of the AND-1B core identified 1,475 natural fractures, i.e. pre-existing fractures in the rock intersected by coring. The most abundant natural fractures are normal faults and calcite veins; reverse faults, brecciated zones, and sedimentary intrusions are also present. In order to better understand Neogene deformation patterns within the southern Terror Rift, we have been conducting strain analyses on mechanically twinned calcite within healed fractures in the drill core. Twinning strains using all of the data from each sample studied to date range from 2% to 10%. The cleaned data (20% of the largest magnitude deviations removed) typically show ≤30% negative expected values, consistent with a single deformation episode or multiple ~coaxial deformation episodes. The majority of the samples record horizontal extension, similar to strain patterns expected in a normal fault regime and/or vertical sedimentary compaction in a continental rift system. The morphology, width, and intensity of twins in the samples suggest that twinning typically occurred at temperatures <170° C. Twinning intensities suggest differential stress magnitudes that caused the twinning ranged from 216 to 295 MPa.

Meso- and microscale structures related to post-magmatic deformation of the outer Izu-Bonin-Mariana fore arc system: preliminary results from IODP Expedition 352

NASA Astrophysics Data System (ADS)

Micheuz, P.; Kurz, W.; Ferre, E. C.

2015-12-01

IODP Expedition 352 aimed to drill through the entire volcanic sequence of the Bonin fore arc. Four sites were drilled, two on the outer fore arc and two on the upper trench slope. Analysis of structures within drill cores, combined with borehole and site survey seismic data, indicates that tectonic deformation in the outer Izu-Bonin-Mariana fore arc is mainly post-magmatic, associated with the development of syn-tectonic sedimentary basins. Within the magmatic basement, deformation was accommodated by shear along cataclastic fault zones, and the formation of tension fractures, hybrid (tension and shear) fractures, and shear fractures. Veins commonly form by mineral filling of tension or hybrid fractures and, generally, show no or limited observable macroscale displacement along the fracture plane. The vein filling generally consists of (Low Mg-) calcite and/or various types of zeolite as well as clay. Vein frequency varies with depth but does not seem to correlate with the proximity of faults. This may indicate that these veins are genetically related to hydrothermal activity taking place shortly after magma cooling. Host-rock fragments are commonly embedded within precipitated vein material pointing to a high fluid pressure. Vein thickness varies from < 1 mm up to 15 mm. The wider veins appear to have formed in incremental steps of extension. Calcite veins tend to be purely dilational at shallow depths, but gradually evolve towards oblique tensional veins at depth, as shown by the growth of stretched calcite and/or zeolites (idiomorphic and/or stretched) with respect to vein margins. With increasing depth, the calcite grains exhibit deformation microstructures more frequently than at shallower core intervals. These microstructures include thin twinning (type I twins), increasing in width with depth (type I and type II twins), curved twins, and subgrain boundaries indicative of incipient plastic deformation.

Carbon-oxygen isotopes and rare earth elements as an exploration vector for Carlin-type gold deposits: A case study of the Shuiyindong gold deposit, Guizhou Province, SW China

NASA Astrophysics Data System (ADS)

Tan, Qin-Ping; Xia, Yong; Wang, Xueqiu; Xie, Zhuo-Jun; Wei, Dong-Tian

2017-10-01

The Shuiyindong gold deposit is a deeply concealed strata-bound Carlin-type deposit in southwestern Guizhou Province, China. The deposit lies on the eastern limb of the Huijiabao anticline with ores mainly along the anticline axis and hosted in bioclastic limestone, containing calcite veins, of the Permian Longtan Formation units. In this study, we measured carbon and oxygen isotopic ratios and rare earth element (REE) concentrations of the host rocks and calcite veins along a profile across the Shuiyindong deposit. Orebodies in the upper unit of the Longtan Formation have higher δ18O values (20.6-22.4‰) and lower δ13C values (-3.7 to -0.5‰) than the country rocks (δ18O: 18.8-21.4‰; δ13C: -0.7 to 0.8‰). However, there are no obvious trends of δ18O and δ13C values from the country rocks to the orebodies in the middle unit of the Longtan Formation. The spatial distribution of the calcite veins displays distinct halos of δ13C and δ18O values and REE concentrations. Calcite veins along the anticlinal axis and major reverse fault are enriched in Middle REE (Sm, Eu, Gd, and Tb) and 18O and depleted in 13C. Surficial veining calcite-filled fractures/faults that connect to deep concealed strata-bound gold mineralization systems can be vectors toward deep ores in southwestern Guizhou Province, China.

The Cocos Ridge hydrothermal system revealed by microthermometry of fluid and melt inclusions

NASA Astrophysics Data System (ADS)

Brandstätter, J.; Kurz, W.; Krenn, K.

2017-12-01

Microthermometric analyses of fluid and melt inclusions in hydrothermal veins and in the Cocos Ridge (CCR) basalt were used to reveal the CCR thermal history at IODP Site 344-U1414 and to constrain fluid source and flow. Hydrothermal veins are hosted by lithified sediments and CCR basalt . Site 344-U1414, located 1 km seaward of the Middle American Trench offshore Costa Rica, serves to evaluate fluid/rock interaction, the hydrologic system and geochemical processes linked with the tectonic evolution of the incoming Cocos Plate from the Early Miocene up to recent times. The veins in the sedimentary rocks are mainly filled by blocky calcite, containing numerous fluid inclusions, and sometimes crosscut fibrous quartz/chalcedony veins. The veins in the basalt can be differentiated into three types: antitaxial fibrous calcite veins, composite veins with fibrous calcite and clay minerals at the vein margins and spherulitic quartz in the center, and syntaxial blocky aragonite veins surrounded by a clay selvage in the uppermost CCR basalt sections. Secondary minerals, clay minerals, fibrous calcite, quartz/chalcedony and pyrite also filled vesicles in the basalt. Fluid inclusions were mainly found in the aragonite veins and rarely in quartz in the composite veins and vesicles. Blocky veins with embedded wall rock fragments appear in the sediments and in the basalt indicate hydraulic fracturing. The occurrence of decrepitated fluid inclusions show high homogenization temperatures up to 400 °C. Decrepitated fluid inclusions are formed by increased internal overpressure, related to isobaric heating. Elongated fluid inclusion planes, arc-like fluid inclusions and low homogenization temperatures indicate subsequent isobaric cooling. The results obtained so far from Raman spectroscopy and microthermometry indicate CO2 inclusions and petrographic observations suggest the presence of silicate melt inclusions in phenocrysts in the basalt (mainly in clinopyroxene and plagioclase). The microthermometric data indicate a seawater/pore water like fluid source in communication with a deeper sourced, up to 400 °C hot fluid. This implies that seawater within the Cocos Ridge aquifer communicated with high-temperature fluids and/or were modified by heat advection.

Meso- and microscale vein structures in fore-arc basalts and boninites related to post-magmatic tectonic deformation in the outer Izu-Bonin-Mariana fore arc system: preliminary results from IODP Expedition 352

NASA Astrophysics Data System (ADS)

Quandt, Dennis; Micheuz, Peter; Kurz, Walter

2016-04-01

The International Ocean Discovery Program (IODP) Expedition 352 aimed to drill through the entire volcanic sequence of the Izu-Bonin-Mariana fore arc. Two drill sites are situated on the outer fore arc composed of fore arc basalts (FAB) whereas two more sites are located on the upper trench slope penetrating the younger boninites. First results from IODP Expedition 352 and preliminary post-cruise data suggest that FAB were generated by decompression melting during near-trench sea-floor spreading, and that fluids from the subducting slab were not involved in their genesis. Subduction zone fluids involved in boninite genesis appear to have been derived from progressively higher temperatures and pressures over time as the subducting slab thermally matured. Structures within the drill cores combined with borehole and site survey seismic data indicate that tectonic deformation in the outer Izu-Bonin-Mariana fore arc is mainly post-magmatic associated with the development of syn-tectonic sedimentary basins. Within the magmatic basement deformation was accommodated by shear along cataclastic fault zones and the formation of tension fractures, shear fractures and hybrid (tension and shear) fractures. Veins form by mineral filling of tension or hybrid fractures and show no or limited observable macroscale displacement along the fracture plane. (Low Mg-) Calcite and/or various types of zeolite are the major vein constituents, where the latter are considered to be alteration products of basaltic glass. Micrite contents vary significantly and are related to neptunian dikes. In boninites calcite develops mainly blocky shapes but veins with fibrous and stretched crystals also occur in places indicating antitaxial as well as ataxial growth, respectively. In FAB calcite forms consistently blocky crystals without any microscopic identifiable growth direction suggesting precipitation from a highly supersaturated fluid under dropping fluid pressure conditions. However, fluid pressure must have been high before calcite precipitation in order to fracture the host rock and to place host rock fragments within the vein. Cross-cutting relationships of veins and zonation consisting of blocky calcite and micritic calcite indicate multiple and probably chaotic fracturing and repeated mineral precipitation or emplacement of micrite, respectively. Hydrothermal fluids affected significantly the vein walls by forming selvages of asbestiform mineral bands and alteration halos along the vein-wall rock contact. Rock fragments show the same selvages as the vein walls. Moreover, volcanic glass can be completely altered to zeolite and/or palagonite. This hydrothermal activity took place shortly after magma cooling since vein frequency varies with depth but does not seem to correlate with the proximity to faults. With increasing depth, calcite grains in both sequences exhibit deformation microstructures more frequently than at shallower core intervals. These microstructures include thin twinning (type I twins), increasing in width with depth (type I and type II twins), slightly curved twins, and subgrain boundaries indicative of incipient plastic deformation. The differential stresses (≥ 50 MPa) that triggered vein deformation were presumably related to IBM forearc extension due to the retreating Pacific lower plate.

Microstructures and composition of brittle faults in claystones: Constraints on the barrier behavior

NASA Astrophysics Data System (ADS)

Kneuker, Tilo; Hammer, Jörg; Jahn, Steffen; Zulauf, Gernold

2017-04-01

Investigations of fault rocks are crucial to evaluate the barrier properties of clay rich formations used for the storage of hydrocarbons, carbon dioxide gas or for the storage of heat generating radioactive waste. Claystones are considered as a geological barrier. However, their barrier capability can be reduced if the claystones are cut by brittle faults. Our study is focusing on the microfabrics and element mobility of artificially and naturally fractured claystones using a multi-method approach. Particular attention was paid to small scale lithological heterogeneities occurring in the clayey sequence. The microfabrics were investigated using SEM and optical microscopy. Geochemical and phase analyses were carried out using XRD, XRF and ICP-MS. In addition, organic (TOC) and inorganic carbon (TIC), total sulphur (TS) as well as the cation exchange capacity (CEC) were determined. Macroscopic observations of fault zones on outcrops and drill cores indicate closely spaced planar and undulating discontinuities, including slickenside striations. The investigated fault zones are often accompanied by calcite veins and calcite enriched zones. The fault core is formed by a mm to cm thick clayey, fine grained, cohesionless fault gouge including reworked calcite fragments. Duplex-like domains are separated by discrete microshears, along which the rocks disintegrate. Calcareous fossils, common in undeformed claystones, appear in these zones fragmented and rotated. In contrast to calcite, quartz is more resistant to solution-precipitation processes. Rarely intracrystalline fracturing was observed. The calcite mineralization in veins, and solution-precipitation processes of calcite, documented by stylolites, reflect enhanced palaeo-permeability and activity of Ca2+- and CO2-rich fluids inside some of the fault zones, mainly along fault parallel shear planes. Elevated Sr and Ba concentrations are bound to the tectonic, secondary calcite veins within and outside the investigated fault zone. The geochemical data presented in form of isocon diagrams suggest volume gain related to the opening of veins and pores, which are now filled with calcite. Our results do not provide evidence for presently open pores or fractures, which might be related to non-artificial tectonic deformation. However, (micro)fractures as well as mineralized veins represent inherited damage in the rock, and are prone to brittle reactivation during fluid pressure increase or during the excavation of underground galleries. A complex, polyphase deformation history including a possible reactivation of older structures is supported by our observations.

Conditions for veining and origin of mineralizing fluids in the Alpi Apuane (NW Tuscany, Italy): Evidence from structural and geochemical analyses on calcite veins hosted in Carrara marbles

NASA Astrophysics Data System (ADS)

Vaselli, Luca; Cortecci, Gianni; Tonarini, Sonia; Ottria, Giuseppe; Mussi, Mario

2012-11-01

This work deals with structural and geochemical (chemical and isotopic) analyses of calcite veins hosted in Carrara marbles in the Alpi Apuane, NW Tuscany, Italy. Geometric features and spatial distribution of veins provided estimations of stress ratio (Φ = (σ2 - σ3)/(σ1 - σ3)), driving stress ratio (R' = (Pf - σ3)/(σ1 - σ3)) and fluid overpressure (Δsi = Pf - σ3) at the time of vein formation. The obtained values of Φ = 32 and R' = 0.43 reveal that fluid pressure was higher than the intermediate principal stress at the time of veins formation, whereas the estimated Δsi ranging from 129 to 207 MPa indicates that veins formed under supra-hydrostatic to lithostatic pressure conditions. Carbon (δ13CV-PDB = 1.81-2.10‰ for veins and 1.95-2.51‰ for host marbles), oxygen (δ18OV-SMOW = 28.71-29.57‰ for veins and 28.90-29.36‰ for host marbles) and strontium (87Sr/86Sr = 0.707716-0.707985 for veins and 0.0707708-0.707900 for host marbles) isotope compositions in vein/host marble pairs were internally quite consistent. Combining our structural and geochemical data, a modeling approach was performed to investigate the compositional features and temperatures of calcite depositing fluids. The results of our studies give evidence that (1) pore-fluids in Carrara marble, consisting of metamorphic formation waters, were re-mobilized during veining event and migrated within the veins in closed system conditions, (2) veins formed after ductile folding phases and before high-angle brittle faulting events, at temperature and pressure around 250 °C and 210 MPa, and finally (3) about 12 g H2O/m3 marble are calculated to have been available as vein parental fluid at the time of vein formation.

Fracturing, fluid-rock interaction and mineralisation during the seismic cycle along the Alpine Fault

NASA Astrophysics Data System (ADS)

Williams, Jack N.; Toy, Virginia G.; Smith, Steven A. F.; Boulton, Carolyn

2017-10-01

The Alpine Fault has a <50 m wide geochemically distinct hanging-wall alteration zone. Using a combination of petrological and cathodoluminescence (CL) microscopy, Energy Dispersive Spectroscopy and X-ray diffraction, we document the habitat and mineralising phases of macro- and micro-fractures within the alteration zone using samples derived from outcrop and the Deep Fault Drilling Project. Veins predominantly contain calcite, chlorite, K-feldspar or muscovite. Gouge-filled fractures are also observed and reflect filling from mechanical wear and chlorite mineralisation. CL imaging suggests that each calcite vein was opened and sealed in one episode, possibly corresponding to a single seismic cycle. The thermal stability of mineralising phases and their mutually cross-cutting relationships indicates a cyclic history of fracture opening and mineralisation that extends throughout the seismogenic zone. Cataclasites contain intragranular veins that are hosted within quartzofeldspathic clasts, as well as veins that cross-cut clasts and the surrounding matrix. Intragranular calcite veins formed prior to or during cataclasis. Cross-cutting veins are interpreted to have formed by fracturing of relatively indurated cataclasites after near-surface slip localisation within the Alpine Fault's principal slip zone gouges (PSZs). These observations clearly demonstrate that shear strain is most localised in the shallowest part of the seismogenic zone.

Multiple deformation mechanisms operating at seismogenic depths: Tectonic pseudotachylyte and associated deformation from the central Sierra Nevada, California

NASA Astrophysics Data System (ADS)

Prante, M. R.; Evans, J. P.

2012-12-01

Description and identification of fault-related deformation products that are diagnostic of seismic slip have implications for the energy budget of earthquakes, fault strength, and fault-rock assemblages. We describe tectonic pseduotachylyte, cataclastic rocks, crystal-plastic deformation, and hydrothermal alteration form faults exhumed from seismogenic depths in the Volcanic Lakes area, in northern Sequoia and Kings Canyon National Park, CA, USA. Fault rock protoliths include Mesozoic granite and granodiorite plutonic and limited metasedimentary and metavolcanic rocks. These plutonic and metamorphic rocks are cross-cut by the E-W striking, steeply dipping, left-lateral strike-slip Granite Pass (GPF) and Glacier Lakes faults (GLF). Cross-cutting relationships and microstructural data suggest that the GPF is the oldest fault in the area and preserves evidence for coeval brittle and plastic crystal deformation, and hydrothermal fluid-flow. Tectonic pseudotachylyte from the area has been dated using the 40Ar/39Ar method at 76.6 ± 0.3 Ma; when placed into a thermochronologic framework for the plutonic host rock it can be inferred that the pseudotachylyte formed at depths between 2.4-6.0 km with ambient temperatures between 110-160°C. Exceptionally well preserved tectonic pseudotachylyte from the GLF and GPF contain evidence for a frictional melt origin including: 1) plagioclase spherulites and microlites, 2) injection vein morphology, 3) amygdules, 4) viscous flow banding and folds, and 5) embayed and corroded clasts. Pseudotachylyte from the GPF and GLF is associated with brittle and plastic deformation in the damage zone of the faults. Evidence for plastic deformation includes undulose extinction, deformation lamellae, subgrain development, and grain boundary bulging in quartz; and limited undulose extinction in feldspar. Additionally, abundant hydrothermal alteration and mineralization has been documented in the GPF and GLF fault zones, including, chlorite pseudomorphs after biotite and alteration of mafic phases to epidote, sericite and calcite alteration of albite, and calcite and chlorite filled veins. Cross-cutting calcite veins contain fine-grained calcite with abundant twins up to 20 μm-thick. Multiple pseudotachylyte injection veins and reworked pseudotachylyte in cataclastic rock suggest multiple earthquakes along the GPF and GLF at depths favorable to pseudotachylyte formation. Abundant hydrothermal alteration and cross-cutting calcite veins with thick (> 1 μm) twins is consistent with ambient temperatures between 170 and 200°C. These temperatures are generally consistent with the reported ambient temperature conditions during pseudotachylyte formation. Crystal-plastic deformation of quartz and feldspar in the GPF and GLF zones is consistent with deformation at temperatures between 200-400°C. Frictional melt and associated brittle and plastic deformation, and fluid alteration are presumed to have occurred at similar temperature conditions and may be coeval. These results have important implication for understanding energy sinks associated with seismic slip and the conditions of tectonic pseudotachylyte formation.

Kinematics of Cone-In-Cone Growth, with Implications for Timing and Formation Mechanism

NASA Astrophysics Data System (ADS)

Hooker, J. N.; Cartwright, J. A.

2015-12-01

Cone-in-cone is an enigmatic structure. Similar to many fibrous calcite veins, cone-in-cone is generally formed of calcite and present in bedding-parallel vein-like accumulations within fine-grained rocks. Unlike most fibrous veins, cone-in-cone contains conical inclusions of host-rock material, creating nested, parallel cones throughout. A long-debated aspect of cone-in-cone structures is whether the calcite precipitated with its conical form (primary cone-in-cone), or whether the cones formed afterwards (secondary cone-in-cone). Trace dolomite within a calcite cone-in-cone structure from the Cretaceous of Jordan supports the primary hypothesis. The host sediment is a siliceous mud containing abundant rhombohedral dolomite grains. Dolomite rhombohedra are also distributed throughout the cone-in-cone. The rhombohedra within the cones are randomly oriented yet locally have dolomite overgrowths having boundaries that are aligned with calcite fibers. Evidence that dolomite co-precipitated with calcite, and did not replace calcite, includes (i) preferential downward extension of dolomite overgrowths, in the presumed growth-direction of the cone-in-cone, and (ii) planar, vertical borders between dolomite crystals and calcite fibers. Because dolomite overgrows host-sediment rhombohedra and forms fibers within the cones, it follows that the host-sediment was included within the growing cone-in-cone as the calcite precipitated, and not afterward. The host-sediment was not injected into the cone-in-cone along fractures, as the secondary-origin hypothesis suggests. This finding implies that cone-in-cone in general does not form over multiple stages, and thus has greater potential to preserve the chemical signature of its original precipitation. Because cone-in-cone likely forms before complete lithification of the host, and because the calcite displaces the host material against gravity, this chemical signature can preserve information about early overpressures in fine-grained sediments.

Petrology, chronology and sequence of vein systems: Systematic magmatic and hydrothermal history of a major intracontinental shear zone, Canadian Appalachians

NASA Astrophysics Data System (ADS)

Pe-Piper, Georgia; Piper, David J. W.; McFarlane, Chris R. M.; Sangster, Chris; Zhang, Yuanyuan; Boucher, Brandon

2018-04-01

Intra-continental shear zones developed during continental collision may experience prolonged magmatism and mineralization. The Cobequid Shear Zone formed part of a NE-SW-trending, orogen-parallel shear system in the late Devonian-early Carboniferous, where syn-tectonic granite-gabbro plutons and volcanic rocks 4 km thick were progressively deformed. In late Carboniferous to Permian, Alleghanian collision of Africa with Laurentia formed the E-W trending Minas Fault Zone, reactivating parts of the Cobequid Shear Zone. The 50 Ma history of hydrothermal mineralization following pluton emplacement is difficult to resolve from field relationships of veins, but SEM study of thin sections provides clear detail on the sequence of mineralization. The general paragenesis is: albite ± quartz ± chlorite ± monazite → biotite → calcite, allanite, pyrite → Fe-carbonates, Fe-oxides, minor sulfides, calcite and synchysite. Chronology was determined from literature reports and new U-Pb LA-ICPMS dating of monazite and allanite in veins. Vein mineralization was closely linked to magmatic events. Vein emplacement occurred preferentially during fault movement recognised from basin-margin inversion, as a result of fractures opening in the damage zone of master faults. The sequence of mineralization, from ca. 355 Ma riebeckite and albite veins to ca. 327 (-305?) Ma siderite-magnetite and sulfide mineralization, resembles Precambrian iron-oxide-copper-gold (IOCG) systems in the literature. The abundant magmatic Na, halogens and CO2 in veins and some magmatic bodies, characteristic of IOCG systems, were derived from the deeply subducted Rheic Ocean slab with little terrigenous sediment. Regional extension of the Magdalen Basin caused asthenospheric upwelling and melting of the previously metasomatized sub-continental lithospheric mantle. Crustal scale strike-slip faulting facilitated the rise of magmas, resulting in high heat flow driving an active hydrothermal system. Table S2 Location of all illustrated samples. Table S3 Monazite geochronology lab data. Table S4 Allanite geochronology lab data. Fig. S1 Monazite geochronology analytical spots. Fig. S2 Allanite geochronology analytical spots.

Metamorphism Near the Dike-Gabbro Transition in the Ocean Crust Based on Preliminary Results from Oman Drilling Project Hole GT3A

NASA Astrophysics Data System (ADS)

Manning, C. E.; Nozaka, T.; Harris, M.; Michibayashi, K.; de Obeso, J. C.; D'Andres, J.; Lefay, R.; Leong, J. A. M.; Zeko, D.; Kelemen, P. B.; Teagle, D. A. H.

2017-12-01

Oman Drilling Project Hole GT3A intersected 400 m of altered basaltic dikes, gabbros, and diorites. The 100% recovery affords an unprecedented opportunity to study metamorphism and hydrothermal alteration near the dike-gabbro transition in the ocean crust. Hydrothermal alteration is ubiquitous; all rocks are at least moderately altered, and mean alteration intensity is 54%. The earliest alteration in all rock types is background replacement of igneous minerals, some of which occurred at clinopyroxene amphibolite facies, as indicated by brown-green hornblende, calcic plagioclase, and secondary cpx. In addition, background alteration includes greenschist, subgreenschist, and zeolite facies minerals. More extensive alteration is locally observed in halos around veins, patches, and zones related to deformation. Dense networks of hydrothermal veins record a complex history of fluid-rock alteration. During core description, 10,727 individual veins and 371 vein networks were logged in the 400 m of Hole GT3A. The veins displayed a range of textures and connectivities. The total density of veins in Hole GT3A is 26.8 veins m-1. Vein density shows no correlation with depth, but may be higher near dike margins and faults. Vein minerals include amphibole, epidote, quartz, chlorite, prehnite, zeolite (chiefly laumontite) and calcite in a range of combinations. Analysis of crosscutting relations leads to classification of 4 main vein types. In order of generally oldest to youngest these are: amphibole, quartz-epidote-chlorite (QEC), zeolite-prehnite (ZP), and calcite. QEC and ZP vein types may contain any combination of minerals except quartz alone; veins filled only by quartz may occur at any relative time. Macroscopic amphibole veins are rare and show no variation with depth. QEC vein densities appear to be higher (>9.3 veins m-1) in the upper 300 m of GT3A, where dikes predominate. In contrast, there are 5.5 veins m-1 at 300-400 m, where gabbros and diorites are abundant. ZP veins increase in density downhole; the highest density of 17.5 ZP veins/m occurs in the lowest 100 m where substantial faulting is observed. Equilibrium coexistence of laumontite and prehnite in ZP veins implies formation at 100-250 °C, lower than amphibole and QEC veins. Calcite veins are abundant only in the uppermost 100 m of the hole.

Fluids along the North Anatolian Fault, Niksar basin, north central Turkey: Insight from stable isotopic and geochemical analysis of calcite veins

NASA Astrophysics Data System (ADS)

Sturrock, Colin P.; Catlos, Elizabeth J.; Miller, Nathan R.; Akgun, Aykut; Fall, András; Gabitov, Rinat I.; Yilmaz, Ismail Omer; Larson, Toti; Black, Karen N.

2017-08-01

Six limestone assemblages along the North Anatolian Fault (NAF) Niksar pull-apart basin in northern Turkey were analyzed for δ18OPDB and δ13CPDB using bulk isotope ratio mass spectrometry (IRMS). Matrix-vein differences in δ18OPDB (-2.1 to 6.3‰) and δ13CPDB (-0.9 to 4.6‰) suggest a closed fluid system and rock buffering. Veins in one travertine and two limestone assemblages were further subjected to cathodoluminescence, trace element (Laser Ablation Inductively Coupled Plasma Mass Spectrometry) and δ18OPDB (Secondary Ion Mass Spectrometry, SIMS) analyses. Fluid inclusions in one limestone sample yield Th of 83.8 ± 7.3 °C (±1σ, mean average). SIMS δ18OPDB values across veins show fine-scale variations interpreted as evolving thermal conditions during growth and limited rock buffering seen at a higher-resolution than IRMS. Rare earth element data suggest calcite veins precipitated from seawater, whereas the travertine has a hydrothermal source. The δ18OSMOW-fluid for the mineralizing fluid that reproduces Th is +2‰, in range of Cretaceous brines, as opposed to negative δ18OSMOW-fluid from meteoric, groundwater, and geothermal sites in the region and highly positive δ18OSMOW-fluid expected for mantle-derived fluids. Calcite veins at this location do not record evidence for deeply-sourced metamorphic and magmatic fluids, an observation that differs from what is reported for the NAF elsewhere along strike.

A response to "Milankovitch theory viewed from Devils Hole" by J. Imbrie, A.C. Mix and D.G. Martinson

USGS Publications Warehouse

Winograd, I.J.; Landwehr, J.M.

1993-01-01

The detailed and well-dated 500,000-yr record of oxygen-18 variations found in vein calcite core DH-11 taken from Devils Hole in Nevada provides several challenges to the Milankovitch theory for the occurrence of Quaternary glaciations. A recent discussion paper (Imbrie and others, 1993) has dismissed the relevance of this well-dated core for determining the timing of global climatic fluctuations and, moreover, asserts that the Devils Hole record provides support for the Milankovitch theory. Upon analysis of the arguments found in this discussion, the authors found nothing to dissuade them from the original conclusion that the Devils Hole chronology does present a serious challenge to the Milankovitch theory.

Geochemical study of calcite veins in the Silurian and Devonian of the Barrandian Basin (Czech Republic): evidence for widespread post-Variscan fluid flow in the central part of the Bohemian Massif

NASA Astrophysics Data System (ADS)

Suchy, V.; Heijlen, W.; Sykorova, I.; Muchez, Ph; Dobes, P.; Hladikova, J.; Jackova, I.; Safanda, J.; Zeman, A.

2000-03-01

Carbonate fracture cements in limestones have been investigated by fluid inclusion and stable isotope analysis to provide insight into fluid evolution and deformation conditions of the Barrandian Basin (Silurian-Devonian) of the Czech Republic. The fractures strike generally north-south and appear to postdate major Variscan deformation. The most common fracture cement is calcite that is locally accompanied by quartz, natural bitumen, dolomite, Mn-oxides and fluorite. Three successive generations of fracture-filling calcite cements are distinguished based on their petrographical and geochemical characteristics. The oldest calcite cements (Stage 1) are moderate to dull brown cathodoluminescent, Fe-rich and exhibit intense cleavage, subgrain development and other features characteristic of tectonic deformation. Less tectonically deformed, variable luminescent Fe-poor calcite corresponds to a paragenetically younger Stage 2 cement. First melting temperatures, Te, of two-phase aqueous inclusions in Stages 1 and 2 calcites are often around -20°C, suggesting that precipitation of the cements occurred from H 2O-NaCl fluids. The melting temperature, Tm, has values between 0 and -5.8°C, corresponding to a low salinity between 0 and 8.9 eq. wt% NaCl. Homogenization temperatures, Th, from calcite cements are interpreted to indicate precipitation at about 70°C or less. No distinction could be made between the calcite of Stages 1 and 2 based on their fluid inclusion characteristics. In some Stage 2 cements, inclusions of highly saline (up to 23 eq. wt% NaCl) brines appear to coexist with low-salinity inclusions. The low salinity fluid possibly contains Na-, K-, Mg- and Ca-chlorides. The high salinity fluid has a H 2O-NaCl-CaCl 2 composition. Blue-to-yellow-green fluorescing hydrocarbon inclusions composed of medium to higher API gravity oils are also identified in some Stages 1 and 2 calcite cements. Stage 1 and 2 calcites have δ18O values between -13.2‰ and -7.2‰ PDB. The lower range of the calculated δ18O values of the ambient fluids (-3.5‰ to +2.7‰ SMOW) indicate precipitation of these cements from deeply circulating meteoric waters. The presence of petroleum hydrocarbon inclusions in some samples is interpreted to reflect partial mixing with deeper basinal fluids. The paragenetically youngest Stage 3 calcite cement has only been encountered in a few veins. These calcites are characterised by an intensely zoned luminescence pattern, with bright yellow and non-luminescent zones. Inclusions of Mn-oxides and siliceous sinters are commonly associated with Stage 3 calcite, which is interpreted to have precipitated from shallower meteoric waters. Regional structural analysis revealed that the calcite veins of the Barrandian basin belong to a large-scale system of north-south-trending lineaments that run through the territory of the Czech Republic. The veins probably reflect episodes of fluid migration that occurred along these lineaments during late stages of the Variscan orogeny.

Stable-isotope studies of rocks and secondary minerals in a vapor-dominated hydrothermal system at The Geysers, Sonoma County, California

NASA Astrophysics Data System (ADS)

Lambert, Steven J.; Epstein, Samuel

1992-11-01

The Geysers, a vapor-dominated hydrothermal system, is developed in host rock of the Franciscan Formation, which contains veins of quartz and calcite whose δ 18O values record the temperatures and isotopic compositions of fluids prevailing during at least two different episodes of rock-fluid interaction. The first episode took place at about 200°C, during which marine silica and carbonate apparently interacted with ocean water entrapped in the sediments to form veins of quartz and calcite whose δ 18O values were around +19 and +16%, respectively. The calculated water/mineral ratios were less than unity. The water may have profoundly influenced the δ 18O values of spilitic basalts during their metamorphism to greenstones. Serpentinization and structural emplacement of ophiolite slabs were isotopically unrelated to this episode, which was essentially a low-grade (post-Cretaceous?) burial metamorphism. D/H ratios of actinolite, chlorite, and micas in host rocks were more profoundly altered during this episode than were 18O/ 16O ratios. A paleogeothermal gradient of about 53°C/km has been inferred for this episode, from δ 18O-depth distributions of vein minerals. The second episode, in part recorded by cogenetic vein quartz and calcite δ 18O values of +4 to +6% and +1 to +3%, respectively, began with large quantities of meteoric water circulating in fractures in the rock at temperatures of 160-180°C in response to the initiation of the Pliocene-Pleistocene Clear Lake magmatism. The temperature rose, and with the restricted circulation of fluids the ancestral hot-water system evolved into the presently active vapor-dominated system, which according to the cogenetic vein quartz and calcite δ 18O values involved temperatures as high as 320°C and fluid/mineral ratios near unity. The change in the oxygen-isotopic composition of the serpentinite within the host rock during this later activity was negligible. The δ 13C values of vein calcite at The Geysers reflect both a marine carbonate and organic component of carbon, but carbon-isotope exchange has been facilitated by the vapor-dominated hydrothermal fluid to a greater degree than in any other episode or in other hot-water systems.

Syntectonic fluid flux during rift faulting: Record from the MIS core, Victoria Land Basin, Antarctica

NASA Astrophysics Data System (ADS)

Millan, C.; Wilson, T. J.; Paulsen, T. S.

2009-12-01

The McMurdo Ice Shelf project successfully recovered 1285 m of Neogene sedimentary core from the Victoria Land Basin, a large rift basin within the West Antarctic Rift System (WARS) of Antarctica. The core contains 1475 natural fractures that were logged as faults, veins and clastic dikes, associated with the southern extension of the Neogene-active? Terror Rift fault zone. Veins constitute about 625 of this population. Most veins are filled with calcite, although zeolites and minor chlorite are common towards the bottom of the core. In the lower ~300 m of the core, veins contain opening-mode fiber fills and are wavy to tightly folded due to vertical shortening. Folded, opening-mode folded veins are filled by calcite fibers that grew normal to vein walls, indicating the host sediment was cohesive enough to fracture but was not fully lithified and accommodated vein buckling during compaction. Fold hinges are fractured and wedging of vein segments is marked by overlapping tips separated by zones with strong chlorite and clay fabrics, suggesting shearing during further vertical contraction of the host rock. Calcite veins are commonly strongly twinned. Cathodoluminescence microscopy shows minor changes in color and intensity and minimal concentric or sectoral zoning, suggesting relatively rapid crystallization of fluids of similar chemistry. However, stable isotope analyses reveal large variations in values, with carbon values ranging from -21.91 to -7.15 (VPBD) and oxygen values ranging from -5.35 to -11.97 (VPBD). Further detailed investigation of the fracture fills using cathodoluminescence and electron microscopy combined with isotopic analysis of carbon and oxygen will document the generations of the filling material in more detail and will constrain the sources and evolution of the fluids. There has clearly been significant structural control on fluid pathways during lithification, compaction and diagenesis of strata deforming within the Terror Rift zone.

Geochemistry of sapphirine-apatite-calcite-bearing gabbroic dykes from the Finero Phlogopite Peridotite (Ivrea-Verbano Zone): evidence for multistage interaction with the ambient peridotite

NASA Astrophysics Data System (ADS)

Tommaso, Giovanardi; Alberto, Zanetti; Maurizio, Mazzucchelli; Tomoaki, Morishita; Antonio, Langone

2016-04-01

The Finero Phlogopite-Peridotite (FPP) is a mantle unit outcropping in the northernmost tip of the Ivrea-Verbano Zone (IVZ, Southern Alps). It shows a virtually complete recrystallization due to pervasive to channelled melt migration. The pervasive metasomatism formed a main lithologic association constituted by phlogopite harzburgites associated to phlogopite pyroxenites (mainly olivine-websterites, websterites and orthopyroxenites). These lithologies are also rich in amphibole and do not show significant chemical gradients among them (Zanetti et al., 1999). The channelled migration stages formed dunite bodies, which sometimes contain stratiform chromitites and, more rarely, pyroxenite layers similar to those associated to phlogopite harzburgite. The FPP also shows a discrete number of other, subordinate rock-types, which are characterised by the presence of apatite usually associated to carbonates (i.e. calcite or dolomite) and exhibit marked modal and chemical gradients with respect to the host phlogopite harzburgite. Examples of these lithologies are apatite-dolomite-bearing wehrlites and harzburgites (e.g. Zanetti et al. 1999; Morishita et al., 2008), apatite-calcite zircon-syenites and hornblendites. Ar-Ar amphibole analysis and U-Pb zircon and apatite data return Triassic ages for these rocks, which have been considered to document the time of melt/fluid injection. Notwithstanding the apparent mineralogical and chemical differences with the main lithologic sequences, apatite-carbonates-bearing rocks have been frequently interpreted as cogenetic to phlogopite harzburgites. To debate the petrogenesis of these rocks, a detailed field, petrological and geochemical investigation has been carried out on a swarm of apatite-calcite-bearing gabbroic veins that randomly cut the main lithologic association. Preliminary investigation evidenced as these veins show complex metasomatic haloes and a symmetric internal layering, characterised by crystallisation of magmatic sapphirine (Giovanardi et al., 2013). The mineral assemblage of the veins is dominated by titanian pargasite towards the host peridotite and by plagioclase at the vein centre. The veins also present phlogopite and spinel. Field and petrographic evidence, major and trace element data and the O isotopic composition of such gabbroic veins indicate that they formed at shallow mantle conditions by multistage fractional crystallisation of a migrating melt unrelated to those forming phlogopite harzburgites. Besides, local strong enrichments in LILE, LREE and 18O in vein minerals confirm that such melt was deeply modified by interaction with the host phlogopite peridotite. The genetic relationships with other intrusive events recorded by the FPP and the associated crustal sequence will be addressed with the aim of placing new constraints on the petrologic and geodynamic evolution of the IVZ. Giovanardi, T., Morishita, T., Zanetti, A., Mazzucchelli, M., Vannucci, R. (2013). Igneous sapphirine as a product of melt-peridotite interactions in the Finero Phlogopite-Peridotite Massif, Western Italian Alps. European Journal of Mineralogy 25, 17-31. Morishita, T., Hattori, K.H., Terada, K., Matsumoto, T., Yamamoto, K., Takebe, M., Ishida, Y., Tamura, A., Arai, S. (2008). Geochemistry of apatite-rich layers in the Finero phlogopite-peridotite massif (Italian Western Alps) and ion microprobe dating of apatite. Chemical Geology 251, 99-111. Zanetti, A., Mazzucchelli, M., Rivalenti, G., Vannucci, R. (1999). The Finero phlogopite-peridotite massif: an example of subduction-related metasomatism. Contributions to Mineralogy and Petrology 134, 107-122.

New type of kinematic indicator in bed-parallel veins, Late Jurassic-Early Cretaceous Vaca Muerta Formation, Argentina: E-W shortening during Late Cretaceous vein opening

NASA Astrophysics Data System (ADS)

Ukar, Estibalitz; Lopez, Ramiro G.; Gale, Julia F. W.; Laubach, Stephen E.; Manceda, Rene

2017-11-01

In the Late Jurassic-Early Cretaceous Vaca Muerta Formation, previously unrecognized yet abundant structures constituting a new category of kinematic indicator occur within bed-parallel fibrous calcite veins (BPVs) in shale. Domal shapes result from localized shortening and thickening of BPVs and the intercalation of centimeter-thick, host-rock shale inclusions within fibrous calcite beef, forming thrust fault-bounded pop-up structures. Ellipsoidal and rounded structures show consistent orientations, lineaments of interlayered shale and fibrous calcite, and local centimeter-scale offset thrust faults that at least in some cases cut across the median line of the BPV and indicate E-W shortening. Continuity of crystal fibers shows the domal structures are contemporaneous with BPV formation and help establish timing of fibrous vein growth in the Late Cretaceous, when shortening directions were oriented E-W. Differences in the number of opening stages and the deformational style of the different BPVs indicate they may have opened at different times. The new domal kinematic indicators described in this study are small enough to be captured in core. When present in the subsurface, domal structures can be used to either infer paleostress orientation during the formation of BPVs or to orient core in cases where the paleostress is independently known.

Kinematics of fibrous vein growth: insights from stable isotopes and trace element data

NASA Astrophysics Data System (ADS)

Fischer, M. P.; Lefticariu, L.; Romanek, C.; Perry, E. C.

2005-12-01

Veins are important recorders of thermal, hydrological, structural, and geochemical conditions during deformation. Fibrous or bladed veins are particularly useful, because the mineral fibers are believed to grow continuously or episodically over what may be a significant geologic time period. Thus, individual mineral fibers document the complex, dynamic changes occurring coeval with vein growth and mineral precipitation. Geochemical and structural analyses have been used to constrain the kinematic history of a bed-parallel fibrous calcite vein from the Upper Jurassic La Casita Formation, Sierra Madre Oriental, Mexico. The La Casita Formation, correlative with the Smackover Formation of the northern US Gulf Coast, consists of shale and is part of a sedimentary succession that unconformably overlies evaporites of the Minas Viejas Formation. The fibrous vein examined in this study was taken from the backlimb of the frontal fold of the Monterrey salient near Saltillo. Optical petrographic observation reveals that the calcite fibers have blade or tapering lath shapes with widths from 0.1-1.0 mm. Other minerals present in the vein are pyrite, gypsum, bitumen, and iron oxides. High-resolution, closely spaced stable isotope and elemental analyses were carried out along five traverses across the vein width. The d18O values vary in a narrow range, with an average value of +20.8 permil (VSMOW). The d13C values increase systematically along the fibers, from the walls of the vein toward the suture plane. In all five traverses, the d13C increase is relatively constant, with lower values next to the vein wall (+1.2 to +1.6 permil PDB) and higher values along the suture line (+3.6 to +4.1 permil PDB). The vein minerals, fibrous calcite and accessory pyrite, are interpreted to be the products of high temperature reactions between light hydrocarbons and dissolved sulfate, known as thermochemical sulfate reduction (TSR). Reactants such as light hydrocarbons and products such as CO2, H2S, and H2O contributed to what are interpreted to have been high fluid pressures during vein growth. The origin of vein minerals is probably related to: (1) methanogenesis and decarbonation reactions within the shale, and (2) migration of high-temperature brine during late stages of folding.

Controls on the long term earthquake behavior of an intraplate fault revealed by U-Th and stable isotope analyses of syntectonic calcite veins

NASA Astrophysics Data System (ADS)

Williams, Randolph; Goodwin, Laurel; Sharp, Warren; Mozley, Peter

2017-04-01

U-Th dates on calcite precipitated in coseismic extension fractures in the Loma Blanca normal fault zone, Rio Grande rift, NM, USA, constrain earthquake recurrence intervals from 150-565 ka. This is the longest direct record of seismicity documented for a fault in any tectonic environment. Combined U-Th and stable isotope analyses of these calcite veins define 13 distinct earthquake events. These data show that for more than 400 ka the Loma Blanca fault produced earthquakes with a mean recurrence interval of 40 ± 7 ka. The coefficient of variation for these events is 0.40, indicating strongly periodic seismicity consistent with a time-dependent model of earthquake recurrence. Stochastic statistical analyses further validate the inference that earthquake behavior on the Loma Blanca was time-dependent. The time-dependent nature of these earthquakes suggests that the seismic cycle was fundamentally controlled by a stress renewal process. However, this periodic cycle was punctuated by an episode of clustered seismicity at 430 ka. Recurrence intervals within the earthquake cluster were as low as 5-11 ka. Breccia veins formed during this episode exhibit carbon isotope signatures consistent with having formed through pronounced degassing of a CO2 charged brine during post-failure, fault-localized fluid migration. The 40 ka periodicity of the long-term earthquake record of the Loma Blanca fault is similar in magnitude to recurrence intervals documented through paleoseismic studies of other normal faults in the Rio Grande rift and Basin and Range Province. We propose that it represents a background rate of failure in intraplate extension. The short-term, clustered seismicity that occurred on the fault records an interruption of the stress renewal process, likely by elevated fluid pressure in deeper structural levels of the fault, consistent with fault-valve behavior. The relationship between recurrence interval and inferred fluid degassing suggests that pore fluid pressure along the fault may have been driven by variations in CO2 content, thereby fundamentally affecting earthquake frequency. Thus, the Loma Blanca fault provides a record of "naturally induced" seismicity, with lessons for better understanding anthropogenic induced seismicity.

Compaction history of Upper Cretaceous shale (Al-Khod Formation) and its relationship to plate margin tectonics, Arabian Plate, Sultanate of Oman

NASA Astrophysics Data System (ADS)

AL-Sarmi, Musaab; Mattern, Frank; Scharf, Andreas; Pracejus, Bernhard; Al-Mamari, Amira; Al-Hinaai, Al-Shima

2017-04-01

Conglomerates of the late Cretaceous Al-Khod Formation have been intruded by older shale of the same formation along faults, which were opened/widened by extension, thus, resulting in shale dike formation. Following intrusion the shale was behaving plastically as its fissility follows the contact contours of the conglomeratic host rock and as stoped sandstone blocks are floating within the shale. Vertical calcite veins were ptygmatically folded with subhorizontal fold axial planes. All these aspects show that the shale contained a high water content in the beginning. The ptygmatically folded calcite veins display vertical shortening amounts of 40 % corresponding to 35 % to 45 % of water loss during compaction. Incalculable numbers of calcite veins of different orientations and thicknesses within the conglomerate along the shale contact indicate that the fluid was expelled from the shale into the conglomerate host rock under high pressure (overpressure?). Shale dyke formation took place after the late Cretaceous obduction of the Semail Ophiolite, before the deposition of early Tertiary carbonate rocks, and during the latest Cretaceous doming of the Saih Hatat area which was caused by deformation and slab breakoff, likely associated with gravitational collapse and elastic rebound. Shale intrusion was followed by deposition of 100 to 200 m thick sediments of the upper part of Al-Khod Formation, leading to compaction and water loss. The shale retained much of its water during the uppermost Cretaceous-late Paleocene stratigraphic hiatus as this interval is marked by erosion and a reduction of overburden, which was probably due to the elastic rebound. Folding of calcite veins together with a high amount of water loss was a consequence of compaction caused by the overburden of 1000 m thick shallow marine limestones which were deposited from the Eocene to Oligocene.

Corrosion Protection by Calcite-Type Coatings

DTIC Science & Technology

1989-10-01

CORROSION PROTECTION BY CALCITE -TYPE COATINGS OCTOBER, 1989 Prepared by: OCEAN CITY RESEARCH CORPORATION Tennessee Avenue & Beach Thorofare Ocean...REPORT DATE OCT 1989 2. REPORT TYPE N/A 3. DATES COVERED - 4. TITLE AND SUBTITLE Corrosion Protection by Calcite -Type Coatings 5a. CONTRACT... calcite -type coatings to segregated seawater ballast tanks. If perfected, a calcite coating approach could substantially reduce the cost of corrosion

A brittle (normal?) shear zone cored in Site C0002 of Nankai Trough Seismogenic Zone Experiment (IODP Expedition 348)

NASA Astrophysics Data System (ADS)

Crespo-Blanc, Ana; Sample, James; Brown, Kevin; Otsubo, Makoto; Yamamoto, Yuzuru

2016-04-01

Integrated Ocean Discovery Program (IODP) Expedition 348, which belongs to the Nankai Trough Seismogenic Zone Experiment, conducted riser-drilling to make deeper an existing hole at Site C0002, up to 3058.5 meters below seafloor (mbsf). This site is located 80 km SE of the Kii Peninsula (Japan) in the Kumano forearc basin, in turn situated on top of the Nankai accretionary prism. Cuttings (875.5-3058.5 mbsf) and cores (2163.0-2217.5 mbsf) were collected in the upper Miocene to Pliocene turbiditic silty claystone with few intercalations of sandstone which characterize the accretionary prism lithological units. A remarkably preserved fault zone has been cored around 2205 mbsf (core section Hole C0002P-348-5R-4). It is characterized by 34 cm of fault breccia, in which an anastomosed cataclastic foliation is present. The rocks of the damaged zone are formed by silty claystone with an incipient scaly fabric and scarce levels of sandstones. Extra-large thin sections were made along the whole core section. In the brittle shear zone, they reveal a catalogue of deformation structures characteristic of a high structural level. In particular, almond-type structures and arrays of microfaults cutting the stratification are the most common structures and outline the cataclastic foliation. The occurrence of calcite veins in the recovered cores is limited to this fault zone, which is indicative of its role as fluid path, accompanied by carbonate cementation. Generally fault veins have lower δ18O values than carbonate cements in the sedimentary matrix, consistent with veins forming at higher temperatures and/or from a fluid more strongly depleted in 18O. A continuum of the relationships between calcite veins and cataclastic deformation is observed, from veins that precipitated early in the fault history, with calcite grains broken during subsequent deformation, to late veins which seal the almond-type structures within the claystones. The geometry of the calcite grains within the veins and the relationship between the veins and the wall rock indicate that the mechanism that actuate during the vein formation is that of crack-seal. It took place along variable growth planes inside the vein and the wall rock (localized and delocalized stretching veins, respectively), which result in asymmetric syntaxial veins. All the observed microfaults produced lengthening of the markers. Together with the mesoscopic criteria (according to the visual core descriptions made onboard), this would indicate that, in its present-day position, this brittle shear zone is associated with a normal fault. Nevertheless, it is not discarded that it could be an early thrust rotated after its development. Acknowledgements: This research used samples provided by IODP. Grants RNM-215 and 451 ("Junta de Andalucía", Spain) and CGL2013-46368-P ("Ministerio de Economía y Competitividad", Spain) supported this study.

Geology of the Devils Hole area, Nevada

USGS Publications Warehouse

Carr, W.J.

1988-01-01

Detailed and reconnaissance mapping of the Devils Hole, Nevada, area has improved definition of the local geologic structure within a regional carbonate aquifer near its primary discharge points -- the springs of Ash Meadows. Several formerly unmapped calcite veins, and other young calcite-lined paleo-spring feeder zones were found, as well as a number of previously unknown small collapse areas in the limestone. Although the predominant structural grain of the area is oriented northwest, the importance of the very subordinate northeast-striking faults and fractures is underscored by their association with Devils Hole itself, with most of the collapse depressions, and with many of the calcite veins in ' lake beds ' and alluvium. Probable channeling of groundwater flow may occur along one important northeast-striking fault zone. The persistent tendency for openings may have been facilitated by underlying low-angle faults that separate brittle carbonate rocks from underlying, less-competent clastic rocks. (Author 's abstract)

Polyphase vein mineralization in the Fennoscandian Shield at Åkerlandet, Järvsand, and Laisvall along the erosional front of the Caledonian orogen, Sweden

NASA Astrophysics Data System (ADS)

Saintilan, Nicolas J.; Stephens, Michael B.; Spikings, Richard; Schneider, Jens; Chiaradia, Massimo; Spangenberg, Jorge E.; Ulianov, Alexey; Fontboté, Lluís

2017-08-01

The Åkerlandet, Järvsand, and Laisvall deposits in Sweden are calcite-fluorite-sulfide vein deposits and occurrences located close to the current erosional front of the Caledonian orogen and hosted by crystalline basement rocks in the Fennoscandian Shield. At Laisvall, basement-hosted veinlets occur beneath Ediacaran to Cambrian sandstones that host a strata-bound Pb-Zn deposit. The mineralized fractures at Åkerlandet and Järvsand occur along fault systems oriented N-S to NNW-SSE. Veins or veinlets strike NNW-SSE and NW-SE at Åkerlandet, NNE-SSW at Järvsand, and NNW-SSE and NNE-SSW to NE-SW at Laisvall. At Åkerlandet and Järvsand, fractures acted as conduits for hydrothermal fluids of variable composition and formed during separate tectonic events. At Åkerlandet, the fault zone with NNW-SSE strike shows kinematic indicators consistent with NE-SW bulk horizontal extension. At Järvsand, the calcite-fluorite-galena veins formed along R-Riedel shears related to the host N-S to NNW-SSE fault system. The kinematic indicators are consistent with NW-SE bulk horizontal extension, similar to the extensional deformation during the later part of the Caledonian orogeny (Silurian to Devonian). At Åkerlandet, adularia-quartz deposition was followed by sphalerite ± galena and finally by precipitation of fluorite and calcite. 40Ar-39Ar thermochronology of a single adularia sample did not yield a well-defined plateau age but the gas released at higher temperatures suggests an early Tonian (980 to 950 Ma) crystallization age, i.e., during the later part of the Sveconorwegian orogeny, although the data do not exclude other less likely interpretations. Previous fluid inclusion microthermometry and geochronological studies and new petrographic and geochemical results suggest that sphalerite ± galena mineralization formed from saline, relatively oxidizing, moderate-temperature, and slightly acidic hydrothermal fluids, either during the Ediacaran or the Middle Ordovician. Metals and H2S were derived from local basement rocks. Based on petrographic evidence, rare earth element composition, and S, C, and O isotope data, fluorite and calcite precipitated under near neutral and relatively reducing conditions. Occurrence of solid bitumen in veins at Åkerlandet and C and O isotope data of calcite at Åkerlandet and in the Laisvall basement veinlets suggest that the precipitation of calcite and fluorite was triggered by interaction of hot and evolved hydrothermal fluids (87Sr/86Sr = 0.718-0.732) with organic matter. Structural, petrographic, and geochemical data at Laisvall suggest that the basement structures hosting calcite-fluorite ± pyrite veinlets were utilized in the Middle Ordovician as the plumbing system for the oxidizing, slightly acidic, metal-bearing brines that caused the economic Pb-Zn mineralization in the overlying sandstones.

Micro- and Nanostructures of SAFOD Core Samples - First Results

NASA Astrophysics Data System (ADS)

Janssen, C.; Wirth, R.; Rybacki, E.; Naumann, R.; Kemnitz, H.; Wenk, H.; Dresen, G. H.

2009-12-01

Microstructures and chemical composition of ultra-cataclastic rocks from the San Andreas Fault drill hole (SAFOD) were examined using TEM, SEM and XRD analyses. The ultra-cataclasites are mainly composed of quartz, clay minerals (illite/smectite, chlorite), feldspar (plagioclase) and calcite with grain sizes between 200 nm and 500 μm. In particular we found: (1) amorphous materials, identified by transmission electron microscopy. Chemical analyses suggest that all amorphous material was formed by comminution (crush-origin) of fragments rather than by melting (melt-origin) and that the observed amorphous phases may act as hydrodynamic lubricating layers that reduce friction in the San Andreas Fault. (2) Pressure solution seams and localized precipitation of hydrous mixed-layered clay minerals suggest intensive dissolution-precipitation processes. These may lead to a thin film covering slip surfaces. (3) Authigenic clay minerals forming a flocculated fabric. (4) The fine-grained (< 1μm) gouge matrix contains clasts (feldspar, quartz) and is frequently cut by fault-related veins. The veins are filled with calcite or quartz. Observed micorstructures in the fine-grained matrix suggest comminution and sliding of the nanoscale grains. Open pore spaces up to 2.25 μm3 have been formed during and after deformation within the gouge matrix. These were possibly filled with hydrothermal fluids at elevated pore fluid pressure preventing closure. (5) Detrital quartz and feldspar grains are partly dissolved and replaced by authigenic illite-smectite (I-S) mixed-layer clay minerals. TEM imaging of these grains reveal that initial alteration processes started within pores and small fissures of grains. The crystallographic-preferred orientation of illite and I/S grains is rather weak with a maximum m.r.d. (multiples of random orientation) of 2.3. (6) Some older fault-related vein-calcites show evidence for intense intracrystalline plasticity (deformation twins and dislocation creep). Dislocation densities in calcite grains indicate a local maximum stress of about 40 MPa. The younger fault-related vein-calcite generation with elongated to fibrous habit suggests slow opening by aseismic slip. These crystals are not fractured or twinned (or only less); indicating that healing processes (cementation) outlasted deformation.

Aragonite-calcite precipitation in vertical fractures of the "Erzberg" siderite deposit (Austria): Hydrogeochemical and neotectonic implications

NASA Astrophysics Data System (ADS)

Boch, Ronny; Wang, Xianfeng; Kluge, Tobias; Kurz, Walter; Leis, Albrecht; Lin, Ke; Pluch, Hannes; Mittermayr, Florian; Dietzel, Martin

2017-04-01

The ore deposit "Erzberg" represents the worldwide largest FeCO3 occurrence and is amongst Austria's most prominent geological places due to its historic, economic and scientific value. The iron-ore (siderite/ankerite) bearing Devonian carbonates of the open pit mine locally host sequential aragonite-calcite precipitates infilling vertical fractures. These typically laminated carbonates are referred to as erzbergite in mineral collections. To study their formation conditions we recovered samples on-site, i.e. from the rare veins being cm to dm in horizontal and tenths of meters in vertical extension. Additionally, samples from our university collection and private collectors were investigated. Some of the fractures filled with aragonite/calcite further exhibit cataclastic sediments, damage zones and slickenside striations. Modern water samples were collected from fractures currently accessible to conduct hydrochemical analyses and modeling. Selected precipitates were analyzed applying microscopic techniques, XRD, electron microprobe elemental mapping, stable and clumped isotopes, and 238U-234U-230Th radiometric dating. Erzbergite veins show either uni- or bidirectional growth, i.e. on one or both fracture/fault planes toward complete infilling depending on vadose water flow. The laminated precipitates are dominated by aragonite relative to pristine as well as partially diagenetic (Mg)-calcite. Intercalated and recurrent brownish Fe-rich layers consisting of goethite, quartz, muscovite are probably of detrital origin. Stable C and O isotopes of the precipitates reveal pronounced spatiotemporal variations in which low δ18O values (-10.4 to -5.1 ‰ VPDB) reflect a meteoric origin and low temperatures of the erzbergite depositing solutions. Carbonate clumped isotope measurements verify formation temperatures ≤25 °C. High δ13C values (-0.7 to +6.8 ‰ VPDB) of the precipitates indicate an origin from dissolution of local ankerite and limestone, without a significant proportion from soil CO2. Prominently high δ13C in DIC (≤+3.8 ‰) were also measured in modern fracture waters next to elevated sulfate (up to 226 mg/l) and high total dissolved solid contents (up to 1273 mg/l). These results suggest intense water-rock interaction based on sulfide oxidation and sulfuric acid evolution providing an efficient mechanism for host rock dissolution, mobilization and typically rapid aragonite-calcite mineralization. Sulfide accessories are widespread at Erzberg and the brownish Fe-rich layers within erzbergite could be explained by corrosion of Fe-sulfides and/or Fe-carbonates. The aragonite-calcite lamination is interpreted as an event lamination (not annual), i.e. variable aqueous Mg2+/Ca2+ ratios and CaCO3 supersaturation states triggering the polymorphism. U-Th analyses yielded surprisingly young ages for erzbergite dated so far, i.e. late Pleistocene and mostly younger than the last glacial maximum. A 4 cm thick sample composed of aragonite exclusively and filling a tenths of meters extending fracture formed 10.4 ±0.2 (sample base, initiation) to 1.03 ±0.04 kyr BP (top, fracture filled). Another 25 cm laminated aragonite-calcite precipitate covers 14.2 ±0.2 to 5.0 ±0.2 kyr. Thus, the precipitates support geologically young and rather short time intervals of infilling and we consider it unlikely that the fractures are much older. An intimate connection with neotectonic activity entailing new vadose water flow routes and fresh reaction surfaces in fractures would be in accordance with our hydrogeochemical and field observations.

Structural control on fluid flow at the Dominga IOCG deposit in Northern Chile: insights from microtextural analysis

NASA Astrophysics Data System (ADS)

Heuser, G.; Arancibia, G.; Veloso, E. A.; Reich, M.; Morales, H.

2017-12-01

The Fe-Cu paragenetic assemblages at the Cretaceous Dominga IOCG deposit in northern Chile (2082 Mt at 23% Fe, 0.07% Cu) show a spatial and genetic affinity with major structural systems in the district: the Early Structural System (ESS), El Tofo Structural System (ETSS) and Intermediate Structural System (ISS), developed under different tectonic regimes, from transtension (ESS) to transpression (ETSS, ISS). The ESS is a NE-ENE-trending right-lateral strike slip duplex related to the formation of biotite-magnetite mineralization in Fe-rich bands parallel to bedding (stage I), and magnetite-apatite-actinolite-quartz hydrothermal breccia (stage II). The ETSS is a NNE left-lateral fault breccia related to K-feldspar veins and anhydrite-chalcopyrite hydrothermal breccia (stage III). The ISS is a NW-WNW left lateral strike slip duplex composed of calcite veins (stage IV). However, an understanding of fault-driven fluid flow mechanisms and their impact on the studied Fe-Cu deposit is still lacking. We analyzed representative textures from veins and hydrothermal breccias of stages II, III and IV. Microstructural analysis was made in thin/polished sections normal and parallel to the vein wall using optical and scanning electron microscopy techniques. Stage II shows euhedral magnetite with ilmenite lamellae exsolution textures and intergrowths between magnetite and anhedral mosaic quartz. Hydrothermal breccias contain euhedral quartz with double-terminated crystal shapes and concentric growth zoning surrounded by plumose quartz. Stage III exhibits zoned K-feldspar veins, banded plumose quartz veins, and mosaic subhedral anhydrite. Stage IV is characterized by banded veins of plumose and rhombic calcite, and dilational jogs with rhombic calcite. The observed microtextures suggest slow cooling of high temperature Fe-Cu-rich fluid, suspension in aqueous fluid during crystal growth, and boiling. Despite the different tectonic regimes, the paleo-fluids at the Dominga IOCG deposit were emplaced under similar conditions during the main activity of each structural system, i.e., 1) development of veins related to fluid overpressure and 2) episodic boiling triggered by abrupt pressure drop. Acknowledgements: CONICYT Ph.D. Scholarship, Millennium Nucleus for Metal Tracing Along Subduction NC 130065.

Geology, mineralization, and hydrothermal alteration and relationships to acidic and metal-bearing surface waters in the Palmetto Gulch area, southwestern Colorado

USGS Publications Warehouse

Bove, Dana J.; Kurtz, Jeffrey P.; Wright, Winfield G.

2002-01-01

The Palmetto Gulch area is affected by low pH and metal-bearing drainage from abandoned mines, and perhaps, from natural weathering around vein zones. To investigate these anthropogenic and potential natural sources of acidity and metals, we mapped the geology, veins, and hydrothermally altered areas; conducted mine dump leachate studies; and collected reconnaissance water quality data. Several small abandoned mines are present in the Palmetto Gulch area that produced small amounts of relatively high-grade silver ore from fault-controlled polymetallic vein deposits. These veins are hosted in lavas, breccias, and related volcaniclastic sediments that ponded within the 28 Ma San Juan-Uncompahgre caldera complex. These rock units generally have conformable contacts and have shallow dips to the northwest. Lava flows of pyroxene andesite, which host the Roy-Pray mine, are massive near their base and typically grade upward into tightly jointed rock with 2-15 cm joint spacing. In general, most hydrothermally altered rock within the Palmetto Gulch area is restricted to envelopes surrounding the mineralized veins and faults. Composite zones of vein-related alteration vary from about 50 to 80 m wide along the high ridgelines and narrow to less than 10 to 15 m beneath an elevation of about 5,462 m. Where unaffected by surficial oxidation, these altered zones contain as much as 7 to 10 volume percent finely-disseminated pyrite. The majority of rocks in the area were affected by regional and vein-related propylitic alteration. These greenish-colored rocks have alteration products consisting of chlorite, illite, and calcite; and feldspars are typically weakly altered. Most of these rocks have detectable amounts of calcite, while as much as 11 percent by weight was detected in samples collected during this study. The Palmetto Gulch area is affected by low pH and metal-bearing drainage from abandoned mines, and perhaps, from natural weathering around vein zones. To investigate these anthropogenic and potential natural sources of acidity and metals, we mapped the geology, veins, and hydrothermally altered areas; conducted mine dump leachate studies; and collected reconnaissance water quality data. Several small abandoned mines are present in the Palmetto Gulch area that produced small amounts of relatively high-grade silver ore from fault-controlled polymetallic vein deposits. These veins are hosted in lavas, breccias, and related volcaniclastic sediments that ponded within the 28 Ma San Juan-Uncompahgre caldera complex. These rock units generally have conformable contacts and have shallow dips to the northwest. Lava flows of pyroxene andesite, which host the Roy-Pray mine, are massive near their base and typically grade upward into tightly jointed rock with 2-15 cm joint spacing. In general, most hydrothermally altered rock within the Palmetto Gulch area is restricted to envelopes surrounding the mineralized veins and faults. Composite zones of vein-related alteration vary from about 50 to 80 m wide along the high ridgelines and narrow to less than 10 to 15 m beneath an elevation of about 5,462 m. Where unaffected by surficial oxidation, these altered zones contain as much as 7 to 10 volume percent finely-disseminated pyrite. The majority of rocks in the area were affected by regional and vein-related propylitic alteration. These greenish-colored rocks have alteration products consisting of chlorite, illite, and calcite; and feldspars are typically weakly altered. Most of these rocks have detectable amounts of calcite, while as much as 11 percent by weight was detected in samples collected during this study.

Magmatic-like fluid source of the Chingshui geothermal field, NE Taiwan evidenced by carbonate clumped-isotope paleothermometry

NASA Astrophysics Data System (ADS)

Lu, Yi-Chia; Song, Sheng-Rong; Wang, Pei-Ling; Wu, Chung-Che; Mii, Horng-Sheng; MacDonald, John; Shen, Chuan-Chou; John, Cédric M.

2017-11-01

The Chingshui geothermal field, a moderate-temperature and water-dominated hydrothermal system, was the site of the first geothermal power plant in Taiwan. Many geological, geophysical and geochemical studies using more than 21 drilled wells have been performed since the 1960s. However, there are still controversies regarding the heat and fluid sources due to the tectonically complicated geological setting. To clarify the heat and fluid sources, we analyzed clumped isotopes with carbon and oxygen isotopic compositions of calcite scaling in geothermal wells and veins on outcrops and calculated the δ18O values of the source fluids. Two populations of δ18O values were calculated: -5.8 ± 0.8‰ VSMOW from scaling in the well and -1.0 ± 1.6‰ to 10.0 ± 1.3‰ VSMOW from outcropping calcite veins, indicative of meteoric and magmatic fluid sources, respectively. Meanwhile, two hydrothermal reservoirs at different depths have been identified by magnetotelluric (MT) imaging with micro-seismicity underneath this area. As a result, we propose a two-reservoir model: the shallow reservoir provides fluids from meteoric water for the scaling sampled from wells, whereas the deep reservoir provides magmatic fluids from deep marble decarbonization recorded in outcropping calcite veins.

Lifetime of an ocean island volcano feeder zone: constraints from U-Pb dating on coexisting zircon and baddeleyite, and 40/39Ar age determinations, Fuerteventura, Canary Islands

USGS Publications Warehouse

Allibon, James; Ovtcharova, Maria; Bussy, Francois; Cosca, Michael; Schaltegger, Urs; Bussien, Denise; Lewin, Eric

2011-01-01

High-precision isotope dilution - thermal ionization mass spectrometry (ID-TIMS) U-Pb zircon and baddeleyite ages from the PX1 vertically layered mafic intrusion Fuerteventura, Canary Islands, indicate initiation of magma crystallization at 22.10 ± 0.07 Ma. The magmatic activity lasted a minimum of 0.52 Ma. 40Ar/39Ar amphibole dating yielded ages from 21.9 ± 0.6 to 21.8 ± 0.3, identical within errors to the U-Pb ages, despite the expected 1% theoretical bias between 40Ar/39Ar and U-Pb dates. This overlap could result from (i) rapid cooling of the intrusion (i.e., less than the 0.3 to 0.6 Ma 40Ar/39Ar age uncertainties) from closure temperatures (Tc) of zircon (699-988 °C) to amphibole (500-600 °C); (ii) lead loss affecting the youngest zircons; or (iii) excess argon shifting the plateau ages towards older values. The combination of the 40Ar/39Ar and U/Pb datasets implies that the maximum amount of time PX1 intrusion took to cool below amphibole Tc is 0.8 Ma, suggesting PX1 lifetime of 520,000 to 800,000 Ma. Age disparities among coexisting baddeleyite and zircon (22.10 ± 0.07/0.08/0.15 Ma and 21.58 ± 0.15/0.16/0.31 Ma) in a gabbro sample from the pluton margin suggest complex genetic relationships between phases. Baddeleyite is found preserved in plagioclase cores and crystallized early from low silica activity magma. Zircon crystallized later in a higher silica activity environment and is found in secondary scapolite and is found close to calcite veins, in secondary scapolite that recrystallised from plagioclase. close to calcite veins. Oxygen isotope δ18O values of altered plagioclase are high (+7.7), indicating interaction with fluids derived from host-rock carbonatites. The coexistence of baddeleyite and zircon is ascribed to interaction of the PX1 gabbro with CO2-rich carbonatite-derived fluids released during contact metamorphism.

Fluid Characteristics and Evolution of Chelungpu fault of Taiwan

NASA Astrophysics Data System (ADS)

Song, S. R.

2017-12-01

We analyzed geochemical characteristics, such as hydrogen and oxygen isotopes, and ionic concentrations, of fluid samples retrieved from various depth along boreholes of the Hole A and Hole B of Taiwan Chelungpu fault Drilling Project(TCDP) to trace the fluid sources. The results show that the source of fluid in the Hole B is mainly the tap water, while there are two probable sources in the Hole A owing to the abrupt shift of ionic concentrations at the depth of 200-300 m. The shallower fluid might be from the leakage above the depth of 300 m and is characteristic of lower ionic concentrations and the isotopic ratios are close to those of adjacent river water. However, the deeper fluid should be the thermal water from Kueichulin formation because of high ionic concentrations, especially HCO3-, and higher oxygen isotope, which suggests higher temperature and more isotope exchange. Two sources of fluid of the Hole A are representative of the fluid systems in the hanging wall and foot wall respectively. The characteristics of fluids in the Hole A imply that the fault zone serves as a barrier in the inter-seismic period, resulting in distinctly different fluid between the Hanging wall and the foot wall. The frequent occurrence and the distribution of calcite veins provide the evidence of the upwelling of HCO3-rich fluid of Kueichulin formation and indicate that the fault served as fluid conduit during faulting and allowed the fluid flow across the fault zone to precipitate calcite veins in fractures of the hanging wall. Thus, we can deduce the mechanism of local groundwater flow during different stages of fault development by evidences such as calcite veins distribution, regional groundwater geology, and fluids characteristics in boreholes of the Hole-A and Hole B. During inter-seismic period, groundwater flows below and above the fault zone are separated by the impermeable fault gouge layer. In co-seismic time, faulting breaks the gouge layer, providing openings that let the over-pressured thermal water which contained high concentration of bicarbonate ion to surge up. After co-seismic period, the gouge layer is sealed again, residual thermal water which contained high concentration of bicarbonate ion in the hanging wall gradually precipitated calcite in fractures and the closer precipitation took place, the more calcite veins.

Cenozoic seawater Sr/Ca evolution

NASA Astrophysics Data System (ADS)

Sosdian, Sindia M.; Lear, Caroline H.; Tao, Kai; Grossman, Ethan L.; O'Dea, Aaron; Rosenthal, Yair

2012-10-01

Records of seawater chemistry help constrain temporal variations in geochemical processes that impact the global carbon cycle and climate through Earth's history. Here we reconstruct Cenozoic seawater Sr/Ca (Sr/Casw) using fossil Conus and turritellid gastropod Sr/Ca. Combined with an oxygen isotope paleotemperature record from the same samples, the gastropod record suggests that Sr/Caswwas slightly higher in the Eocene (˜11.4 ± 3 mmol/mol) than today (˜8.54 mmol/mol) and remained relatively stable from the mid- to late Cenozoic. We compare our gastropod Cenozoic Sr/Casw record with a published turritellid gastropod Sr/Casw record and other published biogenic (benthic foraminifera, fossil fish teeth) and inorganic precipitate (calcite veins) Sr/Caswrecords. Once the uncertainties with our gastropod-derived Sr/Casw are taken into account the Sr/Casw record agrees reasonably well with biogenic Sr/Caswrecords. Assuming a seawater [Ca] history derived from marine evaporite inclusions, all biogenic-based Sr/Casw reconstructions imply decreasing seawater [Sr] through the Cenozoic, whereas the calcite vein Sr/Casw reconstruction implies increasing [Sr] through the Cenozoic. We apply a simple geochemical model to examine the implications of divergence among these seawater [Sr] reconstructions and suggest that the interpretation and uncertainties associated with the gastropod and calcite vein proxies need to be revisited. Used in conjunction with records of carbonate depositional fluxes, our favored seawater Sr/Ca scenarios point to a significant increase in the proportion of aragonite versus calcite deposition in shelf sediments from the Middle Miocene, coincident with the proliferation of coral reefs. We propose that this occurred at least 10 million years after the seawater Mg/Ca threshold was passed, and was instead aided by declining levels of atmospheric carbon dioxide.

Synorogenic crustal fluid infiltration in the Idaho-Montana Thrust Belt

NASA Astrophysics Data System (ADS)

Bebout, Gray E.; Anastasio, David J.; Holl, James E.

Mississippian carbonates in the Sevier thrust belt in Idaho-Montana show shifts in δ18OV-SMOW, from marine carbonate values to as low as +11‰, which are best explained by exchange with externally-derived, low-δ18O fluids. Late-stage, synkinematic calcite veins are depleted in 18O relative to the host-rocks and earlier-formed veins, many having δ18O of +5 to +10‰. These veins could have equilibrated with H2O with δ18O of -7.5 to +2.5‰, perhaps reflecting infiltration of the Sevier thrust wedge by nearshore meteoric waters to depths of ˜10 km. Calcite veins in the hangingwall and footwall of the Pioneer Metamorphic Core Complex, produced during later Paleogene extension, have δ18O of -8.7 to +1.4‰ consistent with equilibration with meteoric waters with δ18O as low as -14‰. Transition from a Cretaceous crustal fluid regime influenced by the nearby Western Interior Seaway to one influenced by lower-δ18O, more inland meteoric waters is consistent with seaway retreat during thrust wedge emergence and Paleogene uplift and subaerial volcanism.

Petro-structural, geochemical and carbon and oxygen isotopic study on carbonates crosscuting the Oman Ophiolite peridotites: evidence of polygenic CO2 trapping

NASA Astrophysics Data System (ADS)

Noël, J.; Godard, M.; Martinez, I.; Oliot, E.; Williams, M. J.; Rodriguez, O.; Chaduteau, C.; Gouze, P.

2017-12-01

Carbon trapping in ophiolitic peridotites contributes to the global carbon cycle between solid Earth and its outer envelopes (through subduction and/or modern alteration). To investigate this process, we performed petro-structural (microtomography, EBSD, EPMA) and geochemical studies (LA-ICP-MS, carbon and oxygen isotopes on bulk and minerals using SHRIMP) of harzburgites cored in the Oman Ophiolite. Studied harzburgites are highly serpentinized (> 90 %) and crosscut by 3 generations of carbonates (> 20 Vol%) with compositions from calcite to dolomite (Mg/Ca = 0-0.85). Type 1 carbonates are fine penetrative veinlets and mesh core after olivine. They have low REE (e.g., Yb = 0.08-0.23 x CI-chondrite) and negative Ce anomalies. They have δ13CPDB = -15.2 to 1.10‰ and δ18OSMOW = 17.5 to 33.7‰, suggesting precipitation temperatures up to 110°C. Type 2 carbonates are pluri-mm veins bounded by cm-thick serpentinized vein selvages, oriented dominantly parallel to mantle foliation. Dynamic recrystallization is observed, indicating polygenetic formation: well crystallized calcite with REE abundances similar to Type 1 carbonates are locally replaced by small dolomite and calcite grains with higher REE (e.g., Yb = 0.35-1.0 x CI-chondrite) and positive Gd anomaly. Type 2 carbonates have δ13CPDB = -12.6 to -4.1‰ and δ18OSMOW = 25.0 to 32.7‰, suggesting precipitation temperatures from 10 to 60°C. Type 3 carbonates are late pluri-mm to cm veins reactivating Type 2 veins. They consist of small grains of dolomite and calcite with REE abundances similar to recrystallized Type 2 carbonates. Type 3 carbonates have δ13CPDB = -8.3 to -5.8‰ and δ18OSMOW = 28.8 to 32.7‰, suggesting precipitation temperatures <35°C. δ13C data indicate an evolution of fluid composition precipitating carbonates from seawater- and sediment-derived fluids to meteoric water. Carbonate formation starts during oceanic lithospheric cooling and occurs as a penetrative process at the expense of olivine (Type 1, at T > 100°C). Formation of carbonate veins (Type 2) indicates localization of fluid flux, while serpentinization remains the dominant alteration process. Low T carbonate veins (Type 3) remain the main flow path through ophiolitic peridotites. Our study suggests that their orientation is controlled by the later stages of oceanic mantle deformation.

Syntectonic Fluid-Rock Interactions Involving Surficial Waters in the Sevier Thrust Belt, Tendoy Mountains, Southwest Montana

NASA Astrophysics Data System (ADS)

Johnson, A. C.; Anastasio, D. J.; Bebout, G. E.

2002-05-01

Calcite veins and Mississippian carbonates from the Sevier thrust front record syntectonic meteoric fluid infiltration and hydrocarbon migration. The Tendoy and Four Eyes Canyon thrust sheets were emplaced onto the western margin of the Late Cretaceous Western Interior Seaway \\{WIS\\}. Low salinity \\{Tice = -0.6° C to +3.6° C\\} and low temperature \\{110° C +/- 10\\} fluids interacted with hanging-wall carbonates at a depth of 5km. Most veins have single or multiple generations of varying apertures, composed predominately of large euhedral crystals with some finer grained layers and protolith inclusions. Orientation analysis of mutually cross-cutting, high-angle vein sets suggest development concurrent with Four Eyes Canyon thrusting but prior to Tendoy thrusting. These vein sets are generally cut by later synfolding bed-parallel shear veins. Reactivation of both the bed-parallel and bed-perpendicular vein sets \\{strike parallel and strike perpendicular\\} in the Four Eyes Canyon thrust sheet occurred subsequent to Sevier compression, creating wide, coarse crystalline veins that often transect Sevier structures. Oxygen and Carbon isotope analyses of veins allow for reconstruction of fluid-rock interactions during thrust sheet emplacement and later reactivation. All veins and variably deformed host-rocks were microsampled and analyzed for δ 18OV-SMOW and δ 13CV-PDB. Small Tendoy veins \\{1mm-1cm wide\\} have calcite δ 18O values of +8.9 to +28.8‰ and calculated fluid \\{as H2O\\} of -8.3 to +11.6‰ \\{100° C\\}, -7.3 to +12.6‰ \\{110° C\\}, and -6.3 to +13.6‰ \\{120° C\\}. Four Eyes Canyon veins \\{1cm-3m wide\\} have calcite δ 18O values of +5.9 to +17.0‰ and calculated fluid of -11.3 to -0.2‰ \\{100° C\\}, -10.3 to +0.8‰ \\{110° C\\}, and -9.3 to +1.8‰ \\{120° C\\}. While there is significant variation in δ 18O there is relatively little systematic variation seen in δ 13C. Protolith carbonate has δ 18O values of +22.2‰ +/- 3.2; and some multi-layered veins are more depleted in δ 18O in earlier-formed generations. For three sites in the Lost River Range \\{LRR\\}, Idaho, the calculated minimum fluid δ 18O is -7.5‰ \\{+150 to +250° C\\} \\{Bebout et al., 2001; GRL\\}. Although the uncertainty of the regional temperature is large, when assuming a temperature of 110° C +/- 10 the Tendoy has a minimum calculated δ 18O H2O value of -8.3 to -6.3‰ and the Four Eyes Canyon has a minimum calculated δ 18O H2O value of -11.3 to -9.3‰ . These fluid O-isotope compositions are similar to the minimum H2O δ 18O calculated for the LRR sites - all pointing to infiltration of the thrust sheets by meteoric waters, possibly relatively nearshore meteoric waters with isotopic compositions strongly influenced by the nearby WIS. Surficial fluids possibly infiltrated into the thrust sheets by topographic recharge and migrated updip towards the foreland, mixing to varying degrees with more deeply roused fluids. Smaller veins and longer travel times and distances favored more extensive fluid-rock interaction and thus more rock-controlled fluid compositions. Microfractures in veins healed by hydrocarbons indicate that hydrocarbons migrated with freshwater fluids. Calcite veins record a dynamic history of fluid pathways and fluid flow as permeability evolved during thrust emplacement.

Hydrocarbon-water interactions during brine migration: Evidence from hydrocarbon inclusions in calcite cements from Danish North Sea oil fields

USGS Publications Warehouse

Jensenius, J.; Burruss, R.C.

1990-01-01

Crude oils in primary and secondary fluid inclusions in calcite from fractures in seven offshore oil fields associated with diapiric salt structures in the Danish sector of the North Sea were analyzed by capillary column gas chromatography and compared with crude oils produced from the same reservoirs. Oils from fluid inclusions in all fields show evidence of biodegradation (decreased n-C17/pristane and n-C18/phytane ratios and loss of n-C7, 2-methyl hexane, and 3-methyl hexane relative to methyl cyclohexane) and water washing (absence of benzene and depletion of toluene). Some oils in inclusions are extremely enriched in C6 and C7 cyclic alkanes suggesting that these samples contain hydrocarbons exsolved from ascending, hotter formation waters. Compared to inclusion oils the produced oils are less biodegraded, but are water washed, indicating that both types of oil interacted with large volumes of formation water. The carbon isotopic composition of the calcite host of the fluid inclusions in the Dagmar and Skjold fields is as light as -16.5%. PDB and the sulfur isotopic composition of pyrite in and adjacent to the calcite veins in the Skjold field is as light as -39.6%. CDT, indicating that biodegradation of the oils was a source of some of the carbon in the calcite and sulfate reduction was the source of sulfur for the pyrite. The evidence for microbial degradation of petroleum is consistent with present-day reservoir temperatures (65??-96??C) but is not consistent with previous estimates of the temperatures of calcite vein filling (95??-130??C) which are much higher than the temperatures of known occurrences of biodegraded oil. ?? 1990.

Hydrocarbon-water interactions during brine migration: Evidence from hydrocarbon inclusions in calcite cements from Danish North Sea oil fields

NASA Astrophysics Data System (ADS)

Jensenius, Jørgen; Burruss, Robert C.

1990-03-01

Crude oils in primary and secondary fluid inclusions in calcite from fractures in seven offshore oil fields associated with diapiric salt structures in the Danish sector of the North Sea were analyzed by capillary column gas chromatography and compared with crude oils produced from the same reservoirs. Oils from fluid inclusions in all fields show evidence of biodegradation (decreased n- C17/pristane and n- C18/phytane ratios and loss of n-C 7, 2-methyl hexane, and 3-methyl hexane relative to methyl cyclohexane) and water washing (absence of benzene and depletion of toluene). Some oils in inclusions are extremely enriched in C 6 and C 7 cyclic alkanes suggesting that these samples contain hydrocarbons exsolved from ascending, hotter formation waters. Compared to inclusion oils the produced oils are less biodegraded, but are water washed, indicating that both types of oil interacted with large volumes of formation water. The carbon isotopic composition of the calcite host of the fluid inclusions in the Dagmar and Skjold fields is as light as -16.5%. PDB and the sulfur isotopic composition of pyrite in and adjacent to the calcite veins in the Skjold field is as light as -39.6%. CDT, indicating that biodegradation of the oils was a source of some of the carbon in the calcite and sulfate reduction was the source of sulfur for the pyrite. The evidence for microbial degradation of petroleum is consistent with present-day reservoir temperatures (65°-96°C) but is not consistent with previous estimates of the temperatures of calcite vein filling (95°-130°C) which are much higher than the temperatures of known occurrences of biodegraded oil.

A transient fault-valve mechanism operating in upper crustal level, Sierras Pampeanas, Argentina

NASA Astrophysics Data System (ADS)

Japas, María Silvia; Urbina, Nilda Esther; Sruoga, Patricia; Garro, José Matías; Ibañes, Oscar

2016-11-01

Located in the Sierras Pampeanas (the broken-foreland of the Pampean flat slab segment in the southern Central Andes), the Cerro Tiporco volcanic field shows Neogene hydrothermal activity linked to migration of arc-magmatism into the foreland. Late Neogene deposits comprise epithermal vein systems emplaced in Precambrian-Early Palaeozoic igneous-metamorphic basement, Late Miocene sedimentary rocks and Early Pliocene volcaniclastic rocks. Mineralization consists of calcareous onyx, aragonite and calcite veins as well as travertine deposits. Onyx and aragonite occur as fill of low-displacement nearly vertical reverse-sinistral faults striking NW, and nearly horizontal dilatant fractures. The latter consist of load-removal induced fractures affecting the igneous-metamorphic rocks, as well as bedding planes in the Late Miocene sediments. The presence of veins recording multiple fracture episodes and crack-and-seal growth of veins suggests relatively low differential stress and supralithostatic fluid pressure, as well as cyclic changes in pore pressure and high mineral-deposition/fracture-opening ratio. These conditions support a mechanism of fault-valve behaviour during onyx and aragonite vein emplacement. The fault-valve mechanism involves fractures associated with impermeable barriers between environments with different fluid pressure. Faulting generated an appreciable directional permeability triggering fluid migration from the highest to the lowest pressure region, with subsequent deposition and sealing that started a new pressurization-faulting-sealing cycle. Late aragonite and calcite veins suggest a change in kinematics indicating the onset of tectonic-load conditions.

Post-metamorphic fluid infiltration into granulites from the Adirondack Mountains, USA

NASA Technical Reports Server (NTRS)

Morrison, J.; Valley, John W.

1988-01-01

Post-metamorphic effects in the anorthosites of the Adirondacks, New York were described. Calcite-chlorite-sericite assemblages occur as veins, in disseminated form and as clots, and document retrograde fluid infiltration. These features are associated with late-state CO2-rich fluid inclusions. Stable isotope analyses of calcites indicates that the retrograde fluids interacted with meta-igneous and supracrustal lithologies, but the precise timing of the retrogression is as yet unknown.

The Bowland Basin, NW England: Base metal mineralisation and its relationship to basin evolution

NASA Astrophysics Data System (ADS)

Gaunt, Jonathan Mark

The Bowland Basin of NW England is a Carboniferous half graben. The Basin was initiated in the Devonian and actively extended during the Carboniferous until the late Westphalian. From the late Westphalian to the early Permian the Bowland Basin underwent inversion in response to Hercynian collision tectonics. Renewed subsidence commenced in the Permian and continued until inversion in the Cenozoic. The sedimentary succession of the Bowland Basin is dominated by Carboniferous strata, but some Permo-Triassic strata are present. The basal sedimentary succession may be comprised of Devonian to early Dinantian syn-rift clastics. The main Dinantian succession is comprised of interbedded limestones, calcareous mudstones and clastic strata. The Dinantian strata include the Waulsortian-facies Clitheroe Limestone and the Limekiln Wood Limestone, both of which host mineralisation. The overlying Namurian is comprised of shales and sandstones. The diagenetic history of the Limekiln Wood Limestone and Waulsortian-facies Clitheroe Limestone in the Cow Ark-Marl Hill Moor district is a function of changes in the burial environment during the Carboniferous. Both exhibit a pre-basin inversion diagenetic sequence that changes with time from shallow to moderate burial depth cements. Late Carbonifeous basin inversion resulted in the formation of tectonic stylolites. Tectonic stylolitisation was postdated by dolomitisation and silicification. Dolomitisation and silicification are suggested to have taken place in the deep burial environment. The base metal mineralisation studied in this work comes from the Cow Ark- Marl Hill Moor district, which is sited on the present basin inversion axis. Mineralisation occurs as four distinct episodes (Period 1, Period 2, Period 3 and Post-Period 3) within a complex multigeneration vein suite. The vein suite, which postdates tectonic stylolitisation and hence end-Carboniferous basin inversion, is comprised of calcite, baroque dolomite, baroque ankerite and siderite. The veins, which are often spatially associated with faults, exhibit a variety of morphologies, and are largely hosted by hydraulic shear fractures. Compositional variations between the different vein carbonates occur with time and the calcites, baroque dolomites, baroque ankerites and siderites are interpreted to have had several different fluid sources. Fluids precipitating siderite, baroque dolomite and baroque ankerite may have been produced by clay mineral transformations and decarboxylation of organic matter within the calcareous strata. The multiple vein calcite generations belong to three MnO:FeO compositional classes, each occupying a specific paragenetic position. The trend from ferroan to manganoan calcite with time may be a consequence of calcite-forming fluids being derived from successively shallower depths within the sedimentary succession, or of increased permeation by meteoric fluids. (Abstract shortened by ProQuest.).

Thermal evolution of Site U1414 by stable isotopes δ13C and δ18O, 87Sr/86Sr and fluid inclusion analyses, IODP Expedition 344

NASA Astrophysics Data System (ADS)

Brandstätter, Jennifer; Kurz, Walter; Krenn, Kurt; Richoz, Sylvain

2017-04-01

IODP Expedition 344 is the second expedition in course of the Costa Rica Seismogenesis Project (Program A), that was designed to reveal processes that effect nucleation and seismic rupture of large earthquakes at erosional subduction zones. Site 344-U1414, located 1 km seaward of the deformation front offshore Costa Rica, serves to evaluate fluid-rock interaction and geochemical processes linked with the tectonic evolution of the incoming Cocos Plate from the Early Miocene up to recent times. Combined isotope analyses and microthermometric analyses of fluid inclusions of hydrothermal veins within lithified sediments and the igneous basement (Cocos Ridge basalt), was used to reveal the thermal history of Site 344-U1414. Veins in the sedimentary rocks are mainly filled by coarse-grained calcite and subordinately by quartz. Veins within the basalt show polymineralic filling of clay minerals, calcite, aragonite and quartz. Blocky veins with embedded wall rock fragments, appearing in the sediments and in the basalt, indicate hydraulic fracturing. The carbon isotopic composition of the vein calcite suggest the influence of a CO2 -rich fluid mixed with seawater (-3.0 to -0.4‰ V-PDB) and the δ18O values can be differentiated in two groups, depending on the formation temperature (-13.6 to -9.3‰ and -10.8 to -4.7‰ V-PDB). 87Sr/86Sr ratios from the veins confirm the results of the stable isotope analyses, with a higher 87Sr/86Sr ratio close to seawater composition and lower ratios indicating the influence of basalt alteration. The hydrothermal veins contain different types of fluid inclusions with high and low entrapment temperatures and low saline fluids. The occurrence of decrepitated fluid inclusions, formed by increased internal overpressure, is related to isobaric heating. Elongated fluid inclusion planes, arc-like fluid inclusions and low homogenization temperatures suggest subsequent isobaric cooling. The stable isotopic content, strontium isotopic composition and the results of fluid inclusion analyses indicate that the source of fluids is a mixture of mobilized pore water and invaded seawater that communicated with high temperature CO2-rich fluids. We propose that lithification of the sediments was accompanied with a first stage of vein development in the Middle Miocene and was a result of the Galapagos hotspot activity. Heat advection led to subsequent vein modification related to isobaric heating. The latest mineralization occurred during crustal cooling up to recent times.

Greenschist-Facies Pseudotachylytes and Gouge: a Microstructural Study of the Deformation Propagation at the Boundary Between Hp-Metabasite and Calcite Bearing Metasediments

NASA Astrophysics Data System (ADS)

Crispini, L.; Scambelluri, M.; Capponi, G.

2013-12-01

Recent friction experiments on calcite-bearing systems reproduce pseudotachylyte structures, that are diagnostic of dinamic calcite recrystallization related to seismic slip in the shallow crust. Here we provide the study of a pseudotachylyte (PT) bearing low angle oblique-slip fault. The fault is linked to the exhumation of Alpine HP-ophiolites and it is syn- to post-metamorphic with respect to retrograde greenschist facies metamorphism. The observed microstructures developed at the brittle-ductile transition and suggest that seismic and interseismic slip was enhanced by interaction with fluids. The fault zone is in-between high-pressure eclogite-facies metabasites (hangingwall) and calcite bearing metasediments (footwall). The mafic rocks largely consist of upper greenschist facies hornblende, albite, chlorite, epidote with relict eclogitic garnet, Na-pyroxene and rutile; metasediments correspond to calcschist and micaschist with quartz, phengite, zoisite, chlorite, calcite and relics of garnet. Key features of the oucrop are: the thickness and geometry of the PT and gouge; the multiple production of PT characterized by overprinting plastic and brittle deformation; the occurrence in footwall metasediments of mm-thick bands of finely recrystallized calcite coeval with PT development in the hangingwall. The damage zone is ca. 2 m-thick and is characterized by two black, ultra-finegrained straight and sharp Principal Slip Zones (PSZ) marked by PT. The damage zone shows a variety of fault rocks (cataclasite and ultracataclasite, gouge and PT) with multiple crosscutting relationships. Within the two main PSZ, PT occurs in 10-20 cm thick layer, in small scale injection veins and in microfractures. In the mafic hanging wall, the PT is recrystallized and does not preserve glass: it shows flow structures with subrounded, embayed and rebsorbed quartz in a fine grained matrix composed of isotropic albite + chlorite + quartz + epidote + titanite, suggesting recrystallization at ca. 270-300°C, 8-10 km of the original glass. PT show plastic deformations overprinted by shear bands and fracturing. The matrix of cataclastic layers has the same mineral assemblage as PT and clasts of recrystallised PT, to indicate polyphase PSZ formation. In the metasedimentary footwall, the original foliation is deflected parallel to the PSZ and is cut by cm-spaced shear bands parallel to PSZ. Deformation propagates in the footwall through mm-thick injections veins, shear bans, P-shears and veins. Pockets of recrystallized PT occur along the pre-existing mylonitic foliation of metasediments. Worthnote is the presence of mm-thick deformation bands (CDB) that are post-mylonitic foliation and mainly composed of fine grained calcite bounded by dissolution seams or ribbon grains of deformed calcite. CDB are characterised by subrounded embayed and rebsorbed quartz grains rimmed by new Ca-Mg amphibole, K-feldspar (90-93%K), in a dinamic recrystallized calcite 2-10 micron in size and slightly elongated. The features of the CDB suggest that these structures can be considered as diagnostic of localised deformation during coesismic slip in metasedimentary rocks.

Petrologic and stable isotopic studies of a fossil hydrothermal system in ultramafic environment (Chenaillet ophicalcites, Western Alps, France): Processes of carbonate cementation

NASA Astrophysics Data System (ADS)

Lafay, Romain; Baumgartner, Lukas P.; Stephane, Schwartz; Suzanne, Picazo; German, Montes-Hernandez; Torsten, Vennemann

2017-12-01

The Late Jurassic Chenaillet ophiolitic complex (Western Alps) represents parts of an oceanic core-complex of the Liguria-Piemonte domain. A model for the origin and evolution of the Chenaillet ophicalcites based on textural and isotopic characterization is presented. The Chenaillet ophicalcites correspond to brecciated serpentinized peridotites that record seafloor shallow serpentinization at a minimum temperatures of 150 °C followed by authigenic carbonation. Carbonation starts with a network of micrometric to millimetric pre- or syn-clast formation calcite veins accompanied by a pervasive carbonation of residual olivine and serpentine inside the serpentinite mesh core. A matrix of small calcite (< 50 μm, 12 μm in average) cemented clasts after their individualization. Texture of the breccia, grain size distribution within the matrix, and chrysotile clusters support rapid cementation from a strongly oversaturated fluid due most likely to hydrothermal fluid cooling and decompression. Later fluids infiltrated by multiple crack formation and some dolomite locally formed along serpentinite-calcite interfaces. Carbonates have δ13C (VPDB) values that range between - 5‰ and + 0.4‰. The lower values were obtained for calcite within the serpentinite clasts. The δ18O (VSMOW) values have a range between + 11‰ and + 16‰ in carbonated clasts. The δ18O values in the matrix are fairly homogeneous with an average at + 12‰ and the late calcite veins have values between + 12.5 and + 15.5‰. These values suggest a relatively high temperature of formation for all the carbonates. Carbonates within clast are mainly characterized by a formation temperature in the range of 110 °C to 180 °C assuming a δ18O value of seawater of 0‰, the matrix forms at a temperature of ca. 165 °C. Late veins are characterized by a formation temperature ranging between 120and 155 °C. We propose a model where serpentinization is followed by discrete carbonation then brecciation and cementation as a consequence of continuous hydrothermal fluid circulation in the serpentinite basement. This is comparable to observations made in the stockwork of present-day long-lived oceanic hydrothermal systems.

Reading a 400,000-year record of earthquake frequency for an intraplate fault

NASA Astrophysics Data System (ADS)

Williams, Randolph T.; Goodwin, Laurel B.; Sharp, Warren D.; Mozley, Peter S.

2017-05-01

Our understanding of the frequency of large earthquakes at timescales longer than instrumental and historical records is based mostly on paleoseismic studies of fast-moving plate-boundary faults. Similar study of intraplate faults has been limited until now, because intraplate earthquake recurrence intervals are generally long (10s to 100s of thousands of years) relative to conventional paleoseismic records determined by trenching. Long-term variations in the earthquake recurrence intervals of intraplate faults therefore are poorly understood. Longer paleoseismic records for intraplate faults are required both to better quantify their earthquake recurrence intervals and to test competing models of earthquake frequency (e.g., time-dependent, time-independent, and clustered). We present the results of U-Th dating of calcite veins in the Loma Blanca normal fault zone, Rio Grande rift, New Mexico, United States, that constrain earthquake recurrence intervals over much of the past ˜550 ka—the longest direct record of seismic frequency documented for any fault to date. The 13 distinct seismic events delineated by this effort demonstrate that for >400 ka, the Loma Blanca fault produced periodic large earthquakes, consistent with a time-dependent model of earthquake recurrence. However, this time-dependent series was interrupted by a cluster of earthquakes at ˜430 ka. The carbon isotope composition of calcite formed during this seismic cluster records rapid degassing of CO2, suggesting an interval of anomalous fluid source. In concert with U-Th dates recording decreased recurrence intervals, we infer seismicity during this interval records fault-valve behavior. These data provide insight into the long-term seismic behavior of the Loma Blanca fault and, by inference, other intraplate faults.

Paleostresses estimated from calcite e-twins suggest a change during a seismic cycle: A case study of Yokonami mélange in Cretaceous Shimanto Belt of SW Japan

NASA Astrophysics Data System (ADS)

Eida, M.; Hashimoto, Y.; Kanagawa, K.

2011-12-01

Paleostresses have been estimated by a stress inversion method in a tectonic mélange zone within an on-land accretionary complex. Paleostresses estimated throughout the Yokonami mélange zone, those estimated adjacent to a seismogenic fault at the northern edge of the mélange zone, and those estimated within calcite veins along minor faults have been compared. Yokonami mélange in the Cretaceous Shimanto Belt of SW Japan contains blocks of mainly sandstone with subordinate red shale, chert and basalt in shale matrix. Pseudotachylytes found along its northern boundary fault (the Goshikino-Hama fault) suggest that the fault was once a seismogenic fault. Minor faults are present throughout the Yokonami mélange and also adjacent to the Goshikino-Hama fault, and they clearly cut the mélange fabrics. Minor faults are commonly accompanied by calcite slicken fiber veins on which slicken steps are well developed. Pressures and temperatures during the minor faulting are estimated to be about 180 MPa and 200°C, respectively, on the basis of fluid inclusion thermometry. We have determined slip planes and directions of e-twinning in calcite veins, orientations of which were measured by using a universal stage. 829 data sets were obtained from 20 samples in the northern part of the Yokonami mélange. In addition, we obtained slip-data from minor faults throughout the Yokonami mélange as well as from those adjacent to the seismogenic Goshikino-hama fault. We then used HIM (Hough inversion method) by Yamaji et al. (2006), an inversion method to estimate the orientation and ratio of paleostress from fault slip data, where the stress ratio Φ is defined as (σ2 - σ3 ) / (σ1 - σ3 ). Calcite e-twin data yield two different sets of paleostress; a vertical axial compression with Φ = 0.0446 and an axial extension with Φ = 0.9125. Minor faults adjacent to the Goshikino-Hama fault also yield two sets of paleostress; a vertical axial compression and an axial extension with Φ = 0.1029 and 0.8111, respectively. In contrast, minor faults throughout the Yokonami mélange yield a triaxial paleostress with Φ = 0.6071 and horizontal σ1 in the NW direction. Thus the paleostresses estimated from calcite e-twins are consistent with those estimated from minor faults adjacent to the seismogenic Goshikino-Hama fault, but not with those estimated from minor faults throughout the Yokonami mélange not only in orientations but also in stress ratio. This suggests that a change in stress state occurred in the Yokonami mélange after calcite vein filling, and also that the stress change corresponds to a change in faulting from interseismic faulting in Yokonami mélange to seismic faulting along the Goshikino-Hama fault, as inferred from the dynamic coulomb wedge model by Wang and Hu (2006).

Post-magmatic structural evolution of the Troodos Ophiolite Pillow Lavas revealed by microthermometry within vein precipitates, with application to Alpine-Mediterranean supra-subduction zone settings

NASA Astrophysics Data System (ADS)

Klöcking, M.; White, N. J.; Maclennan, J.; Fitton, J. G.

2016-12-01

The Troodos ophiolite, Cyprus, is one of the best preserved ophiolites. Based on geochemical data a supra-subduction zone (SSZ) setting was proposed. Microtextures and fluid inclusions of veins and vesicles within the Pillow Lavas record the post-magmatic structural and geochemical evolution of this SSZ beginning at 75 Ma. Three different vein types from the Upper and Lower Pillow Lavas are distinguished and imply vein precipitation under a dominant extensional regime: (1) syntaxial calcite-, quartz- and zeolite-bearing veins are interpreted as mineralized extension fractures that were pervaded by seawater. This advective fluid flow in an open system changed later into a closed system characterized by geochemical self-organization. (2) Blocky and (3) antitaxial fibrous calcite veins are associated with brecciation due to hydrofracturing and diffusion-crystallization processes, respectively. Based on aqueous fluid inclusion chemistry with seawater salinities in all studied vein types, representative fluid inclusion isochores crossed with calculated litho- and hydrostatic pressure conditions yield mineral precipitation temperatures between 180 and 210 °C, for veins and vesicles hosted in the Upper and Lower Pillow Lavas. This points to a heat source for the circulating seawater and implies that vein and vesicle minerals precipitated shortly after pillow lava crystallization under dominant isobaric cooling conditions. Compared to previous suggestions derived from secondary mineralization a less steep geothermal gradient of 200 °C from the Sheeted Dyke Complex to the Pillow Lavas of the Troodos SSZ is proposed. Further fossil and recent SSZ like the Mirdita ophiolite, Albania, the South-Anatolian ophiolites, Turkey, and the Izu-Bonin fore arc, respectively, reveal similar volcanic sequences. Vein samples recovered during International Ocean Discovery Program expedition 351 and 352 in the Izu-Bonin back and fore arc, respectively, indicate also seawater infiltration into fractures but low-temperature (<150 °C) mineral precipitation. This comparison of spatially and temporally unrelated vein systems contributes to the understanding of post-magmatic structural and geochemical processes in SSZ. This study was granted by the Austrian Science Fund (FWF-P 27982-N29).

Post-magmatic structural evolution of the Troodos Ophiolite Pillow Lavas revealed by microthermometry within vein precipitates, with application to Alpine-Mediterranean supra-subduction zone settings

NASA Astrophysics Data System (ADS)

Kurz, W.; Quandt, D.; Micheuz, P.; Krenn, K.

2017-12-01

The Troodos ophiolite, Cyprus, is one of the best preserved ophiolites. Based on geochemical data a supra-subduction zone (SSZ) setting was proposed. Microtextures and fluid inclusions of veins and vesicles within the Pillow Lavas record the post-magmatic structural and geochemical evolution of this SSZ beginning at 75 Ma. Three different vein types from the Upper and Lower Pillow Lavas are distinguished and imply vein precipitation under a dominant extensional regime: (1) syntaxial calcite-, quartz- and zeolite-bearing veins are interpreted as mineralized extension fractures that were pervaded by seawater. This advective fluid flow in an open system changed later into a closed system characterized by geochemical self-organization. (2) Blocky and (3) antitaxial fibrous calcite veins are associated with brecciation due to hydrofracturing and diffusion-crystallization processes, respectively. Based on aqueous fluid inclusion chemistry with seawater salinities in all studied vein types, representative fluid inclusion isochores crossed with calculated litho- and hydrostatic pressure conditions yield mineral precipitation temperatures between 180 and 210 °C, for veins and vesicles hosted in the Upper and Lower Pillow Lavas. This points to a heat source for the circulating seawater and implies that vein and vesicle minerals precipitated shortly after pillow lava crystallization under dominant isobaric cooling conditions. Compared to previous suggestions derived from secondary mineralization a less steep geothermal gradient of 200 °C from the Sheeted Dyke Complex to the Pillow Lavas of the Troodos SSZ is proposed. Further fossil and recent SSZ like the Mirdita ophiolite, Albania, the South-Anatolian ophiolites, Turkey, and the Izu-Bonin fore arc, respectively, reveal similar volcanic sequences. Vein samples recovered during International Ocean Discovery Program expedition 351 and 352 in the Izu-Bonin back and fore arc, respectively, indicate also seawater infiltration into fractures but low-temperature (<150 °C) mineral precipitation. This comparison of spatially and temporally unrelated vein systems contributes to the understanding of post-magmatic structural and geochemical processes in SSZ. This study was granted by the Austrian Science Fund (FWF-P 27982-N29).

Geology and Fluorspar Deposits of the Levias-Keystone and Dike-Eaton Areas, Crittenden County, Kentucky

USGS Publications Warehouse

Trace, Robert Denny

1962-01-01

The fault systems of the Levias-Keystone and Dike-Eaton areas, in the Kentucky-Illinois fiuorspar district, are a complex northeastward-trending sys- tem and a simple northwestward-trending system of steeply dipping normal faults, associated in part with a lamprophyre dike. Fluorspar mining started in the area about 1900 and, as of 1945, more than 200,000 tons of crude ore probably has been mined; most of the ore was from the Levias-Keystone area. A small quantity of zinc and lead ore also is present in the Dike-Eaton area. The deposits are localized along faults that displace fiat-lying or low-dipping limestones, sandstones, and shales of the Meramec and Chester series of Missis- sippian age. Movement along most of the faults was principally vertical, with displacement as much as 600 feet. Some horizontal movement occurred along at least one fault. Geologic mapping of the surface and data from underground workings have revealed 13 faults in an area of four-fifths of a square mile. Only a few of these faults are known to contain economically important deposits of fiuorspar. The most abundant vein minerals are calcite and fiuorite with subordinate quantities of sphalerite, galena, barite, and quartz. Some weathering products of sphalerite and galena are present also. The veins are dominantly calcite that contains fiuorite lenses but in places are mainly fiuorite having lesser quantities of calcite. Sphalerite- and galena-bearing deposits are present in the Dike-Eaton area. The ore bodies mainly are the result of fissure filling and replacement of calcite by fiuorite; in addition a small amount of limestone wallrock probably has been replaced. Residual concentrations of high-grade fluorspar in the overburden above faults have yielded some so-called gravel fiuorspar. The position of the veins within the faults may be related to one or more factors such as type of wallrock, change in dip of the fault, and amount of displacement.

Field and Laboratory Observations on Fluid Budget of the Cascadia Episodic Tremor and Slip System, Olympic Peninsula, Washington

NASA Astrophysics Data System (ADS)

Rotman, H.; Mattinson, C. G.

2009-12-01

Fluid movement in accretionary prisms has been linked to the recently discovered episodic tremor and slip (ETS) events along subduction zones. This study focuses on the exhumed accretionary prism of the Cascadia subduction zone, where ETS events are well-documented. The exposed sandstone, shale, siltstone and minor basalt in the study location were buried to 6 - 15 km, within the depth constraints of ETS. This past summer, field work focused on observations of subduction related fluid budget as evidenced by veins, metamorphism, and pore space took place along an east-west transect of the Olympic Peninsula. Approximately 40 representative samples were collected near Obstruction Peak, Hurricane Ridge, Lake Mills (Elwha), and Sore Thumb (Sol Duc). Observations indicate progressively increasing grade of metamorphism from west to east, in agreement with previous studies. Mudrocks show a clear progression from shale to phyllite, while sandstones generally appear equally micaceous across the transect, with the exception of one location. This location is unique in that micas are larger, other metamorphic indicators are visible in hand specimen, and veins make up a significant percent of the outcrop. Epidotes are visible in the rock body and veins, and the veins also contain quartz and calcite, usually as the primary mineral. Veins are oriented perpendicular to bedding and are primarily found in the coarser units. In addition to the veins, water is present in pore spaces and mineral structure. Preliminary observations indicate the veins and pore space decrease to the east, while evidence for fluid movement increases to the east. These observations will be tested and quantified by a variety of laboratory analyses. Thin section examination will determine pore space and mineral assemblages at different locations, and the mechanisms (e.g., blocky or fibrous) of vein growth. Element concentrations from whole rock analysis will determine bulk composition and element mobilization at different temperatures. Oxygen ratios from quartz and calcite, and titanium activity, will constrain temperatures.

Fingerprinting stress: Stylolite and calcite twinning paleopiezometry revealing the complexity of progressive stress patterns during folding—The case of the Monte Nero anticline in the Apennines, Italy

NASA Astrophysics Data System (ADS)

Beaudoin, Nicolas; Koehn, Daniel; Lacombe, Olivier; Lecouty, Alexandre; Billi, Andrea; Aharonov, Einat; Parlangeau, Camille

2016-07-01

In this study we show for the first time how quantitative stress estimates can be derived by combining calcite twinning and stylolite roughness stress fingerprinting techniques in a fold-and-thrust belt. First, we present a new method that gives access to stress inversion using tectonic stylolites without access to the stylolite surface and compare results with calcite twin inversion. Second, we use our new approach to present a high-resolution deformation and stress history that affected Meso-Cenozoic limestone strata in the Monte Nero Anticline during its late Miocene-Pliocene growth in the Umbria-Marche Arcuate Ridge (northern Apennines, Italy). In this area an extensive stylolite-joint/vein network developed during layer-parallel shortening (LPS), as well as during and after folding. Stress fingerprinting illustrates how stress in the sedimentary strata did build up prior to folding during LPS. The stress regime oscillated between strike slip and compressional during LPS before ultimately becoming strike slip again during late stage fold tightening. Our case study shows that high-resolution stress fingerprinting is possible and that this novel method can be used to unravel temporal relationships that relate to local variations of regional orogenic stresses. Beyond regional implications, this study validates our approach as a new powerful toolbox to high-resolution stress fingerprinting in basins and orogens combining joint and vein analysis with sedimentary and tectonic stylolite and calcite twin inversion techniques.

Shear localization in the shallow part of megathrusts: understanding active megathrusts trough the study of fossil analogues.

NASA Astrophysics Data System (ADS)

Cerchiari, Anna; MIttempergher, Silvia; Remitti, Francesca; Festa, Andrea

2017-04-01

The shallowest part of active megathrusts has an intriguing behaviour, characterized by the coexistence of coseismic slips and aseismic creep, slow slip events, low and very low frequency earthquakes. Origins and interplays of these phenomena are actually little known. In this respect, the study of exhumed shallow parts of fossil megathrusts is an advantageous approach in terms of accessibility, costs and resolution. The Sestola-Vidiciatico tectonic Unit in the Northern Apennines has been interpreted as a possible analogue of a shallow, hectometer scale megathrust shear zone, which accommodated subduction of the Adria plate under the Ligurian prism during early-middle Miocene by involving sediments from the seafloor to burial depth corresponding to 150° C maximum temperature. Performing detailed microstructural analysis on samples through optical, cathodoluminescence and scanning electron microscopy, we studied a 5 m thick fault zone marking the base of the SVU. Here, more or less competent marls make up a heterogeneous fault zone assemblage, with a strongly deformed tectonic fabric characterized by mesoscopic cleavage, boudinage, faults and low-angle thrusts coated by calcite veins. At the top of the shear zone, a sharp and continuous shear vein, 20 cm thick cuts all other structures. At the microscale, we identified a primary sedimentary layering, consisting of alternating fine and coarse marly or shaly laminae that are crosscut by "soft-sediment"-type deformation bands derived from the reorientation of mineral grains without fracturing. Parallel to the sedimentary laminae, oriented phyllosilicates define a pervasive foliation in clay-rich domains. More competent calcareous portions are strongly boudinaged and cut by calcite shear veins displaying crack-and-seal texture and locally implosion breccias. Multiple mutually crosscutting generations of extensional veins are recognizable, with dispersed orientations and complex relations with shear veins. Calcite veins appear also to be partially dissolved by pressure-solution processes. Our microstructural findings suggest that deformation started acting on not completely lithified sediments, with a progressive and differential embrittlement of the shear zone, depending on lithology (i. e. competence contrast) and fluid pressure cycles. Features described point out also for thrusting under low differential stress, with decoupling from the footwall and progressive migration and thinning of the shear zone.

Microstructural analysis and calcite piezometry on hydrothermal veins: Insights into the deformation history of the Cocos Plate at Site U1414 (IODP Expedition 344)

NASA Astrophysics Data System (ADS)

Brandstätter, Jennifer; Kurz, Walter; Rogowitz, Anna

2017-08-01

In this study we present microstructural data from hydrothermal veins in the sedimentary cover and the igneous basement recovered from Hole U1414A, Integrated Ocean Drilling Program (IODP) Expedition 344 (Costa Rica Seismogenesis Project), to constrain deformation mechanism operating in the subducting Cocos Plate. Cathodoluminescence studies, mechanical e-twin piezometry and electron backscatter diffraction (EBSD) analyses of carbonate veins were used to give insights into the deformation conditions and to help to understand the tectonic deformation history of the Cocos Plate offshore Costa Rica. Analyses of microstructures in the sedimentary rocks and in the basalt of the igneous basement reveal brittle deformation, as well as crystal-plastic deformation of the host rock and the vein material. Cathodoluminescence images showed that in the basalt fluid flow and related precipitation occurred over several episodes. The differential stresses, obtained from two different piezometers using the same parameter (twin density), indicate various mean differential stresses of 49 ± 11 and 69 ± 30 MPa and EBSD mapping of calcite veins reveals low-angle subgrain boundaries. Deformation temperatures are restricted to the range from 170°C to 220°C, due to the characteristics of the existing twins and the lack of high-temperature intracrystalline deformation mechanisms (>220°C). The obtained results suggest that deformation occurred over a period associated with changes of ambient temperatures, occurrence of fluids and hydrofracturing, induced differential stresses due to the bending of the plate at the trench, and related seismic activity.

Microstructural analysis and calcite piezometry on hydrothermal veins: Insights into the deformation history of the Cocos Plate at Site U1414 (IODP Expedition 344).

PubMed

Brandstätter, Jennifer; Kurz, Walter; Rogowitz, Anna

2017-08-01

In this study we present microstructural data from hydrothermal veins in the sedimentary cover and the igneous basement recovered from Hole U1414A, Integrated Ocean Drilling Program (IODP) Expedition 344 (Costa Rica Seismogenesis Project), to constrain deformation mechanism operating in the subducting Cocos Plate. Cathodoluminescence studies, mechanical e-twin piezometry and electron backscatter diffraction (EBSD) analyses of carbonate veins were used to give insights into the deformation conditions and to help to understand the tectonic deformation history of the Cocos Plate offshore Costa Rica. Analyses of microstructures in the sedimentary rocks and in the basalt of the igneous basement reveal brittle deformation, as well as crystal-plastic deformation of the host rock and the vein material. Cathodoluminescence images showed that in the basalt fluid flow and related precipitation occurred over several episodes. The differential stresses, obtained from two different piezometers using the same parameter (twin density), indicate various mean differential stresses of 49 ± 11 and 69 ± 30 MPa and EBSD mapping of calcite veins reveals low-angle subgrain boundaries. Deformation temperatures are restricted to the range from 170°C to 220°C, due to the characteristics of the existing twins and the lack of high-temperature intracrystalline deformation mechanisms (>220°C). The obtained results suggest that deformation occurred over a period associated with changes of ambient temperatures, occurrence of fluids and hydrofracturing, induced differential stresses due to the bending of the plate at the trench, and related seismic activity.

Microstructural analysis and calcite piezometry on hydrothermal veins: Insights into the deformation history of the Cocos Plate at Site U1414 (IODP Expedition 344)

PubMed Central

Kurz, Walter; Rogowitz, Anna

2017-01-01

Abstract In this study we present microstructural data from hydrothermal veins in the sedimentary cover and the igneous basement recovered from Hole U1414A, Integrated Ocean Drilling Program (IODP) Expedition 344 (Costa Rica Seismogenesis Project), to constrain deformation mechanism operating in the subducting Cocos Plate. Cathodoluminescence studies, mechanical e‐twin piezometry and electron backscatter diffraction (EBSD) analyses of carbonate veins were used to give insights into the deformation conditions and to help to understand the tectonic deformation history of the Cocos Plate offshore Costa Rica. Analyses of microstructures in the sedimentary rocks and in the basalt of the igneous basement reveal brittle deformation, as well as crystal‐plastic deformation of the host rock and the vein material. Cathodoluminescence images showed that in the basalt fluid flow and related precipitation occurred over several episodes. The differential stresses, obtained from two different piezometers using the same parameter (twin density), indicate various mean differential stresses of 49 ± 11 and 69 ± 30 MPa and EBSD mapping of calcite veins reveals low‐angle subgrain boundaries. Deformation temperatures are restricted to the range from 170°C to 220°C, due to the characteristics of the existing twins and the lack of high‐temperature intracrystalline deformation mechanisms (>220°C). The obtained results suggest that deformation occurred over a period associated with changes of ambient temperatures, occurrence of fluids and hydrofracturing, induced differential stresses due to the bending of the plate at the trench, and related seismic activity. PMID:29081570

Fluid inclusion petrography and microthermometry of the Cocos Ridge hydrothermal system, IODP Expedition 344 (CRISP 2), Site U1414

NASA Astrophysics Data System (ADS)

Brandstätter, J.; Kurz, W.; Krenn, K.; Micheuz, P.

2015-12-01

We present new data from microthermometric analyses of fluid inclusions entrapped in hydrothermal veins within lithified sediments and Cocos Ridge (CCR) basalt from IODP Expedition 344 site U1414 (Costa Rica) and concern on a primary task of Expedition 344, i.e. to evaluate fluid/rock interaction, the hydrologic system, and the geochemical processes (indicated by composition and volume of fluids) active within the incoming Cocos Plate. Mineralization of the veins and crosscutting relationships gives constraints for the different generation of veins. Calcium carbonate, commonly aragonite in the upper part and calcite in the lower part of the igneous basement, is usually present in veins as a late phase following the quartz precipitation and the clay minerals formation. The sequence of vein generations in the lithified sediments close to the contact within the CCR basalt is characterized by smaller veins filled by quartz, followed by massive intersecting calcite veins. A high fluid pressure can be concluded, due to wall rock fragments embedded within the filling and fractured mineral grains in the ground mass, which are close to the veins. This requires that the magmatic basement and the lithified sediments were covered by sequences of low permeability sediments forming a barrier that enabled build up elevated fluid pressure. The investigation of fluid inclusions in the lowest units of borehole 344-U1414, give clues about the source of the fluids and about the vein evolution within the incoming Cocos Plate close to Middle American Trench. The microthermometric analyses of the primary, almost aqueous, inclusions indicate a temperature range during entrapment between 200 and 420°C. The data indicate that seawater within the Cocos Ridge aquifer communicated with high-temperature fluids and/or were modified by heat advection. We consider the Galapagos hotspot and/ or the Cocos-Nazca spreading center as heat source. Fluids originated from mobilized sediment pore water and invaded seawater. Isotope and heat flow data indicate a deep fluid source within the Cocos Plate oceanic crust too.

Magmatic Fluid Source of the Chingshui Geothermal Field: Evidence of Carbonate Isotope data

NASA Astrophysics Data System (ADS)

Song, S. R.; Lu, Y. C.; Wang, P. L.; John, C. M.; MacDonald, J.

2015-12-01

The Chingshui geothermal field is located at the northern tip of the Miocene Lushan Slate Formation, which was part of the Eurasian continental margin subject to the Plio-Pleistocene collision associated with the Luzon Arc. The remnant heat of the Taiwan orogeny has long been considered to drive the circulation of hydrothermal fluids in the Chingshui geothermal field. However, recent studies based on magnetic anomalies and helium isotopic ratios suggest that the heat might instead be derived from igneous bodies. By examining isotope data of calcite veins and scaling in geothermal wells, this study aimed to clarify the fluid origin and possible heat source accounting for the geothermal fluids in the Chingshui geothermal field. Carbon and oxygen isotope analyses indicate that veins from outcrops and scalings in geothermal wells have high and low d values, respectively. Data for veins in drilled cores fall in between outcrop veins and scalings values. Such an isotopic pattern could be interpreted as the mixing of two end member fluids. The clumped isotope analysis of calcite veins from the outcrops yielded precipitation temperatures of up to 232 ± 16 ℃ and a reconstructed d18O fluid value of 9.5 ‰(magmatic fluid: 6-11 ‰; metamorphic fluid: 5-28 ‰ by Taylor, 1974). The inferred d18O values of hot fluids for the vein formation are significantly different from that of meteoric water in Chingshui area (around -5.4 ‰) as well as the scaling in geothermal wells (around -7.6 ‰). Previous study of magnetotelluric image demonstrated two possible fluid reservoirs at different depths (Chen et al. 2012). Our isotope data combined with these lines of evidence suggest that the scaling in geothermal wells could be derived from fluids originating from the shallower reservoir. In contrast, the veins present at outcrops could have been formed from 18O-enriched, deeply-sourced fluids related to either metamorphic dehydration or magmatic processes.

A demonstration of an affinity between pyrite and organic matter in a hydrothermal setting

PubMed Central

2011-01-01

One of the key-principles of the iron-sulphur world theory is to bring organic molecules close enough to interact with each other, using the surface of pyrite as a substrate in a hydrothermal setting. The present paper explores the relationship of pyrite and organic matter in a hydrothermal setting from the geological record; in hydrothermal calcite veins from Carboniferous limestones in central Ireland. Here, the organic matter is accumulated as coatings around, and through, pyrite grains. Most of the pyrite grains are euhedral-subhedral crystals, ranging in size from ca 0.1-0.5 mm in diameter, and they are scattered throughout the matrix of the vein calcite. The organic matter was deposited from a hydrothermal fluid at a temperature of at least 200°C, and gives a Raman signature of disordered carbon. This study points to an example from a hydrothermal setting in the geological record, demonstrating that pyrite can have a high potential for the concentration and accumulation of organic materials. PMID:21299877

Fluid inclusion and stable isotopes studies of epithermal gold-bearing veins in the SE Afar Rift (Djibouti)

NASA Astrophysics Data System (ADS)

Moussa, N.; Boiron, M. C.; Grassineau, N.; Fouquet, Y.; Le Gall, B.; Mohamed, J.

2015-12-01

The Afar rift results from the interaction of a number of actively-propagating tectono-magmatic axes. Recent field investigations in the SE Afar rift have emphasized the importance of hydrothermal system in rift-related volcanic complexes. Mineralization occur as gold-silver bearing veins and are associated with felsic volcanism. Late carbonate veins barren of sulfides and gold are common. The morphologies and textures of quartz show crustiform colloform banding, massive and breccias. Microthermometric measurements were made on quartz-hosted two phases (liquid + vapor) inclusions; mean homogenization temperature range from 150°C to 340°C and ice-melting temperatures range from -0.2° to 1.6°C indicating that inclusion solutions are dilute and contain 0.35 to 2.7 equivalent wt. % NaCl. Furthermore, δ18O and δ13C values from calcite range from 3.7 to 26.6 ‰ and -7.5 to 0.3‰, respectively. The presence of platy calcite and adularia indicate that boiling condition existed. This study shows that precious-metal deposition mainly occurred from hydrothermal fluids at 200°C at around 300 and 450 m below the present-day surface in a typical low-sulphidation epithermal environment.

Evidence for de-sulfidation to form native electrum in the Fire Creek epithermal gold-silver deposit, north-central Nevada

NASA Astrophysics Data System (ADS)

Perez, J.; Day, J. M.; Cook, G. W.

2012-12-01

The Fire Creek property is a newly developed and previously unstudied epithermal Au-Ag deposit located in the Northern Shoshone range of north central Nevada. The mineralization occurs within and above en echelon N-NW trending basaltic dykes that are hosted within a co-genetic and bimodal suite of mid-Miocene basalts and andesites formed in association with the Yellowstone hotspot-track. Previous studies of Au-Ag mineralization in the Great Basin have focused primarily on extensively mined and/or low-grade deposits. Therefore, the ability for unrestricted sampling of a major Au-Ag deposit early in its exploration and development represents an opportunity for refined understanding of epithermal ore genesis processes. New petrology reveals at least two distinct pulses of mineralization that in relative order of timing are: 1) S-rich veins which are associated with initial host-rock alteration; 2) quartz- and/or calcite-rich veins which vary from fine-grained to lath-like quartz crystals with large calcite crystals in vein centers. Native electrum occurs only within the second phase of mineralization and typically occurs within quartz and adjacent to cross-cut first-phase S-rich veins. In places the electrum appears to replace or form overgrowths around existing sulfide phases. High levels of gold and silver are found in both the first (0.8 g Au/tonne) and second-phase pulses (37 g Au/tonne). Fire Creek shares many similarities with its northern neighbor, the Mule Canyon Au-Ag deposit, with high Fe sulfide contents for some of the ores, altered wall-rocks and the presence of narrow and discontinuous gold-bearing siliceous veins. Like Fire Creek, Mule Canyon possesses two distinct mineralizing phases, a sulfide rich and a late stage calcite/silica assemblage. The first pulse appears to be identical in both locations with a variation of disseminated to euhedral iron-sulfides and associated intense alteration of host rock. However, Fire Creek differs from Mule Canyon in that the second phase of mineralization shows spatial and petrographic association with coarser silica and carbon phases. Conversely associations of electrum in Mule Canyon are typically with chalcedony or opal veins and hydrothermal breccia matrices (John et al. Econ. Geol. 98, 425-463, 2003). Opal and chalcedony phases do not appear within fracture-filled veins in Fire Creek, but occur as cap rocks on the surface. These associations are likely driven by impingement of basaltic dikes into ground waters in both the Fire Creek and Mule Canyon deposits. However, in the case of Fire Creek, our study demonstrates that there is a clear spatial dependence between the electrum, primary S-rich mineralized veins and phases of coarse carbonate and silica. We postulate that this occurs through increased brecciation and sub-surface boiling of hydrothermal fluids leading to de-sulfidation and a marked change in alteration and mineral assemblage.

Brittle fracture damage around the Alpine Fault, New Zealand

NASA Astrophysics Data System (ADS)

Williams, J. N.; Toy, V.; Smith, S. A. F.; Boulton, C. J.; Massiot, C.; Mcnamara, D. D.

2017-12-01

We use field and drill-core samples to characterize macro- to micro-scale brittle fracture networks within the hanging-wall of New Zealand's Alpine Fault, an active plate-boundary fault that is approaching the end of its seismic cycle. Fracture density in the hanging-wall is roughly constant for distances of up to 500 m from the principal slip zone gouges (PSZs). Fractures >160 m from the PSZs are typically open and parallel to the regional mylonitic foliation or host rock schistosity, and likely formed as unloading joints during rapid exhumation of the hanging-wall at shallow depths. Fractures within c. 160 m of the PSZs are broadly oriented shear-fractures filled with gouge or cataclasite, and are interpreted to constitute the hanging-wall damage zone of the Alpine Fault. This is comparable to the 60-200 m wide "geophysical damage zone" estimated from low seismic wave velocities surrounding the Alpine Fault. Veins are pervasive within the c. 20 m-thick hanging-wall cataclasites and are most commonly filled by calcite, chlorite, muscovite and K-feldspar. Notably, there is a set of intragranular clast-hosted veins, as well as a younger set of veins that cross-cut both clasts and cataclasite matrix. The intragranular veins formed prior to cataclasis or during synchronous cataclasis and calcite-silicate mineralisation. Broad estimates for the depth of vein formation indicate that the cataclasites formed a c. 20 m wide actively deforming zone at depths of c. 4-8 km. Conversely, the cross-cutting veins are interpreted to represent off-fault damage within relatively indurated cataclasites following slip localization onto the <10 cm wide smectite-bearing PSZ gouges at depths of <4 km. Our observations therefore highlight a strong depth-dependence of the width of the actively deforming zone within the brittle seismogenic crust around the Alpine Fault.

Defects in Calcite.

DTIC Science & Technology

1991-05-13

AD-A245 645 A TRIDENT SCHOLAR PROJECT REPORT NO. 181 "DEFECTS IN CALCITE " DTTC %N FEB 5-1912 UNITED STATES NAVAL ACADEMY ANNAPOLIS, MARYLAND 92-02841...report; no. 181 (1991) "DEFECTS IN CALCITE " A Trident Scholar Project Report by Midshipman Anthony J. Kotarski, Class of 1991 U. S. Naval Academy Annapolis...REPORT TYPE AND DATES COVERED 13 May 1991 Final 1990/91 . TITLE AND SUBTITLE s. FUNDING NUMBERS DEFECTS IN CALCITE 6. AUTHOR(S) Anthony J. Kotarski 7

Petrography, fluid inclusion analysis, and geochronology of the End uranium deposit, Kiggavik, Nunavut, Canada

NASA Astrophysics Data System (ADS)

Chi, Guoxiang; Haid, Taylor; Quirt, David; Fayek, Mostafa; Blamey, Nigel; Chu, Haixia

2017-02-01

The End deposit is one of several uranium deposits in the Kiggavik area near the Proterozoic Thelon Basin, which is geologically similar to the Athabasca Basin known for its unconformity-related uranium deposits. The mineralization occurs as uraninite and coffinite in quartz veins and wall rocks (psammopelitic gneisses) in the sub-Thelon basement and is associated with clay- and hematite-altered fault zones. Fluid inclusions were studied in quartz cementing unmineralized breccias formed before mineralization (Q2), quartz veins that were formed before mineralization but spatially associated with uranite (Q4), and calcite veins that were formed after mineralization. Four types of fluid inclusions were recognized, namely liquid-dominated biphase (liquid + vapor), vapor-dominated biphase (vapor + liquid), monophase (vapor-only), and triphase (liquid + vapor + halite) inclusions. The first three types were found in Q2, whereas all four types were found in Q4 and calcite. The coexistence of these different types of inclusions within individual fluid inclusion assemblages is interpreted to indicate fluid immiscibility and heterogeneous trapping. Based on microthermometry, the fluids associated with Q2 are characterized by low salinities (0.4 to 6.6 wt%) and moderate temperatures from 148 to 261 °C, and the fluids associated with calcite show high salinities (26.8 to 29.3 wt%) and relatively low temperatures from 146 to 205 °C, whereas the fluids associated with Q4 have a wide range of salinities from 0.7 to 38.8 wt% and temperatures from 80 to 332 °C. Microthermometric and cryogenic Raman spectroscopic studies indicate that the high-salinity fluids in Q4 and calcite belong to the H2O-NaCl-CaCl2 ± MgCl2 system, with some dominated by NaCl and others by CaCl2. The fluid inclusions in Q2 are interpreted to be unrelated to mineralization, whereas those in Q4 and calcite reflect the mineralizing fluids. The fluid inclusion data are consistent with a genetic link of mineralization with basinal brines derived from the Thelon Basin. However, unlike the conventional deep-burial (>5 km) diagenetic-hydrothermal model proposed for the unconformity-related uranium deposits, the uranium mineralization in the End deposit is inferred to have formed in a shallow environment (probably <2 km), based on fluid immiscibility and low fluid pressures obtained in this study. The U-Pb age of uraninite (1295 ± 12 Ma) is interpreted to reflect isotopic resetting after the primary mineralization.

Geology and geochemistry of the shear-hosted Julie gold deposit, NW Ghana

NASA Astrophysics Data System (ADS)

Amponsah, Prince Ofori; Salvi, Stefano; Béziat, Didier; Siebenaller, Luc; Baratoux, Lenka; Jessell, Mark W.

2015-12-01

The Leo Man Craton in West Africa is host to numerous economic gold deposits. If some regions, such as the SW of Ghana, are well known for world-class mineralizations and have been extensively studied, gold occurrences elsewhere in the craton have been discovered only in the last half a century or so, and very little is known about them. The Julie gold deposit, located in the Paleoproterozoic Birimian terrane of NW Ghana, is one such case. This deposit is hosted in a series of granitoid intrusives of TTG composition, and consists of a network of deformed, boudinaged quartz lodes (A-type veins) contained within an early DJ1 E-W trending shear zone with dextral characteristics. A conjugate set of veins (C-type) perpendicular to the A-type veins contains low grade mineralization. The main ore zone defines a lenticular corridor about 20-50 m in width and about 3.5 km along strike, trending E-W and dipping between 30 and 60°N. The corridor is strongly altered, by an assemblage of sericite + quartz + ankerite + calcite + tourmaline + pyrite. This is surrounded by a second alteration assemblage, consisting of albite + sericite + calcite + chlorite + pyrite + rutile, which marks a lateral alteration that fades into the unaltered rock. Mass balance calculations show that during alteration overall mass was conserved and elemental transfer is generally consistent with sulfidation, sericitization and carbonatization of the host TTG. Gold is closely associated with pyrite, which occurs as disseminated grains in the veins and in the host rock, within the mineralized corridor. SEM imagery and LA-ICP-MS analyses of pyrites indicate that in A-type veins gold is associated with bismuth, tellurium, lead and silver, while in C-type veins it is mostly associated with silver. Pyrites in A-type veins contain gold as inclusions and as free gold on its edges and fractures, while pyrites from C-type veins contains mostly free gold. Primary and pseudosecondary fluid inclusions from both type veins indicate circulation in the system of an aqueous-carbonic fluid of low to moderate salinity, which entered the immiscibility PT region of the H2O-CO2-NaCl system, at about 220 °C and <1 kbar.

In search of early life: Carbonate veins in Archean metamorphic rocks as potential hosts of biomarkers

NASA Astrophysics Data System (ADS)

Peters, Carl A.; Piazolo, Sandra; Webb, Gregory E.; Dutkiewicz, Adriana; George, Simon C.

2016-11-01

The detection of early life signatures using hydrocarbon biomarkers in Precambrian rocks struggles with contamination issues, unspecific biomarkers and the lack of suitable sedimentary rocks due to extensive thermal overprints. Importantly, host rocks must not have been exposed to temperatures above 250 °C as at these temperatures biomarkers are destroyed. Here we show that Archean sedimentary rocks from the Jeerinah Formation (2.63 billion yrs) and Carawine Dolomite (2.55 billion yrs) of the Pilbara Craton (Western Australia) drilled by the Agouron Institute in 2012, which previously were suggested to be suitable for biomarker studies, were metamorphosed to the greenschist facies. This is higher than previously reported. Both the mineral assemblages (carbonate, quartz, Fe-chlorite, muscovite, microcline, rutile, and pyrite with absence of illite) and chlorite geothermometry suggest that the rocks were exposed to temperatures higher than 300 °C and probably ∼400 °C, consistent with greenschist-facies metamorphism. This facies leads to the destruction of any biomarkers and explains why the extraction of hydrocarbon biomarkers from pristine drill cores has not been successful. However, we show that the rocks are cut by younger formation-specific carbonate veins containing primary oil-bearing fluid inclusions and solid bitumens. Type 1 veins in the Carawine Dolomite consist of dolomite, quartz and solid bitumen, whereas type 2 veins in the Jeerinah Formation consist of calcite. Within the veins fluid inclusion homogenisation temperatures and calcite twinning geothermometry indicate maximum temperatures of ∼200 °C for type 1 veins and ∼180 °C for type 2 veins. Type 1 veins have typical isotopic values for reprecipitated Archean sea-water carbonates, with δ13CVPDB ranging from - 3 ‰ to 0‰ and δ18OVPDB ranging from - 13 ‰ to - 7 ‰, while type 2 veins have isotopic values that are similar to hydrothermal carbonates, with δ13CVPDB ranging from - 18 ‰ to - 4 ‰ and δ18OVPDB ranging from - 18 ‰ to - 12 ‰. Evidently, the migration and entrapment of hydrocarbons occurred after peak metamorphism under temperatures congruous with late catagenesis and from fluids of different compositions. The relatively high temperatures of vein formation and the known geotectonic history of the rocks analysed suggest a probable minimum age of 1.8 billion yrs (Paleoproterozoic). Our results demonstrate that post peak-metamorphic veins provide an exciting opportunity in the search for evidence of early life. The integration of petrological and organic geochemical techniques is crucial for any future studies that use biomarkers to reconstruct the early biosphere.

The Genesis of Precious and Base Metal Mineralization at the Miguel Auza Deposit, Zacatecas, Mexico

NASA Astrophysics Data System (ADS)

Findley, A. A.; Olivo, G. R.; Godin, L.

2009-05-01

The Miguel Auza mine located in Zacatecas State, Mexico, is a vein-type polymetallic epithermal deposit hosted in deformed argillite, siltstone and, greywacke of the Cretaceous Caracol Formation. Silver-rich base metal veins (0.2 m to >1.5 m wide) are spatially associated with the NE-striking, steeply SE- dipping (70-80°) Miguel Auza fault over a strike length of 1.6 km and a depth of 460 m. A 2 km2 monzonitic stock located in the proximity of the mineralized zones, has previously been interpreted as the source of the mineralizing fluids. Four distinct structural stages are correlated with hydrothermal mineral deposition: (I) The Pre-ore stage is characterized by normal faulting, fracturing of host rock, and rotation of bedding planes. This stage consists of quartz, illite, chlorite, +/- pyrite alteration of sedimentary wall rocks. (II) The Pyrite-vein stage is associated with reverse-sense reactivation of early normal faults, dilation of bedding planes/fractures, and deposition of generally barren calcite + pyrite veinlets. (III) The Main-ore stage is related to the development of reverse-fault- hosted massive sulphide veins. During this stage three phases of mineral deposition are recorded: early pyrite and arsenopyrite, intermediate chalcopyrite, pyrite, arsenopyrite, and base metals, and late base metals and Ag-bearing minerals. Associated gangue minerals during the main ore stage are quartz, muscovite, calcite and chlorite. (IV) The Post-ore stage involves late NW-SE striking block faulting, brecciation and calcite veining. Later supergene oxidation of veins led to deposition of Fe-oxides and hydroxides, commonly filling fractures or replacing early-formed sulphide assemblages. The various vein types display classic epithermal textures including open space filling, banding, comb quartz and brecciation. The Ag-bearing minerals comprise pyrargyrite [Ag3(Sb,As)S3], argentotennantite [(Cu,Ag)10(Zn,Fe)2(Sn,As)4S13], polybasite-pearceite [(Ag,Cu)16(Sb,As)2S11], and acanthite [AgS2]; associated sulphides include galena, sphalerite, chalcopyrite, arsenopyrite and pyrite. In the main ore zone, base metal sulphides are commonly intergrown with the Ag-bearing sulfosalts. Analyses of galena show no significant silver values indicating that silver grades are exclusively associated with the Ag-bearing sulfosalts and sulphides. The distribution of the Sb/(Sb + As) ratios in the silver sulfosalts indicate that the ore forming fluid(s) was consistently antimony-rich during the Ag-rich ore deposition with no significant variation laterally, vertically, or along strike of the vein systems. However, Ag/(Ag + Cu) values in argentotennantite decrease along-strike from NE to SW and with depth. Compositions of argentotennantite + pyrargyrite + sphalerite indicate a primary depositional temperature around 325-350° C for the late phase of the Main-ore stage. Compositions of sphalerite also show an increasing trend in FeS (mol %) along strike of the deposit from NE to SW. The geometric relationship between the various structures, vein types, and the regional Miguel Auza fault zone suggest episodic reverse-sense reactivation of normal faults. It is argued that the structural evolution of the area, and, in particular, the Main-ore stage, provided transport pathways for metal-rich fluids and controlled the orientations of ore-bearing veins. Variations in mineral chemistry suggest that the rocks in the NE sector interacted with hotter fluids than in the SW part of the deposit.

The Damage and Geochemical Signature of a Crustal Scale Strike-Slip Fault Zone

NASA Astrophysics Data System (ADS)

Gomila, R.; Mitchell, T. M.; Arancibia, G.; Jensen Siles, E.; Rempe, M.; Cembrano, J. M.; Faulkner, D. R.

2013-12-01

Fluid-flow migration in the upper crust is strongly controlled by fracture network permeability and connectivity within fault zones, which can lead to fluid-rock chemical interaction represented as mineral precipitation in mesh veins and/or mineralogical changes (alteration) of the host rock. While the dimensions of fault damage zones defined by fracture intensity is beginning to be better understood, how such dimensions compare to the size of alteration zones is less well known. Here, we show quantitative structural and chemical analyses as a function of distance from a crustal-scale strike-slip fault in the Atacama Fault System, Northern Chile, to compare fault damage zone characteristics with its geochemical signature. The Jorgillo Fault (JF) is a ca. 18 km long NNW striking strike-slip fault cutting Mesozoic rocks with sinistral displacement of ca. 4 km. In the study area, the JF cuts through orthogranulitic and gabbroic rocks at the west (JFW) and the east side (JFE), respectively. A 200 m fault perpendicular transect was mapped and sampled for structural and XRF analyses of the core, damage zone and protolith. The core zone consists of a ca. 1 m wide cataclasite zone bounded by two fault gouge zones ca. 40 cm. The damage zone width defined by fracture density is ca. 50 m wide each side of the core. The damage zone in JFW is characterized by NW-striking subvertical 2 cm wide cataclastic rocks and NE-striking milimetric open fractures. In JFE, 1-20 mm wide chlorite, quartz-epidote and quartz-calcite veins, cut the gabbro. Microfracture analysis in JFW reveal mm-wide cataclasitic/ultracataclasitic bands with clasts of protolith and chlorite orientated subparallel to the JF in the matrix, calcite veins in a T-fractures orientation, and minor polidirectional chlorite veins. In JFE, chlorite filled conjugate fractures with syntaxial growth textures and evidence for dilational fracturing processes are seen. Closest to the core, calcite veins crosscut chlorite veins. Whole-rock XRF analyses show Al and Ca content decrease with increasing Si, whereas Na increases towards the core. This can be interpreted as compositional changes of plagioclase to albite-rich ones due to chloritic-propylitic alteration. In the damage zone, LOI increases towards the core but decreases inside of it. This is explained by H2O-rich clays and gypsum in the fault core boundary represented as fault gouge zones whereas in the cataclastic core zone, the decrease in LOI is explained by epidote. Our results show the JF had an evolving permeability structure where a cataclasite-rich core is formed at an early stage, and then a gouge-bounded core is developed which acted as a barrier to fluid from east to west of the fault.

Mass change calculations of hydrothermal alterations within the volcanogenic metasediments hosted Cu-Pb (-Zn) mineralization at Halilar area, NW Turkey

NASA Astrophysics Data System (ADS)

Kiran Yildirim, Demet; Abdelnasser, Amr; Doner, Zeynep; Kumral, Mustafa

2016-04-01

The Halilar Cu-Pb (-Zn) mineralization that is formed in the volcanogenic metasediments of Bagcagiz Formation at Balikesir province, NW Turkey, represents locally vein-type deposit as well as restricted to fault gouge zone directed NE-SW along with the lower boundary of Bagcagiz Formation and Duztarla granitic intrusion in the study area. Furthermore, This granite is traversed by numerous mineralized sheeted vein systems, which locally transgress into the surrounding metasediments. Therefore, this mineralization closely associated with intense hydrothermal alteration within brecciation, and quartz stockwork veining. The ore mineral assemblage includes chalcopyrite, galena, and some sphalerite with covellite and goethite formed during three phases of mineralization (pre-ore, main ore, and supergene) within an abundant gangue of quartz and calcite. The geologic and field relationships, petrographic and mineralogical studies reveal two alteration zones occurred with the Cu-Pb (-Zn) mineralization along the contact between the Bagcagiz Formation and Duztarla granite; pervasive phyllic alteration (quartz, sericite, and pyrite), and selective propylitic alteration (albite, calcite, epidote, sericite and/or chlorite). This work, by using the mass balance calculations, reports the mass/volume changes (gain and loss) of the chemical components of the hydrothermal alteration zones associated with Halilar Cu-Pb (-Zn) mineralization at Balikesir area (Turkey). It revealed that the phyllic alteration has enrichments of Si, Fe, K, Ba, and LOI with depletion of Mg, Ca, and Na reflect sericitization of alkali feldspar and destruction of ferromagnesian minerals. This zone has high Cu and Pb with Zn contents represents the main mineralized zone. On the other hand, the propylitic zone is characterized by addition of Ca, Na, K, Ti, P, and Ba with LOI and Cu (lower content) referring to the replacement of plagioclase and ferromagnesian minerals by albite, calcite, epidote, and sericite with chlorite. Keywords: Mass balance calculations; hydrothermal alterations; Cu-Pb (-Zn) mineralization; Halilar area; NW Turkey

U-Th dating of calcite corals from the Gulf of Aqaba

NASA Astrophysics Data System (ADS)

Yehudai, Maayan; Lazar, Boaz; Bar, Neta; Kiro, Yael; Agnon, Amotz; Shaked, Yonathan; Stein, Mordechai

2017-02-01

Most of the fossil corals in the elevated reef terraces along the Gulf of Aqaba (GOA) were extensively altered to calcite. This observation indicates extensive interaction with freshwater, possibly when the terraces passed through a coastal aquifer that existed along the shores of the GOA, implying a wetter climate during the time of recrystallization from aragonite to calcite. Thus, dating of the recrystallization events should yield the timing of past wetter conditions in the current hyper-arid area of the GOA. In the present study, 18 aragonite and calcite corals were collected from several elevated coral reef terraces off the coast, south of the city of Aqaba. While aragonite corals were dated with the conventional closed system age equation (assuming zero initial Th), the dating of the calcite corals required the development of adequate equations to allow the calculation of both the initial formation age of the aragonite corals and the time of recrystallization to calcite. The two age calculations were based on the assumptions that each reef terrace went through a single and rapid recrystallization event and that the pristine aragonite corals were characterized by a rather uniform initial U concentration, typical for pristine modern corals. Two recrystallization events were identified at 104 ± 6 ka and 124 ± 8 ka. The ages coincide with the timing of sapropel events S4 and S5, respectively, when the African monsoon induced enhanced wetness in the desert area. Considering the age uncertainties, the times of formation of the two major reef terraces are estimated to be ∼124 ka (reef terrace R2) and ∼130 ka (reef terrace R3), matching the peaks in the global sea level during the last interglacial MIS 5e stage. Apparently, sea level of the GOA did not fluctuate a lot during the period between ∼130 ka and ∼104 ka and remained close to the Marine Isotopic stage (MIS) 5e highstand. The availability of freshwater (during the sapropel periods) and limited sea level fluctuations facilitated the recrystallization of the GOA reef corals to calcite.

Geochemical assessment of hydrocarbon migration phenomena: Case studies from the south-western margin of the Dead Sea Basin

NASA Astrophysics Data System (ADS)

Sokol, Ella; Kozmenko, Olga; Smirnov, Sergey; Sokol, Ivan; Novikova, Sofya; Tomilenko, Anatoliy; Kokh, Svetlana; Ryazanova, Tatyana; Reutsky, Vadim; Bul'bak, Taras; Vapnik, Yevgeny; Deyak, Michail

2014-10-01

Calcite veins with fluid and solid bitumen inclusions have been discovered in the south-western shoulder of the Dead Sea rift within the Masada-Zohar block, where hydrocarbons exist in small commercial gas fields and non-commercial fields of heavy and light oils. The gas-liquid inclusions in calcite are dominated either by methane or CO2, and aqueous inclusions sometimes bear minor dissolved hydrocarbons. The enclosed flake-like solid bitumen matter is a residue of degraded oil, which may be interpreted as “dead carbon”. About 2/3 of this matter is soot-like amorphous carbon and 1/3 consists of n-C8sbnd C18 carboxylic acids and traces of n-alkanes, light dicarboxylic acids, and higher molecular weight (>C20) branched and/or cyclic carboxylic acids. Both bitumen and the host calcites show genetic relationship with mature Maastrichtian chalky source rocks (MCSRs) evident in isotopic compositions (δ13C, δ34S, and δ18O) and in REE + Y patterns. The bitumen precursor may have been heavy sulfur-rich oil which was generated during the burial compaction of the MCSR strata within the subsided blocks of the Dead Sea graben. The δ18O and δ13C values and REE + Y signatures in calcites indicate mixing of deep buried fluids equilibrated with post-mature sediments and meteoric waters. The temperatures of fluid generation according to Mg-Li-geothermometer data range from 55 °С to 90 °С corresponding to the 2.5-4.0 km depths, and largely overlap with the oil window range (60-90 °С) in the Dead Sea rift (Hunt, 1996; Gvirtzman and Stanislavsky, 2000; Buryakovsky et al., 2005). The bitumen-rich vein calcites originated in the course of Late Cenozoic rifting and related deformation, when tectonic stress triggers damaged small hydrocarbon reservoirs in the area, produced pathways, and caused hydrocarbon-bearing fluids to rise to the subsurface; the fluids filled open fractures and crystallized to calcite with entrapped bitumen. The reported results are in good agreement with the existing views of maturation, migration, and accumulation of hydrocarbons, as well as basin fluid transport processes in the Dead Sea area.

Trace element abundances in major minerals of Late Permian coals from southwestern Guizhou province, China

USGS Publications Warehouse

Zhang, Jiahua; Ren, D.; Zheng, C.; Zeng, R.; Chou, C.-L.; Liu, J.

2002-01-01

Fourteen samples of minerals were separated by handpicking from Late Permian coals in southwestern Guizhou province, China. These 14 minerals were nodular pyrite, massive recrystallized pyrite, pyrite deposited from low-temperature hydrothermal fluid and from ground water; clay minerals; and calcite deposited from low-temperature hydrothermal fluid and from ground water. The mineralogy, elemental composition, and distribution of 33 elements in these samples were studied by optical microscopy, scanning electron microscope equipped with energy-dispersive X-ray spectrometer (SEM-EDX), X-ray diffraction (XRD), cold-vapor atomic absorption spectrometry (CV-AAS), atomic fluorescence spectrometry (AFS), inductively coupled-plasma mass spectrometry (ICP-MS), and ion-selective electrode (ISE). The results show that various minerals in coal contain variable amounts of trace elements. Clay minerals have high concentrations of Ba, Be, Cs, F, Ga, Nb, Rb, Th, U, and Zr. Quartz has little contribution to the concentration of trace elements in bulk coal. Arsenic, Mn, and Sr are in high concentrations in calcite. Pyrite has high concentrations of As, Cd, Hg, Mo, Sb, Se, Tl, and Zn. Different genetic types of calcite in coal can accumulate different trace elements; for example Ba, Co, Cr, Hg, Ni, Rb, Sn, Sr, and Zn are in higher concentrations in calcite deposited from low-temperature hydrothermal fluid than in that deposited from ground water. Furthermore, the concentrations of some trace elements are quite variable in pyrite; different genetic types of pyrites (Py-A, B, C, D) have different concentrations of trace elements, and the concentrations of trace elements are also different in pyrite of low-temperature hydrothermal origin collected from different locations. The study shows that elemental concentration is rather uniform in a pyrite vein. There are many micron and submicron mosaic pyrites in a pyrite vein, which is enriched in some trace elements, such as As and Mo. The content of trace element in pyrite vein depends upon the content of mosaic pyrite and of trace elements in it. Many environmentally sensitive trace elements are mainly contained in the minerals in coal, and hence the physical coal cleaning techniques can remove minerals from coal and decrease the emissions of potentially hazardous trace elements. ?? 2002 Elsevier Science B.V. All rights reserved.

Natural radionuclide mobility and its influence on U-Th-Pb dating of secondary minerals from the unsaturated zone at Yucca Mountain, Nevada

USGS Publications Warehouse

Neymark, L.A.; Amelin, Y.V.

2008-01-01

Extreme U and Pb isotope variations produced by disequilibrium in decay chains of 238U and 232Th are found in calcite, opal/chalcedony, and Mn-oxides occurring as secondary mineral coatings in the unsaturated zone at Yucca Mountain, Nevada. These very slowly growing minerals (mm my-1) contain excess 206Pb and 208Pb formed from excesses of intermediate daughter isotopes and cannot be used as reliable 206Pb/238U geochronometers. The presence of excess intermediate daughter isotopes does not appreciably affect 207Pb/235U ages of U-enriched opal/chalcedony, which are interpreted as mineral formation ages. Opal and calcite from outer (younger) portions of coatings have 230Th/U ages from 94.6 ?? 3.7 to 361.3 ?? 9.8 ka and initial 234U/238U activity ratios (AR) from 4.351 ?? 0.070 to 7.02 ?? 0.12, which indicate 234U enrichment from percolating water. Present-day 234U/238U AR is ???1 in opal/chalcedony from older portions of the coatings. The 207Pb/235U ages of opal/chalcedony samples range from 0.1329 ?? 0.0080 to 9.10 ?? 0.21 Ma, increase with microstratigraphic depth, and define slow long-term average growth rates of about 1.2-2.0 mm my-1, in good agreement with previous results. Measured 234U/238U AR in Mn-oxides, which pre-date the oldest calcite and opal/chalcedony, range from 0.939 ?? 0.006 to 2.091 ?? 0.006 and are >1 in most samples. The range of 87Sr/86Sr ratios (0.71156-0.71280) in Mn-oxides overlaps that in the late calcite. These data indicate that Mn-oxides exchange U and Sr with percolating water and cannot be used as a reliable dating tool. In the U-poor calcite samples, measured 206Pb/207Pb ratios have a wide range, do not correlate with Ba concentration as would be expected if excess Ra was present, and reach a value of about 1400, the highest ever reported for natural Pb. Calcite intergrown with opal contains excesses of both 206Pb and 207Pb derived from Rn diffusion and from direct ??-recoil from U-rich opal. Calcite from coatings devoid of opal/chalcedony contains 206Pb and 208Pb excesses, but no appreciable 207Pb excesses. Observed Pb isotope anomalies in calcite are explained by Rn-produced excess Pb. The Rn emanation may strongly affect 206Pb-238U ages of slow-growing U-poor calcite, but should be negligible for dating fast-growing U-enriched speleothem calcite.

Microstructural observations on hydrothermal veins of Site U1414, IODP Expedition 344 (CRISP 2)

NASA Astrophysics Data System (ADS)

Brandstätter, Jennifer; Kurz, Walter; Rogowitz, Anna

2017-04-01

The erosive active margin offshore Osa Peninsula (Costa Rica) is characterized by the subducting Cocos Plate with its topographic height, the aseismic Cocos Ridge, which has lifted the seismogenic zone in the reach of scientific drilling. To understand the processes occurring in the subducting Cocos Plate in the vicinity to the Middle America Trench, we investigated microstructures in hydrothermal veins, transecting the lithified sediments and the igneous basement of IODP Hole U-1414A. Mechanical e-twinning occurred mainly in the blocky calcite veins in the lithified sediments, rather than in the fibrous calcite veins within the Cocos Ridge basalt. The differential stress, obtained from two different piezometers, indicate mean differential stresses of approximately 53 and 82 MPa. The majority of the twins show a significant thickness (up to 120 µm), straight twin boundaries and are indicative for deformation temperatures between 150 to 300°C. The presence of additional deformation structures, such as undulose extinction and subgrain boundaries, indicates intracrystalline-plastic deformation by dislocation creep. The comparison of the EBSD data from two samples within the lithified sedimentary unit indicates diverse deformation temperatures. Variation in subgrain size observed for the different samples can be related to local variations in differential stress. The results of different microstructural observations showed, that the deformational history of Site 344-U1414 is characterized by distinct tectonic phases, occurring during the movement of the Cocos Ridge from its location of origin (the Galapagos hotspot) to the convergent margin offshore Costa Rica. The causes for these changes in deformation mechanisms in the studied rocks are ascribed to magmatic advection resulting in an increase of temperature and decrease of critical resolved shear stresses, as well as the bending of the Cocos plate adjacent to the Middle American trench.

Castiglione (Oletta, Corsica): relationships between phenomena of calcification and tectonic fossiliferous fracture dating

NASA Astrophysics Data System (ADS)

Pereira, Elisabeth; Rouzaud, François; Salotti, Michelle; Dubois, Jean-Noël; Ferrandini, Jean; Ottaviani-Spella, Marie-Madeleine; Quinif, Yves

Six cavities have been discovered in the Oletta massif. The massif, today constitued of Schistes lustrés with several metres of calcareous layers above them, has undergone intense fracturing. The networks of cavities are organised along north-south and subequatorial directions, and form a narrow bayonnet-network. All the elements in the galleries appear to be karstic: stalagmites, stalactites and calcitic deposits along the walls; but no trace of dissolution or excavation was found. Thus, the origin of the galleries is only tectonic, while the calcitic deposits result from the dissolution of the old, thick calcareous layers above, which are no longer present. The thickness and the volume of the calcitic deposits, which is variable depending on the galleries, indicates the chronology of the different tectonic periods which have fractured the massif. Five tectonic and successsive events have been detected. Calcitic datings confirm the timing of successional fracturing, indicating also the variable age of the fossiliferous Middle Pleistocene deposits found in these cavities.

Fault zone processes in mechanically layered mudrock and chalk

NASA Astrophysics Data System (ADS)

Ferrill, David A.; Evans, Mark A.; McGinnis, Ronald N.; Morris, Alan P.; Smart, Kevin J.; Wigginton, Sarah S.; Gulliver, Kirk D. H.; Lehrmann, Daniel; de Zoeten, Erich; Sickmann, Zach

2017-04-01

A 1.5 km long natural cliff outcrop of nearly horizontal Eagle Ford Formation in south Texas exposes northwest and southeast dipping normal faults with displacements of 0.01-7 m cutting mudrock, chalk, limestone, and volcanic ash. These faults provide analogs for both natural and hydraulically-induced deformation in the productive Eagle Ford Formation - a major unconventional oil and gas reservoir in south Texas, U.S.A. - and other mechanically layered hydrocarbon reservoirs. Fault dips are steep to vertical through chalk and limestone beds, and moderate through mudrock and clay-rich ash, resulting in refracted fault profiles. Steeply dipping fault segments contain rhombohedral calcite veins that cross the fault zone obliquely, parallel to shear segments in mudrock. The vertical dimensions of the calcite veins correspond to the thickness of offset competent beds with which they are contiguous, and the slip parallel dimension is proportional to fault displacement. Failure surface characteristics, including mixed tensile and shear segments, indicate hybrid failure in chalk and limestone, whereas shear failure predominates in mudrock and ash beds - these changes in failure mode contribute to variation in fault dip. Slip on the shear segments caused dilation of the steeper hybrid segments. Tabular sheets of calcite grew by repeated fault slip, dilation, and cementation. Fluid inclusion and stable isotope geochemistry analyses of fault zone cements indicate episodic reactivation at 1.4-4.2 km depths. The results of these analyses document a dramatic bed-scale lithologic control on fault zone architecture that is directly relevant to the development of porosity and permeability anisotropy along faults.

Fluvial/lacustrine diagenesis: Significance for hydrocarbon production and entrapment in the carboniferous Albert Fm, Moncton basin, NB

DOE Office of Scientific and Technical Information (OSTI.GOV)

Noble, J.P.A.; Chowdhury, A.H.; Yu, H.

1996-12-31

The Carboniferous Horton Group Albert Formation sediments include lacustrine source-rock oil shales and fluvial porous reservoir sandstones. The petrography, stable isotopes, fluid inclusions, cathodoluminescence and mirror/trace element chemistry of these sandstones are used to establish the diagenetic history and controlling factors. Early diagenetic calcite, quartz and albite cements with minor chlorite and kaolinite are variably present and related to depositional mineralogy and lake levels winch controlled the porewater chemistry. Antitaxial veins occurring preferentially in shales are shown, from heavy {delta}C{sup 13} values and fluid inclusions, to be related to methanogenesis in overpressured zones at shallow depths. Later burial calcite andmore » extensive albitisation are related to mineral reactions during the phase of rapid subsidence at temperatures of 80{degrees} to 150{degrees} in the deepest segment of the basin, together with significant dissolution of carbonates and feldspars related mainly to organic acids generated by organic maturation processes. Mass balance calculations indicate that not enough organic matter was present to account for all the estimated secondary porosity and some evidence suggests that reactions between kaolinite and calcite/ankerite to produce chlorite, and mixed layer illite-smectite ordering reactions, produced significant secondary porosity. Burial history reconstructions and thermal modelling of the Albert Fm. sediments using Arrhenius type maturity models and reflectance and rock-eval data suggest locally variable maturation and reservoir production related to the locally different fault tectonic histories characteristic of strike-slip lacustrine segmented basins. The Horton depositional cycle was followed by major dextral transpression with local faulting and inversion and vein cementation.« less

Fluvial/lacustrine diagenesis: Significance for hydrocarbon production and entrapment in the carboniferous Albert Fm, Moncton basin, NB

DOE Office of Scientific and Technical Information (OSTI.GOV)

Noble, J.P.A.; Chowdhury, A.H.; Yu, H.

1996-01-01

The Carboniferous Horton Group Albert Formation sediments include lacustrine source-rock oil shales and fluvial porous reservoir sandstones. The petrography, stable isotopes, fluid inclusions, cathodoluminescence and mirror/trace element chemistry of these sandstones are used to establish the diagenetic history and controlling factors. Early diagenetic calcite, quartz and albite cements with minor chlorite and kaolinite are variably present and related to depositional mineralogy and lake levels winch controlled the porewater chemistry. Antitaxial veins occurring preferentially in shales are shown, from heavy [delta]C[sup 13] values and fluid inclusions, to be related to methanogenesis in overpressured zones at shallow depths. Later burial calcite andmore » extensive albitisation are related to mineral reactions during the phase of rapid subsidence at temperatures of 80[degrees] to 150[degrees] in the deepest segment of the basin, together with significant dissolution of carbonates and feldspars related mainly to organic acids generated by organic maturation processes. Mass balance calculations indicate that not enough organic matter was present to account for all the estimated secondary porosity and some evidence suggests that reactions between kaolinite and calcite/ankerite to produce chlorite, and mixed layer illite-smectite ordering reactions, produced significant secondary porosity. Burial history reconstructions and thermal modelling of the Albert Fm. sediments using Arrhenius type maturity models and reflectance and rock-eval data suggest locally variable maturation and reservoir production related to the locally different fault tectonic histories characteristic of strike-slip lacustrine segmented basins. The Horton depositional cycle was followed by major dextral transpression with local faulting and inversion and vein cementation.« less

Paleomagnetic Reorientation of Structural Elements in Drill Cores: an example from Tolhuaca Geothermal Field

NASA Astrophysics Data System (ADS)

Perez-Flores, P.; Veloso, E. E.; Cembrano, J. M.; Sánchez, P.; Iriarte, S.; Lohmar, S.

2013-12-01

Reorientation of mesoscopic faults, veins and fractures recovered from drilling is critical to construct reliable structural models that can account for their architecture and deformation regime. However, oriented cores are expensive and time consuming to drill. Some techniques achieve reorientation by introducing tools into the borehole. Problems arise when boreholes are unstable or collapse. One alternative technique allowing reorientation is to obtain reliable paleomagnetic vectors to reorient each core piece after drilling. Here, we present stable and reliable remnant magnetic vectors calculated from the Tol-1 core to analyze the geometry of the fracture network and its relationship to regional tectonic. Tol-1 core is a vertical, 1073 m deep geothermal well, drilled at the Tolhuaca Geothermal Field in the Southern Volcanic Zone of the Andes by MRP Geothermal Chile Ltda (formerly GGE Chile SpA) in 2009. The core consists of basaltic/andesitic volcanic rocks with subordinate pyroclastic/volcaniclastic units, with probable Pleistocene age. Fault planes with slickenlines and mineral fiber kinematic indicators are common in the upper 700 m of the core. Calcite, quartz and calcite-quartz veins are recognized along of entire core, whereas epidote-quartz and calcite-epidote veins occur in the last 350 m, minor chlorite, anhydrite and clay-minerals are present. Orientations of structural features in the core were measured with a goniometer using the core's axis and a false north for each piece; hence, orientation data has a false strike but a real dip. To achieve total reorientation of the pieces, we collected 200 standard-size paleomagnetic specimens, ensuring that at least four of them were recovered from continuous pieces. Thermal (up to 700°C) and alternating field demagnetization (up to 90mT on steps of 2mT) methods were used to isolate a stable remnant magnetization (RM) vector, and each technique yielded similar results. RM vectors were recovered between 0 to 25mT, and between 0 to 625°C. The declination of RM vectors was used to bring pieces to a common anchor orientation calculated through the Geocentric Axial Dipole Model (GAD). The paleomagnetic technique proved to be reliable to reorient the Tol-1 core. Structural analyses along the core show N50-60E-striking preferential vein orientation. In addition, N40-50E- and N60-70W-striking preferential fault orientations were identified. Kinematic analysis of fault-slip data shows a N60E-striking bulk fault plane solution with normal strain regime. The veins and faults orientation show strain axes compatible with published regional stress field (σmax N238E).

Illite authigenesis during faulting and fluid flow - a microstructural study of fault rocks

NASA Astrophysics Data System (ADS)

Scheiber, Thomas; Viola, Giulio; van der Lelij, Roelant; Margreth, Annina

2017-04-01

Authigenic illite can form synkinematically during slip events along brittle faults. In addition it can also crystallize as a result of fluid flow and associated mineral alteration processes in hydrothermal environments. K-Ar dating of illite-bearing fault rocks has recently become a common tool to constrain the timing of fault activity. However, to fully interpret the derived age spectra in terms of deformation ages, a careful investigation of the fault deformation history and architecture at the outcrop-scale, ideally followed by a detailed mineralogical analysis of the illite-forming processes at the micro-scale, are indispensable. Here we integrate this methodological approach by presenting microstructural observations from the host rock immediately adjacent to dated fault gouges from two sites located in the Rolvsnes granodiorite (Bømlo, western Norway). This granodiorite experienced multiple episodes of brittle faulting and fluid-induced alteration, starting in the Mid Ordovician (Scheiber et al., 2016). Fault gouges are predominantly associated with normal faults accommodating mainly E-W extension. K-Ar dating of illites separated from representative fault gouges constrains deformation and alteration due to fluid ingress from the Permian to the Cretaceous, with a cluster of ages for the finest (<0.1 µm) fraction in the early to middle Jurassic. At site one, high-resolution thin section structural mapping reveals a complex deformation history characterized by several coexisting types of calcite veins and seven different generations of cataclasite, two of which contain a significant amount of authigenic and undoubtedly deformation-related illite. At site two, fluid ingress along and adjoining the fault core induced pervasive alteration of the host granodiorite. Quartz is crosscut by calcite veinlets whereas plagioclase, K-feldspar and biotite are almost completely replaced by the main alteration products kaolin, quartz and illite. Illite-bearing micro-domains were physically separated by means of microsawing and drilling devices. K-Ar and XRD data from these separates are compared with bulk K-Ar and XRD data from the adjacent fault gouges, which may help to further unravel complex histories archived in multiply activated brittle fault zones. Scheiber, T., Viola, G., Wilkinson, C.M., Ganerød, M., Skår, Ø., and D. Gasser (2016): Direct 40Ar/39Ar dating of Late-Ordovician and Silurian brittle faulting in the southwestern Norwegian Caledonides. Terra Nova 28, 374-382.

Strain partitioning and deformation mode analysis of the normal faults at Red Mountain, Birmingham, Alabama

NASA Astrophysics Data System (ADS)

Wu, Schuman

1989-12-01

In a low-temperature environment, the thin-section scale rock-deformation mode is primarily a function of confining pressure and total strain at geological strain rates. A deformation mode diagram is constructed from published experimental data by plotting the deformation mode on a graph of total strain versus the confining pressure. Four deformation modes are shown on the diagram: extensional fracturing, mesoscopic faulting, incipient faulting, and uniform flow. By determining the total strain and the deformation mode of a naturally deformed sample, the confining pressure and hence the depth at which the rock was deformed can be evaluated. The method is applied to normal faults exposed on the gently dipping southeast limb of the Birmingham anticlinorium in the Red Mountain expressway cut in Birmingham, Alabama. Samples of the Ordovician Chickamauga Limestone within and adjacent to the faults contain brittle structures, including mesoscopic faults and veins, and ductile deformation features including calcite twins, intergranular and transgranular pressure solution, and deformed burrows. During compaction, a vertical shortening of about 45 to 80% in shale is indicated by deformed burrows and relative compaction of shale to burrows, about 6% in limestone by stylolites. The normal faults formed after the Ordovician rocks were consolidated because the faults and associated veins truncate the deformed burrows and stylolites, which truncate the calcite cement. A total strain of 2.0% was caused by mesoscopic faults during normal faulting. A later homogenous deformation, indicated by the calcite twins in veins, cement and fossil fragments, has its major principal shortening strain in the dip direction at a low angle (about 22°) to bedding. The strain magnitude is about 2.6%. By locating the observed data on the deformation mode diagram, it is found that the normal faulting characterized by brittle deformation occurred under low confining pressure (< 18 MPa) at shallow depth (< 800 m), and the homogenous horizontal compression characterized by uniform flow occurred under higher confining pressure (at least 60 MPa) at greater depth (> 2.5 km).

Palaeoclimate determination from cave calcite deposits

NASA Astrophysics Data System (ADS)

Gascoyne, M.

Calcite deposits formed in limestone caves have been found to be an excellent repository of palaeoclimatic data for terrestrial environments. The very presence of a relict deposit indicates non-glacial conditions at the time of formation, and both 14C and uranium-series methods can be used to date the deposit and, hence, the age of these climatic conditions. Variations in 13C and 18O content of the calcite, in 2H and 18O content of fluid inclusions, in trace element concentrations and, more recently, in pollen assemblages trapped in the calcite, are all potentially available as synchronous palaeoclimatic indicators. Previous work has tended to concentrate mainly on abundance of deposits as a palaeoclimatic indicator for the last 300,000 years. This literature is briefly reviewed here, together with the theory and methods of analysis of the U-series and stable isotopic techniques. The combined use of U-series ages and 13C and 18O variations in cave calcites illustrates the potential for palaeoclimate determination. Previously unpublished results of stable isotopic variations in dated calcites from caves in northern England indicate the level of detail of stable isotopic variations and time resolution that can be obtained, and the complexity of interpretation that may arise. Tentative palaeoclimatic signals for the periods 90-125 ka and 170-300 ka are presented. More comprehensive studies are needed in future work, especially in view of the difficulty in obtaining suitable deposits and the ethics of cave deposits conservation.

Carbon dioxide generation and drawdown during active orogenesis of siliciclastic rocks in the Southern Alps, New Zealand

NASA Astrophysics Data System (ADS)

Menzies, Catriona D.; Wright, Sarah L.; Craw, Dave; James, Rachael H.; Alt, Jeffrey C.; Cox, Simon C.; Pitcairn, Iain K.; Teagle, Damon A. H.

2018-01-01

Collisional mountain building influences the global carbon cycle through release of CO2 liberated by metamorphic reactions and promoting mechanical erosion that in turn increases chemical weathering and drawdown of atmospheric CO2. The Southern Alps is a carbonate-poor, siliciclastic mountain belt associated with the active Australian Pacific plate boundary. On-going, rapid tectonic uplift, metamorphism and hydrothermal activity are mobilising carbon. Here we use carbon isotope measurements of hot spring fluids and gases, metamorphic host rocks, and carbonate veins to establish a metamorphic carbon budget. We identify three major sources for CO2 within the Southern Alps: (1) the oxidation of graphite; (2) consumption of calcite by metamorphic reactions at the greenschist-amphibolite facies boundary, and (3) the dissolution of groundmass and vein-hosted calcite. There is only a minor component of mantle CO2 arising on the Alpine Fault. Hot springs have molar HCO3-/Ca2+ ∼9, which is substantially higher than produced by the dissolution of calcite indicating that deeper metamorphic processes must dominate. The total CO2 flux to the near surface environment in the high uplift region of the Southern Alps is estimated to be ∼6.4 × 108 mol/yr. Approximately 87% of this CO2 is sourced from coupled graphite oxidation (25%) and disseminated calcite decarbonation (62%) reactions during prograde metamorphism. Dissolution of calcite and mantle-derived CO2 contribute ∼10% and ∼3% respectively. In carbonate-rich orogens CO2 production is dominated by metamorphic decarbonation of limestones. The CO2 flux to the atmosphere from degassing of hot springs in the Southern Alps is 1.9 to 3.2 × 108 mol/yr, which is 30-50% of the flux to the near surface environment. By contrast, the drawdown of CO2 through surficial chemical weathering ranges between 2.7 and 20 × 109 mol/yr, at least an order of magnitude greater than the CO2 flux to the atmosphere from this orogenic belt. Thus, siliciclastic mountain belts like the Southern Alps are net sinks for atmospheric CO2, in contrast to orogens involving abundant carbonate rocks, such as the Himalaya, that are net CO2 sources.

Regional fluid and metal mobility in the Dalradian metamorphic belt, Southern Grampian Highlands, Scotland

NASA Astrophysics Data System (ADS)

Craw, D.

1990-10-01

A prominent set of veins was formed during post-metamorphic deformation of the Caledonian Dalradian metamorphic belt. These veins are concentrated in dilational zones in fold hinges, but apophyses follow schistosity and fold axial surface fractures. The veins are most common in the cores of regional structures, especially the Dalradian Downbend and consist of quartz, calcite, chlorite and metallic sulphides and oxides. Metals, including gold, have been concentrated in the veins. The fluid which formed the veins was low salinity (1 5 wt% NaCl and KCl) CO2-bearing (3 16 wt% CO2) water of metamorphic origin. The fluid varies slightly in composition within and between samples, but is essentially uniform in composition over several hundred km2. Vein formation occurred at about 350±50 °C and 200 300 MPa pressure. Further quartz mineralization occurred in some dilational zones at lower temperatures (160 180 °C). This later mineralization was accompanied by CO2 immiscibility. Dilution and oxidation of the metamorphic fluid occurred due to mixing with meteoric water as the rocks passed through the brittle-ductile transition. A similar metamorphic fluid is thought to have been responsible for gold mineralization in the nearby Tyndrum Fault at a later stage in the Dalradian uplift.

Microstructures imply cataclasis and authigenic mineral formation control geomechanical properties of New Zealand's Alpine Fault

NASA Astrophysics Data System (ADS)

Schuck, B.; Janssen, C.; Schleicher, A. M.; Toy, V. G.; Dresen, G.

2018-05-01

The Alpine Fault is capable of generating large (MW > 8) earthquakes and is the main geohazard on South Island, NZ, and late in its 250-291-year seismic cycle. To minimize its hazard potential, it is indispensable to identify and understand the processes influencing the geomechanical behavior and strength-evolution of the fault. High-resolution microstructural, mineralogical and geochemical analyses of the Alpine Fault's core demonstrate wall rock fragmentation, assisted by mineral dissolution, and cementation resulting in the formation of a fine-grained principal slip zone (PSZ). A complex network of anastomosing and mutually cross-cutting calcite veins implies that faulting occurred during episodes of dilation, slip and sealing. Fluid-assisted dilatancy leads to a significant volume increase accommodated by vein formation in the fault core. Undeformed euhedral chlorite crystals and calcite veins that have cut footwall gravels demonstrate that these processes occurred very close to the Earth's surface. Microstructural evidence indicates that cataclastic processes dominate the deformation and we suggest that powder lubrication and grain rolling, particularly influenced by abundant nanoparticles, play a key role in the fault core's velocity-weakening behavior rather than frictional sliding. This is further supported by the absence of smectite, which is reasonable given recently measured geothermal gradients of more than 120 °C km-1 and the impermeable nature of the PSZ, which both limit the growth of this phase and restrict its stability to shallow depths. Our observations demonstrate that high-temperature fluids can influence authigenic mineral formation and thus control the fault's geomechanical behavior and the cyclic evolution of its strength.

MicroCT vs. Hg porosimetry: microporosity in commercial stones

NASA Astrophysics Data System (ADS)

Fusi, N.; Martinez-Martinez, J.; Barberini, V.; Galimberti, L.

2009-04-01

Decay of rocks, due both to extrinsic and intrinsic factors, can show up in several different forms, such as neoformation of minerals, decohesion of grains and/or crystals, magnification of previous defects, new discontinuities, etc. Intrinsic factors include the type of material, its properties and microstructure, in particular porosity and microporosity. Extrinsic factors relate to atmosphere and usage of the material itself. Rock degradation has several heavy consequences for commercial stones, such as increase of permeability, loss of material, loss of mechanical strength; these consequences are of crucial importance for conservation of historical buildings. Aim of this study is to compare microporosity of some massive commercial stones by means of X ray microtomography, a non destructive technique, and Hg porosimetry. Nine of the most used Spanish limestones and dolostones have been analysed. The lithotypes have been chosen for their homogeneous mineralogical composition (calcitic or dolomitic) and for their low porosity; some of them have been widely used in Spain for historical buildings. Different lithotypes have been described in thin section: Ambarino (A) and Beige Serpiente (BS): brecciated dolostone, composed by microcrystalline dolomitic clasts, in a dolomitic and/or calcitic microcrystalline matrix. Amarillo Triana (AT): yellow dolomitic marble, with fissures filled up by calcite and Fe oxides. Blanco Alconera (BA): a white-pink homogeneous limestone, with veins. Blanco Tranco (BT): a homogeneous white calcitic marble, without any fissures and/or fractures. Crema Valencia (CV): a pinkish limestone, characterized by abundant stilolythes, filled mainly by quartz (80%) and kaolin (11%). Gris Macael (GM): a calcitic marble wiht darker and lighter beds, conferring a strong anisotropy. Rojo Cehegin (RC): a red fossiliferous limestone with white calcitic veins. Travertino Blanco (TB): a massive white calcitic travertine. Prismatic samples of about 2x1x1 cm have been cut and scanned by means of a X ray microCT system before and after mercury saturation with Hg porosimeter. The microCT system used is a BIR Actis 130/150 with nominal resolution of 5 micron; for our samples resolution is of 25 microns. Generator and detector are fixed, while the sample rotates; the scanning plane is horizontal. Samples reduce the X rays energy passing through, as a function of its density and atomic number. X rays are then collected on a detector, which converts them into light radiations; a digital camera collects light radiations in raw data and send them to the computer, where they are processed as black/white images. The Hg porosimeter used is a Pascal 140/240 Thermo Fisher. Samples were first degassed and then intruded by Hg. Apparent density, bulk density, porosity and open pore size distribution (pore diameter between 3.7 and 58000 nm) of each sample have been computed using the PASCAL (Pressurization with Automatic Speed-up by Continuous Adjustametnt Logic) method and the Washburn equation; this equation assumes: cylindrical pores, a contact angle between mercury and sample of 140°, a surface tension of mercury vacuum of 0,480 N/m and mercury density equal to 13.5 g/cm³. MicroCT images and porosity data from Hg porosimeter have been compared by several authors both for rocks (Klobes et alii, 1997) and for artificial materials with medical applications (Lin-Gibson et alii, 2007) In samples with no density/composition differences microCT images are homogeneous and gives no information on the internal structure of the sample. This is the case of massive samples (such as BA, BT, GM and TB) and of samples without any significant density differences between clasts and matrix (A and BS) or rock and veins (RC). MicroCT images of the same sample after mercury saturation offer a detailed map of microporosity of the rock, due to the high density contrast between mercury (13.6 g/cm3) and the rock (2.71 g/cm3 for calcite and 2.86 g/cm3 for dolomite). In some cases microporosity coincide with structural features of the rock, such as stylolythes (CV), fissures (AT) and veins (RC). This method works for samples with low porosity (less than 1%); on the other hand for samples with higher porosity (4%; A and BS) microCT images after Hg saturation present artefacts, due to the spreading of Hg within the sample, which obliterates the true structure of the rock. References Klobes, P., Riesemeier, H., Meyer, K., Goebbles, J. and Hellmuth, K.H. (1997). Rock porosity determination by combination of K-ray computerized tomography with mercury porosimetry. Fresenius J. Anal. Chem., 357, 543-547 Lin-Gibson, S., Cooper, J.A., Forrest, A.L. and Cicerone, M.T. (2007). Systematic investigation of porogen size and content on scaffold morphometric parameters and properties. Biomacromolecules, 8, 1511-1518.

Origin of ore-forming fluids of the Haigou gold deposit in the eastern Central Asian Orogenic belt, NE China: Constraints from H-O-He-Ar isotopes

NASA Astrophysics Data System (ADS)

Zeng, Qingdong; He, Huaiyu; Zhu, Rixiang; Zhang, Song; Wang, Yongbin; Su, Fei

2017-08-01

The Haigou lode deposit contains 40 t of gold at an average grade of 3.5 g/t, and is one of the largest deposits in the Jiapigou gold belt located along the eastern segment of the northern margin of the North China Craton. The deposit comprises 15 gold-bearing quartz veins hosted in a Carboniferous monzonite-monzogranite stock. Cretaceous dikes consisting of diorite, diabase, and granodiorite porphyries are well developed in the deposit. The diorite porphyry dikes (130.4 ± 6.3 Ma) occur together with gold-bearing quartz veins in NNE- and NE-striking faults. Gold-bearing quartz veins crosscut the diorite porphyry dikes, and the veins are in turn crosscut by E-W-striking 124.6 ± 2.2 Ma granodiorite porphyry dikes. The mineralization mainly occurs as auriferous quartz veins with minor amounts of sulfide minerals, including pyrite, galena, chalcopyrite, and molybdenite. Gold occurs as either native gold or calaverite. Common gangue minerals in the deposit include quartz, sericite, and calcite. The deposit is characterized by various types of hydrothermal alteration, including silicification, sericitization, chloritization, potassic alteration, and carbonatization. Three stages of hydrothermal activity have been recognized in the deposit: (1) a barren quartz stage; (2) a polymetallic sulfide (gold) stage; (3) a calcite stage. Fluid inclusions in hydrothermal pyrites have 3He/4He ratios of 0.3 to 3.3 Ra and 40Ar/36Ar ratios of 351 to 1353, indicating mixing of fluids of mantle and crustal origin. Hydrothermal quartz yielded δ18O values of -1.3‰ to +7.2‰ and δD values of fluid inclusions in the quartz vary between -80‰ and -104‰. These stable isotope data also suggest mixing of magmatic and meteoric fluids. Noble gas and stable isotopic data suggest that the ore fluids have a predominant mantle source with a significant crustal component. Based on the spatial association of gold-bearing quartz veins with early Cretaceous intrusions, and the H-O-He-Ar isotopic data from the deposit and intrusions, we propose that gold mineralization in the Haigou deposit was formed in an extensional setting and was related to the early Cretaceous, mantle-derived intrusions.

Episodic formation of the world-class Waihi epithermal Au-Ag vein system, Hauraki Goldfield, New Zealand

USGS Publications Warehouse

Gasston, Erin; Mauk, Jeffrey L.; Cosca, Michael A.; Morgan, Leah; Hall, Chris M.

2017-01-01

The world-class Waihi vein system in New Zealand has produced more than 248,400 kg Au and 1.43 million kg Ag. New high-precision 40Ar/39Ar dates of adularia from different veins show that some veins formed at different times (6.15 Ma Martha vs. 5.83 and 5.85 Ma Empire and Welcome, respectively), even though they have similar mineralogy. The Martha vein formed over a period of approximately 150,000 years. The Moonlight vein, which has a different ore mineral assemblage, appears to have formed over a longer time interval that spanned formation of the Martha, Welcome, and Empire veins. These dates suggest that some veins in the Waihi vein system formed relatively quickly during only part of the lifetime of the hydrothermal system, whereas other veins may have formed over longer periods of time. However, the Au endowment of the Martha vein exceeds the Au endowment of the Moonlight vein, indicating that the total lifetime of the vein-forming hydrothermal system does not determine metal endowment.

Magnetite-apatite mineralization in Khanlogh iron deposit, northwest of Neyshaboor, NE Iran

NASA Astrophysics Data System (ADS)

Najafzadeh Tehrani, Parvin; Asghar Calagari, Ali; Velasco Roldan, Francisco; Simmonds, Vartan; Siahcheshm, Kamal

2016-04-01

Khanlogh iron deposit lies on Sabzehvar-Ghoochan Cenozoic magmatic belt in northwest of Neyshaboor, NE Iran. The lithologic units in this area include a series of sub-volcanic intrusive rocks like diorite porphyry, quartz-diorite porphyry, and micro-granodiorite of Oligocene age. Mineralization in this area occurred as veins, dissemination, and open space filling in brecciated zones within the host sub-volcanic intrusive bodies. Three distinct types of mineral associations can be distinguished, (1) diopside-magnetite, (2) magnetite-apatite, and (3) apatite-calcite. Microscopic examinations along with SEM and EPMA studies demonstrated that magnetite is the most common ore mineral occurring as solitary crystals. The euhedral magnetite crystals are accompanied by lamellar destabilized ilmenite and granular fluorapatite in magnetite-apatite ores. The results of EPMA revealed that the lamellar ilmenite, relative to host magnetite crystal, is notably enriched in MgO and MnO (average of 3.3 and 2.6 wt%, respectively; n=5), whereas magnetite is slighter enriched in Ti (TiO2 around 1.8 wt%) being average of MgO, MnO and V2O3 of 0.6wt%, 0.2wt%, and 0.6 wt% (respectively; n=20). Minerals such as chlorapatite, calcite, and chalcedony are also present in the magnetite-apatite ores. The samples from apatite-calcite ores contain coarse crystals of apatite and rhomboedral calcite. The plot of the EPMA data of Khanlogh iron ore samples on diagram of TiO2-V2O5 (Hou et al, 2011) illustrated that the data points lies between the well-known Kiruna and El Laco (Chile) iron deposits. The magnetite crystals in the sub-volcanic host rocks were possibly formed by immiscible iron oxide fluids during magmatic stage. However, the magnetite and apatite existing in the veins and breccia zones may have developed by high temperature hydrothermal fluids. Studies done by Purtov and Kotelnikova (1993) proved that the proportion of Ti in magnetite is related to fluoride complex in the hydrothermal fluids. The high fluorine content of the apatite at Khanlogh may testify to the presence of Ti-fluoride complex in the fluids. Formation of apatite crystals was concurrent with development of titanium lamellae in magnetite. The apatite possesses high REE content which is possibly associated with monazite inclusions. The SEM studies better show these inclusions are occasionally present at the margin of apatite crystals and veins. Based upon field relations, microscopic examinations, and the results of XRD analyses, sodic (albite), propylitic (epidote, chlorite, calcite), and argillic (montmorillonite) alterations are developed in the study area. The principal minerals in these alteration zones are albite, epidote, sericite, chlorite, quartz, calcite, and montmorllonite. Mineralogy, alteration, geochemistry, structure, and texture of the ores at Khanlogh indicate that the magnetite and apatite were chiefly formed by hydrothermal solutions which were enriched in iron mainly transported by F- and Cl- rich fluids. Reference Hou,,T., Zhaochong, Z., Timothy, K., (2011). Gushan magnetite-apatite deposit in the Ningwu basin, Lower Yangtze River Valley, SE China: Hydrothermal or Kiruna-type? Ore geology review, 43, 333-346. Purtov, V.K., Kotelnikova, A.L. (1993). Solubility of titanium in chloride and fluoride hydrothermal solution. International Geology Review 35, 274 -287.

Ages and stable-isotope compositions of secondary calcite and opal in drill cores from Tertiary volcanic rocks of the Yucca Mountain area, Nevada

USGS Publications Warehouse

Szabo, B. J.; Kyser, T.K.

1990-01-01

Stable-isotope compositions of fracture- and cavity-filling calcite from the unsaturated zone of three drill cores at Yucca Mountain Tertiary volcanic complex indicate that the water from which the minerals precipitated was probably meteoric in origin. A decrease in 18O in the calcite with depth is interpreted as being due to the increase in temperature in drill holes corresponding to an estimated average geothermal gradient of 34?? per kilometer. A few of the calcite samples and all of the opal samples yielded uranium-series ages older than 400 000 yr, although most of the calcite samples yielded ages between 26 000 and 310 000 yr. The stable-isotope and uranium-series dates from precipitated calcite and opal of this reconnaissance study suggest a complex history of fluid movement through the volcanic pile, and episodes of fracture filling predominantly from meteoric water during at least the past 400 000 yr. -Authors

Sinter-vein correlations at Buckskin Mountain, National district, Humboldt County, Nevada

USGS Publications Warehouse

Vikre, P.G.

2007-01-01

At Buckskin Mountain (elev 2,650 m, 8,743 ft), Humboldt County, Nevada, a hydrothermal system, imposed on a middle Miocene volcanic sequence with contrasting permeabilities and tensile strengths, produced alteration assemblages controlled by elevation, from Hg-mineralized sinter to subjacent precious metal veins over a vertical distance exceeding 790 m. Sinter and epiclastic deposits, interpreted to be remnant paleosurface basinal strata enclosed by 16.6 to 16.1 Ma rhyolites, overlie older volcaniclastic basinal deposits and were part of a regional fluvial-lacustrine system developed among ca. 16 to 12 Ma basalt-rhyolite eruptive centers throughout the northern Great Basin. Because of contrasting erosional resistance among altered and unaltered rocks, Buckskin Mountain represents inverse topography with sinter and silicified epiclastic deposits at the summit. Sinter and veins, correlated by common elements, similar mineralogy, age constraints, textures, S isotope compositions, and fluid inclusion microthermometry, were deposited by sinter-vein fluid, the first of two sequential hydrothermal fluid regimes that evolved in response to magmatism, tectonism, hydrology, and topography. Thermal quenching of distally derived sinter-vein fluid in planar conduits caused deposition of banded quartz-silicate-selenide-sulfide veins ???270 to > 440 m below sinter at 16.1 Ma; vei??ns were initially enveloped by zoned selvages of proximal K-feldspar + K-mica + quartz + pyrite and distal illite + chlorite + calcite + pyrite. Mixing of sinter-vein fluid with local meteoric water in saturated basinal deposits caused deposition of silica, Hg-Se-S-Cl minerals, and precious metals in sinter and epiclastic deposits. Elevated ???Se/???S in sinter-vein fluid, and the relatively large stability fields of reduced aqueous selenide species in the temperature range of 250?? to <100??C, enabled (but was not the cause of) codeposition of selenide-sulfide minerals and common element associations in veins and sinter. Acid-sulfate fluid of the second fluid regime was derived from oxidation of H2S and other volatiles exsolved from sinter-vein fluid. Acid-sulfate fluid produced (1) a subhorizontal zone of partially leached basinal deposits and rhyolite from the paleosurface to a depth of ???60 m, and (2) laterally pervasive zones, ???100 to 200 m thick, of quartz + alunite ?? hematite and quartz + kaolinite + pyrite in volcaniclastic deposits immediately beneath partially leached rocks, but this fluid did not decompose selenide-sulfide-precious metal phases in sinter. Paragenetically late vein and wall-rock assemblages, including marcasite + pyrite, calcite, and kaolinite-replaced K minerals, record deeper transition of sinter-vein fluid into acid-sulfate fluid in vein conduits. This transition occurred as regional subsidence, manifested by the Goosey Lake depression immediately east of Buckskin Mountain, lowered the pieziometric surface at Buckskin Mountain, terminated sinter deposition, and caused boiling and/or degassing of sinter-vein fluid. The timing of subsidence is recorded by a decrease in alunite ages, from ca. 15.8 to 15.6 Ma, with depth below sinter. Lateral replacement of sinter and partially leached epiclastic deposits and rhyolite by opal-A marks the termination of the two hydrothermal regimes that lasted ???0.5 m.y. and followed rhyolitic volcanism of similar duration. Veins and sinter display textures that attest to plastic deformation, spalling, and gravitational settling, and indicate fluid-flow direction, velocity, and density stratification which, with conduit topology, may have influenced precious metal tenor in the veins. Components of sinter and veins were transported as colloids, formed in supersaturated sinter-vein fluid, that aggregated or coagulated as incompetent gelatinous layers in shallow pools and in underlying, near-vertical conduits in rhyolite and initially crystallized as opal and chalcedony. The low thermal conductivity of ho

Hydrochemical and 14C constraints on groundwater recharge and interbasin flow in an arid watershed: Tule Desert, Nevada

NASA Astrophysics Data System (ADS)

Hagedorn, Benjamin

2015-04-01

Geochemical data deduced from groundwater and vein calcite were used to quantify groundwater recharge and interbasin flow rates in the Tule Desert (southeastern Nevada). 14C age gradients below the water table suggest recharge rates of 1-2 mm/yr which correspond to a sustainable yield of 5 × 10-4 km3/yr to 1 × 10-3 km3/yr. Uncertainties in the applied effective porosity value and increasing horizontal interbasin flow components at greater depths may bias these estimates low compared to those previously reported using the water budget method. The deviation of the groundwater δ18O time-series pattern for the Pleistocene-Holocene transition from that of the Devils Hole vein calcite (which is considered a proxy for local climate change) allows interbasin flow rates of northerly derived groundwater to be estimated. The constrained rates (75.0-120 m/yr) are slightly higher than those previously calculated using Darcy's Law, but translate into hydraulic conductivity values strikingly similar to those obtained from pump tests. Data further indicate that production wells located closer to the western mountainous margin will be producing mainly from locally derived mountain-system recharge whereas wells located closer to the eastern margin are more influenced by older, regionally derived carbonate groundwater.

A hydrothermal system associated with the Siljan impact structure, Sweden--implications for the search for fossil life on Mars.

PubMed

Hode, Tomas; von Dalwigk, Ilka; Broman, Curt

2003-01-01

The Siljan ring structure (368 +/- 1.1 Ma) is the largest known impact structure in Europe. It isa 65-km-wide, eroded, complex impact structure, displaying several structural units, including a central uplifted region surrounded by a ring-shaped depression. Associated with the impact crater are traces of a post-impact hydrothermal system indicated by precipitated and altered hydrothermal mineral assemblages. Precipitated hydrothermal minerals include quartz veins and breccia fillings associated with granitic rocks at the outer margin of the central uplift, and calcite, fluorite, galena, and sphalerite veins associated with Paleozoic carbonate rocks located outside the central uplift. Two-phase water/gas and oil/gas inclusions in calcite and fluorite display homogenization temperatures between 75 degrees C and 137 degrees C. With an estimated erosional unloading of approximately 1 km, the formation temperatures were probably not more than 10-15 degrees C higher. Fluid inclusion ice-melting temperatures indicate a very low salt content, reducing the probability that the mineralization was precipitated during the Caledonian Orogeny. Our findings suggest that large impacts induce low-temperature hydrothermal systems that may be habitats for thermophilic organisms. Large impact structures on Mars may therefore be suitable targets in the search for fossil thermophilic organisms.

Precipitation source inferred from stable isotopic composition of Pleistocene groundwater and carbonate deposits in the western desert of Egypt.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sultan, M.; Sturchio, N.; Hassan, F. A.

1997-01-01

An Atlantic source of precipitation can be inferred from stable isotopic data (H and O) for fossil groundwaters and uranium-series-dated carbonate spring deposits from oases in the Western Desert of Egypt. In the context of available stable isotopic data for fossil groundwaters throughout North Africa, the observed isotopic depletions ({delta}D -72 to -81{per_thousand}; {delta}{sup 18}O -10.6 to -11.5{per_thousand}) of fossil ({ge}32,000 yr B.P.) groundwaters from the Nubian aquifer are best explained by progressive condensation of water vapor from paleowesterly wet oceanic air masses that traveled across North Africa and operated at least as far back as 450,000 yr before themore » present. The values of {delta}{sup 18}O (17.1 to 25.9{per_thousand}) for 45,000- to >450,000-yr-old tufas and vein-filling calcite deposits from the Kharga and Farafra Oases are consistent with deposition from groundwaters having oxygen isotopic compositions similar to those of fossil groundwaters sampled recently at these locations.« less

U-Pb Dating of Calcite to Constrain Basinal Brine Flux Events: An Example from the Upper Midwest USA

NASA Astrophysics Data System (ADS)

Rasbury, T.; Luczaj, J.

2017-12-01

Calcite forms in a variety of settings and can be the product of surface to deep basinal fluids. As such, this mineral can uniquely record details of the fluids responsible for its formation. The forms of calcium carbonates and their stratigraphic relationships from the thin section to the regional scale give important insights on pulses of fluids. A fundamental question is the age of such fluid pulses. While calcite excludes uranium (U) from its crystal structure, some is incorporated and depending on the U/Pb ratio, this provides an opportunity for radiometric dating. Calcite crystals of various sizes and crystal habits are found in Paleozoic carbonate rocks throughout the region from the western Michigan basin to the upper Mississippi valley. These are typically associated with Mississippi Valley-type (MVT) mineralization, including galena, sphalerite, and iron sulfides, but typically post-date the main MVT event. We have analyzed a variety of these calcites and find multiple generations of calcite, separated by tens of millions of years. The initial Pb isotope ratios are similar to the isotope ratios of nearby galena, strongly suggesting a genetic relationship. Our oldest ages are 200 Ma, and we find ages ranging into the Cenozoic. Based on the Paleozoic-hosted galena Pb-isotope isoscapes from the region, the fluids may have been sourced from both the Michigan and Illinois basins. An important and unanswered question is what would cause significant fluid movement out of the basins substantially after Appalachian orogenesis. Noble gas data from brines in the Michigan Basin have a mantle component and have been suggested to be responsible for recognized elevated temperatures across the basin (Ma et al., 2009). Multiple thermal events during the Paleozoic and Mesozoic eras may have an internal heat source related to reactivation of faults of the Keweenawan Rift system below the Michigan Basin. Perhaps a mantle heat source from below episodically fluxes into the basins and displaces brines with important ore metals out of the basin. More work on the calcites will help to establish the geographic extent of the various fluid pulses in the region, which will lead to an improved understanding of the sources and paths of these fluids.

The Geology and Petrography of Yücebelen and Surrounding Area, Torul-Gümüşhane

NASA Astrophysics Data System (ADS)

Doǧacan, Özcan; Özpınar, Yahya

2013-04-01

The study area is located in the tectono-stratigraphic zone named "Eastern Pontide Zone" from the northeastern part of Turkey. Eastern Pontides were formed by the subduction of Tethys Ocean under the Eurasian plate, during the Early Cretaceous - Late Eocene. Eastern Pontide orogenic zone can be divided in two tectono-stratigraphic subgroups as the northern and southern zones. The study area is located very close to border of these two subgroups but located in northern zone. In this project, the first geological map of the study area at the scale 1:5000 was made. Subsequently, detailed geological maps at the scale 1:2000 were made for the areas rich in ores. In the study area, Upper Cretaceous volcanic rocks consisting of basalts and basaltic andesites take place at the bottom of the rock sequence. Basalts and basaltic andesites with hyaloophitic, vitrophiric and microporphyric texture comprise plagioclase +pyroxene +chlorite +calcite ±epidote ±chalcedony ±opaque minerals. They are overlain by concordant pyroclastic and dacitic-rhyodacitic rocks. Quarts + K-feldispar ±plagioclase? ±biotite ±chlorite ±calcite ±chalcedony minerals are determined as a result of microscope investigation on samples taken from these rocks. These rocks are overlain by sedimentary rocks intercalated with pyroclastic rocks. All those units mentioned above, were intruded by granitoids of supposed Upper Cretaceous-Eocene age. Granitoids that crop out in the area were classified in terms of Q-ANOR parameters as granodiorites (Adile Hamlet occurrence - investigated in detail), diorites (Tuzlak Hill occurrence- eastern-part of study area) and quartz monzodiorites (İstavroma Hill occurrence- northern part of study area). Adile Hamlet granodiorites comprise plagioclase +pyroxene +chlorite +calcite ±quarts ±epidote +opaque minerals. A sequence of quarts +orthoclase +plagioclase ±chlorite ±epidote ±calcite ±opaque minerals have been determined after investigation of the rock samples collected from Tuzlak Hill surrounding area. Also, petrographic investigation gave us plagioclase +hornblende ±biotite ±chlorite ±calcite ±quarts ±opaque minerals mineral sequence for the occurrences seen around İstavroma Hill. All of these units are intruded Late Eocene andesitic and dacitic dykes. It was determined that Cu-Pb-Zn mineralization depends on the quartz veins developed in the fracture zones of the granitoid body and its contacts with sedimentary rocks. These veins revealed a paragenesis consisting Cu-Pb-Zn minerals. Key words: Eastern Pontides, Gümüşhane-Torul, Granitoid, Cu-Pb-Zn mineralization, Gümüşhane-Torul

Microstructural record of pressure solution and crystal plastic deformation in carbonate fault rocks from a shallow crustal strike-slip fault, Northern Calcareous Alps (Austria)

NASA Astrophysics Data System (ADS)

Bauer, Helene; Rogowitz, Anna; Grasemann, Benhard; Decker, Kurt

2017-04-01

This study presents microstructural investigations of natural carbonate fault rocks that formed by a suite of different deformation processes, involving hydro-fracturing, dissolution-precipitation creep and cataclasis. Some fault rocks show also clear indications of crystal plastic deformation, which is quite unexpected, as the fault rocks were formed in an upper crustal setting, raising the question of possible strongly localised, low temperature ductile deformation in carbonate rocks. The investigated carbonate fault rocks are from an exhumed, sinistral strike-slip fault at the eastern segment of the Salzachtal-Ennstal-Mariazell-Puchberg (SEMP) fault system in the Northern Calcareous Alps (Austria). The SEMP fault system formed during eastward lateral extrusion of the Eastern Alps in the Oligocene to Lower Miocene. Based on vitrinite reflectance data form intramontane Teritary basins within the Northern Calcareous Alps, a maximum burial depth of 4 km for the investigated fault segment is estimated. The investigated fault accommodated sinistral slip of several hundreds of meters. Microstructural analysis of fault rocks includes scanning electron microscopy, optical microscopy and electron backscattered diffraction mapping. The data show that fault rocks underwent various stages of evolution including early intense veining (hydro-fracturing) and stylolite formation reworked by localised shear zones. Cross cutting relationship reveals that veins never cross cut clay seams accumulated along stylolites. We conclude that pressure solution processes occured after hydro-fracturing. Clay enriched zones localized further deformation, producing a network of small-scale clay-rich shear zones of up to 1 mm thickness anastomosing around carbonate microlithons, varying from several mm down to some µm in size. Clay seams consist of kaolinit, chlorite and illite matrix and form (sub) parallel zones in which calcite was dissolved. Beside pressure solution, calcite microlithons show also ductile deformation microstructures, including deformation twinning, undulose extinction, subgrain rotation recrystallization and even grain boundary migration. Especially coarse grained calcites from veins localized ductile deformation and record dislocation glide. The investigated fault rocks are excellent examples of frictional, pressure solution and crystal plastic deformation processes. We speculated that crystal plastic deformation typical for higher metamorphic shear zones in marbles, can be either produced under much lower temperature conditions or the temperature necessary for crystal plastic deformation was generated by frictional slip or strain heating within the fault zone.

Wall-rock control of cortain pitchblende deposits in Golden Gate Canyon, Jefferson County, Colorado

USGS Publications Warehouse

Adams, John W.; Stugard, Frederick

1954-01-01

Carbonate veins cutting pre-Cambrian metamorphic rocks in Golden Gate Canyon contain pitchblende and base-metal sulfides. The veins occupy extensive faults of Laramide age but normally contain pitchblende only where the cut hornblende gneiss. At the Union Pacific prospect, which was studied in detail, pitchblende, hermatite, and some ankerite formed in advance of sulfides, except possibly for minor pyrite. Base-metal sulfides and the bulk of ankerite-calcite vein-filling were deposited after the pitchblende. Chemical analyses show a high ferrous iron content in the hornblende gneiss in contrast to low ferrous iron in the adjacent biotite gneiss. It is hypothesized that ferrous iron released by alteration of hornblende was partly oxidized to hematite by the ore-bearing solutions and, contemporaneously, uranium was reduced and deposited as pitchblende. In other veins, biotite or iron sulfides may have been similarly effective in precipitating pitchblende. Apparently both the ferrous ion and the sulfide ion can serve as reducing agents and control pitchblende deposition. It is suggested that conditions particularly favorable for uranium deposition are present where uranium-bearing solutions had access to rocks rich in ferrous iron or pre-existing sulfides.

Microchemical evidence for episodic growth of antitaxial veins during fracture-controlled fluid flow

NASA Astrophysics Data System (ADS)

Barker, Shaun L. L.; Cox, Stephen F.; Eggins, Stephen M.; Gagan, Michael K.

2006-10-01

The mechanism by which syntectonic hydrothermal veins form is widely debated, with some workers suggesting that certain vein textures are related to specific fluid flow regimes. Central to the debate is whether vein formation involves advective fluid flow, or occurs by local diffusion of material from the surrounding wall rock. To address this issue, we integrated textural observations and microchemical analyses of a hydrothermal vein from the Lachlan Orogen, southeast Australia, to reveal information about vein growth history, changes in fluid chemistry, and the evolution of fluid flow pathways during vein growth. The study area is part of a regional-scale fault-fracture network in an interbedded limestone-shale sequence, which formed at depths of ˜ 5-10 km (˜ 150-200 °C) during late Devonian crustal shortening. This integrated approach demonstrates that the zonation of textures, Sr isotopes, stable isotopes (C, O), and trace and rare earth elements is distinctly asymmetrical about the median growth-line of the vein. δ 18O values in vein calcite (17.0-18.8‰, VSMOW) are lower than those in surrounding unaltered limestones (23-25‰, VSMOW), and vary systematically across the vein. In contrast, δ 13C values are relatively constant across most of the vein, but become markedly depleted ( ca. 4‰) immediately adjacent to the wall rock. This strong depletion in δ 13C was probably caused by the influx of more oxidised fluids during the latest stages of vein growth. Strontium isotope ratios ( 87Sr/ 86Sr) vary between 0.70912 and 0.70931 across the vein. Abrubt changes in 87Sr/ 86Sr, δ 18O, Ce/Ce *, Eu/Eu * and trace element concentrations indicate that vein growth was accompanied by stepwise changes in the fluid flow pathway and consequent variations in fluid chemistry. Taken together, our findings are not consistent with growth of fibrous antitaxial veins by diffusional transfer of material from the surrounding wall rock. Instead, they suggest that externally sourced fluids migrated along episodically changing fracture-controlled flow pathways. This has implications for the dynamics of crustal permeability and mineralisation.

Arc-related porphyry molybdenum deposit model: Chapter D in Mineral deposit models for resource assessment

USGS Publications Warehouse

Taylor, Ryan D.; Hammarstrom, Jane M.; Piatak, Nadine M.; Seal, Robert R.

2012-01-01

Geoenvironmental concerns are generally low because of low volumes of sulfide minerals. Most deposits are marginally acid-generating to non-acid-generating with drainage waters being near-neutral pH because of the acid generating potential of pyrite being partially buffered by late-stage calcite-bearing veins. The low ore content results in a waste:ore ratio of nearly 1:1 and large tailings piles from the open-pit method of mining.

Isotopic evidence for the infiltration of mantle and metamorphic CO2-H2O fluids from below in faulted rocks from the San Andreas Fault System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pili, E.; Kennedy, B.M.; Conrad, M.E.

To characterize the origin of the fluids involved in the San Andreas Fault (SAF) system, we carried out an isotope study of exhumed faulted rocks from deformation zones, vein fillings and their hosts and the fluid inclusions associated with these materials. Samples were collected from segments along the SAF system selected to provide a depth profile from upper to lower crust. In all, 75 samples from various structures and lithologies from 13 localities were analyzed for noble gas, carbon, and oxygen isotope compositions. Fluid inclusions exhibit helium isotope ratios ({sup 3}He/{sup 4}He) of 0.1-2.5 times the ratio in air, indicatingmore » that past fluids percolating through the SAF system contained mantle helium contributions of at least 35%, similar to what has been measured in present-day ground waters associated with the fault (Kennedy et al., 1997). Calcite is the predominant vein mineral and is a common accessory mineral in deformation zones. A systematic variation of C- and O-isotope compositions of carbonates from veins, deformation zones and their hosts suggests percolation by external fluids of similar compositions and origin with the amount of fluid infiltration increasing from host rocks to vein to deformation zones. The isotopic trend observed for carbonates in veins and deformation zones follows that shown by carbonates in host limestones, marbles, and other host rocks, increasing with increasing contribution of deep metamorphic crustal volatiles. At each crustal level, the composition of the infiltrating fluids is thus buffered by deeper metamorphic sources. A negative correlation between calcite {delta}{sup 13}C and fluid inclusion {sup 3}He/{sup 4}He is consistent with a mantle origin for a fraction of the infiltrating CO{sub 2}. Noble gas and stable isotope systematics show consistent evidence for the involvement of mantle-derived fluids combined with infiltration of deep metamorphic H{sub 2}O and CO{sub 2} in faulting, supporting the involvement of deep fluids percolating through and perhaps weakening the fault zone. There is no clear evidence for a significant contribution from meteoric water, except for overprinting related to late weathering.« less

Formation of amorphous calcium carbonate in caves and its implications for speleothem research.

PubMed

Demény, Attila; Németh, Péter; Czuppon, György; Leél-Őssy, Szabolcs; Szabó, Máté; Judik, Katalin; Németh, Tibor; Stieber, József

2016-12-22

Speleothem deposits are among the most valuable continental formations in paleoclimate research, as they can be dated using absolute dating methods, and they also provide valuable climate proxies. However, alteration processes such as post-depositional mineralogical transformations can significantly influence the paleoclimatic application of their geochemical data. An innovative sampling and measurement protocol combined with scanning and transmission electron microscopy, X-ray diffraction and Fourier transform infrared spectroscopy is presented, demonstrating that carbonate precipitating from drip water in caves at ~10 °C contains amorphous calcium carbonate (ACC) that later transforms to nanocrystalline calcite. Stable oxygen isotope fractionations among calcite, ACC and water were also determined, proving that ACC is 18 O-depleted (by >2.4 ± 0.8‰) relative to calcite. This, in turn, has serious consequences for speleothem-based fluid inclusion research as closed system transformation of ACC to calcite may induce a negative oxygen isotope shift in fluid inclusion water, resulting in deterioration of the original compositions. ACC formation increases the speleothems' sensitivity to alteration as its interaction with external solutions may result in the partial loss of original proxy signals. Mineralogical analysis of freshly precipitating carbonate at the studied speleothem site is suggested in order to determine the potential influence of ACC formation.

Calcio-carbonatite melts and metasomatism in the mantle beneath Mt. Vulture (Southern Italy)

NASA Astrophysics Data System (ADS)

Rosatelli, Gianluigi; Wall, Frances; Stoppa, Francesco

2007-12-01

At Mt. Vulture volcano (Basilicata, Italy) calcite globules (5-150 μm) are hosted by silicate glass pools or veins cross-cutting amphibole-bearing, or more common spinel-bearing mantle xenoliths and xenocrysts. The carbonate globules are rounded or elongated and are composed of a mosaic of 2-20 μm crystals, with varying optical orientation. These features are consistent with formation from a quenched calciocarbonatite melt. Where in contact with carbonate amphibole has reacted to form fassaitic pyroxene. Some of these globules contain liquid/gaseous CO 2 bubbles and sulphide inclusions, and are pierced by quench microphenocrysts of silicate phases. The carbonate composition varies from calcite to Mg-calcite (3.8-5.0 wt.% MgO) both within the carbonate globules and from globule to globule. Trace element contents of the carbonate, determined by LAICPMS, are similar to those of carbonatites worldwide including ΣREE up to 123 ppm. The Sr-Nd isotope ratios of the xenolith carbonate are similar to the extrusive carbonatite and silicate rocks of Mt. Vulture testifying to derivation from the same mantle source. Formation of immiscibile silicate-carbonatite liquids within mantle xenoliths occurred via disequilibrium immiscibility during their exhumation.

Does serpentinite carbonation occur during recharge or discharge of hydrothermal fluids? A case of study from the Newfoundland margin

NASA Astrophysics Data System (ADS)

Picazo, Suzanne; Malvoisin, Benjamin; Baumgartner, Lukas P.; Bouvier, Anne-Sophie

2017-04-01

Hydrothermal fluid circulation in extensional systems occurrs along the spreading axis of passive, hyper-extended margins and mid-ocean ridges. The most studied feature resulting from hydrothermal circulation is the sub-seafloor chimneys because of their accessibility. Here we focus on the less studied carbonation process of the associated serpentinites. Carbonation of partially to totally serpentinized peridotite i.e. peridotite/serpentinite replacement by carbonate is usually described as a process of veining or matrix formation but not direct replacement of serpentinite. Carbonates that crystallize in veins or as a matrix in a sedimentary setting is known in near-surface environments like Oman (Kelemen et al, 2011), however the processes and timing of carbonation are still not well understood. This study is examins in detail the onset of carbonation in the footwall of the detachment faults responsible for mantle exhumation in hyper-extended rifted margins. It is based on drilled samples from ODP Leg 210 Site 1277 in the Newfoundland margin. We observed calcite grains in the mesh core replacing serpentine and we measured δ18O from core to rim of the calcite grain using the Secondary Ion Mass Spectrometer (SIMS, SwissSIMS facility, University of Lausanne). Ultimately δ18O measurements lead us to infer the temperature of calcite growth. We suplement the study with equilibrium thermodynamic modeling in an open system where fluid can be transported either upwards or downwards. The model allows us determining the influence of fluid flow direction, temperature, pressure and fluid/rock ratio on the stability of carbonates and serpentine, and thus to discuss if carbonation occurs during recharge or discharge of the fluids. Kelemen, P. B., Matter, J., Streit, E. E., Rudge, J. F., Curry, W. B., & Blusztajn, J. (2011). Rates and mechanisms of mineral carbonation in peridotite: natural processes and recipes for enhanced, in situ CO2 capture and storage. Annual Review of Earth and Planetary Sciences, 39, 545-576.

Formation of the Wiesloch Mississippi Valley-type Zn-Pb-Ag deposit in the extensional setting of the Upper Rhinegraben, SW Germany

USGS Publications Warehouse

Pfaff, Katharina; Hildebrandt, Ludwig H.; Leach, David L.; Jacob, Dorrit E.; Markl, Gregor

2010-01-01

The Mississippi Valley-type (MVT) Zn-Pb-Ag deposit in the Wiesloch area, Southwest Germany, is controlled by graben-related faults of the Upper Rhinegraben. Mineralization occurs as vein fillings and irregular replacement ore bodies consisting of sphalerite, banded sphalerite, galena, pyrite, sulfosalts (jordanite and geocronite), barite, and calcite in the Middle Triassic carbonate host rock. Combining paragenetic information, fluid inclusion investigations, stable isotope and mineral chemistry with thermodynamic modeling, we have derived a model for the formation of the Wiesloch deposit. This model involves fluid mixing between ascending hot brines (originating in the crystalline basement) with sedimentary formation waters. The ascending brines originally had a near-neutral pH (around 6) and intermediate oxidation state, reflecting equilibrium with granites and gneisses in the basement. During fluid ascent and cooling, the pH of the brine shifted towards more acidic (around 4) and the oxidation state increased to conditions above the hematite-magnetite buffer. These chemical characteristics contrast strongly with those of the pore and fracture fluid residing in the limestone aquifer, which had a pH between 8 and 9 in equilibrium with calcite and was rather reduced due to the presence of organic matter in the limestone. Mixing between these two fluids resulted in a strong decrease in the solubility of silver-bearing sphalerite and galena, and calcite. Besides Wiesloch, several Pb-Zn deposits are known along the Upper Rhinegraben, including hydrothermal vein-type deposits like Badenweiler and the Michael mine near Lahr. They all share the same fluid origin and formation process and only differ in details of their host rock and fluid cooling paths. The mechanism of fluid mixing also seems to be responsible for the formation of other MVT deposits in Europe (e.g., Reocin, Northern Spain; Treves, Southern France; and Cracow-Silesia, Poland), which show notable similarities in terms of their age, mineralogy, and mineral chemistry to the MVT deposit near Wiesloch.

Geology, geochemistry and geochronology of the Songwe Hill carbonatite, Malawi

NASA Astrophysics Data System (ADS)

Broom-Fendley, Sam; Brady, Aoife E.; Horstwood, Matthew S. A.; Woolley, Alan R.; Mtegha, James; Wall, Frances; Dawes, Will; Gunn, Gus

2017-10-01

Songwe Hill, Malawi, is one of the least studied carbonatites but has now become particularly important as it hosts a relatively large rare earth deposit. The results of new mapping, petrography, geochemistry and geochronology indicate that the 0.8 km diameter Songwe Hill is distinct from the other Chilwa Alkaline Province carbonatites in that it intruded the side of the much larger (4 × 6 km) and slightly older (134.6 ± 4.4 Ma) Mauze nepheline syenite and then evolved through three different carbonatite compositions (C1-C3). Early C1 carbonatite is scarce and is composed of medium-coarse-grained calcite carbonatite containing zircons with a U-Pb age of 132.9 ± 6.7 Ma. It is similar to magmatic carbonatite in other carbonatite complexes at Chilwa Island and Tundulu in the Chilwa Alkaline Province and others worldwide. The fine-grained calcite carbonatite (C2) is the most abundant stage at Songwe Hill, followed by a more REE- and Sr-rich ferroan calcite carbonatite (C3). Both stages C2 and C3 display evidence of extensive (carbo)-hydrothermal overprinting that has produced apatite enriched in HREE (<2000 ppm Y) and, in C3, synchysite-(Ce). The final stages comprise HREE-rich apatite fluorite veins and Mn-Fe-rich veins. Widespread brecciation and incorporation of fenite into carbonatite, brittle fracturing, rounded clasts and a fenite carapace at the top of the hill indicate a shallow level of emplacement into the crust. This shallow intrusion level acted as a reservoir for multiple stages of carbonatite-derived fluid and HREE-enriched apatite mineralisation as well as LREE-enriched synchysite-(Ce). The close proximity and similar age of the large Mauze nepheline syenite suggests it may have acted as a heat source driving a hydrothermal system that has differentiated Songwe Hill from other Chilwa carbonatites.

Microstructural study of natural fractures in Cape Roberts Project 3 core, Western Ross Sea, Antarctica

USGS Publications Warehouse

Millan, C.; Wilson, T.; Paulsen, T.

2007-01-01

Microstructures in natural fractures in core recovered offshore from Cape Roberts, Ross Sea, Antarctica, provide new constraints on the relative timing of faulting and sedimentation in the Victoria Land Basin along the Transantarctic Mountain rift flank. This study characterizes the textures, fabrics and grain-scale structures from thin section analysis of samples of microfaults, veins, and clastic dikes. Microfaults are abundant and display two different types of textures, interpreted to record two different deformation modes: pre-lithification shearing and brittle faulting of cohesive sediment. Both clastic dikes and calcite veins commonly follow fault planes, indicating that injections of liquefied sediment and circulating fluids used pre-existing faults as conduits. The close association of clastic injections, diagenetic mineralization, and faulting indicates that faulting was synchronous with deposition in the rift basin

Genesis of the central zone of the Nolans Bore rare earth element deposit, Northern Territory, Australia

NASA Astrophysics Data System (ADS)

Schoneveld, Louise; Spandler, Carl; Hussey, Kelvin

2015-08-01

The Nolans Bore rare earth element (REE) deposit consists of a network of fluorapatite-bearing veins and breccias hosted within Proterozoic granulites of the Reynolds Range, Central Australia. Mineralisation is divided into three zones (north, central, and south-east), with the north and south-east zones consisting of massive REE-bearing fluorapatite veins, with minor brecciation and carbonate infill. The central zone is distinctively different in mineralogy and structure; it features extensive brecciation, a high allanite content, and a large, epidote-rich enveloping alteration zone. The central zone is a reworking of the original solid apatite veins that formed during the Chewings Orogeny at ca. 1525 Ma. These original apatite veins are thought to derive from phosphate-rich magmatic-hydrothermal fluid exsolved from as-yet unrecognised alkaline magmatic bodies at depth. We define four ore breccia types (BX1-4) in the central zone on the basis of detailed petrological and geochemical analysis of drillcore and thin sections. BX1 ore comprises fluorapatite with minor crackle brecciation with carbonate infill and resembles ore of the north and south-east zones. Breccia types BX2, BX3, and BX4 represent progressive stages of ore brecciation and development of calc-silicate mineral (amphibole, epidote, allanite, calcite) infill. Comparison of bulk ore sample geochemistry between breccia types indicates that REEs were not mobilised more than a few centimetres during hydrothermal alteration and brecciation. Instead, most of the REEs were partitioned from the original REE fluorapatite into newly formed allanite, REE-poor fluorapatite and minor REE carbonate in the breccias. Negative europium (Eu) anomalies in the breccia minerals are accounted for by a large positive Eu anomaly in epidote from the alteration zones surrounding the ore breccias. This observation provides a direct link between ore recrystallisation and brecciation, and the formation of the alteration halo in the surrounding host rocks. Where allanite and fluorapatite are texturally related, the fluorapatite is relatively depleted in the light rare earth elements (LREEs), whereas allanite is relatively LREE enriched, suggesting co-crystallisation. We tentatively date the BX1 ore stage to 1440 ± 80 Ma based on U-Pb dating of thorianite. Sm-Nd isotope isochrons derived from in situ isotope analysis of cognate apatite and allanite date the BX2 and BX3 events to ca. 400 Ma, while U-Pb dating of late-stage monazite from the BX4 ore stage returned an age of ca. 350 Ma. Therefore, formation of the central zone at Nolans Bore involved multiple alteration/brecciation events that collectively span over 1 billion years in duration. We suggest that the BX1-type veins and breccias were formed from REE-rich, saline (F- and Cl-bearing) fluids that infiltrated the granulite-grade host rocks in association with either shear activation events of the Redbank Shear Zone (1500-1400 Ma) or intrusion of late-stage pegmatites of the Mt Boothby area. BX2, BX3, and BX4 events record deformation and hydrothermal alteration associated with the Alice Springs Orogeny (400-350 Ma). These hydrothermal events occurred at temperatures of 450 to ~600 °C, due to inflow of highly acidic hydrous fluids derived from a magmatic source, or from mixing of meteoric and metamorphic fluids. Our data testify to the long and complex geological history of not only the Nolans Bore REE deposit, but also of the rocks of the eastern Reynolds Range, and demonstrate the great utility of using hydrothermally derived REE minerals to trace the timing of crustal deformation events and source of associated hydrothermal fluids.

Quartz-molybdenite veins in the Priestly Lake granodiorite, north-central Maine

USGS Publications Warehouse

Ayuso, Robert A.; Shank, Stephen G.

1983-01-01

Quartz-molybdenite veins up to 15 cm in width occur in fine to medium-grained porphyritic biotite-hornblende granodiorite at Priestly Lake north-central Maine. An area of about 150 m x 150 m contains quartz-molybdenite veins; a larger area is characterized by barren quartz veins. Quartz-molybdenite veins are concentrated within the most felsic variants of the intrusion as suggested by lower mafic mineral contents. The pluton has a narrow range in SiO2 (67-70 wt.%), major oxides, and in trace-element compositions. Molybdenite occurs as coarse grained clusters in pockets within the quartz veins, and fills fractures in the quartz veins and host rocks. Disseminated molybdenite in the granodiorite is relatively rare and occurs only in the area characterized by a high density of quartz veins (up to 50 veins per square meter). Alteration envelopes along the quartz veins are very thin or absent, although in some areas the granodiorite appears to be selectively and pervasively altered. Sericite, chlorite, epidote, calcite, pyrite, and quartz are concentrated near the quartz-molybdenite veins. Many of the field and geochemical characteristics of the Priestly Lake pluton are unlike those of major molybdenum-producing areas (Climax, Henderson, Urad). For example, the area of alteration seems to be of limited extent, the host rock is not intensely altered hydrothermally at the surface, the density of fractures is rather low in the mineralized area, and the amount of disseminated molybdenite appears to be small. However, the Priestly Lake pluton may be a small fraction of a concealed batholith as suggested by geophysical data. It is conceivable that the type of mineralization at the surface might be the expression of more extensive molybdenite mineralization at depth. The quartz-molybdenite veins in the Priestly Lake pluton are significant because they indicate that potential molybdenum sources for producing mineralized granites were available at depth. Future studies should be aimed at delineating the area of quartz-molybdenite mineralization, documenting hydrothermal alteration and zonation, determining fracture density, and evaluating the sulfide assemblage.

Veins in Paleo-reservoir as a Natural Indication of Coupled Changes in Pore Pressure and Stress, Salt Wash Graben of SE Utah, USA

NASA Astrophysics Data System (ADS)

Gwon, S.; Edwards, P.; Kim, Y. S.

2015-12-01

Hydrofracturing associated with elevated fluid pressure coupled with changes in stress has been crucial in enhancing the production and recovery of hydrocarbons. Furthermore, it is also an important issue to access the efficiency and stability of long-term CO2 geologic storage reservoirs. Veins are mineral-filled extension fractures developed along the plane of σ1-σ2 and perpendicular to σ3, and the fluid pressure must exceed σ3applied to the plane when the vein opens. Therefore, vein is a well-known natural analogue for fluid migration in a paleo-reservoir. In the Salt Wash Graben of SE Utah, CO2-charged vein systems hosted in the bleached Entrada Formation are well developed and examined to understand the conditions of fluid pressure and stress during the injections of CO2-charged fluid. Based on color and relative cross-cutting relationship in the field, veins are subdivided into two sets; sub-vertical black mineral-rich veins and orthogonal calcite veins that have previously been described as 'grid-lock fractures'. The vein distribution and fluid leakage along through-going fractures in mechanic units allow us to determine the stress regime and driving stress condition through 3D-Mohr circle reconstruction. The results of this statistical analysis for the veins show that the orthogonal veins indicate a 'stress transition' with maximum principal stress direction changing from vertical to NNW-SSE sub-horizontal which coincides with the current regional stress regime. The possible causes of the stress transition can be considered. The process of repeated sealing, reactivation and localization of veins within the bleached zone is a natural indication of a coupled change in pore pressure and stress in the reservoir. Thus, an understanding of the effect of stress changes due to the volumetric injection of CO2 in the subsurface as well as a knowledge of how pre-existing fractures affect fluid flow with respect to elevated pore pressures in layered rocks are important for reservoir characterization and efficient site selection of geologic CO2 storage in the subsurface.

Postmagmatic magnetite-apatite assemblage in mafic intrusions: a case study of dolerite at Olympic Dam, South Australia

NASA Astrophysics Data System (ADS)

Apukhtina, Olga B.; Kamenetsky, Vadim S.; Ehrig, Kathy; Kamenetsky, Maya B.; McPhie, Jocelyn; Maas, Roland; Meffre, Sebastien; Goemann, Karsten; Rodemann, Thomas; Cook, Nigel J.; Ciobanu, Cristiana L.

2016-01-01

An assemblage of magnetite and apatite is common worldwide in different ore deposit types, including disparate members of the iron-oxide copper-gold (IOCG) clan. The Kiruna-type iron oxide-apatite deposits, a subtype of the IOCG family, are recognized as economic targets as well. A wide range of competing genetic models exists for magnetite-apatite deposits, including magmatic, magmatic-hydrothermal, hydrothermal(-metasomatic), and sedimentary(-exhalative). The sources and mechanisms of transport and deposition of Fe and P remain highly debatable. This study reports petrographic and geochemical features of the magnetite-apatite-rich vein assemblages in the dolerite dykes of the Gairdner Dyke Swarm (~0.82 Ga) that intruded the Roxby Downs Granite (~0.59 Ga), the host of the supergiant Olympic Dam IOCG deposit. These symmetrical, only few mm narrow veins are prevalent in such dykes and comprise besides usually colloform magnetite and prismatic apatite also further minerals (e.g., calcite, quartz). The genetic relationships between the veins and host dolerite are implied based on alteration in the immediate vicinity (~4 mm) of the veins. In particular, Ti-magnetite-ilmenite is partially to completely transformed to titanite and magmatic apatite disappears. We conclude that the mafic dykes were a local source of Fe and P re-concentrated in the magnetite-apatite veins. Uranium-Pb ages for vein apatite and titanite associated with the vein in this case study suggest that alteration of the dolerite and healing of the fractures occurred shortly after dyke emplacement. We propose that in this particular case the origin of the magnetite-apatite assemblage is clearly related to hydrothermal alteration of the host mafic magmatic rocks.

PRIMARY MINERALIZATION OF URANIUM-BEARING "SILICEOUS REEF" VEINS IN THE BOULDER BATHOLITH, MONTANA. PART I. THE HOST ROCKS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wright, H.D.; Bieler, B.H.

1960-01-01

Between 1952 and 1956 a study was made of some of the uranium-bearing hydrothermal veins in the northern part of the Boulder batholith, Montana. Three mines, the W. Wilson, G. Washington, and Free Enterprise, were investigated in detail. The veins are characterized by a microcrystalline quartz gangue containing sparsely scattered, very fine-grained sulfide minerals and uraninite. Above the present water table, secondary uranium minerals are abundant locally. Throughout the area the veins --called "siliceous reefs"--strike east to northeast, are of steep dip, and vary in thickness from a fraction of an inch to several feet. The country rock is granodioritemore » containing, in order of abundance, plagioclase (An/sub 30/ to An/sub 36/), quartz, orthoclase, biotite, and hornblende, with apatite, zircon, and sphene. Small bodies of aplite, pegmatite, and alaskite occur along some veins. The granodiorite adjacent to the veins is rather strongly altered. The alteration is similar throughout all of the deposits studied, in barren and orebearing portions alike. The essential minerals show a characteristic sequence of alteration, in the order hornblende, andesine, biotite, orthoclase, and quartz. Successive zones of alteration are characterized, from the vein outward, by maximum development of sericite (muscovite polytype 1M, in part), kaolinite, and montmorillonite. Other alteration products are quartz, pyrite, calcite, leucoxene, and chlorite. The alteration resulted in an increase in silica and ferric iron, a decrease in alumina, total iron, ferrous iron, lime, soda, and magnesia, and little change in potash, titania, phosphorus, carbon dioxide, and sulfur. Consideration of the stability fields of the sheet structure silicate minerals indicates little basis for interpretation of the temperatures prevailing during mineralization. (auth)« less

Geometric Analysis of Vein Fracture Networks From the Awibengkok Core, Indonesia

NASA Astrophysics Data System (ADS)

Khatwa, A.; Bruhn, R. L.; Brown, S. R.

2003-12-01

Fracture network systems within rocks are important features for the transportation and remediation of hazardous waste, oil and gas production, geothermal energy extraction and the formation of vein fillings and ore deposits. A variety of methods, including computational and laboratory modeling have been employed to further understand the dynamic nature of fractures and fracture systems (e.g. Ebel and Brown, this session). To substantiate these studies, it is also necessary to analyze the characteristics and morphology of naturally occurring vein systems. The Awibengkok core from a geothermal system in West Java, Indonesia provided an excellent opportunity to study geometric and petrologic characteristics of vein systems in volcanic rock. Vein minerals included chlorite, calcite, quartz, zeolites and sulphides. To obtain geometric data on the veins, we employed a neural net image processing technique to analyze high-resolution digital photography of the veins. We trained a neural net processor to map the extent of the vein using RGB pixel training classes. The resulting classification image was then converted to a binary image file and processed through a MatLab program that we designed to calculate vein geometric statistics, including aperture and roughness. We also performed detailed petrographic and microscopic geometric analysis on the veins to determine the history of mineralization and fracturing. We found that multi-phase mineralization due to chemical dissolution and re-precipitation as well as mechanical fracturing was a common feature in many of the veins and that it had a significant role for interpreting vein tortuosity and history of permeability. We used our micro- and macro-scale observations to construct four hypothetical permeability models that compliment the numerical and laboratory modeled data reported by Ebel and Brown. In each model, permeability changes, and in most cases fluctuates, differently over time as the tortuosity and aperture of veins are affected by the precipitation, dissolution, and re-precipitation of minerals, and also by mechanical fracturing. In all of our cases we interpret a first-phase mineral dissolution stage where permeability gradually declines as the vein is blocked by inward growing minerals. Hereafter, permeability may briefly increase with the onset of internal fracturing within the vein or by a phase of mineral dissolution opening up new pathways for fluid flow. Eventually we infer that permeability will decline again as second stage minerals are deposited in the fluid flow pathways.

Fluid inclusion petrology and microthermometry of the Cocos Ridge hydrothermal system, IODP Expedition 344 (CRISP 2), Site U1414.

PubMed

Brandstätter, Jennifer; Kurz, Walter; Krenn, Kurt; Micheuz, Peter

2016-04-01

In this study, we present new data from microthermometry of fluid inclusions entrapped in hydrothermal veins along the Cocos Ridge from the IODP Expedition 344 Site U1414. The results of our study concern a primary task of IODP Expedition 344 to evaluate fluid/rock interaction linked with the tectonic evolution of the incoming Cocos Plate from the Early Miocene up to recent times. Aqueous, low saline fluids are concentrated within veins from both the Cocos Ridge basalt and the overlying lithified sediments of Unit III. Mineralization and crosscutting relationships give constraints for different vein generations. Isochores from primary, reequilibrated, and secondary fluid inclusions crossed with litho/hydrostatic pressures indicate an anticlockwise PT evolution during vein precipitation and modification by isobaric heating and subsequent cooling at pressures between ∼210 and 350 bar. Internal over and underpressures in the inclusions enabled decrepitation and reequilibration of early inclusions but also modification of vein generations in the Cocos Ridge basalt and in the lithified sediments. We propose that lithification of the sediments was accompanied with a first stage of vein development (VU1 and VC1) that resulted from Galapagos hotspot activity in the Middle Miocene. Heat advection, either related to the Cocos-Nazca spreading center or to hotspot activity closer to the Middle America Trench, led to subsequent vein modification (VC2, VU2/3) related to isobaric heating. The latest mineralization (VC3, VU3) within aragonite and calcite veins and some vesicles of the Cocos Ridge basalt occurred during crustal cooling up to recent times. Fluid inclusion analyses and published isotope data show evidence for communication with deeper sourced, high-temperature hydrothermal fluids within the Cocos Plate. The fluid source of the hydrothermal veins reflects aqueous low saline pore water mixed with invaded seawater.

Fluid inclusion petrology and microthermometry of the Cocos Ridge hydrothermal system, IODP Expedition 344 (CRISP 2), Site U1414

PubMed Central

Brandstätter, Jennifer; Krenn, Kurt; Micheuz, Peter

2016-01-01

Abstract In this study, we present new data from microthermometry of fluid inclusions entrapped in hydrothermal veins along the Cocos Ridge from the IODP Expedition 344 Site U1414. The results of our study concern a primary task of IODP Expedition 344 to evaluate fluid/rock interaction linked with the tectonic evolution of the incoming Cocos Plate from the Early Miocene up to recent times. Aqueous, low saline fluids are concentrated within veins from both the Cocos Ridge basalt and the overlying lithified sediments of Unit III. Mineralization and crosscutting relationships give constraints for different vein generations. Isochores from primary, reequilibrated, and secondary fluid inclusions crossed with litho/hydrostatic pressures indicate an anticlockwise PT evolution during vein precipitation and modification by isobaric heating and subsequent cooling at pressures between ∼210 and 350 bar. Internal over and underpressures in the inclusions enabled decrepitation and reequilibration of early inclusions but also modification of vein generations in the Cocos Ridge basalt and in the lithified sediments. We propose that lithification of the sediments was accompanied with a first stage of vein development (VU1 and VC1) that resulted from Galapagos hotspot activity in the Middle Miocene. Heat advection, either related to the Cocos‐Nazca spreading center or to hotspot activity closer to the Middle America Trench, led to subsequent vein modification (VC2, VU2/3) related to isobaric heating. The latest mineralization (VC3, VU3) within aragonite and calcite veins and some vesicles of the Cocos Ridge basalt occurred during crustal cooling up to recent times. Fluid inclusion analyses and published isotope data show evidence for communication with deeper sourced, high‐temperature hydrothermal fluids within the Cocos Plate. The fluid source of the hydrothermal veins reflects aqueous low saline pore water mixed with invaded seawater. PMID:27570496

Jointing patterns and tectonic evolution of the Maciço Calcário Estremenho, Lusitanian Basin, Portugal

NASA Astrophysics Data System (ADS)

Carvalho, Jorge M. F.

2018-05-01

The Maciço Calcário Estremenho (MCE) is an uplifted Jurassic limestone massif unit of the Lusitanian Basin, Portugal, where five main joint sets trending NNE-SSW, WSW-ENE, WNW-ESE, NW-SE, and NNW-SSE are recognized. Except for the NNW-SSE set, all the other sets host calcite veins and barren joints, evidencing a multistage development by several deformation episodes, including shear reactivation. Orthogonal patterns defined by the NNE-SSW/WNW-ESE and NNW-SSE/WSW-ENE systems are characteristic of some tectonostratigraphic units of the MCE, but the sets of each one of the systems are genetically independent. They result from specific deformation episodes undergone by the studied area in the course of its Meso-Cenozoic evolution. NNE-SSW calcite veins were the first to form during Middle Jurassic fault-controlled subsidence. A renewal of this set as barren joints took place during the Eocene Pyrenean compressive phase. The WSW-ENE and WNW-ESE sets have a restricted spatial distribution and relate to transient compressive episodes of the Middle - Late Jurassic and Jurassic - Cretaceous transitions, respectively. The NW-SE set, also characteristic of a specific region, formed during the Late Jurassic rifting and is related to local NE-SW tension dependent on block tilting towards a major NW-SE fault. The Miocene Betic compressive phase is responsible for the formation of the NNW-SSE set, which is widespread throughout the MCE.

Glacial to Interglacial Climate and Sea Level Changes Recorded in Submerged Speleothems, Argentarola, Italy

NASA Astrophysics Data System (ADS)

Folz-Donahue, K.; Dutton, A.; Antonioli, F.; Richards, D. A.; Nita, D. C.; Lambeck, K.

2014-12-01

Direct records of Quaternary sea level change can provide insight on the timing and nature of ice sheet retreat during glacial terminations. Such records are generally rare, particularly prior to the last deglaciation, due in part to the difficulty of recovering material from sites that have been submerged by subsequent sea-level rise. A suite of stalagmites recovered from a submerged cave on Argentarola Island in the Tyrrhenian Sea contains hiatuses that were formed when the cave became submerged by seawater. These hiatuses are remarkable due to the presence of calcite tubes secreted by serpulid worms, providing direct evidence of marine inundation. As sea level drops during the following glacial inception, the cave is drained and dense spelean calcite encases the serpulid worm tubes, forming alternating layers of spelean and serpulid calcite. U-Th dates of spelean calcite directly above and below these serpulid layers has previously been used to constrain timing and amplitude of sea level highstands in the Mediterranean. Stable isotope records from the same cave have also been used to indicate increased precipitation across the Mediterranean during Sapropel 6 (175 ka). Here we present U-Th dates and stable isotope records for three Argentarola stalagmites. These specimens were recovered from -22, -18, and -14 m relative to present sea level (rpsl), and complement previously published data for Argentarola stalagmites at -21, -18.5, and -18 m rpsl. The timing and elevation of spelean calcite directly above and below serpulid tube layers provide rare insight on rates of sea-level change between -14 and -22 m during glacial terminations and inceptions prior to the last termination. Stable isotope records from the same stalagmites are used to investigate changes in western Mediterranean climate and potential relationships to Mediterranean sapropel events.

Radial patterns of bitumen dykes around Quaternary volcanoes, provinces of northern Neuquén and southernmost Mendoza, Argentina

NASA Astrophysics Data System (ADS)

Cobbold, Peter R.; Ruffet, Gilles; Leith, Leslie; Loseth, Helge; Rodrigues, Nuno; Leanza, Hector A.; Zanella, Alain

2014-12-01

Where the Neuquén Basin of Argentina abuts the Andes, hundreds of veins of solid hydrocarbon (bitumen) are visible at the surface. Many of these veins became mines, especially in the last century. By consensus, the bitumen has resulted from maturation of organic-rich shales, especially the Vaca Muerta Fm of Late Jurassic age, but also the Agrio Fm of Early Cretaceous age. To account for their maturation, recent authors have invoked regional subsidence, whereas early geologists invoked magmatic activity. During 12 field seasons (since 1998), we have tracked down the bitumen localities, mapped the veins and host rocks, sampled them, studied their compositions, and dated some of them. In the provinces of northern Neuquén and southernmost Mendoza, the bitumen veins are mostly sub-vertical dykes. They tend to be straight and continuous, crosscutting regional structures and strata of all ages, from Jurassic to Palaeocene. Most of the localities lie within 70 km of Tromen volcano, although four are along the Rio Colorado fault zone and another two are at the base of Auca Mahuida volcano. On both volcanic edifices, lavas are of late Pliocene to Pleistocene age. Although regionally many of the bitumen dykes tend to track the current direction of maximum horizontal tectonic stress (ENE), others do not. However, most of the dykes radiate outward from the volcanoes, especially Tromen. Thicknesses of dykes tend to be greatest close to Tromen and where the host rocks are the most resistant to fracturing. Many of the dykes occur in the exhumed hanging walls of deep thrusts, especially at the foot of Tromen. Here the bitumen is in places of high grade (impsonite), whereas further out it tends to be of medium grade (grahamite). A few bitumen dykes contain fragments of Vaca Muerta shale, so that we infer forceful expulsion of source rock. At Curacó Mine, some shale fragments contain bedding-parallel veins of fibrous calcite (beef) and these contain some bitumen, which is geochemically of low grade. In contrast, a large crosscutting bitumen dyke is of higher grade and formed later. At other localities, near basement faults, bitumen dykes have cap-rocks of hydrothermal calcrete. Other dykes or their wall rocks contain hydrothermal minerals. Finally, some dykes splay upward towards the current land surface. We conclude that (1) the bitumen dykes formed during volcanic activity in Pliocene-Pleistocene times, and that (2) heat advection by hydrothermal fluids helped to generate oil, which migrated upwards or downwards from the source rock and filled intrusive veins, before solidifying to bitumen, by loss of volatile elements. This unconventional hydrocarbon system may have significant implications for regional exploration in the foothills of the Andes.

Deformational History and Rotation of the Leeward Antilles Island Arc: Results of the BOLIVAR Project

NASA Astrophysics Data System (ADS)

Beardsley, A. G.; Avé Lallemant, H. G.

2005-12-01

The Leeward Antilles island arc is located offshore northern Venezuela and includes Aruba, Curaçao, and Bonaire (ABCs). The ABCs trend WNW-ESE parallel to the obliquely convergent Caribbean-South American plate boundary zone. Field work on the ABCs has provided new structural data supporting a minimum of 90° clockwise rotation of the islands within the diffuse plate boundary zone. Analysis of faulting, bedding, and cleavages suggest three phases of deformation (D1-D3). The oldest phase of deformation, D1, is characterized by northeast trending normal faults, northwest trending fold axes and cleavages, and northeast striking dextral strike-slip faults. East striking sinstral strike-slip faults are rare. The second phase of deformation, D2, is represented by west-northwest trending thrust faults, north-northeast striking normal faults, northwest trending dextral strike-slip faults, and northeast striking sinstral strike-slip faults. Finally, the youngest phase of deformation, D3, is characterized by northeast striking thrust faults, northwest striking normal faults, east-west dextral strike-slip faults, and north-northwest sinstral strike-slip faults. Quartz and calcite veins were also studied on the ABCs. Cross-cutting relationships in outcrop suggest three phases of veining (V1-V3). The oldest veins, V1, trend northeastward; V2 veins trend northward; and the youngest veins, V3, trend northwestward. Additionally, joints were measured on the ABCs. On Bonaire and Curaçao, joints trend approximately northeast while joints on Aruba are almost random with a slight preference for west-northwest. Fluid inclusion analysis of quartz and calcite veins provides additional information about the pressure and temperature conditions of the deformation phases. Preliminary results from the earliest veins (V1) show a single deformational event on Aruba and Bonaire. On Bonaire, they exhibit both hydrostatic and lithostatic pressure conditions. This new data supports three stages of deformation accompanied by rotation of the ABCs. The structures identified suggest a clockwise rotation of the principal stress orientation since the Late Cretaceous. D1 deformation and rotation occurred at the southeastern Caribbean plate margin beginning approximately 73 Ma on Aruba. Arc-parallel strike-slip motion rotated the islands clockwise 90° Internal deformation features of the island blocks are consistent with an obliquely convergent plate boundary. D2 deformation is characterized by clockwise block rotation facilitated by dextral strike-slip faults defining the northern and southern boundaries of the diffuse plate boundary zone. Most likely, D2 correlates to the Eocene change in plate motions due to convergence between North and South America, approximately 55 Ma. The youngest phase of deformation and rotation, D3, happens along the arcuate South Caribbean Deformed Belt. Since approximately 25 Ma, rotation and development of northwest trending pull-apart basins between the ABCs progressed. Northeastward motion of the Maracaibo block may also contribute to recent rotation of the island arc.

SHRIMP U-Pb and 40Ar/39Ar age constraints for relating plutonism and mineralization in the Boulder batholith region, Montana

USGS Publications Warehouse

Lund, K.; Aleinikoff, J.N.; Kunk, Michael J.; Unruh, D.M.; Zeihen, G.D.; Hodges, W.C.; du Bray, E.A.; O'Neill, J. M.

2002-01-01

The composite Boulder batholith, Montana, hosts a variety of mineral deposit types, including important silver-rich polymetallic quartz vein districts in the northern part of the batholith and the giant Butte porphyry copper-molybdenum pre-Main Stage system and crosscutting copper-rich Main Stage vein system in the southern part of the batholith. Previous dating studies have identified ambiguous relationships among igneous and mineralizing events. Mineralizing hydrothermal fluids for these types of deposits and magma for quartz porphyry dikes at Butte have all been considered to be late-stage differentiates of the Boulder batholith. However, previous dating studies indicated that the Boulder batholith plutons cooled from about 78 to 72 Ma, whereas copper-rich Main Stage veins at Butte were dated at about 61 Ma. Recent efforts to date the porphyry copper-molybdenum pre-Main Stage deposits at Butte resulted in conflicting estimates of both 64 and 76 Ma for the mineralizing events. Silver-rich polymetallic quartz vein deposits elsewhere in the batholith have not been dated previously. To resolve this controversy, we used the U.S. Geological Survey, Stanford, SHRIMP RG ion mic??roprobe to date single-age domains within zircons from plutonic rock samples and 40Ar/39Ar geochronology to date white mica, biotite, and K-feldspar from mineral deposits. U-Pb zircon ages are Rader Creek Granodiorite, 80.4 ?? 1.2 Ma; Unionville Granodiorite, 78.2 ?? 0.8 Ma; Pulpit Rock granite, 76.5 ?? 0.8 Ma; Butte Granite, 74.5 ?? 0.9 Ma; altered Steward-type quartz porphyry dike (I-15 roadcut), 66.5 ?? 1.0 Ma; altered Steward-type quartz porphyry dike (Continental pit), 65.7 ?? 0.9 Ma; and quartz monzodiorite of Boulder Baldy (Big Belt Mountains), 66.2 ?? 0.9 Ma. Zircons from Rader Creek Granodiorite and quartz porphyry dike samples contain Archean inheritance. The 40Ar/39Ar ages are muscovite, silver-rich polymetallic quartz vein (Basin district), 74.4 ?? 0.3 Ma; muscovite, silver-rich polymetallic quartz vein (Boulder district), 74.4 ?? 1.2 Ma; muscovite, early dark micaceous vein (Continental pit), 63.6 ?? 0.2 Ma; biotite, early dark micaceous vein (Continental pit), 63.6 ?? 0.2 Ma; potassium feldspar, early dark micaceous vein (Continental pit), 63 to 59 Ma; and biotite, biotite breccia dike (Continental pit), 63.6 ?? 0.2 Ma. Outlying silver-rich polymetallic quartz veins of the Basin and Boulder mining districts probably are directly related to the 74.5 Ma Butte Granite, whereas Steward-type east-west quartz porphyry dikes and Butte pre-Main Stage deposits are parts of a 66 to 64 Ma magmatic-mineralization system unrelated to emplacement of the Boulder batholith. The age of the crosscutting Main Stage veins may be about 61 Ma as originally reported but can only be bracketed as younger than the 64 Ma pre-Main Stage mineralization and older than the about 50 Ma Eocene Lowland Creek intrusions. The 66 Ma age for the quartz monzodiorite of Boulder Baldy and consideration of previous dating studies in the region indicate that small ca. 66 Ma plutonic systems may be common in the Boulder batholith region and especially to the east. The approximately 64 Ma porphyry copper systems at Butte and gold mineralization at Miller Mountain are indicative of regionally important mineralizing systems of this age in the Boulder batholith region. Resolution of the age and probable magmatic source of the Butte pre-Main Stage porphyry copper-molybdenum system and of the silver-rich polymetallic quartz vein systems in the northern part of the Boulder batholith documents that these deposits formed from two discrete periods of hydrothermal mineralization related to two discrete magmatic events.

Orogenic-type copper-gold-arsenic-(bismuth) mineralization at Flatschach (Eastern Alps), Austria

NASA Astrophysics Data System (ADS)

Raith, Johann G.; Leitner, Thomas; Paar, Werner H.

2015-10-01

Structurally controlled Cu-Au mineralization in the historic Flatschach mining district (Styria, Austria) occurs in a NE-SW to NNE-WSW oriented vein system as multiple steep-dipping calcite-(dolomite)-quartz veins in amphibolite facies metamorphic rocks (banded gneisses/amphibolites, orthogneisses, metagranitoids) of the poly-metamorphosed Austroalpine Silvretta-Seckau nappe. Vein formation postdated ductile deformation events and Eoalpine (Late Cretaceous) peak metamorphism but predated Early to Middle Miocene sediment deposition in the Fohnsdorf pull-apart basin; coal-bearing sediments cover the metamorphic basement plus the mineralized veins at the northern edge of the basin. Three gold-bearing ore stages consist of a stage 1 primary hydrothermal (mesothermal?) ore assemblage dominated by chalcopyrite, pyrite and arsenopyrite. Associated minor minerals include alloclasite, enargite, bornite, sphalerite, galena, bismuth and matildite. Gold in this stage is spatially associated with chalcopyrite occurring as inclusions, along re-healed micro-fractures or along grain boundaries of chalcopyrite with pyrite or arsenopyrite. Sericite-carbonate alteration is developed around the veins. Stage 2 ore minerals formed by the replacement of stage 1 sulfides and include digenite, anilite, "blue-remaining covellite" (spionkopite, yarrowite), bismuth, and the rare copper arsenides domeykite and koutekite. Gold in stage 2 is angular to rounded in shape and occurs primarily in the carbonate (calcite, Fe-dolomite) gangue and less commonly together with digenite, domeykite/koutekite and bismuth. Stage 3 is a strongly oxidized assemblage that includes hematite, cuprite, and various secondary Cu- and Fe-hydroxides and -carbonates. It formed during supergene weathering. Stage 1 and 2 gold consists mostly of electrum (gold fineness 640-860; mean = 725; n = 46), and rare near pure gold (fineness 930-940; n = 6). Gold in stage 3 is Ag-rich electrum (fineness 350-490, n = 12), and has a high Hg content (up to 11 mass %). The Cu-Au deposits in the Flatschach area show similarities with meso- to epizonal orogenic lode gold deposits regarding the geological setting, the structural control of mineralization, the type of alteration, the early (stage 1) sulfide assemblage and composition of gold. Unique about the Flatschach district is the lower-temperature overprint of copper arsenides (domeykite and koutekite) and copper sulfides (djurleite, yarrowite/spionkopite) on earlier formed sulfide mineralization. Based on mineralogical considerations temperature of stage 2 mineralization was between about 70 °C and 160 °C. Gold was locally mobilized during this low-temperature hydrothermal overprint as well as during stage 3 supergene oxidation and cementation processes.

The Magnet Cove Rutile Company mine, Hot Spring County, Arkansas

USGS Publications Warehouse

Kinney, Douglas M.

1949-01-01

The Magnet Cove Rutile Company mine was mapped by the U.S. Geological Survey in November 1944. The pits are on the northern edge of Magnet Cove and have been excavated in the oxidized zone of highly weathered and altered volcanic agglomerate. The agglomerate is composed of altered mafic igneous rocks in a matrix of white to gray clay, a highly altered tuff. The agglomerate appears layered and is composed of tuffaceous clay material below and igneous blocks above. The agglomerate is cut by aplite and lamprophyre dikes. Alkalic syenite dikes crop out on the ridge north of the pits. At the present stage of mine development the rutile seems to be concentrated in a narrow zone beneath the igneous blocks of the agglomerate. Rutile, associated with calcite and pyrite, occurs as disseminated acicular crystals and discontinuous vein-like masses in the altered tuff. Thin veins of rutile locally penetrate the mafic igneous blocks of the agglomerate.

Fluid overpressure estimates from the aspect ratios of mineral veins

NASA Astrophysics Data System (ADS)

Philipp, Sonja L.

2012-12-01

Several hundred calcite veins and (mostly) normal faults were studied in limestone and shale layers of a Mesozoic sedimentary basin next to the village of Kilve at the Bristol Channel (SW-England). The veins strike mostly E-W (239 measurements), that is, parallel with the associated normal faults. The mean vein dip is 73°N (44 measurements). Field observations indicate that these faults transported the fluids up into the limestone layers. The vein outcrop (trace) length (0.025-10.3 m) and thickness (0.1-28 mm) size distributions are log-normal. Taking the thickness as the dependent variable and the outcrop length as the independent variable, linear regression gives a coefficient of determination (goodness of fit) of R2 = 0.74 (significant with 99% confidence), but natural logarithmic transformation of the thickness-length data increases the coefficient of determination to R2 = 0.98, indicating that nearly all the variation in thickness can be explained in terms of variation in trace length. The geometric mean of the aspect (length/thickness) ratio, 451, gives the best representation of the data set. With 95% confidence, the true geometric mean of the aspect ratios of the veins lies in the interval 409-497. Using elastic crack theory, appropriate elastic properties of the host rock, and the mean aspect ratio, the fluid overpressure (that is, the total fluid pressure minus the normal stress on the fracture plane) at the time of vein formation is estimated at around 18 MPa. From these results, and using the average host rock and water densities, the depth to the sources of the fluids (below the present exposures) forming the veins is estimated at between around 300 m and 1200 m. These results are in agreement to those obtained by independent isotopic studies and indicate that the fluids were of rather local origin, probably injected from sill-like sources (water sills) inside the sedimentary basin.

Postorogenic carbonatites at Eden Lake, Trans-Hudson Orogen (northern Manitoba, Canada): Geological setting, mineralogy and geochemistry

NASA Astrophysics Data System (ADS)

Chakhmouradian, A. R.; Mumin, A. H.; Demény, A.; Elliott, B.

2008-07-01

The Eden Lake pluton in the Trans-Hudson Orogen is the first known occurrence of carbonatites in Manitoba. The pluton is largely made up of modally and geochemically diverse syenitic rocks derived from postorogenic magma(s) of shoshonitic affinity. Their diversity can be accounted for by a combination of crystal fractionation and fluid release in the final evolutionary stage (crystallization of quartz alkali-feldspar syenite). At Eden Lake, carbonatites, represented predominantly by coarse-grained massive to foliated sövite, occur as branching veins and lenticular bodies up to 4 m in thickness showing crosscutting relations with respect to all of the syenitic units. The host rocks are intensely fenitized at the contact, and there is also abundant mineralogical and textural evidence for assimilation of silicate material by carbonatitic magma through wallrock reaction and xenolith fragmentation and digestion. The bulk of the carbonatites are composed of (in order of crystallization): Sr-REE-rich fluorapatite, aegirine-augite, and coarse calcite crystals surrounded by fine-grained calcite (on average, ˜ 90 vol.% of the rock). Noteworthy accessory constituents are celestine, bastnäsite-(Ce) (both as primary inclusions in calcite), Nb-Zr-rich titanite, low-Hf zircon, allanite-(Ce) and andradite. The calcite is chemically uniform (Sr-rich, Mg-Mn-Fe-poor and low in 13C), but shows clear evidence of ductile deformation and syndeformational cataclasis. Geochemically, the carbonatites are enriched in Sr, Ba, light rare-earth elements, Th and U, but depleted in high-field-strength elements (particularly, Ti, Nb and Ta). The stable-isotope composition of coarse- and fine-grained calcite from the carbonatites and interstitial calcite from syenites is remarkably uniform: ca. - 8.16 ± 0.27‰ δ13C (PDB) and + 8.04 ± 0.19‰ δ18O (SMOW). The available textural and geochemical evidence indicates that the Eden Lake carbonatites are not consanguineous with the associated syenites and may have been derived from a Nb-Ti-retentive and 13C-depleted source such as the subducted crustal material underlying the Eden Lake deformation corridor.

Physicochemical Processes and the Evolution of Strength in Calcite Fault Gouge at Room Temperature

NASA Astrophysics Data System (ADS)

Carpenter, B. M.; Viti, C.; Collettini, C.

2015-12-01

The presence of calcite in and near faults, as the dominant material, cement, or vein fill, indicates that the mechanical behavior of carbonate-dominated material likely plays an important role in shallow- and mid-crustal faulting. Furthermore, a variety of physical and chemical processes control the evolution of strength and style of slip along seismogenic faults and thus play a critical role in the seismic cycle. Determining the role and contributions of these types of mechanisms is essential to furthering our understanding of the processes and timescales that lead to the strengthening of faults during interseismic periods and their behavior during the earthquake nucleation process. To further our understanding of these processes, we performed laboratory-shearing experiments on calcite gouge at normal stresses from 1 to 100 MPa, under conditions of saturation and at room temperature. We performed velocity stepping (0.1-1000μm/s) and slide-hold-slide (1-3000s) tests, to measure the velocity dependence of friction and the amount of frictional strengthening respectively, under saturated conditions with pore fluid that was in equilibrium with CaCO3. At 5 MPa normal stress, we also varied the environmental conditions by performing experiments under conditions of 5% RH and 50 % RH, and saturation with: silicone oil, demineralized water, and the equilibrated solution combined with 0.5M NaCl. Finally, we collected post experimental samples for microscopic analysis. Our combined analyses of rate-dependence, strengthening behavior, and microstructures show that calcite fault gouge transitions from brittle to semi-brittle behavior at high normal stress and low sliding velocities. Furthermore, our results also highlight how changes in pore water chemistry can have significant influence on the mechanical behavior of calcite gouge in both the laboratory and in natural faults. Our observations have important implications for earthquake nucleation and propagation on faults in carbonate-dominated lithologies.

Relating Mechanical Behavior and Microstructural Observations in Calcite Fault Gouge

NASA Astrophysics Data System (ADS)

Carpenter, B. M.; Di Stefano, G.; Viti, C.; Collettini, C.

2013-12-01

Many important earthquakes, magnitude 5-7, nucleate and/or propagate through carbonate-dominated lithologies. Additionally, the presence of precipitated calcite in (cement) and near (vein fill) faults indicates that the mechanical behavior of carbonate-dominated material likely plays an important role in shallow- and mid-crustal faulting. We report on laboratory experiments designed to explore the mechanical behavior of calcite and relate that behavior to post experiment microstructural observations. We sheared powdered gouge of Carrara Marble, >98% CaCO3, at constant normal stresses between 1 and 50 MPa under saturated conditions at room temperature. We performed velocity-stepping tests, 0.1-1000 μm/s, to evaluate frictional stability, and slide-hold-slide tests, 1-10,000 seconds, to measure the amount of frictional healing. Small subsets of experiments were performed under different environmental conditions and shearing velocities to better elucidate physicochemical processes and their role in the mechanical behavior of calcite fault gouge. All experimental samples were collected for SEM analysis. We find that the frictional healing rate is 7X higher under saturated conditions than under nominally dry conditions. We also observe a divergence between the rates of creep relaxation (increasing) and frictional healing (decreasing) as shear velocity is increased from 1 to 3000 μm/s. Our highest healing rates are observed at our lowest normal stresses. We observe a frictional strength of μ = 0.64, consistent with previous data under similar conditions. Furthermore, although we observe velocity-weakening frictional behavior in both the saturated and dry cases, rate- and-state friction parameters are distinctly different for each case. Our combined observations of rapid healing and of velocity-weakening frictional behavior indicate that faults where calcite-dominated gouge is present are likely to be seismic and have the ability to regain their strength quickly. Furthermore, our mechanical results highlight the important role of fluids in the evolution of frictional strength and thus fault behavior.

Mineralogy of the epithermal precious and base metal deposit Banská Hodruša at the Rozália Mine (Slovakia)

NASA Astrophysics Data System (ADS)

Kubač, Alexander; Chovan, Martin; Koděra, Peter; Kyle, J. Richard; Žitňan, Peter; Lexa, Jaroslav; Vojtko, Rastislav

2018-03-01

The Au-Ag-Pb-Zn-Cu epithermal deposit Banská Hodruša of intermediate-sulphidation type is located in the Middle Miocene Štiavnica stratovolcano on the inner side of the Carpathian arc in Slovakia. This deposit represents an unusual subhorizontal multi-stage vein system, related to processes of underground cauldron subsidence and exhumation of a subvolcanic granodiorite pluton. Veins are developed on a low-angle normal shear zone, possibly representing a detachment zone in andesitic wall rocks that formed during emplacement and exhumation of the granodiorite pluton. The deposit consists of two parts, separated by a thick sill of quartz-diorite porphyry. The eastern part is currently mined, and the western part has already been depleted. The Banská Hodruša mineralization was formed during four stages: (1) low-grade silicified breccia at subhorizontal structures at the base of the deposit; (2) stockwork of steep veins with rhodonite-rhodochrosite, quartz-sulphide-carbonate and quartz-gold assemblages; (3) thin quartz-gold veins with medium dip in tension cracks inside the shear zone and complementary detachment hosted quartz-base metals-gold veins; (4) Post-ore veins. Gold and electrum (920-730) occur as intergrowths with base metal sulphides or hosted in quartz and carbonates, accompanied by Au-Ag tellurides (hessite, petzite). Rare Te-polybasite and Cu-cervelleite result from re-equilibration of early Te-bearing minerals during cooling. Sulphide minerals include low Fe sphalerite ( 1.25 wt%), galena, chalcopyrite, and pyrite. The wall rock alteration is represented mostly by adularia, illite, chlorite, quartz, calcite and pyrite. Precipitation of gold, Au-Ag tellurides, Mn-bearing minerals and adularia resulted from boiling of fluids due to hydraulic fracturing, as well as opening of dilatational structures within the shear zone.

Fluid inclusion characteristics and geological significance of the Dajinshan W-Sn polymetallic deposit in Yunfu, Guangdong Province

NASA Astrophysics Data System (ADS)

Yu, Zhangfa; Chen, Maohong; Zhao, Haijie

2015-05-01

The Dajinshan tungsten-tin polymetallic deposit is a quartz-vein-type ore deposit located in Western Guangdong Province. The ore bodies show a fairly simple shape and mainly occur as tungsten-tin polymetallic-bearing sulfide quartz veins, including quartz vein, quartz-greisens, and sulfide quartz veins, and their distribution is spatially related to Dajinshan granitoids. The formation of the deposit experienced three stages: a wolframite-molybdenite-quartz stage, a wolframite-cassiterite-sulfide-quartz stage, and a fluorite-calcite-carbonate stage. Based on detailed petrographic observations, we conducted microthermometric and Raman microspectroscopic studies of fluid inclusions formed at different ore-forming stages in the Dajinshan tungsten-tin polymetallic deposit, identifying four dominant types of fluid inclusions: aqueous two-phase inclusions, CO2-bearing inclusions, solid or daughter mineral-bearing inclusions, and gas-rich inclusions. The gas compositions of ore-forming fluids in the Dajinshan tungsten-tin polymetallic deposit are mostly CO2, CH4, and H2O. The hydrogen, oxygen, and sulfur isotopic data imply that the ore-forming fluids in the Dajinshan tungsten-tin polymetallic deposit were mainly derived from magmatic fluids, mixed with meteoric water in the ore-formation process. These results indicate that the fluid mixing and boiling led to the decomposition of the metal complex in ore-forming fluids and ore deposition.

Direct Measurement of Initial 230TH/ 232TH Ratios in Central Texas Speleothems for More Accurate Age Determination

NASA Astrophysics Data System (ADS)

Wortham, B. E.; Banner, J. L.; James, E.; Loewy, S. L.

2013-12-01

Speleothems, calcite deposits in caves, preserve a record of climate in their growth rate, isotope ratios and trace element concentrations. These variables must be tied to precise ages to produce pre-instrumental records of climate. The 238U-234U- 230Th disequilibrium method of dating can yield precise ages if the amount of 230Th from the decay of radiogenic 238U can be constrained. 230Th in a speleothem calcite growth layer has two potential sources - 1) decay of radioactive 238U since the time of growth of the calcite layer; and 2) initial detrital 230Th, incorporated along with detrital 232Th, into the calcite layer at the time it grew. Although the calcite lattice does not typically incorporate Th, samples can contain impurities with relatively high Th contents. Initial 230Th/232Th is commonly estimated by assuming a source with bulk-Earth U/Th values in a state of secular equilibrium in the 238U-decay chain. The uncertainty in this 230Th/232Th estimate is also assumed, typically at +/-100%. Both assumptions contribute to uncertainty in ages determined for young speleothems. If the amount of initial detrital 230Th can be better quantified for samples or sites, then U-series ages will have smaller uncertainties and more precisely define the time series of climate proxies. This study determined the initial 230Th/232Th of modern calcite to provide more precise dates for central Texas speleothems. Calcite was grown on glass-plate substrates placed under active drips in central Texas caves. The 230Th/232Th of this modern calcite was determined using thermal ionization mass spectrometry. Results show that: 1) initial 230Th/232Th ratios can be accurately determined in these young samples and 2) measuring 230Th/232Th reduces the uncertainties in previously-determined ages on stalagmites from under the same drips. For example, measured initial 230Th/232Th in calcite collected on substrates from different locations in the cave at Westcave Preserve are 15.3 × 0.67 ppm, 14.6 × 0.83 ppm, 5.8 × 0.56 ppm, and 5.9 × 0.60 ppm, which are higher and more precise than the value commonly assumed for initial 230Th/232Th, 4.4 × 4.4 ppm. Soil sampled above Westcave, a potential source of detrital Th incorporated into speleothems, also has a high calculated 230Th/232Th. We calculate soil 230Th/232Th from measured U and Th concentrations of soil leachates (using DI water and ammonium acetate). Calculated 230Th/232Th for Westcave soils range from 0.39 to 28.4 ppm, which encompasses the range of initial 230Th/232Th values found in the modern calcite. Soil leachates from Natural Bridge Caverns and Inner Space Cavern were analyzed by the same method, yielding calculated 230Th/232Th ranging from 1.5 to 12.6 ppm (Natural Bridge), and from 1.43 to 272 ppm (Inner Space). Soil and calcite data indicate that the commonly assumed initial 230Th/232Th is not always applicable and that initial 230Th/232Th can be estimated more accurately by measuring Th isotope ratios in modern calcite and soils to determine speleothem U-series ages.

From vein precipitates to deformation and fluid rock interaction within a SSZ: Insights from the Izu-Bonin-Mariana fore arc

NASA Astrophysics Data System (ADS)

Micheuz, Peter; Quandt, Dennis; Kurz, Walter

2017-04-01

International Ocean Discovery Program (IODP) expeditions 352 and 351 drilled through oceanic crust of the Philippine Sea plate. The two study areas are located near the outer Izu-Bonin-Mariana (IBM) fore arc and in the Amami Sankaku Basin. The primary objective was to improve our understanding of supra-subduction zones (SSZ) and the process of subduction initiation. The recovered drill cores during IODP expedition 352 represent approximately 50 Ma old fore arc basalts (FAB) and boninites revealing an entire volcanic sequence of a SSZ. Expedition 351 drilled FAB like oceanic crust similar in age to the FABs of expedition 352. In this study we present data on vein microstructures, geochemical data and isotopic signatures of vein precipitates to give new insights into fluid flow and precipitation processes and deformation within the Izu-Bonin fore arc. Veins formed predominantly as a consequence of hydrofracturing resulting in the occurrence of branched vein systems and brecciated samples. Along these hydrofractures the amount of altered host rock fragments varies and locally alters the host rock completely to zeolites and carbonates. Subordinately extensional veins released after the formation of the host rocks. Cross-cutting relationships of different vein types point to multiple fracturing events subsequently filled with minerals originating from a fluid with isotopic seawater signature. Based on vein precipitates, their morphology and their growth patterns four vein types have been defined. Major vein components are (Mg-) calcite and various zeolites determined by Raman spectra and electron microprobe analyses. Zeolites result from alteration of volcanic glass during interaction with a seawaterlike fluid. Type I veins which are characterized by micritic infill represent neptunian dykes. They predominantly occur in the upper levels of drill cores being the result of an initial volume change subsequently to crystallization of the host rocks. Type II veins are characterized by blocky carbonates and idiomorphic to blocky zeolites. Blocky carbonates locally exhibit zonation patterns. Type III and type IV veins are both assumed to be extensional veins. Type III is characterized by syntaxial growth and elongate blocky carbonate minerals. They predominantly occur as asymmetric syntaxial veins, locally exhibiting more than one crack-seal event. Type IV veins are defined as antitaxial fibrous carbonates. Type II veins commonly show deformation microstructures like twinning (type I/II twins), slightly curved twins, and subgrain boundaries indicative of incipient plastic deformation. Based on these observations differential stresses around 50 MPa were needed to deform vein minerals, presumably related to IBM fore arc extension due to the retreat of the subducted Pacific plate. We acknowledge financial support by the Austrian Research Fund (P27982-N29) to W. Kurz

DOE Office of Scientific and Technical Information (OSTI.GOV)

Trofanenko, J.; Williams-Jones, A. E.; Simandl, G. J.

The Wicheeda carbonatite is a deformed plug or sill that hosts relatively high grade light rare earth elements (LREE) mineralization in the British Columbia alkaline province. It was emplaced within metasedimentary rocks belonging to the Kechika Group, which have been altered to potassic fenite near the intrusion and sodic fenite at greater distances from it. The intrusion comprises a ferroan dolomite carbonatite core, which passes gradationally outward into calcite carbonatite. The potentially economic REE mineralization is hosted by the dolomite carbonatite. We recognized three types of dolomite. Dolomite constitutes the bulk of the dolomite carbonatite, dolomite replaced dolomite near veinsmore » and vugs, and dolomite occurs in veins and vugs together with the REE mineralization. Carbon and oxygen isotope ratios indicate that the calcite carbonatite crystallized from a magma of mantle origin, that dolomite is of primary igneous origin, that dolomite has a largely igneous signature with a small hydrothermal component, and that dolomite is of hydrothermal origin. Furthermore, the REE minerals comprise REE fluorocarbonates, ancylite-(Ce), and monazite-(Ce). In addition to dolomite, they occur with barite, molybdenite, pyrite, and thorite. Minor concentrations of niobium are present as magmatic pyrochlore in the calcite carbonatite. model is proposed in which crystallization of calcite carbonatite preceded that of dolomite carbonatite. During crystallization of the latter, an aqueous-carbonic fluid was exsolved, which mobilized the REE as chloride complexes into vugs and fractures in the dolomite carbonatite, where they precipitated mainly in response to the increase in pH that accompanied fluid-rock interaction and, in the case of the REE fluorocarbonates, decreasing temperature. These fluids altered the host metasedimentary rock to potassic fenite adjacent to the carbonatite and, distal to it, they mixed with formational waters to produce sodic fenite.« less

The Nature and Origin of the REE Mineralization in the Wicheeda Carbonatite, British Columbia, Canada

DOE PAGES

Trofanenko, J.; Williams-Jones, A. E.; Simandl, G. J.; ...

2016-01-01

The Wicheeda carbonatite is a deformed plug or sill that hosts relatively high grade light rare earth elements (LREE) mineralization in the British Columbia alkaline province. It was emplaced within metasedimentary rocks belonging to the Kechika Group, which have been altered to potassic fenite near the intrusion and sodic fenite at greater distances from it. The intrusion comprises a ferroan dolomite carbonatite core, which passes gradationally outward into calcite carbonatite. The potentially economic REE mineralization is hosted by the dolomite carbonatite. We recognized three types of dolomite. Dolomite constitutes the bulk of the dolomite carbonatite, dolomite replaced dolomite near veinsmore » and vugs, and dolomite occurs in veins and vugs together with the REE mineralization. Carbon and oxygen isotope ratios indicate that the calcite carbonatite crystallized from a magma of mantle origin, that dolomite is of primary igneous origin, that dolomite has a largely igneous signature with a small hydrothermal component, and that dolomite is of hydrothermal origin. Furthermore, the REE minerals comprise REE fluorocarbonates, ancylite-(Ce), and monazite-(Ce). In addition to dolomite, they occur with barite, molybdenite, pyrite, and thorite. Minor concentrations of niobium are present as magmatic pyrochlore in the calcite carbonatite. model is proposed in which crystallization of calcite carbonatite preceded that of dolomite carbonatite. During crystallization of the latter, an aqueous-carbonic fluid was exsolved, which mobilized the REE as chloride complexes into vugs and fractures in the dolomite carbonatite, where they precipitated mainly in response to the increase in pH that accompanied fluid-rock interaction and, in the case of the REE fluorocarbonates, decreasing temperature. These fluids altered the host metasedimentary rock to potassic fenite adjacent to the carbonatite and, distal to it, they mixed with formational waters to produce sodic fenite.« less

Stress and strain patterns, kinematics and deformation mechanisms in a basement-cored anticline: Sheep Mountain Anticline, Wyoming

NASA Astrophysics Data System (ADS)

Amrouch, Khalid; Lacombe, Olivier; Bellahsen, Nicolas; Daniel, Jean-Marc; Callot, Jean-Paul

2010-02-01

In order to characterize and compare the stress-strain record prior to, during, and just after folding at the macroscopic and the microscopic scales and to provide insights into stress levels sustained by folded rocks, we investigate the relationship between the stress-strain distribution in folded strata derived from fractures, striated microfaults, and calcite twins and the development of the Laramide, basement-cored Sheep Mountain Anticline, Wyoming. Tectonic data were mainly collected in Lower Carboniferous to Permian carbonates and sandstones. In both rock matrix and veins, calcite twins recorded three different tectonic stages: the first stage is a pre-Laramide (Sevier) layer-parallel shortening (LPS) parallel to fold axis, the second one is a Laramide LPS perpendicular to the fold axis, and the third stage corresponds to Laramide late fold tightening with compression also perpendicular to the fold axis. Stress and strain orientations and regimes at the microscale agree with the polyphase stress evolution revealed by populations of fractures and striated microfaults, testifying for the homogeneity of stress record at different scales through time. Calcite twin analysis additionally reveals significant variations of differential stress magnitudes between fold limbs. Our results especially point to an increase of differential stress magnitudes related to Laramide LPS from the backlimb to the forelimb of the fold possibly in relation with motion of an underlying basement thrust fault that likely induced stress concentrations at its upper tip. This result is confirmed by a simple numerical model. Beyond regional implications, this study highlights the potential of calcite twin analyses to yield a representative quantitative picture of stress and strain patterns related to folding.

Middle Miocene paleotemperature anomalies within the Franciscan Complex of northern California: Thermo-tectonic responses near the Mendocino triple junction

USGS Publications Warehouse

Underwood, M.B.; Shelton, K.L.; McLaughlin, R.J.; Laughland, M.M.; Solomon, R.M.

1999-01-01

This study documents three localities in the Franciscan accretionary complex of northern California, now adjacent to the San Andreas fault, that were overprinted thermally between 13.9 and 12.2 Ma: Point Delgada-Shelter Cove (King Range terrane); Bolinas Ridge (San Bruno Mountain terrane); and Mount San Bruno (San Bruno Mountain terrane). Vein assemblages of quartz, carbonate, sulfide minerals, and adularia were precipitated locally in highly fractured wall rock. Vitrinite reflectance (Rm) values and illite crystallinity decrease away from the zones of metalliferous veins, where peak wall-rock temperatures, as determined from Rm, were as high as 315??C. The ??18O values of quartz and calcite indicate that two separate types of fluid contributed to vein precipitation. Higher ??18O fluids produced widespread quartz and calcite veins that are typical of the regional paleothermal regime. The widespread veins are by-products of heat conduction and diffuse fluid flow during zeolite and prehnite-pumpellyite-grade metamorphism, and we interpret their paleofluids to have evolved through dehydration reactions and/or extensive isotopic exchange with accreted Franciscan rocks. Lower ??18O fluids, in contrast, evolved from relatively high temperature exchange between seawater (or meteoric water) and basaltic and/or sedimentary host rocks; focused flow of those fluids resulted in local deposition of the metalliferous veins. Heat sources for the three paleothermal anomalies remain uncertain and may have been unrelated to one another. Higher temperature metalliferous fluids in the King Range terrane could have advected either from a site of ridge-trench interaction north of the Mendocino fracture zone or from a "slabless window" in the wake of the northward migrating Mendocino triple junction. A separate paradox involves the amount of Quaternary offset of Franciscan basement rocks near Shelter Cove by on-land faults that some regard as the main active trace of the San Andreas plate boundary. Contouring of vitrinite reflectance values to the north of an area affected by A.D. 1906 surface rupture indicates that the maximum dextral offset within the interior of the King Range terrane is only 2.5 km. If this fault extends inland, and if it has been accommodating most of the strike-slip component of San Andreas offset at a rate of 3-4 cm/yr, then its activity began only 83-62 ka. This interpretation would also mean that a longer term trace of the San Andreas fault must be nearby, either offshore or along the northeast boundary of the King Range terrane. An offshore fault trace would be consistent with peak heating of King Range strata north of the Mendocino triple junction. Conversely, shifting the fault to the east would be compatible with a slabless window heat source and long-distance northward translation of the King Range terrane after peak heating.

Hydrothermal karst and associated breccias in Neoproterozoic limestone from the Barker-Villa Cacique area (Tandilia belt), Argentina

NASA Astrophysics Data System (ADS)

Dristas, Jorge A.; Martínez, Juan C.; van den Kerkhof, Alfons M.; Massonne, Hans-Joachim; Theye, Thomas; Frisicale, María C.; Gregori, Daniel A.

2017-07-01

In the Barker-Villa Cacique area (Tandilia belt), remarkable megabreccias, limestone breccias and phosphate-bearing breccias hosted in black limestone and along the contact with the upper section of the sedimentary succession are exposed. These rocks are the result of extensive hydrothermal alteration of the original micritic limestone and other fine-grained clastic sediments. Typical alteration minerals are sericite, chlorite, interstratified chlorite/K-white mica, kaolinite, dickite, pyrite, chalcopyrite, goethite, quartz, calcite, Fe-calcite, dolomite, ankerite, fluor-apatite, barite and aluminium-phosphate-sulfate (APS) minerals. Quartz and calcite cements from hydraulic breccias in the limestone contain low-salinity aqueous fluid inclusions. Corresponding homogenization temperatures display 200-220 °C and 110-140 °C in hydrothermal quartz, and 130-150 °C in late calcite cement. Carbon and oxygen stable isotope analyses of carbonates from the Loma Negra quarry (LNQ) support the major role of hydrothermal activity. A significant difference was found between δ18Ocar values from unaltered micritic limestone (ca. 23.8‰ SMOW) and secondary calcite (ca. 18.5‰ SMOW). The lower δ18Ocar values are interpreted as a result of calcite precipitation from hot hydrothermal fluids. At a late stage, the hydrothermal fluid containing H2S mixed with descending and oxidizing meteoric waters. Circulation of the ensuing acid fluids resulted in the partly dissolution and collapse brecciation of the Loma Negra Formation. The hydrothermal stage can be tentatively dated ca. 590-620 Ma corresponding to the Brasiliano orogeny.

Evolution of the Bucium Rodu and Frasin magmatic-hydrothermal system, Metaliferi Mountains, Romania

NASA Astrophysics Data System (ADS)

Iatan, Elena Luisa; Berbeleac, Ion; Visan, Madalina; Minut, Adrian; Nadasan, Laurentiu

2013-04-01

The Miocene Bucium Rodu and Frasin maar-diatreme structures and related Au-Ag epithermal low sulfidation with passing to mesothermal mineralizations are located in the Bucium-Rosia Montana-Baia de Aries metallogenetic district, within so called the "Golden Quatrilaterum", in the northeastern part of the Metaliferi Mountains. These structures are situated at about 5 km southeast from Rosia Montana, the largest European Au-Ag deposit. The total reserves for Bucium Rodu-Frasin are estimated at 43.3 Mt with average contents of 1.3 g/t Au and 3 g/t Ag. The Miocene geological evolution of Bucium Rodu and Frasin magmatic-hydrothermal system took place in closely relationships with tectonic, magmatic and metallogenetic activity from Bucium-Rosia Montana-Baia de Aries district in general, and adjacent areas, in special. The hydrothermal alteration is pervasive; adularia followed by phyllic, carbonatization and silicification alterations, usually show a close relationship with the mineralizations. Propylitic alteration occurs dominantly towards the depth; argillic alteration shows a local character. The mineralization occurs in veins, breccias, stockworks and disseminations and is hosted within two volcanic structures emplaced into a sequence of Cretaceous sediments in closely genetically relations with the Miocene phreatomagmatic fracturing and brecciation events. Within Rodu maar-diatreme structure the mineralizations follow especially the contact between the diatreme and Cretaceous flysch. The vein sets with low, moderately and near vertical dippings, cover 400x400m with N-S trend. The most important mineralization style is represented by veins, accompanied by hydrothermal breccias and disseminations. The veins spatial distribution relives as "en echelon" tension veins. They carry gold, minor base metal sulphides (pyrite, chalcopyrite, sphalerite, galena, tetrahedrite, arsenopyrite). Gangue is represented by carbonates (calcite, dolomite, ankerite, siderite, rhodochrosite) and quartz. In contrast, in Frasin maar-diatreme structure, the mineralizations are focused especially along the northeastern contact between the andesite dome and polimictic breccias. Stockwork is the main style of mineralization and consists of pyrite, small amounts of chalcopyrite, sphalerite, galena, arsenopyrite and gold within a gangue of quartz and carbonates similar to Rodu mineralizations. The ore minerals deposition from hydrothermal fluids have pulsated character with a three stage evolution and mineral assemblages: 1) magnetite (hematite) - pyrite (marcasite) - quartz in the first stage, epithermal low sulfidation with passing to mesothermal; 2) arsenopyrite (Au) - (-base metal sulfides) - quartz, "Chinga" (pyrite (Au)-quartz-adularia) - carbonates (calcite, aragonite, dolomite, ankerite, ± rhodochrosite ± kutnahorite) - quartz - adularia in the second stage, epithermal low sulfidation and 3) pyrite - marcasite - carbonates - quartz, (Au) - carbonates (dominant rhodochrosite) - quartz - adularia and alabandite - rhodochrosite - quartz in the third stage, epithermal low sulfidation. The mineralizing hydrothermal fluids had near neutral pH with the gold transported probably as a bisulfide complex; boiling seems to be the main way of gold precipitation.

High Resolution Mineral Mapping of the Oman Drilling Project Cores with Imaging Spectroscopy: Preliminary Results

NASA Astrophysics Data System (ADS)

Greenberger, R. N.; Ehlmann, B. L.; Kelemen, P. B.; Manning, C. E.; Teagle, D. A. H.; Harris, M.; Michibayashi, K.; Takazawa, E.

2017-12-01

The Oman Drilling Project provides an unprecedented opportunity to study the formation and alteration of oceanic crust and peridotite. Key to answering the main questions of the project are a characterization of the primary and secondary minerals present within the drill core and their spatial relationships. To that end, we used the Caltech imaging spectrometer system to scan the entire 1.5-km archive half of the core from all four gabbro and listvenite boreholes (GT1A, GT2A, GT3A, and BT1B) at 250 µm/pixel aboard the JAMSTEC Drilling Vessel Chikyu during the ChikyuOman core description campaign. The instrument measures the visible and shortwave infrared reflectance spectra of the rocks as a function of wavelength from 0.4 to 2.6 µm. This wavelength range is sensitive to many mineral groups, including hydrated minerals (phyllosilicates, zeolites, amorphous silica polytypes), carbonates, sulfates, and transition metals, most commonly iron-bearing mineralogies. To complete the measurements, the core was illuminated with a halogen light source and moved below the spectrometer at 1 cm/s by the Chikyu's Geotek track. Data are corrected and processed to reflectance using measurements of dark current and a spectralon calibration panel. The data provide a unique view of the mineralogy at high spatial resolution. Analysis of the images for complete downhole trends is ongoing. Thus far, a variety of minerals have been identified within their petrologic contexts, including but not limited to magnesite, dolomite, calcite, quartz (through an Si-OH absorption due to minor H2O), serpentine, chlorite, epidote, zeolites, mica (fuchsite), kaolinite, prehnite, gypsum, amphibole, and iron oxides. Further analysis will likely identify more minerals. Results include rapidly distinguishing the cations present within carbonate minerals and identifying minerals of volumetrically-low abundance within the matrix and veins of core samples. This technique, for example, accurately identifies mm-thick dolomite or calcite veins among dense sets of magnesite veins in the listvenite, indicating cross-cutting relationships that reflect changing alteration conditions with time. It also highlights key zones for sampling and additional analyses. Further data processing will provide mineralogical maps of the full 1.5 km of core.

The origin of the Tongkeng-Changpo tin deposit, Dachang metal district, Guangxi, China: clues from fluid inclusions and He isotope systematics

NASA Astrophysics Data System (ADS)

Minghai, Cai; Jingwen, Mao; Ting, Liang; Pirajno, Franco; Huilan, Huang

2007-08-01

Tongkeng-Changpo is the largest tin deposit within the giant Dachang polymetallic tin ore field in Guangxi, southern China, which is part of a large skarn system associated with Cretaceous granitoids. The Tongkeng-Changpo mineralization consists of veins and stockworks in the upper levels and replacement stratiform orebodies (mantos) at lower levels. Based on textural relationships, three major mineralizing stages can be recognized: stage I with cassiterite, sulphides, stannite, tourmaline, and quartz; stage II with cassiterite, sulphides, sulphosalts, quartz, and calcite; and stage III with calcite as the main phase. The study of fluid inclusions has shown that there are two main fluid types: CO2 and NaCl-H2O. Homogenization temperatures are 270 to 365°C, 210 to 240°C, and 140 to 190°C for stages I, II, and III, respectively. Salinities range from 1 to 7 wt.% NaCl equiv. in the early ore stage and 3 to 10 wt.% NaCl equiv. in the late stages. Laser Raman Spectroscopy indicates that the inclusion fluids in stages I and II were of carbono-aqueous composition, with minor amounts of CH4 and H2S, whereas those in stage III were aqueous. Helium isotopic analyses of inclusion fluids indicate that the 3He/4He ratios in the ore veins are in between 1.2 to 2.9 Ra (Ra = 1.4 × 10-6, modern atmospheric ratio), and range from 1.6 to 2.5 Ra in the stratiform orebodies. This range of 3He/4He ratios is significantly higher than that of crustal fluids (0.01-0.05 Ra). The similar characteristics of fluid inclusions and their He isotopic composition, as well as age constraints, indicate that the ore veins and stratiform orebodies of the Tongkeng-Changpo deposit formed from the same hydrothermal system, likely related to granite intrusions of the Mesozoic Yanshanian tectono-thermal event. In addition, the high R/Ra ratios indicate a mantle contribution in the ore fluids.

Reconstruction of seasonal temperature variability in the tropical Pacific Ocean from the shell of the scallop, Comptopallium radula

NASA Astrophysics Data System (ADS)

Thébault, Julien; Chauvaud, Laurent; Clavier, Jacques; Guarini, Jennifer; Dunbar, Robert B.; Fichez, Renaud; Mucciarone, David A.; Morize, Eric

2007-02-01

We investigated the oxygen isotope composition (δ 18O) of shell striae from juvenile Comptopallium radula (Mollusca; Pectinidae) specimens collected live in New Caledonia. Bottom-water temperature and salinity were monitored in-situ throughout the study period. External shell striae form with a 2-day periodicity in this scallop, making it possible to estimate the date of precipitation for each calcite sample collected along a growth transect. The oxygen isotope composition of shell calcite (δ 18O shell calcite) measured at almost weekly resolution on calcite accreted between August 2002 and July 2003 accurately tracks bottom-water temperatures. A new empirical paleotemperature equation for this scallop species relates temperature and δ 18O shell calcite: t(°C)=20.00(±0.61)-3.66(±0.39)×(δ18O-δ18O) The mean absolute accuracy of temperature estimated using this equation is 1.0 °C at temperatures between 20 and 30 °C. Uncertainties regarding the precise timing of CaCO 3 deposition and the actual variations in δ 18O water at our study sites probably contribute to this error. Comparison with a previously published empirical paleotemperature equation indicates that C. radula calcite is enriched in 18O by ˜0.7‰ relative to equilibrium. Given the direction of this offset and the lack of correlation between shell growth rate and δ 18O shell calcite, this disequilibrium is unlikely to be related to kinetic isotope effects. We suggest that this enrichment reflects (1) a relatively low pH in the scallop's marginal extrapallial fluid (EPF), (2) an isotopic signature of the EPF different from that of seawater, or (3) Rayleigh fractionation during the biocalcification process. Relative changes in δ 18O shell calcite reflect seawater temperature variability at this location and we suggest that the shell of C. radula may be useful as an archive of past seawater temperatures.

Geology and mineral deposits of the Minnie Moore and Bullion mineralized areas, Blaine County, Idaho

USGS Publications Warehouse

Link, Paul Karl; Worl, Ronald G.

2001-01-01

In the early 1880?s the discovery of rich ores in the Minnie Moore and Bullion mineralized areas sparked a rush to settle and develop the Wood River valley. Silver and lead discoveries in these areas spurred the boom in mining after completion of the Oregon Short Line Railroad to Hailey in 1883. In both areas the ore comprises galena, sphalerite, and tetrahedrite in a gangue of siderite, calcite, or quartz. Minor goldbearing quartz veins are also present. The ore is in fissure and replacement veins along fracture systems that formed in Late Cretaceous time, after intrusion of nearby granodiorite or quartz diorite stocks. The ore formed under mesothermal conditions and heat was supplied by the nearby plutons. In the Minnie Moore area, the mineralized veins are cut by low-angle normal faults that are of probable Eocene age. In the Minnie Moore mineralized area, the host rock is the middle part of the Devonian Milligen Formation, (the informal Lucky Coin limestone and Triumph argillite), which is the same stratigraphic level as the host ore in the rich Triumph mine northeast of Hailey. In the Bullion mineralized area, the ore is hosted by the lower member of the Middle Pennsylvanian to Lower Permian Dollarhide Formation. Rich ore was mined in several tunnels that reached the Mayflower vein, a northwest-striking mineralized shear zone. The deposits are thought to be mainly mesothermal veins that formed in association with Cretaceous magmatism. The syngenetic stratiform model of ore formation has often been applied to these deposits, however, no evidence of syngenetic mineralization was found in this study. Faulting has displaced most of the major orebodies and thus has made mining these deposits a challenge.

The timing of high-temperature retrogression in the Reynolds Range, central Australia: constraints from garnet and epidote Pb-Pb dating

NASA Astrophysics Data System (ADS)

Buick, Ian S.; Frei, Robert; Cartwright, Ian

Lower Calcsilicate Unit metasediments and underlying migmatitic Napperby Gneiss metagranite at Conical Hill in the Reynolds Range, central Australia, underwent regional high-grade ( 680 to 720°C), low-pressure/high-temperature metamorphism at 1594+/- 6Ma. The Lower Calcsilicate Unit is extensively quartz veined and epidotised, and discordant grandite garnet+epidote quartz veins may be traced over tens of metres depth into pegmatites that pooled at the Lower Calcsilicate Unit-Napperby Gneiss contact. The quartz veins were probably precipitated by water-rich fluids that exsolved from partial melts derived from the Napperby Gneiss during cooling from the peak of regional metamorphism to the wet granite solidus. Pb stepwise leaching (PbSL) on garnet from three discordant quartz veins yielded comparable single mineral isochrons of 1566+/-32Ma, 1576+/-3Ma and 1577+/-5Ma, which are interpreted as the age of garnet growth in the veins. These dates are in good agreement with previous Sensitive High Resolution Ion Microprobe (SHRIMP) ages of zircon and monazite formed during high-temperature retrogression (1586+/-5 to 1568+/-4Ma) elsewhere in the Reynolds Range. The relatively small age difference between peak metamorphism and retrograde veining suggests that partial melting and melt crystallisation controlled fluid recycling in the high-grade rocks. However, PbSL experiments on epidote intergrown with, and partially replacing, garnet in two of the veins yielded isochrons of 1454+/-34 and 1469+/- 26Ma. The 100-120Ma age difference between intergrown garnet and late epidote from the same vein suggests that the vein systems may have experienced multiple episodes of fluid flow.

Geochemistry of speleothems affected by aragonite to calcite recrystallization - Potential inheritance from the precursor mineral

NASA Astrophysics Data System (ADS)

Domínguez-Villar, David; Krklec, Kristina; Pelicon, Primož; Fairchild, Ian J.; Cheng, Hai; Edwards, Lawrence R.

2017-03-01

Formerly aragonite speleothems recrystallized to calcite result from solutions subsaturated in aragonite and supersaturated in calcite that infiltrate into the speleothem through the interconnected porosity. In most cases, the crystal replacement takes place through a thin solution film. This diagenetic process can occur under open or semi-closed geochemical conditions. Thus, secondary calcite crystals record the composition of the fluid at the time of diagenesis affected by calcite partition coefficients and fractionation factors (open system) or partly inherit the composition of the primary aragonite (semi-closed system). So, whether or not recrystallized aragonite speleothems can record reliable geochemical signals from the time of speleothem primary deposition still is an open debate. We studied a stalagmite from Eagle Cave (Spain) predominantly composed of secondary calcite that replaced aragonite, although a core of primary aragonite extending 45 mm along the growth direction was preserved at the base of the sample. We obtained Mg and Sr compositional maps, paired U-Th dating and δ18O and δ13C profiles across the diagenetic front. Additionally, two parallel isotope records were obtained along the speleothem growth direction in the aragonite and calcite sectors. Our results support that recrystallization of this speleothem took place in open system conditions for δ18O, δ13C, Mg and Sr, but in semi-closed system conditions for U and Th. The recrystallization of this sample took place during one or several events, likely after the Younger Dryas as a result of climate change influencing drip water composition. Based on compositional zoned patterns, we suggest that the advance of diagenetic fronts in this speleothem had an average rate of 50 ± 45 μm/yr. Such recrystallization rate can transform any aragonite speleothem into calcite within a few centuries. We suggest that the volume of water interacting with the speleothem at the time of recrystallization is of critical importance for inheritance of different elements. The volume of solution is controlled by (1) the discharge of water passing through the sample and (2) the lapse time between aragonite dissolution and calcite precipitation. Hydrology and hydrochemistry of the interacting solution, together with the mineralogy and texture of the speleothem are the essential controls for the diagenesis of the speleothem. Recrystallization of aragonite speleothems does not follow stratigraphical levels of the sample but occurs along sites with preferential flow paths in any sector of the speleothem. In these cases the relationship between age and distance from base is not preserved. However, alternation of periods of recrystallization with periods of aragonite precipitation causing speleothem accretion can result in recrystallized speleothems with coherent distance from the base-age relationship. Thus, early diagenesis of speleothems affected by seasonal or inter-annual oscillation of drip waters supersaturated and subsaturated in aragonite may provide best-scenario conditions for dating and preservation of paleoenvironmental records along recrystallized speleothems. However, even in this scenario, the variable discharge and the diagenetic rate control the geochemical inheritance from the primary aragonite crystals.

The paleomagnetism of clastic and precipitate deposits in limestone and dolomite caves

DOE Office of Scientific and Technical Information (OSTI.GOV)

Latham, A.G.; Ford, D.C.

1991-03-01

Clastic sediments and calcite precipitates (stalagmites, flowstones, etc.) are abundant in modern limestone caves and normally are the dominant infillings in buried (paleokarst) caves. Clastic sediment fillings are chiefly of fluviatile or local breakdown origin, but lacustrine, colluvial, eolian, and glacial deposits are known. Paleomagnetism has been studied in the fluviatile and lacustrine types: (1) reversal stratigraphy aids dating of geomorphic and paleoclimatic events in the late Pliocene/Pleistocene; (2) fine magnetostratigraphy has yielded estimates of the westward drift. Calcite precipitates (speleothems) may display natural remanent magnetism of either depositional (DRM) or chemical (CRM) origin. NRMs of modern speleothems are primary,more » not diagenetic; CRMs are invariably associated with the degradation of surface organic matter. (1) Coarse reversal stratigraphy dates geomorphic, etc., events and erosion rates. (2) Fine stratigraphy combined with {sup 230}Th:{sup 234}U dating gives high precision estimates of secular variation, westward drift, and rate of change of geomagnetic anomalies in upper Pleistocene and Holocene deposits. Magnetostratigraphy of paleokarst speleothem fillings associated with hydrocarbons in Ordovician limestones suggest a Permian age for the karstification. Potential applications of magnetostratigraphy to paleokarst deposits of many different scales are considerable.« less

Geology and geochemistry of the Mammoth breccia pipe, Copper Creek mining district, southeastern Arizona: Evidence for a magmatic-hydrothermal origin

USGS Publications Warehouse

Anderson, E.D.; Atkinson, William W.; Marsh, T.; Iriondo, A.

2009-01-01

The Copper Creek mining district, southeastern Arizona, contains more than 500 mineralized breccia pipes, buried porphyry-style, copper-bearing stockworks, and distal lead-silver veins. The breccia pipes are hosted by the Copper Creek Granodiorite and the Glory Hole volcanic rocks. The unexposed Mammoth breccia pipe, solely recognized by drilling, has a vertical extent of 800 m and a maximum width of 180 m. The pipe consists of angular clasts of granodiorite cemented by quartz, chalcopyrite, bornite, anhydrite, and calcite. Biotite 40Ar/ 39Ar dates suggest a minimum age of 61.5??0.7 Ma for the host Copper Creek Granodiorite and 40Ar/39Ar dates on hydrothermal sericite indicate an age of 61.0??0.5 Ma for copper mineralization. Fluid inclusion studies suggest that a supercritical fluid with a salinity of approximately 10 wt.% NaCl equiv. condensed to a dilute aqueous vapor (1-2.8 wt.% NaCl equiv.) and a hypersaline brine (33.4-35.1 wt.% NaCl equiv.). Minimum trapping temperatures are 375??C and trapping depths are estimated at 2 km. Sulfur isotope fractionation of cogenetic anhydrite and chalcopyrite yields a temperature of mineralization of 469??25??C. Calculated oxygen and hydrogen isotope values for fluids in equilibrium with quartz and sericite range from 10.2??? to 13.4??? and -60??? to -39???, respectively, suggesting that the mineralizing fluid was dominantly magmatic. Evidence from the stable isotope and fluid inclusion analyses suggests that the fluids responsible for Cu mineralization within the Mammoth breccia pipe exsolved from a gray porphyry phase found at the base of the breccia pipe. ?? Springer-Verlag 2008.

Siderite deposits in northern Italy: Early Permian to Early Triassic hydrothermalism in the Southern Alps

NASA Astrophysics Data System (ADS)

Martin, Silvana; Toffolo, Luca; Moroni, Marilena; Montorfano, Carlo; Secco, Luciano; Agnini, Claudia; Nimis, Paolo; Tumiati, Simone

2017-07-01

We present a minero-petrographic, geochemical and geochronological study of siderite orebodies from different localities of the Southern Alps (northern Italy). Siderite occurs as veins cutting the Variscan basement and the overlying Lower Permian volcano-sedimentary cover (Collio Fm.), and as both veins and conformable stratabound orebodies in the Upper Permian (Verrucano Lombardo and Bellerophon Fms.) and Lower Triassic (Servino and Werfen Fms.) sedimentary sequences of the Lombardian and the Venetian Alps. All types of deposits show similar major- and rare-earth (REE)-element patterns, suggesting a common iron-mineralizing event. The compositions of coexisting siderite, Fe-rich dolomite and calcite suggest formation from hydrothermal fluids at relatively high temperature conditions (≥ 250 °C). Geochemical modelling, supported by REE analyses and by literature and new δ13C and δ18O isotopic data, suggests that fluids responsible for the formation of siderite in the Variscan basement and in the overlying Lower Permian cover were derived from dominant fresh water, which leached Fe and C from volcanic rocks (mainly rhyolites/rhyodacites) and organic carbon-bearing continental sediments. On the basis of U-Th-Pb microchemical dating of uraninite associated with siderite in the Val Vedello and Novazza deposits (Lombardian Alps), the onset of hydrothermalism is constrained to 275 ± 13 Ma (Early-Mid Permian), i.e., it was virtually contemporaneous to the plutonism and the volcanic-sedimentary cycle reported in the same area (Orobic Basin). The youngest iron-mineralizing event is represented by siderite veins and conformable orebodies hosted in Lower Triassic shallow-marine carbonatic successions. In this case, the siderite-forming fluids contained a seawater component, interacted with the underlying Permian successions and eventually replaced the marine carbonates at temperatures of ≥ 250 °C. The absence of siderite in younger rocks suggests an Early Triassic upper limit for the iron pulse in the Southern Alps, which would thus predate the Middle Triassic magmatism. Based on the overlap between hydrothermalism, extensional tectonics and, in part, magmatism, the genesis of siderite in the Southern Alps may be related to plutonic activity and/or magmatic underplating occurring since the Permian in a geodynamic scenario preluding the opening of the Neo-Tethys.

Meteoric calcite cementation: diagenetic response to relative fall in sea-level and effect on porosity and permeability, Las Negras area, southeastern Spain

NASA Astrophysics Data System (ADS)

Li, Zhaoqi; Goldstein, Robert H.; Franseen, Evan K.

2017-03-01

A dolomitized Upper Miocene carbonate system in southeast Spain contains extensive upper and lower zones of calcite cementation that cut across the stratigraphy. Cement textures including isopachous and circumgranular, which are consistent with phreatic-zone cementation. Cements in the upper cemented zone are non-luminescent, whereas those in the lower cemented zone exhibit multiple bands of luminescent and non-luminescent cements. In the upper cemented zone, isotopic data show two meteoric calcite lines (MCL) with mean δ18O at - 5.1‰ and - 5.8‰ VPDB, whereas no clear MCL is defined in the lower cemented zone where mean δ18O for calcite cement is at - 6.7‰ VPDB. δ13C values in both cement zones are predominantly negative, ranging from - 10 to + 2‰ VPDB, suggestive of carbon from soil gas or decayed organics. Measurements of Tm ice in primary fluid inclusions yield a mode of 0.0 °C in both zones, indicating calcite cementation from fresh water. These two zones define the positions of two different paleo-water tables that formed during a relative sea-level fall and erosional downcutting during the Plio-Pleistocene. The upper cemented zone pre-dated the lower cemented zone on the basis of known relative sea-level history. Meteoric calcite cementation reduced porosity and permeability, but measured values are inconsistent with simple filling of open pore space. Each texture, boundstone, grainstone, packstone, wackestone, produces a different relationship between percent calcite cement and porosity/permeability. Distribution of cements may be predictable on the basis of known sea-level history, and the effect of the cementation can be incorporated into subsurface geomodels by defining surfaces of rock boundaries that separate cemented zones from uncemented zones, and applying texture-specific relationships among cementation, porosity and permeability.

Application of U/Th and 40Ar/39Ar Dating to Orgnac 3, a Late Acheulean and Early Middle Palaeolithic Site in Ardèche, France

PubMed Central

Michel, Véronique; Shen, Guanjun; Shen, Chuan-Chou; Wu, Chung-Che; Vérati, Chrystèle; Gallet, Sylvain; Moncel, Marie-Hélène; Combier, Jean; Khatib, Samir; Manetti, Michel

2013-01-01

Refined radio-isotopic dating techniques have been applied to Orgnac 3, a Late Acheulean and Early Middle Palaeolithic site in France. Evidence of Levallois core technology appeared in level 4b in the middle of the sequence, became predominant in the upper horizons, and was best represented in uppermost level 1, making the site one of the oldest examples of Levallois technology. In our dating study, fourteen speleothem samples from levels 7, 6 and 5b, were U/Th-dated. Four pure calcite samples from the speleothem PL1 (levels 5b, 6) yield ages between 265 ± 4 (PL1-3) and 312 ± 15 (PL1-6) thousand years ago (ka). Three samples from the top of a second stalagmite, PL2, yield dates ranging from 288 ± 10 ka (PL2-1) to 298 ± 17 ka (PL2-3). Three samples from the base of PL2 (level 7) yield much younger U/Th dates between 267 and 283 ka. These dates show that the speleothems PL1 and PL2 are contemporaneous and formed during marine isotope stage (MIS) 9 and MIS 8. Volcanic minerals in level 2, the upper sequence, were dated by the 40Ar/39Ar method, giving a weighted mean of 302.9 ± 2.5 ka (2σ) and an inverse isochron age of 302.9 ± 5.9 ka (2σ). Both 40Ar/39Ar dating of volcanic sanidines and U/Th dating of relatively pure and dense cave calcites are known to be well established. The first parallel application of the two geochronometers to Orgnac 3 yields generally consistent results, which point to the reliability of the two methods. The difference between their age results is discussed. PMID:24349273

Application of U/Th and 40Ar/39Ar dating to Orgnac 3, a Late Acheulean and Early Middle Palaeolithic site in Ardèche, France.

PubMed

Michel, Véronique; Shen, Guanjun; Shen, Chuan-Chou; Wu, Chung-Che; Vérati, Chrystèle; Gallet, Sylvain; Moncel, Marie-Hélène; Combier, Jean; Khatib, Samir; Manetti, Michel

2013-01-01

Refined radio-isotopic dating techniques have been applied to Orgnac 3, a Late Acheulean and Early Middle Palaeolithic site in France. Evidence of Levallois core technology appeared in level 4b in the middle of the sequence, became predominant in the upper horizons, and was best represented in uppermost level 1, making the site one of the oldest examples of Levallois technology. In our dating study, fourteen speleothem samples from levels 7, 6 and 5b, were U/Th-dated. Four pure calcite samples from the speleothem PL1 (levels 5b, 6) yield ages between 265 ± 4 (PL1-3) and 312 ± 15 (PL1-6) thousand years ago (ka). Three samples from the top of a second stalagmite, PL2, yield dates ranging from 288 ± 10 ka (PL2-1) to 298 ± 17 ka (PL2-3). Three samples from the base of PL2 (level 7) yield much younger U/Th dates between 267 and 283 ka. These dates show that the speleothems PL1 and PL2 are contemporaneous and formed during marine isotope stage (MIS) 9 and MIS 8. Volcanic minerals in level 2, the upper sequence, were dated by the (40)Ar/(39)Ar method, giving a weighted mean of 302.9 ± 2.5 ka (2σ) and an inverse isochron age of 302.9 ± 5.9 ka (2σ). Both (40)Ar/(39)Ar dating of volcanic sanidines and U/Th dating of relatively pure and dense cave calcites are known to be well established. The first parallel application of the two geochronometers to Orgnac 3 yields generally consistent results, which point to the reliability of the two methods. The difference between their age results is discussed.

Sedimentological and geochimical features of chaotic deposits in the Ventimiglia Flysch (Roya-Argentina valley- NW Italy)

NASA Astrophysics Data System (ADS)

Perotti, Elena; Bertok, Carlo; D'Atri, Anna; Martire, Luca; Musso, Alessia; Piana, Fabrizio; Varrone, Dario

2010-05-01

The Ventimiglia Flysch is a Upper Eocene turbidite succession deposited in the SE part of the Eocene Alpine foreland basin, truncated at the top by the basal thrust of the Helminthoides Flysch, a Ligurian tectonic unit that presently covers part of the Dauphinois and Briançonnais successions of Western Ligurian Alps. The Ventimiglia Flysch is made of alternations of sandstones and shales. The upper part is characterized by chaotic deposits. The chaotic deposits are constituted by: - km to hm-sized intrabasinal blocks (Ventimiglia Flysch) and extrabasinal blocks (Cretaceous sediments of Dauphinois Domain, Nummulite Limestone of the Alpine foreland basin and Helminthoides Flysch ); - conglomerates with block-in-matrix fabric interpreted as debris flow deposits. They occur as m-thick beds interbedded with the normal turbidite succession or locally as matrix of the larger blocks. Debris flow clasts show: - different sizes, ranging from metre to centimetre; - different shapes, from rounded to subangular; - different lithologies, such as fine-grained quartz-arenites, marls, dark shales and fine-grained calcisiltites. They may be referred to both coeval, intrabasinal lithologies (Ventimiglia Flysch), and extrabasinal formations (Nummulite Limestone, Globigerina Marl and Helminthoides Flysch). The clasts are disposed randomly into a chaotic matrix that consists of a dark mudstone in which submillimetre- to millimetre-sized lithic grains, with the same compositions of larger clasts, are present. Locally matrix consists of sandstones with quartz and feldspar grains and fragments of nummulitids that suggest reworking of unlithified Eocene sediments. Cathodoluminescence observations allow the distinction of two kinds of clasts: dull clasts that underwent a cementation before the formation of conglomerates, and clasts with the same orange luminescence as the matrix that may be interpreted as soft mud clasts that were cemented together with the matrix. Debris flow deposits are cross-cut by a network of crumpled and broken veins, 10's mm to cm-large, filled with orange luminescing calcite and locally with quartz. Their complex cross-cutting relationships with clasts and matrix show that several systems of veins are present, that may be referred to different fracturing events. Some clasts are crossed or bordered by veins that end at the edge of the clasts. These veins show the same features as those that crosscut the whole rock. This indicates reworking of plastic sediments crossed by calcite-filled veins by mass gravity flows. Polyphase debris flow processes, proceeding along with fluid expulsion and veining, are thus documented. Ellipsoidal, dm-large concretions of cemented pelites also occur. They represent a previous phase of concretionary growth within homogenous pelites subsequently involved in the mass gravity flow. Stable O and C isotope analyses, performed on matrix, clasts, concretions and veins, show: - δ13C close to normal marine values (-3 to 0 δ13C ‰ PDB) - δ18O markedly negative (-9 to -7 δ18O ‰ PDB) that could be related to precipitation from relatively hot waters (60-70 ° C). The block-in-matrix fabric and the variable composition and size of blocks show that these sediments are a sedimentary mélange related to mass wasting processes involving both extrabasinal and intrabasinal sediments. These gravitational movements took place along slopes of submarine tectonic ridges created by transpressional faults (Piana et al., 2009) that juxtaposed tectonic slices of different paleogeographic domains (Dauphinois, Briançonnais, Ligurian Units) in Late Eocene times, and involved both rock fall processes of huge blocks of lithified, older formations, and debris flows of unlithified intrabasinal sediment. Faults also acted as conduits for an upward flow of hot fluids supersaturated in calcium carbonate. These fluids crossed unlithified sediments close to the sea floor resulting in localized concretionary cementation and formation of vein swarms within unlithified sediments prone to subsequent mass wasting.

Origin of ultramafic-hosted magnesite on Margarita Island, Venezuela

NASA Astrophysics Data System (ADS)

Abu-Jaber, N. S.; Kimberley, M. M.

1992-06-01

Ultramafic-hosted deposits of magnesite (MgCO3) have been studied on Margarita Island, Venezuela, to elucidate the source of carbon and conditions of formation for this type of ore. Petrographic, mineralogic, and δ18O data indicate that magnesite precipitated on Margarita in near-surface environments at low P and T. δ13C ranges from -9 to -16‰ PDB within the magnesite and -8 to -10‰ PDB within some calcite and dolomite elsewhere on the island. The isotopically light dolomite fills karst and the calcite occurs as stock-work veins which resemble the magnesite deposits. These carbon isotopic ratios are consistent with a deep-seated source rather than an overlying source from a zone of surficial weathering. However, there is not much enrichment of precious metals and no enrichment of heavy rare-earth elements, as would be expected if the carbon had migrated upward as aqueous carbonate ions. The carbon probably has risen as a gaseous mixture of CO2 and CH4 which partially dissolved in near-surface water before leaching cations and precipitating as magnesite and other carbonates. The process probably is ongoing, given regional exhalation of carbonaceous gases.

Zeolites in the Miocene Briones Sandstone and related formations of the central Coast Ranges, California

USGS Publications Warehouse

Murata, K.J.; Whiteley, Karen R.

1973-01-01

Authigenic zeolites present in the generally tuffaceous Miocene Briones Sandstone and related formations of the central Coast Ranges of California indicate three stages of diagenetic history: (1) Initial alteration of pyroclastic materials to clinoptilolite (and montmorillonite) that is widely distributed in small amounts throughout the region. (2) Subsequent crystallization of heulandite followed by stilbite in fractures at a few places. (3) Widespread development of laumontite in only the southern part of the region, where the sandstone appears to have been downfolded and faulted to greater depths than elsewhere. Laumontite occurs both as pervasive cement of sandstone and as filling of fractures, and was produced through the reaction of interstitial solutions with other zeolites and with such major constituents of the sandstone as plagioclase, montmorillonite, and calcite at temperatures of 100° C or higher. Mordenite was found at only one locality, closely associated with clinoptilolite and opal. Analcite occurs in diverse settings, and its relation to the other zeolites is obscure.  Sparry calcite and coexisting stilbite, laumontite, or analcite in veins seem to make up nonequilibrium assemblages.

Probing the prodigious strain fringes from Lourdes

NASA Astrophysics Data System (ADS)

Aerden, Domingo G. A. M.; Sayab, Mohammad

2017-12-01

We investigate the kinematics of classic sigmoidal strain fringes from Lourdes (France) and review previous genetic models, strain methods and strain rates for these microstructures. Displacement controlled quartz and calcite fibers within the fringes yield an average strain of 195% with the technique of Ramsay and Huber (1983). This agrees well with strains measured from boudinaged pyrite layers and calcite veins in the same rocks, but conflicts with ca. ∼675% strain in previous analogue models for the studied strain fringes produced by progressive simple shear. We show that the detailed geometry and orientation of fiber patterns are insufficiently explained by simple shear but imply two successive, differently oriented strain fields. Although all strain fringes have the same overall asymmetry, considerable morphological variation resulted from different amounts of rotation of pyrite grains and fringes. Minor rotation led to sharply kinked fibers that record a ca. 70° rotation of the kinematic frame. Larger (up to 145°) rotations, accommodated by antithetic sliding on pyrite-fringe contacts, produced more strongly and smoothly curved fibers. Combined with published Rb-Sr ages for the studied microstructures, our new strain data indicate an average strain rate of 1.41 10-15 s-1 during ca. 37 Myr. continuous growth.

NWA 2736: An Unusual New Graphite-bearing Aubrite

NASA Technical Reports Server (NTRS)

Lowe, J. J.; Hill, D. H.; Domanik, K. J.; Lauretta, D. S.; Drake, M. J.; Killgore, M.

2005-01-01

Aubrites are enstatite-rich achondrites that are probably related to enstatite chondrite parent bodies. The exact link, if any, is not understood. They may have formed from melting within one or more enstatite chondrite parent bodies. Description of NWA 2736: One complete stone weighing 171.51 grams was recovered from the Sahara Desert by nomads sometime before September 2004. It was completely covered with fusion crust and desert varnish. This stone is severely weathered, with caramel brown coloration throughout and calcite veins that extend into the interior of the sample. Mineral analyses were performed and elemental x-ray maps were obtained with a CAMECA SX-50 electron microprobe at the Lunar and Planetary Laboratory at the University of Arizona. The relatively high modal abundance of albitic plagioclase, presence of euhedral graphite, depletion of troilite, and occurrence of pervasive kamacite veins (some with daubreelite) all indicate that NWA 2736 has a complex history and may sample a new region of the aubrite parent body. A discussion and analysis on the overall texture of NWA 2736 is presented.

Hydrothermal alteration and Cu–Ni–PGE mobilization in the charnockitic rocks of the footwall of the South Kawishiwi intrusion, Duluth Complex, USA

PubMed Central

Benkó, Zsolt; Mogessie, Aberra; Molnár, Ferenc; Krenn, Kurt; Poulson, Simon R.; Hauck, Steven; Severson, Mark; Arehart, Greg B.

2015-01-01

In the Neoarchean (~ 2.7 Ga) contact metamorphosed charnockitic footwall of the Mesoproterosoic (1.1 Ga) South Kawishiwi intrusion of the Duluth Complex, the primary metamorphic mineral assemblage and Cu–Ni–PGE sulfide mineralization is overprinted by an actinolite + chlorite + cummingtonite + prehnite + pumpellyite + quartz + calcite hydrothermal mineral assemblage along 2–3 cm thick veins. In calcite, hosted by the hydrothermal alteration zones and in a single recrystallized quartz porphyroblast, four different fluid inclusion assemblages are documented; the composition of these fluid inclusions provide p–T conditions of the fluid flow, and helps to define the origin of the fluids and evaluate their role in the remobilization and reprecipitation of the primary metamorphic sulfide assemblage. Pure CO2 fluid inclusions were found as early inclusions in recrystallized quartz porphyroblast. These inclusions may have been trapped during the recrystallization of the quartz during the contact metamorphism of the footwall charnockite in the footwall of the SKI. The estimated trapping pressure (1.6–2.0 kbar) and temperature (810–920 °C) conditions correspond to estimates based on felsic veins in the basal zones of the South Kawishiwi intrusion. Fluid inclusion assemblages with CO2–H2O–NaCl and CH4–N2–H2O–NaCl compositions found in this study along healed microfractures in the recrystallized quartz porphyroblast establish the heterogeneous state of the fluids during entrapment. The estimated trapping pressure and temperature conditions (240–650 bar and 120–150 °C for CO2–H2O–NaCl inclusions and 315–360 bar and 145–165 °C for CH4–N2–H2O–NaCl inclusions) are significantly lower than the p–T conditions (> 700 °C and 1.6–2 kbar) during the contact metamorphism, indicating that this fluid flow might not be related to the cooling of the Duluth Complex and its contact aureole. The presence of chalcopyrite inclusions in these fluid inclusions and in the trails of these fluid inclusion assemblages confirms that at least on local scale these fluids played a role in base metal remobilization. No evidences have been observed for PGE remobilization and transport in the samples. The source of the carbonic phase in the carbonic assemblages (CO2; CH4) could be the graphite, present in the metasedimentary hornfelsed inclusions in the basal zones of the South Kawishiwi intrusion. The hydrothermal veins in the charnockite can be characterized by an actinolite + cummingtonite + chlorite + prehnite + pumpellyite + calcite (I–II) + quartz mineral assemblage. Chlorite thermometry yields temperatures around 276–308 °C during the earliest phase of the fluid flow. In the late calcite (II) phase, high salinity (21.6–28.8 NaCl + CaCl2 equiv. wt.%), low temperature (90–160 °C), primary aqueous inclusions were found. Chalcopyrite (± sphalerite ± millerite), replacing and intersecting the early hydrothermal phases, are associated to the late calcite (II) phase. The composition of the formational fluids in the Canadian Shield is comparable with the composition of the studied fluid inclusions. This suggests that the composition of the fluids did not change in the past 2 Ga and base metal remobilization by formational fluids could have taken place any time after the formation of the South Kawishiwi intrusion. Sulfur isotope studies carried out on the primary metamorphic (δ34S = 7.4–8.9‰) and the hydrothermal sulfide mineral assemblage (δ34S = 5.5–5.7‰) proves, that during the hydrothermal fluid flow the primary metamorphic ores were remobilized. PMID:26594080

3D characterization of crack propagation in building stones

NASA Astrophysics Data System (ADS)

Fusi, N.; Martinez-Martinez, J.; Crosta, G. B.

2012-04-01

Opening of fractures can strongly modify mechanical characteristics of natural stones and thus significantly decrease stability of historical and modern buildings. It is commonly thought that fractures origin from pre-existing structures of the rocks, such as pores, veins, stylolythes (Meng and Pan, 2007; Yang et al., 2008). The aim of this study is to define relationships between crack formation and textural characteristics in massive carbonate lithologies and to follow the evolution of fractures with loading. Four well known Spanish building limestones and dolostones have been analysed: Amarillo Triana (AT): a yellow dolomitic marble, with fissures filled up by calcite and Fe oxides or hydroxides; Blanco Tranco (BT): a homogeneous white calcitic marble with pore clusters orientated parallel to metamorphic foliation; Crema Valencia (CV): a pinkish limestone (mudstone), characterized by abundant stilolythes, filled mainly by quartz (80%) and kaolin (11%); Rojo Cehegin (RC): a red fossiliferous limestone (packstone) with white veins, made up exclusively by calcite in crystals up to 300 micron. All lithotypes are characterized by homogeneous mineralogical composition (calcitic or dolomitic) and low porosity (<10%). Three cores 20 mm in diameter have been obtained for each lithotype. Uniaxial compressive tests have been carried out in order to induce sample fracturing by a series of successive steps with application of a progressive normal stress. Crack propagation has been checked after each stress level application by microCT-RX following Hg impregnation of the sample (in a Hg porosimeter). Combination of both tests (microCT-RX and Hg porosimeter) guarantees a better characterization of small defects and their progressive propagation inside low-porous rocks than by employing solely microCT-RX (Fusi et al., 2009). Due to the reduced dimensions of sample holder (dilatometers) in porosimeter, cores have been cut with a non standard h/d = 1.5. Several cycles of: a) Hg impregnation with mercury porosimeter, b) scanning with microCT system, c) uniaxial compression, have been performed on each core. Cores have been firstly impregnated with mercury in Thermo Fisher Scientific Pascal porosimeters 140 and 240, in order to fill up the pores and obtain a good density contrast between rock matrix (2.71 g/cm3 for calcite and 2.86 g/cm3 for dolomite) and voids filled by mercury (13.6 g/cm3). Microporosity coincides with structural features of the rock, such as stylolythes (CV), fissures (AT), clusters of pores (BT) and/or veins (RC). At the end of each cycle of impregnation-scanning-loading, the cores have been impregnated again in both porosimeters 140 and 240 in order to fill up the new micro cracks and fractures. Uniaxial compression has been performed with a GDS Vis (Virtual Infinite Stiffness) loading apparatus, in axial displacement control. For each core four to six loading steps have been performed on the basis of the maximum loading obtained in previous uniaxial tests on standard cores of the same lithologies. Once the maximum load of each step has been achieved, the specimen has been unloaded at the same velocity. A BIR Actis 130/150 industrial micro CT was used for imaging the interior of the samples (100keV/80mA). The dimensions of the voxel, corresponding to the resolution of the images, are 0.024x0.024x0.027 mm. Core position has been accurately checked in order to maintain the same orientation and numbering of CT slices throughout the cores after different loading cycles. The main results of this study, clearly imaged by microCT scanning, can be summed up as follows: - in all the lithotypes (AT, BT, CV and RC) fracture patterns are unrelated to major textural characters of the rock (fig. 1). - In all the cases, first phases of fracture opening can be seen in CT images but there is not a corresponding load drop in the stress-strain curve. - For all the samples, fractures begin to open at about 50% or less of the maximum load.

Petrology, geochemistry and zirconology of impure calcite marbles from the Precambrian metamorphic basement at the southeastern margin of the North China Craton

NASA Astrophysics Data System (ADS)

Liu, Yi-Can; Zhang, Pin-Gang; Wang, Cheng-Cheng; Groppo, Chiara; Rolfo, Franco; Yang, Yang; Li, Yuan; Deng, Liang-Peng; Song, Biao

2017-10-01

Impure calcite marbles from the Precambrian metamorphic basement of the Wuhe Complex, southeastern margin of the North China Craton, provide an exceptional opportunity to understand the depositional processes during the Late Archean and the subsequent Palaeoproterozoic metamorphic evolution of one of the oldest cratons in the world. The studied marbles are characterized by the assemblage calcite + clinopyroxene + plagioclase + K-feldspar + quartz + rutile ± biotite ± white mica. Based on petrography and geochemistry, the marbles can be broadly divided into two main types. The first type (type 1) is rich in REE with a negative Eu anomaly, whereas the second type (type 2) is relatively poor in REE with a positive Eu anomaly. Notably, all marbles exhibit remarkably uniform REE patterns with moderate LREE/HREE fractionation, suggesting a close genetic relationship. Cathodoluminescence imaging, trace elements and mineral inclusions reveal that most zircons from two dated samples display distinct core-rim structures. Zircon cores show typical igneous features with oscillatory growth zoning and high Th/U ratios (mostly in the range 0.3-0.7) and give ages of 2.53 - 2.48 Ga, thus dating the maximum age of deposition of the protolith. Zircon rims overgrew during granulite-facies metamorphism, as evidenced by calcite + clinopyroxene + rutile + plagioclase + quartz inclusions, by Ti-in-zircon temperatures in the range 660-743 °C and by the low Th/U (mostly < 0.1) and Lu/Hf (< 0.001) ratios. Zircon rims from two dated samples yield ages of 1839 ± 7 Ma and 1848 ± 23 Ma, respectively, suggesting a Palaeoproterozoic age for the granulite-facies metamorphic event. These ages are consistent with those found in other Precambrian basement rocks and lower-crustal xenoliths in the region, and are critical for the understanding of the tectonic history of the Wuhe Complex. Positive Eu anomalies and high Sr and Ba contents in type 2 marbles are ascribed to syn-depositional felsic hydrothermal activity which occurred at 2.53 - 2.48 Ga. Our results, together with other published data and the inferred tectonic setting, suggest that the marbles' protolith is an impure limestone, rich in detrital silicates of igneous origin, deposited in a back-arc basin within an active continental margin during the late Archean and affected by synchronous high-T hydrothermalism at the southeastern margin of the North China Craton.

Risk factors for deep vein thrombosis and pulmonary embolism during pregnancy or post partum: a population-based, case-control study.

PubMed

Danilenko-Dixon, D R; Heit, J A; Silverstein, M D; Yawn, B P; Petterson, T M; Lohse, C M; Melton, L J

2001-01-01

We sought to determine risk factors for deep vein thrombosis and pulmonary embolism during pregnancy or post partum. We performed a population-based case-control study. All Olmsted County, Minnesota, residents with a first lifetime deep vein thrombosis or pulmonary embolism during pregnancy or post partum from 1966 to 1990 were identified (N = 90). Where possible, a resident without deep vein thrombosis or pulmonary embolism was matched to each patient by date of the first live birth after the patient's child. The medical records of all remaining patients and all control subjects were reviewed for >25 baseline characteristics, which were tested as risk factors for deep vein thrombosis or pulmonary embolism. In multivariate analysis smoking (odds ratio, 2.4) and prior superficial vein thrombosis (odds ratio, 9.4) were independent risk factors for deep vein thrombosis or pulmonary thrombosis during pregnancy or post partum. Venous thromboembolism prophylaxis may be warranted for pregnant women with prior superficial vein thrombosis. Smoking cessation should be recommended, especially during pregnancy and the postpartum period.

The Nolans Bore rare-earth element-phosphorus-uranium mineral system: geology, origin and post-depositional modifications

NASA Astrophysics Data System (ADS)

Huston, David L.; Maas, Roland; Cross, Andrew; Hussey, Kelvin J.; Mernagh, Terrence P.; Fraser, Geoff; Champion, David C.

2016-08-01

Nolans Bore is a rare-earth element (REE)-U-P fluorapatite vein deposit hosted mostly by the ~1805 Ma Boothby Orthogneiss in the Aileron Province, Northern Territory, Australia. The fluorapatite veins are complex, with two stages: (1) massive to granular fluorapatite with inclusions of REE silicates, phosphates and (fluoro)carbonates, and (2) calcite-allanite with accessory REE-bearing phosphate and (fluoro)carbonate minerals that vein and brecciate the earlier stage. The veins are locally accompanied by narrow skarn-like (garnet-diopside-amphibole) wall rock alteration zones. SHRIMP Th-Pb analyses of allanite yielded an age of 1525 ± 18 Ma, interpreted as the minimum age of mineralisation. The maximum age is provided by a ~1550 Ma SHRIMP U-Pb age for a pegmatite that predates the fluorapatite veins. Other isotopic systems yielded ages from ~1443 to ~345 Ma, implying significant post-depositional isotopic disturbance. Calculation of initial ɛNd and 87Sr/86Sr at 1525 Ma and stable isotope data are consistent with an enriched mantle or lower crust source, although post-depositional disturbance is likely. Processes leading to formation of Nolans Bore began with north-dipping subduction along the south margin of the Aileron Province at 1820-1750 Ma, producing a metasomatised, volatile-rich, lithospheric mantle wedge. About 200 million years later, near the end of the Chewings Orogeny, this reservoir and/or the lower crust sourced alkaline low-degree partial melts which passed into the mid- and upper-crust. Fluids derived from these melts, which may have included phosphatic melts, eventually deposited the Nolans Bore fluorapatite veins due to fluid-rock interaction, cooling, depressurisation and/or fluid mixing. Owing to its size and high concentration of Th (2500 ppm), in situ radiogenic heating caused significant recrystallisation and isotopic resetting. The system finally cooled below 300 °C at ~370 Ma, possibly in response to unroofing during the Alice Springs Orogeny. Surface exposure and weathering of fluorapatite produced acidic fluids and intense, near-surface kaolinitised zones that include high-grade, supergene-enriched cheralite-rich ores.

Microstructural record of cataclastic and dissolution-precipitation processes from shallow crustal carbonate strike-slip faults, Northern Calcareous Alps (Austria)

NASA Astrophysics Data System (ADS)

Bauer, Helene; Grasemann, Bernhard; Decker, Kurt

2015-04-01

The concept of coseismic slip and aseismic creep deformation along faults is supported by the variability of natural fault rocks and their microstructures. Faults in carbonate rocks are characterized by very narrow principal slip zones (cm to mm wide) containing (ultra)cataclastic fault rocks that accommodate most of the fault displacement. Fluidization of ultracataclastic sub layers and thermal decomposition of calcite due to frictional heating have been proposed as possible indicators for seismic slip. Dissolution-precipitation (DP) processes are possible mechanism of aseismic sliding, resulting in spaced cleavage solution planes and associated veins, indicating diffusive mass transfer and precipitation in pervasive vein networks. We investigated exhumed, sinistral strike-slip faults in carbonates of the Northern Calcareous Alps. The study presents microstructural investigations of natural carbonate fault rocks that formed by cataclastic and dissolution-precipitation related deformation processes. Faults belong to the eastern segment of the Salzachtal-Ennstal-Mariazell-Puchberg (SEMP) fault system that was formed during eastward lateral extrusion of the Eastern Alps in Oligocene to Lower Miocene. The investigated faults accommodated sinistral slip between several tens and few hundreds of meters. Microstructural analysis of fault rocks was done with scanning electron microscopy and optical microscopy. Deformation experiments of natural fault rocks are planned to be conducted at the Sapienza University of Roma and should be available at the meeting. The investigated fault rocks give record of alternating cataclastic deformation and DP creep. DP fault rocks reveal various stages of evolution including early stylolites, pervasive pressure solution seams and cleavage, localized shear zones with syn-kinematic calcite fibre growth and mixed DP/cataclastic microstructures, involving pseudo sc- and scc'-fabrics. Pressure solution seams host fine grained kaolinit, chlorite and illite while the protolith shows only weak evidence of detrital clay content. Our studies suggest that velocity weakening and strengthening mechanisms alternated during the accumulation of displacement along the SEMP fault zone.

Study of the Nankai seismogenic fault using dynamic wave propagation modelling of digital rock from the Nobeoka Fault

NASA Astrophysics Data System (ADS)

Eng, Chandoeun; Ikeda, Tatsunori; Tsuji, Takeshi

2018-10-01

To understand the characteristics of the Nankai seismogenic fault in the plate convergent margin, we calculated the P- and S-wave velocities (VP and VS) of digital rock models constructed from core samples of an ancient plate boundary fault at Nobeoka, Kyushu Island, Japan. We first constructed 3D digital rock models from microcomputed tomography images and identified their heterogeneous textures such as cracks and veins. We replaced the cracks and veins with air, water, quartz, calcite and other materials with different bulk and shear moduli. Using the Rotated Staggered Grid Finite-Difference Method, we performed dynamic wave propagation simulations and quantified the effective VP, VS and the ratio of VP to VS (VP/VS) of the 3D digital rock models with different crack-filling minerals. Our results demonstrate that the water-saturated cracks considerably decreased the seismic velocity and increased VP/VS. The VP/VS of the quartz-filled rock model was lower than that in the water-saturated case and in the calcite-filled rock model. By comparing the elastic properties derived from the digital rock models with the seismic velocities (e.g. VP and VP/VS) around the seismogenic fault estimated from field seismic data, we characterised the evolution process of the deep seismogenic fault. The high VP/VS and low VP observed at the transition from aseismic to coseismic regimes in the Nankai Trough can be explained by open cracks (or fractures), while the low VP/VS and high VP observed at the deeper coseismic fault zone suggests quartz-filled cracks. The quartz-rich fault zone characterised as low VP/VS and high VP in this study could partially relate to the coseismic behaviour as suggested by previous studies, because quartz exhibits slip-weakening behaviour (i.e. unstable coseismic slip).

Fluid inclusions in the Stripa granite and their possible influence on the groundwater chemistry

USGS Publications Warehouse

Nordstrom, D. Kirk; Lindblom, S.; Donahoe, R.J.; Barton, C.C.

1989-01-01

Fluid inclusions in quartz and calcite of the Proterozoic Stripa granite, central Sweden, demonstrate that the rock and its fracture fillings have a complex evolutionary history. The majority of inclusions indicate formation during a hydrothermal stage following emplacement of the Stripa pluton. Total salinities of quartz inclusions range from 0-18 eq.wt% NaCl for unfractured rock and from 0-10 eq.wt% for fractured rock. Vein calcites contain up to 25 eq.wt% NaCl but the inclusion size is larger and the population density is lower. Homogenization temperatures are 100-150??C for unfractured rock and 100-250?? for fractured rock. Pressure corrections, assuming immediate post-emplacement conditions of 2 kbar, give temperatures about 160??C higher. Measurements of fluid-inclusion population-densities in quartz range from about 108 inclusions/cm3 in grain quartz to 109 inclusions/cm3 in vein quartz. Residual porosity from inclusion densities has been estimated to be at least 1% which is two orders of magnitude greater than the flow porosity. Breakage and leaching of fluid inclusions is proposed as an hypothesis for the origin of major solutes (Na-Ca-Cl) in the groundwater. Evidence for the hypothesis is based on (1) mass balance-only a small fraction of the inclusions need to leak to account for salt concentrations in the groundwater, (2) chemical signatures- Br Cl ratios of fluid inclusion leachates (0.0101) match those ratios for the deep groundwaters (0.0107), (3) leakage mechanisms-micro-stresses from isostatic rebound or mining activities acting on irregular-shaped inclusions could cause breakage and provide connection with the flow porosity, and (4) experimental studies-water forced through low permeability granites leach significant quantities of salt. This hypothesis is consistent with the available data although alternate hypotheses cannot be excluded. ?? 1989.

Constraining the Thermal History of the Midcontinent Rift System with Clumped Isotopes and Organic Thermal Maturity Indices

NASA Astrophysics Data System (ADS)

Gallagher, T. M.; Sheldon, N. D.; Mauk, J. L.; Gueneli, N.; Brocks, J. J.

2015-12-01

The Mesoproterozoic (~1.1 Ga) North American Midcontinent Rift System (MRS) has been of widespread interest to researchers studying its economic mineral deposits, continental rifting processes, and the evolution of early terrestrial life and environments. For their age, the MRS rocks are well preserved and have not been deeply buried, yet a thorough understanding of the regional thermal history is necessary to constrain the processes that emplaced the mineral deposits and how post-burial alteration may have affected various paleo-records. To understand the thermal history of the MRS better, this study presents carbonate clumped isotope (Δ47) temperatures from deposits on the north and south sides of the rift. Due to the age of these deposits and known post-depositional processes, uncertainties exist about whether the clumped isotope signature has been reset. To test this, three generations of calcite were analyzed from the Nonesuch Fm. from the White Pine mine in Michigan including: sedimentary limestone beds, early diagenetic carbonate nodules, and hydrothermal calcite veins associated with the emplacement of copper mineralization. Clumped isotope temperatures from the White Pine mine range from 84 to 131°C, with a hydrothermal vein producing the hottest temperature. The clumped isotope temperature range for samples throughout the rift expands to 41-134°C. The hottest temperatures are associated with areas of known copper mineralization, whereas the coolest temperatures are found on the northern arm of the rift in Minnesota, far from known basin-bounding faults. Our hottest temperatures are broadly consistent with preexisting maximum thermal temperature estimates based on clay mineralogy, fluid inclusions, and organic geochemistry data. Clumped isotope results will also be compared to new hydrocarbon maturity data from the Nonesuch Fm., which suggest that bitumen maturities consistently fall within the early oil window across Michigan and Wisconsin.

Paleoclimatic Inferences from a 120,000-Yr Calcite Record of Water-Table Fluctuation in Browns Room of Devils Hole, Nevada

USGS Publications Warehouse

Szabo, B. J.; Kolesar, Peter T.; Riggs, A.C.; Winograd, I.J.; Ludwig, K. R.

1994-01-01

The petrographic and morphologic differences between calcite precipitated below, at, or above the present water table and uranium-series dating were used to reconstruct a chronology of water-table fluctuation for the past 120,000 yr in Browns Room, a subterranean air-filled chamber of Devils Hole fissure adjacent to the discharge area of the large Ash Meadows groundwater flow system in southern Nevada. The water table was more than 5 m above present level between about 116,000 and 53,000 yr ago, fluctuated between about +5 and +9 m during the period between about 44,000 and 20,000 yr ago, and declined rapidly from +9 to its present level during the past 20,000 yr. Because the Ash Meadows groundwater basin is greater than 12,000 km2 in extent, these documented water-table fluctuations are likely to be of regional significance. Although different in detail, water-level fluctuation recorded by Browns Room calcites generally correlate with other Great Basin proxy palcoclimatic data.

Raman spectroscopic analysis of a belltower commemorative wall decoration

NASA Astrophysics Data System (ADS)

Fernandes, R. F.; de Oliveira, L. F. C.; Edwards, H. G. M.; Brooke, C. J.; Pepper, M.

2017-02-01

The Raman spectroscopic analysis of a rare wall decoration in a church belltower, depicting the initials of couples married there in circular roundels over some 230 years, since 1777, has been undertaken prior to their impending restoration. The spectral data indicate that the red pigment is exclusively haematite which has been applied to plaster which exhibits the signatures variously of calcite, gypsum, anhydrite, calcium phosphate and dolomitic limestone; evidence of amorphous carbon is attributed to the deposition of soot from candle illumination, which has been recorded in historical documentation. The presence of biosignatures attributed to carotenoids in several samples is evidence of biological colonisation and potential deterioration which requires special treatment in the restoration strategies. The blackened areas near the upper edges of the wall decoration indicate carbon deposition and organic contamination. The latest addition to the decoration accomplished in 2008 shows that haematite has been used over a calcite ground. In earlier dated specimens, the presence of limewash is evident, which has only been partially converted into calcite by aerial attack from carbon dioxide in moist conditions.

Pollen from accurately dated speleothems supports alpine glacier low-stands during the early Holocene

NASA Astrophysics Data System (ADS)

Festi, Daniela; Hoffmann, Dirk L.; Luetscher, Marc

2016-07-01

Deciphering pollen assemblages from alpine speleothems holds potential to provide unique information about past vegetation in rapidly changing environments. Here, we reconstruct subsurface aerosol transport at Milchbach cave (Switzerland, 1840 m asl) based on the pollen content of two Holocene stalagmites. We demonstrate that pollen is chiefly associated with bacterially mediated calcite fabrics, typical of a well-ventilated cave system. In contrast, pollen is absent from columnar calcite fabrics confirming that hydrological transport is not a significant process for the incorporation of pollen into speleothems at Milchbach cave. Our results support significant changes in the subsurface ventilation regime, which can be associated with the waxing and waning of Upper Grindelwald glacier. Pollen assemblages obtained from six carbonate sub-samples attest the presence of a mixed deciduous forest in the Grindelwald valley during the early and middle Holocene, in agreement with coeval regional pollen records. This study demonstrates that even small amounts of calcite (0.3-2.8 cm3) are capable of delivering pollen spectra representative of the original vegetation if sufficiently elevated deposition fluxes are provided.

Inversion of calcite twin data for paleostress orientations and magnitudes: A new technique tested and calibrated on numerically-generated and natural data

NASA Astrophysics Data System (ADS)

Parlangeau, Camille; Lacombe, Olivier; Schueller, Sylvie; Daniel, Jean-Marc

2018-01-01

The inversion of calcite twin data is a powerful tool to reconstruct paleostresses sustained by carbonate rocks during their geological history. Following Etchecopar's (1984) pioneering work, this study presents a new technique for the inversion of calcite twin data that reconstructs the 5 parameters of the deviatoric stress tensors from both monophase and polyphase twin datasets. The uncertainties in the parameters of the stress tensors reconstructed by this new technique are evaluated on numerically-generated datasets. The technique not only reliably defines the 5 parameters of the deviatoric stress tensor, but also reliably separates very close superimposed stress tensors (30° of difference in maximum principal stress orientation or switch between σ3 and σ2 axes). The technique is further shown to be robust to sampling bias and to slight variability in the critical resolved shear stress. Due to our still incomplete knowledge of the evolution of the critical resolved shear stress with grain size, our results show that it is recommended to analyze twin data subsets of homogeneous grain size to minimize possible errors, mainly those concerning differential stress values. The methodological uncertainty in principal stress orientations is about ± 10°; it is about ± 0.1 for the stress ratio. For differential stresses, the uncertainty is lower than ± 30%. Applying the technique to vein samples within Mesozoic limestones from the Monte Nero anticline (northern Apennines, Italy) demonstrates its ability to reliably detect and separate tectonically significant paleostress orientations and magnitudes from naturally deformed polyphase samples, hence to fingerprint the regional paleostresses of interest in tectonic studies.

The effect of water on recrystallization behavior and grain boundary morphology in calcite observations of natural marble mylonites

NASA Astrophysics Data System (ADS)

Schenk, Oliver; Urai, Janos L.; Evans, Brian

2005-10-01

Fluids are inferred to play a major role in the deformation and recrystallization of many minerals (e.g. quartz, olivine, halite, feldspar). In this study, we sought to identify the effect of fluids on grain boundary morphology and recrystallization processes in marble mylonites during shear zone evolution. We compared the chemistry, microstructure and mesostructure of calcite marble mylonites from the Schneeberg Complex, Southern Tyrole, Italy, to that from the Naxos Metamorphic Core Complex, Greece. These two areas were selected for comparison because they have similar lithology and resemble each other in chemical composition. In addition, calcite-dolomite geothermometry indicates similar temperatures for shear zone formation: 279±25 °C (Schneeberg Complex) and 271±15 °C (Naxos high-grade core). However, the two settings are different in the nature of the fluids present during the shear zone evolution. In the Schneeberg mylonites, both the alteration of minerals during retrograde metamorphism in the neighboring micaschists and the existence of veins suggest that aqueous fluids were present during mylonitization. The absence of these features in the Naxos samples indicates that aqueous fluids were not as prevalent during deformation. This conclusion is also supported by the stable isotope signature. Observations of broken and planar surfaces using optical and scanning electron microscopes did not indicate major differences between the two mylonites: grain boundaries in both settings display pores with shapes controlled by crystallography, and have pore morphologies that are similar to observations from crack and grain-boundary healing experiments. Grain size reduction was predominantly the result of subgrain rotation recrystallization. However, the coarse grains inside the wet protomylonites (Schneeberg) are characterized by intracrystalline shear zones.

The Northwest Africa (NWA) 5790 meteorite: A mesostasis-rich nakhlite with little or no Martian aqueous alteration

NASA Astrophysics Data System (ADS)

Tomkinson, Tim; Lee, Martin R.; Mark, Darren F.; Dobson, Katherine J.; Franchi, Ian A.

2015-02-01

Northwest Africa (NWA) 5790 is the most recently discovered member of the nakhlite group. Its mineralogy differs from the other nakhlites with a high abundance mesostasis (38.1 ± 3.6 vol%) and scarcity of olivine (4.0 ± 2.2 vol%). Furthermore, zoning of augite phenocrysts, and other petrographic and chemical characteristics suggest that NWA 5790 samples the chilled margin of its parent lava flow/sill. NWA 5790 contains calcite and rare clay minerals that are evidence for its exposure to liquid water. The calcite forms a cement to coatings of dust on the outer surface of the find and extends into the interior of the meteorite within veins. The presence of microbial remains within the coating confirms that the dust and its carbonate cement are terrestrial in origin, consistent with the carbon and oxygen isotope composition of the calcite. The clay minerals are finely crystalline and comprise ~0.003 vol% of the meteorite. δD values of the clay minerals range from -212 ± 109‰ to -96 ± 132‰, and cannot be used to distinguish between a terrestrial or Martian origin. As petrographic results are also not definitive, we conclude that secondary minerals produced by Martian groundwaters are at best very rare within NWA 5790. The meteorite has therefore sampled a region of the lava flow/sill with little or no exposure to the aqueous solutions that altered other nakhlites. This isolation could relate to the scarcity of olivine in NWA 5790 because dissolution of olivine in other nakhlites by Martian groundwaters enhanced their porosity and permeability, and provided solutes for secondary minerals.

Fossilized microorganisms from the Emperor Seamounts: implications for the search for a subsurface fossil record on Earth and Mars.

PubMed

Ivarsson, M; Lausmaa, J; Lindblom, S; Broman, C; Holm, N G

2008-12-01

We have observed filamentous carbon-rich structures in samples drilled at 3 different seamounts that belong to the Emperor Seamounts in the Pacific Ocean: Detroit (81 Ma), Nintoku (56 Ma), and Koko Seamounts (48 Ma). The samples consist of low-temperature altered basalts recovered from all 3 seamounts. The maximum depth from which the samples were retrieved was 954 meters below seafloor (mbsf). The filamentous structures occur in veins and fractures in the basalts, where they are attached to the vein walls and embedded in vein-filling minerals like calcite, aragonite, and gypsum. The filaments were studied with a combination of optical microscopy, environmental scanning electron microscopy (ESEM), Raman spectroscopy, and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Minerals were identified by a combination of optical microscopy, X-ray diffraction, Raman spectrometry, and energy dispersive spectrometry on an environmental scanning electron microscope. Carbon content of the filaments ranges between approximately 10 wt % and approximately 50 wt % and is not associated with carbonates. These results indicate an organic origin of the carbon. The presence of C(2)H(4), phosphate, and lipid-like molecules in the filaments further supports a biogenic origin. We also found microchannels in volcanic glass enriched in carbon (approximately 10-40 wt %) compatible with putative microbial activity. Our findings suggest new niches for life in subseafloor environments and have implications for further exploration of the subseafloor biosphere on Earth and beyond.

Fossilized Microorganisms from the Emperor Seamounts: Implications for the Search for a Subsurface Fossil Record on Earth and Mars

NASA Astrophysics Data System (ADS)

Ivarsson, M.; Lausmaa, J.; Lindblom, S.; Broman, C.; Holm, N. G.

2008-12-01

We have observed filamentous carbon-rich structures in samples drilled at 3 different seamounts that belong to the Emperor Seamounts in the Pacific Ocean: Detroit (81 Ma), Nintoku (56 Ma), and Koko Seamounts (48 Ma). The samples consist of low-temperature altered basalts recovered from all 3 seamounts. The maximum depth from which the samples were retrieved was 954 meters below seafloor (mbsf). The filamentous structures occur in veins and fractures in the basalts, where they are attached to the vein walls and embedded in vein-filling minerals like calcite, aragonite, and gypsum. The filaments were studied with a combination of optical microscopy, environmental scanning electron microscopy (ESEM), Raman spectroscopy, and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Minerals were identified by a combination of optical microscopy, X-ray diffraction, Raman spectrometry, and energy dispersive spectrometry on an environmental scanning electron microscope. Carbon content of the filaments ranges between ˜10 wt % and ˜50 wt % and is not associated with carbonates. These results indicate an organic origin of the carbon. The presence of C2H4, phosphate, and lipid-like molecules in the filaments further supports a biogenic origin. We also found microchannels in volcanic glass enriched in carbon (˜10 40 wt %) compatible with putative microbial activity. Our findings suggest new niches for life in subseafloor environments and have implications for further exploration of the subseafloor biosphere on Earth and beyond.

Ore genesis of the Wusihe carbonate-hosted Zn-Pb deposit in the Dadu River Valley district, Yangtze Block, SW China: evidence from ore geology, S-Pb isotopes, and sphalerite Rb-Sr dating

NASA Astrophysics Data System (ADS)

Xiong, Suo-Fei; Gong, Yong-Jun; Jiang, Shao-Yong; Zhang, Xiao-Jing; Li, Qian; Zeng, Guo-Ping

2018-01-01

The Wusihe carbonate-hosted Zn-Pb deposit (3.7 Mt. Zn + Pb at a grade of 8.6% Zn and 2.0% Pb) is the largest deposit in the Dadu River Valley district of the Sichuan-Yunnan-Guizhou metallogenic province of southwest China. Three types of orebodies occur: (1) stratiform, banded and lamellar, within dolomite of the Neoproterozoic Dengying Formation; (2) vein type; and (3) breccia type. Four stages of mineralization are distinguished: (i) pyrite stage, (ii) pyrite-pyrrhotite-galena-sphalerite-bitumen stage, (iii) sphalerite-galena stage, and (iv) bitumen-calcite stage. Sphalerite and galena from stages II and III show δ34S ranges from +7.1 to +9.7‰ and +9.1 to +13.1‰, respectively. High-precision in situ lead isotope analyses of sulfides show 208Pb/204Pb, 207Pb/204Pb, and 206Pb/204Pb ratios of 37.938 to 38.336, 15.579 to 15.682, and 17.951 to 18.195, respectively, which suggest a mixing of lead from the basement and the host rocks. Rb-Sr isotope analyses for six sphalerite samples of stage II yielded an isochron age of 411 ± 10 Ma (MSWD = 1.4). Combining all available ore geology and geochemical data, together with fluid inclusion data reported previously, we suggest that the Wusihe deposit is a Mississippi Valley-type (MVT) deposit.

Geochemical survey of the Lusk Creek Roadless Area, Pope County, Illinois

USGS Publications Warehouse

Klasner, John S.; Day, Gordon W.

1984-01-01

The Lusk Creek Roadless Area (Index map) lies along the western edge of the Illinois-Kentucky fluorspar district in which flourite deposits occur as lenticular-type veins emplaced along fult zones or as tratiform-shaped bedding-replacement deposits that occur along fault zones (Grogan and Bradbury, 1967; Trace, 1974). Although mineralogy varies between deposits, Trace (1974) points out that the principal minerals are fluorite (CaF) and calcite (CaCO3), and associated with these minerals are lesser amounts of sphalerite (ZnS), galena (PbS), and barite (BaSO4). Minor quantites of iron-rich dolomite (CaMg(CO3)2), pyrite (FeS2),  and alteration products of zinc, lead, and copper minerals also are found. 

Speleothem chronology with sub-annual resolution in a near-entrance cave setting using oxygen isotope and trace element records

NASA Astrophysics Data System (ADS)

Carlson, P. E.; Miller, N. R.; Banner, J.; Breecker, D.

2016-12-01

Speleothems that grow in well-ventilated zones of caves are typically avoided when selecting specimens for paleoclimate reconstruction, due to concerns about evaporation and kinetic isotope effects. Near-entrance cave environments are characterized by near-ambient CO2 concentrations year-round and are influenced by surface temperature fluctuations. At Westcave Preserve (Westcave), a shallow, well-ventilated cave in central Texas, we have found seasonal temperature differences recorded in both the oxygen isotope and trace element compositions of speleothem calcite. The seasonal nature of these records has been confirmed by monitoring the chemical composition of drip water and substrate calcite since 2009 (Feng et al., 2014; Casteel and Banner, 2015). We present an ultrahigh-resolution (weekly to monthly) record of δ18O, Mg, Sr, and Ba in Westcave stalagmite WC-3, as well as monthly measurements of drip water geochemistry. We find drip water δ18O and [Mg] are essentially invariant, while seasonal variations in stalagmite calcite δ18O and Mg compositions are in good agreement with predicted temperature-dependent fractionation between water and calcite. Both drip water and speleothem calcite Sr and Ba vary seasonally, which we hypothesize is due to seasonal changes in moisture conditions in the epikarst. We use each of these annual geochemical cycles as independent chronological controls in order to develop a single age model for the stalagmite. These independent chronological counts are consistent with each other, and with 14C bomb-peak and U-series evidence. We argue that the potential for this kind of multi-proxy, seasonally-resolved dating in near-entrance stalagmites makes them especially valuable paleoclimate archives that should not be ignored in speleothem studies.

Kinematics of the Neogene Terror Rift: Constraints from calcite twinning strain in AND-1B core, McMurdo Ice Shelf

NASA Astrophysics Data System (ADS)

Paulsen, T.; Wilson, T. J.; Demosthenous, C.; Millan, C.; Jarrard, R. D.; Laufer, A.

2013-12-01

Strain analyses of mechanically twinned calcite in veins and faults hosted by Neogene (13.6 Ma to 4.3 Ma) sedimentary and volcanic rocks recovered within the ANDRILL AND-1B drill core from the Terror Rift in the southern Ross Sea, Antarctica, yield prolate and oblate ellipsoids with principal shortening and extension strains ranging from 0.1% to 8.5%. The majority of samples show homogeneous coaxial strain predominantly characterized by subvertical shortening, which we attribute to lithostatic loading in an Andersonian normal faulting stress regime during sedimentary and ice sheet burial of the stratigraphic sequence. The overall paucity of a non-coaxial layer-parallel shortening signal in the AND-1B twin populations suggests that horizontal compressive stresses predicted by Neogene transtensional kinematic models for the rift system have been absent or of insufficient magnitude to cause a widespread noncoaxial strain overprint. Limited numbers of oriented samples yield a possible average ESE extension direction for the rift that is subparallel to other indicators of Neogene extension. The lack of horizontal shortening in the twin data suggests the Neogene Terror Rift system either lacks a strong longitudinal strike-slip component, or that spatial partitioning of strain controls the maximum shortening axes seen in rocks of this age.

Mass transfer and fluid evolution in late-metamorphic veins, Rhenish Massif (Germany): insight from alteration geochemistry and fluid-mineral equilibria modeling

NASA Astrophysics Data System (ADS)

Marsala, Achille; Wagner, Thomas

2016-08-01

Element mobility and fluid-rock interaction related to the formation of late-metamorphic quartz veins have been studied by combination of mineral chemistry, whole-rock geochemistry, mass balance analysis and fluid-mineral equilibria modeling. The quartz veins are hosted by very low-grade metasedimentary rocks of the fold-and-thrust belt of the Rhenish Massif (Germany). The veins record two stages of evolution, a massive vein filling assemblage with elongate-blocky quartz, chlorite, apatite and albite, and a later open space filling assemblage with euhedral crystals of quartz, ankerite-dolomite and minor calcite and sulfides. Detailed mass balance analysis of an alteration profile adjacent to a representative quartz vein demonstrates that element mobility is restricted to the proximal zone. The most important element changes are gain of Ca, Fe, Mg, Mn, P and CO2, and loss of Si, K and Na. The data demonstrate that wall-rock carbonation is one of the main alteration features, whereas mobility of Si, K and Na are related to dissolution of quartz and destruction of detrital feldspar and muscovite. The whole-rock geochemical data, in conjunction with fluid composition data and pressure-temperature estimates, were used as input for fluid-mineral equilibria modeling in the system Si-Al-Fe-Mg-Ca-Na-K-C-S-O-H-B-F-Cl. Modeling involved calculation of rock-buffered fluid compositions over the temperature interval 100-500 °C, and reaction-path simulations where a rock-buffered high-temperature fluid reacts with fresh host-rocks at temperatures of 400, 300 and 200 °C. Calculated rock-buffered fluid compositions demonstrate that retrograde silica solubility is a strong driving force for quartz leaching in the temperature-pressure window of 380-450 °C and 0.5 kbar. These conditions overlap with the estimated temperatures for the initial stage of vein formation. Reaction-path models show that high-temperature alteration can produce the observed silica leaching, suggesting that fast advection of external hot fluids from deeper crustal levels was essential for the early stage of vein formation. Fluid advection must have occurred as multiple pulses, which allowed for periods of influx of fluids that leached quartz, alternating with periods of cooling and quartz precipitation in the veins. Reaction-path models at high temperatures (300-400 °C) do not produce carbonate alteration, whereas fluid-rock reaction at 200 °C produces carbonate alteration, consistent with the temperature estimates for the late-stage vein carbonate assemblage. Comparison between modeling results and geochemical data suggests that the observed alteration features are the product of fluid-rock reaction under conditions where the external fluid gradually cooled down and evolved with time. The results of this study highlight the importance of late-orogenic fluid migration for the formation of quartz vein arrays in fold-and-thrust belts.

Luminescent microbanding in speleothems: High-resolution chronology and paleoclimate

NASA Astrophysics Data System (ADS)

Shopov, Y. Y.; Ford, D. C.; Schwarcz, H. P.

1994-05-01

When illuminated by ultraviolet light, many calcite speleothems (stalagmites, stalactites, flowstones) display luminescence caused by the presence of organic (humic) substances occluded in the calcite. The amplitude of luminescence varies in a banded pattern parallel to growth layering. Through 14C and thermal ionization mass spectrometry uranium-series dating, we show that cyclical oscillations in the luminescence have periodicities ranging from a few days to ≥105 yr. A well-defined annual cycle is present in many vadose-zone speleothems and can be used to define the chronology of short-term events. This cycle is probably a response to hydrological events in the recharge to the cave. Longer term oscillations are inferred to be controlled by climate, through its effect on organic activity in the overlying soil.

U-Pb-Th geochronology of monazite and zircon in albitite metasomatites of the Rožňava-Nadabula ore field (Western Carpathians, Slovakia): implications for the origin of hydrothermal polymetallic siderite veins

NASA Astrophysics Data System (ADS)

Hurai, V.; Paquette, J.-L.; Lexa, O.; Konečný, P.; Dianiška, I.

2015-10-01

Sodic metasomatites (albitites) occur around and within siderite veins in the southern part of the Gemeric tectonic unit of the Western Carpathians. Accessory minerals of the metasomatites represented by monazite, zircon, apatite, rutile, tourmaline and siderite are basically identical with the quartz-tourmaline stage of other siderite and stibnite veins of the tectonic unit. Statistical analysis of chemical Th-U(total)-Pb isochron method (CHIME) of monazite dating yielded Jurassic-Cretaceous ages subdivided into 3-4 modes, spreading over time interval between 78 and 185 Ma. In contrast, LA-ICPMS 206Pb/238U dating carried out on the same monazite grains revealed a narrow crystallization interval, showing ages of Th-poor cores with phengite inclusions identical within the error limit with Th-rich rims with cauliflower-like structure. The determined lower intercept at 139 ± 1 Ma overlapped the Vallanginian-Berriasian boundary, thus corroborating the model of formation of hydrothermal vein structures within an arcuate deformation front built up in the Variscan basement as a response to Early Cretaceous compression, folding and thrusting. In contrast, associated zircons are considerably older than the surrounding Early-Palaeozoic volcano-sedimentary rocks, showing Neoproterozoic ages. The zircon grains in albitite metasomatites are thus interpreted as fragments of Pan-African magmatic detritus incorporated in the vein structures by buoyant hydrothermal fluids.

The Marianas-San Marcos vein system: characteristics of a shallow low sulfidation epithermal Au-Ag deposit in the Cerro Negro district, Deseado Massif, Patagonia, Argentina

NASA Astrophysics Data System (ADS)

Vidal, Conrado Permuy; Guido, Diego M.; Jovic, Sebastián M.; Bodnar, Robert J.; Moncada, Daniel; Melgarejo, Joan Carles; Hames, Willis

2016-08-01

The Cerro Negro district, within the Argentinian Deseado Massif province, has become one of the most significant recent epithermal discoveries, with estimated reserves plus resources of ˜6.7 Moz Au equivalent. The Marianas-San Marcos vein system contains about 70 % of the Au-Ag resources in the district. Mineralization consists of Upper Jurassic (155 Ma) epithermal Au- and Ag-rich veins of low to intermediate sulfidation style, hosted in and genetically related to Jurassic intermediate composition volcanic rocks (159-156 Ma). Veins have a complex infill history, represented by ten stages with clear crosscutting relationships that can be summarized in four main episodes: a low volume, metal-rich initial episode (E1), an extended banded quartz episode with minor mineralization (E2), a barren waning stage episode (E3), and a silver-rich late tectonic-hydrothermal episode (E4). The first three episodes are interpreted to have formed at the same time and probably from fluids of similar composition: a 290-230 °C fluid dominated by meteoric and volcanic waters (-3‰ to -0‰ δ18Owater), with <3 % NaCl equivalent salinity and with a magmatic source of sulfur (-1 to -2 ‰ δ34Swater). Metal was mainly precipitated at the beginning of vein formation (episode 1) due to a combination of boiling at ˜600 to 800 m below the paleowater table, and associated mixing/cooling processes, as evidenced by sulfide-rich bands showing crustiform-colloform quartz, adularia, and chlorite-smectite banding. During episodes 2 and 3, metal contents progressively decrease during continuing boiling conditions, and veins were filled by quartz and calcite during waning stages of the hydrothermal system, and the influx of bicarbonate waters (-6 to -8.5 ‰ δ18Owater). Hydrothermal alteration is characterized by proximal illite, adularia, and silica zone with chlorite and minor epidote, intermediate interlayered illite-smectite and a distal chlorite halo. This assemblage is in agreement with measured fluid inclusion temperatures. A striking aspect of the Marianas-San Marcos vein system is that the high-grade/high-temperature veins are partially covered by breccia and volcaniclastic deposits of acidic composition, and are spatially associated with hot spring-related deposits and an advanced argillic alteration blanket. A telescoped model is therefore proposed for the Marianas-San Marcos area, where deeper veins were uplifted and eroded, and then partially covered by non-explosive, post-mineral rhyolitic domes and reworked volcaniclastic deposits, together with shallow geothermal features. The last tectonic-hydrothermal mineralization episode (E4), interpreted to have formed at lower temperatures, could be related to this late tectonic and hydrothermal activity.

Interventional Therapy for Upper Extremity Deep Vein Thrombosis

PubMed Central

Carlon, Timothy A.; Sudheendra, Deepak

2017-01-01

Approximately 10% of all deep vein thromboses occur in the upper extremity, and that number is increasing due to the use of peripherally inserted central catheters. Sequelae of upper extremity deep vein thrombosis (UEDVT) are similar to those for lower extremity deep vein thrombosis (LEDVT) and include postthrombotic syndrome and pulmonary embolism. In addition to systemic anticoagulation, there are multiple interventional treatment options for UEDVT with the potential to reduce the incidence of these sequelae. To date, there have been no randomized trials to define the optimal management strategy for patients presenting with UEDVT, so many conclusions are drawn from smaller, single-center studies or from LEDVT research. In this article, the authors describe the evidence for the currently available treatment options and an approach to a patient with acute UEDVT. PMID:28265130

Petrography, geochemistry and U-Pb zircon age of the Matongo carbonatite Massif (Burundi): Implication for the Neoproterozoic geodynamic evolution of Central Africa

NASA Astrophysics Data System (ADS)

Midende, Gilbert; Boulvais, Philippe; Tack, Luc; Melcher, Frank; Gerdes, Axel; Dewaele, Stijn; Demaiffe, Daniel; Decrée, Sophie

2014-12-01

The Matongo carbonatite intrusion belongs to the Neoproterozoic Upper Ruvubu alkaline plutonic complex (URAPC), that is located in Burundi along the western branch of the East African Rift. Beside the Matongo carbonatite, the URAPC alkaline complex comprises feldspathoidal syenites, diorites, quartz-bearing syenites and granites. Three main facies have been recognized in the Matongo carbonatite: (1) Sövites represent the dominant facies. Two varieties have been recognized. A scarce coarse-grained sövite (sövite I), which is altered and poorly enriched in REE (4 < ΣREE < 8 ppm), is encountered in highly fractured zones. A fine-grained sövite (sövite II), which is made of saccharoidal calcite, commonly associated with apatite, aegirine and amphibole, is abundant in the intrusion. Sövite II is enriched in LREE (442 < ΣREE < 1550 ppm, 49 < LaN/YbN < 175). (2) Ferrocarbonatites, that form decimeter-wide veins crosscutting the sövites, are characterized by a LREE enriched patterns (225 < ΣREE < 1048 ppm, 17 < LaN/YbN < 64). (3) K-feldspar and biotite-rich fenite facies (silicocarbonatites) have been recognized at the contact between the carbonatites and the country rock. They are likewise LREE-enriched (134 < ΣREE < 681 ppm, 25 < LaN/YbN < 46). Additionaly, "late" hydrothermal MREE-rich carbonatite veinlets can be found in sövite I. They are characterized by moderate enrichment in REE (ΣREE = 397 ppm), with a MREE-humped pattern (LaN/YbN = 3.7). The different facies represent the typical magmatic evolution of a carbonatite, while the silicocarbonatites are interpreted as resulting from the fenitisation of the country host-rocks. In addition, the most REE-depleted and fractionated facies, i.e. the coarse-grained sövite facies and the "late" calcite veinlets testify for hydrothermal processes that occurred after carbonatite emplacement and result from REE mobilization and redistribution. Large idiomorphic zircon crystals (megacrysts), found in the vicinity of the carbonatite can directly be related to the carbonatite evolution. They have been dated at 705.5 ± 4.5 Ma (U-Pb concordant age, LA-ICP-MS). Similar zircon megacrysts of the Lueshe carbonatite (DRCongo) have been dated and give a concordant age at 798.5 ± 4.9 Ma (U-Pb, LA-ICP-MS). Considering that an extensional tectonic regime occured at that time in Central Africa - what remains debated - both ages could relate to different stages of Rodinia breakup, with uprise of mantle-derived magmas along Palaeoproterozoic lithospheric zones of weakness.

Characteristics and 40Ar/39Ar geochronology of the Erdenet Cu-Mo deposit, Mongolia

USGS Publications Warehouse

Kavalieris, Imants; Khashgerel, Bat-Erdene; Morgan, Leah; Undrakhtamir, Alexander; Borohul, Adiya

2017-01-01

The Early to Middle Triassic Erdenet porphyry Cu-Mo deposit, in northern Mongolia, developed in a continent-continent arc collision zone, within the Central Asian orogenic belt. The porphyry system is related to multiple intrusions of crystal-crowded biotite granodiorite porphyry, which formed a composite stock about 900 m in diameter, with multiple porphyritic microgranodiorite dikes. Wall rocks are Late Permian to Early Triassic, medium-grained granodiorite, with similar whole-rock geochemistry, mineralogy, and composition to the granodiorite porphyry. Whole-rock analysis of the granodiorite porphyry and wall rocks shows that these rocks cannot be discriminated, but both have depleted middle heavy rare earth elements and Y, typical of fertile porphyry magmatic suites.At the current pit level (1,250 m elev), early porphyry-style quartz veins (A and B type) are locally infilled by pyrite-chalcopyrite, with subordinate bornite, but most of the chalcopyrite occurs in D veins that constitute more than 50% of the Cu grade (~0.5 wt % Cu). The 0.3 wt % Cu shell resembles a molar tooth, enveloping the granodiorite porphyry, with deeper roots extending down the wal-rock contacts. Molybdenite occurs in monomineralic veins, and in finely laminated to massive quartz-molybdenite veins.The most important alteration is quartz-muscovite, which occurs as relatively coarse (100–500 μm) alteration selvages (1–5 cm) that envelop D veins. The D veins cut illite ± kaolinite-smectite (or intermediate argillic) alteration. Intermediate argillic alteration, together with abundant pink anhydrite (commonly hydrated to gypsum), extends from at least 1,300- to 900-m elevation in the deepest drill holes, and has overprinted early potassic alteration, or relatively unaltered red granodiorite. Meter-wide zones of kaolinite cut the anhydrite-gypsum at all levels. There is an abrupt transition outward from the intermediate argillic alteration to chlorite-epidote (propylitic) alteration, at 50 to 200 m from the granodiorite porphyry contact, although D veins (and chalcopyrite) extend outward to the propylitic zone.The Erdenet porphyry system, was overprinted by advanced argillic alteration, which outcrops 2 km northwest of the pit, and forms a lithocap that extends over 10 × 2.5 km. It is characterized by residual quartz, andalusite, Na-Ca and K-alunite, diaspore, pyrophyllite, zunyite, topaz, dickite, and kaolinite. The upper part of the porphyry Cu-Mo deposit (removed by mining), comprised a bornite-chalcocite enriched zone up to 300 m thick with an average grade of 0.7 wt % Cu and up to 5 wt % Cu locally. Based on hypogene bornite-chalcocite mineral textures and high-sulfidation state mineralogy, the enriched zone is inferred to be of hypogene origin, but modified by supergene processes. Consequently, it may be related to formation of the lithocap.Previous Re-Os dates of 240.4 and 240.7 ± 0.8 Ma for molybdenite in quartz veins are comparable to new 40Ar/39Ar dates of 239.7 ± 1.6 and 240 ± 2 Ma for muscovite that envelops D veins. One 40Ar/39Ar date on K-alunite from the lithocap of 223.5 ± 1.9 Ma suggests that it may be about 16 m.y. younger than Erdenet, but this result needs to be verified by further dating.

Structural analysis of a fractured basement reservoir, central Yemen

NASA Astrophysics Data System (ADS)

Veeningen, Resi; Rice, Hugh; Schneider, Dave; Grasemann, Bernhard; Decker, Kurt

2013-04-01

The Pan-African Arabian-Nubian Shield (ANS), within which Yemen lies, formed as a result of Neoproterozoic collisional events between c. 870-550 Ma. Several subsequent phases of extension occurred, from the Mesozoic (due to the breakup of Gondwana) to the Recent (forming the Gulf of Aden and the Red Sea). These resulted in the formation of numerous horst- and-graben structures and the development of fractured basement reservoirs in the southeast part of the ANS. Two drill cores from the Mesozoic Marib-Shabwa Basin, central Yemen, penetrated the upper part of the Pan-African basement. The cores show both a lithological and structural inhomogeneity, with variations in extension-related deformation structures such as dilatational breccias, open fractures and closed veins. At least three deformation events have been recognized: D1) Ductile to brittle NW-SE directed faulting during cooling of a granitic pluton. U-Pb zircon ages revealed an upper age limit for granite emplacement at 627±3.5 Ma. As these structures show evidence for ductile deformation, this event must have occurred during the Ediacaran, shortly after intrusion, since Rb/Sr and (U-Th)/He analyses show that subsequent re-heating of the basement did not take place. D2) The development of shallow dipping, NNE-SSW striking extensional faults that formed during the Upper Jurassic, simultaneously with the formation of the Marib-Shabwa Basin. These fractures are regularly cross-cut by D3. D3) Steeply dipping NNE-SSW to ENE-WSW veins that are consistent with the orientation of the opening of the Gulf of Aden. These faults are the youngest structures recognized. The formation of ductile to brittle faults in the granite (D1) resulted in a hydrothermally altered zone ca. 30 cm wide replacing (mainly) plagioclase with predominantly chlorite, as well as kaolinite and heavy element minerals such as pyrite. The alteration- induced porosity has an average value of 20%, indicating that the altered zone is potentially a good fluid-flow pathway and also a suitable reservoir for hydrocarbons. The youngest faults (D3) are often filled with calcite, (saddle) dolomite and pyrite that formed at temperatures between 100 and 150° C. Fluid inclusions within calcite have abundant hydrocarbon-rich components indicating that these veins formed synchronously with hydrocarbon migration. The same minerals were deposited within the ductile to brittle faults within the granite (formed during D1). This resulted in significant porosity reduction, especially in the faults themselves, reducing the fluid flow efficiency within the altered granite, locking up hydrocarbons and reducing the reservoir quality.

Helium diffusion in carbonates

NASA Astrophysics Data System (ADS)

Amidon, W. H.; Cherniak, D. J.; Watson, E. B.; Hobbs, D.

2013-12-01

The abundance and large grain size of carbonate minerals make them a potentially attractive target for 4He thermochronology and 3He cosmogenic dating, although the diffusive properties of helium in carbonates remain poorly understood. This work characterizes helium diffusion in calcite and dolomite to better understand the crystal-chemical factors controlling He transport and retentivity. Slabs of cleaved natural calcite and dolomite, and polished sections of calcite cut parallel or normal to c, were implanted with 3He at 3 MeV with a dose of 5x1015/cm2. Implanted carbonates were heated in 1-atm furnaces, and 3He distributions following diffusion anneals were profiled with Nuclear Reaction Analysis using the reaction 3He(d,p)4He. For 3He transport normal to cleavage surfaces in calcite, we obtain the following Arrhenius relation over the temperature range 78-300°C: Dcalcite = 9.0x10-9exp(-55 × 6 kJ mol-1/RT) m2sec-1. Diffusion in calcite exhibits marked anisotropy, with diffusion parallel to c about two orders of magnitude slower than diffusion normal to cleavage faces. He diffusivities for transport normal to the c-axis are similar in value to those normal to cleavage surfaces. Our findings are broadly consistent with helium diffusivities from step-heating measurements of calcite by Copeland et al. (2007); these bulk degassing data may reflect varying effects of diffusional anisotropy. Helium diffusion normal to cleavage surfaces in dolomite is significantly slower than diffusion in calcite, and has a much higher activation energy for diffusion. For dolomite, we obtain the following Arrhenius relation for He diffusion over the temperature range 150-400°C: Ddolomite = 9.0x10-8exp(-92 × 9 kJ mol-1/RT) m2sec-1. The role of crystallographic structure in influencing these differences among diffusivities was evaluated using the maximum aperture approach of Cherniak and Watson (2011), in which crystallographic structures are sectioned along possible diffusion directions and the maximum interstitial apertures in each 'slice' in the structure are identified. Preliminary results show that observed differences in diffusivities are consistent with the size of the smallest maximum aperture along each diffusion direction. In calcite, the smallest maximum apertures are ~0.92 and ~0.66 angstroms for cleavage-normal and c-axis parallel directions respectively. In dolomite, the smallest maximum aperture is ~0.78 angstroms for the cleavage normal direction. Work is in progress on characterizing helium diffusion for other orientations in dolomite, and in other carbonates, including aragonite and magnesite, and in implementing these diffusion findings in the interpretation and modeling of bulk volume diffusion in heterogeneous calcite crystals common in many geologic applications. Copeland et al. (2007) GCA 71, 4488-4511 Cherniak and Watson, (2011) Chem. Geo. 288, 149-161

Mid Carboniferous lamprophyres, Cobequid Fault Zone, eastern Canada, linked to sodic granites, voluminous gabbro, and albitization

NASA Astrophysics Data System (ADS)

Pe-Piper, Georgia; Piper, David J. W.; Papoutsa, Angeliki

2018-01-01

Major intra-continental shear zones developed during the later stages of continental collision in a back-arc setting are sites of prolonged magmatism. Mantle metasomatism results from both melting of subducted sediments and oceanic crust. In the Cobequid Fault Zone of the northern Appalachians, back-arc A-type granites and gabbros dated ca. 360 Ma are locally intruded by lamprophyric dykes dated ca. 335 Ma. All the lamprophyres are kersantites with biotite and albite, lesser ilmenite, titanite and fluorapatite, and minor magmatic calcite, allanite, pyrite, magnetite, quartz and K-feldspar in some samples. The lamprophyres show enrichment in Rb, Ba, K, Th and REE and classify as calc-alkaline lamprophyre on the basis of biotite and whole rock chemistry. Pb isotopes lie on a mixing line between normal mantle-derived gabbro and OIB magma. Nd isotopes range from 1.3-3.5 εNdt, a little lower than in local gabbro. Most lamprophyres have δ18O = 3.8-4.4‰. Country rock is cut by pyrite-(Mg)-chlorite veins with euhedral allanite crystals that resemble the lamprophyres mineralogically, with the Mg-chlorite representing chloritized glass. Early Carboniferous unenriched mafic dykes and minor volcanic rocks are widespread along the major active strike-slip fault zones. The lamprophyres are geographically restricted to within 10 km of a small granitoid pluton with some sodic amphibole and widespread albitization. This was displaced by early Carboniferous strike-slip faulting from its original position close to the large Wentworth Pluton, the site of mantle-derived sodic amphibole granite, a major late gabbro pluton, and a volcanic carapace several kilometres thick, previously demonstrated to be the site of mantle upwelling and metasomatism. The age of the lamprophyres implies that enriched source material in upper lithospheric mantle or lower crust was displaced 50 km by crustal scale strike-slip faulting after enrichment by the mantle upwelling before lamprophyre emplacement. This indicates a multi-stage process to emplace lamprophyric magma.

Mineralogical and isotopic record of biotic and abiotic diagenesis of the Callovian-Oxfordian clayey formation of Bure (France)

NASA Astrophysics Data System (ADS)

Lerouge, C.; Grangeon, S.; Gaucher, E. C.; Tournassat, C.; Agrinier, P.; Guerrot, C.; Widory, D.; Fléhoc, C.; Wille, G.; Ramboz, C.; Vinsot, A.; Buschaert, S.

2011-05-01

The Callovian-Oxfordian (COx) clayey unit is being studied in the Eastern part of the Paris Basin at depths between 400 and 500 m depth to assess of its suitability for nuclear waste disposal. The present study combines new mineralogical and isotopic data to describe the sedimentary history of the COx unit. Petrologic study provided evidence of the following diagenetic mineral sequence: (1) framboidal pyrite and micritic calcite, (2) iron-rich euhedral carbonates (ankerite, sideroplesite) and glauconite (3) limpid calcite and dolomite and celestite infilling residual porosity in bioclasts and cracks, (4) chalcedony, (5) quartz/calcite. Pyrite in bioturbations shows a wide range of δ 34S (-38‰ to +34.5‰), providing evidence of bacterial sulphate reduction processes in changing sedimentation conditions. The most negative values (-38‰ to -22‰), measured in the lower part of the COx unit indicate precipitation of pyrite in a marine environment with a continuous sulphate supply. The most positive pyrite δ 34S values (-14‰ up to +34.5‰) in the upper part of the COx unit indicate pyrite precipitation in a closed system. Celestite δ 34S values reflect the last evolutionary stage of the system when bacterial activity ended; however its deposition cannot be possible without sulphate supply due to carbonate bioclast dissolution. The 87Sr/ 86Sr ratio of celestite (0.706872-0.707040) is consistent with deposition from Jurassic marine-derived waters. Carbon and oxygen isotopic compositions of bulk calcite and dolomite are consistent with marine carbonates. Siderite, only present in the maximum clay zone, has chemical composition and δ 18O consistent with a marine environment. Its δ 13C is however lower than those of marine carbonates, suggesting a contribution of 13C-depleted carbon from degradation of organic matter. δ 18O values of diagenetic chalcedony range between +27‰ and +31‰, suggesting precipitation from marine-derived pore waters. Late calcite crosscutting a vein filled with chalcedony and celestite, and late euhedral quartz in a limestone from the top of the formation have lower δ 18O values (˜+19‰), suggesting that they precipitated from meteoric fluids, isotopically close to present-day pore waters of the formation. Finally, the study illustrates the transition from very active, biotic diagenesis to abiotic diagenesis. This transition appears to be driven by compaction of the sediment, which inhibited movement of bacterial cells by reduction of porosity and pore sizes, rather than a lack of inorganic carbon or sulphates.

Coulomb Fault Mechanics at Work in the Proterozoic: Strike-Slip Faults and Regional-Scale Veining in the Mt. Isa Inlier, Australia

NASA Astrophysics Data System (ADS)

Begbie, M. J.; Sibson, R. H.; Ghisetti, F. C.

2005-12-01

The Proterozoic Mt Isa inlier, comprising greenschist to amphibolite facies metamorphic assemblages intruded by granites during the Isan Orogeny (1590-1500 Ma), is disrupted by brittle, late- or post-orogenic strike-slip faults. The faults occur in two mutually cross-cutting sets; a set of NE-SW subvertical dextral strike-slip faults, and a conjugate set of NW-SE sinistral faults. These faults thus define a regional stress field with σ1 oriented approximately E-W and σ3 oriented approximately N-S. Locally, the faults outcrop as linear blade-like ridges of silicified microbreccias-cataclasites and quartz veining that extends for kilometres across the semi-arid terrain. The informally named Spinifex Fault is one of the dextral set of subvertical faults. This fault is a classic example of coulomb fault mechanics at work in the Proterozoic. The Spinifex Fault trends ~065° across an outcropping granitic pluton, the margins of which it offsets dextrally by ~0.75 km. Locally within the pluton, the fault refracts to ~075° across an amphibolite layer. In the surrounding granitic pluton the fault trace is comparatively inconspicuous and unmineralized but where it transects the amphibolite it is defined by an upstanding ridge of silicified microbreccia-cataclasite (~10 m thick). Associated with the Spinifex Fault is a swarm of predominantly extensional subvertical quartz veins (cm to m thick) trending 090-95° and a series of mineralised fault splays trending 070-080°. Extension veins define the σ1-σ2 plane, with the Spinifex fault lying at an angle of ~25-30° to the inferred σ1. These veins are composed of colloform and crustiform banded quartz, brecciated fragments of quartz vein and wallrock that are typically rimmed with cockade overgrowths and bladed quartz after calcite pseudomorphs. Mineralised fault splays are < 50 m or so wide with a composite brittle fabric comprising: (1) bounding subvertical cataclastic `walls' <10 m or so thick made up of silicified microbreccias and cataclasites containing vein fragments; (2) innumerable subvertical quartz veins (cm to m thick) lying subparallel to the bounding shear zones with textures ranging from pure dilation to multiply recemented breccias of wallrock and quartz fragments; (3) irregular non-systematic veins; and (4) occasional minor faults from the complementary set. Mutual cross-cutting relationships between all the structural components indicate penecontemporaneous development within the inferred stress field. Slickenfibers and striations along fault components indicate predominantly strike slip motion on subvertical planes. Homogenisation temperatures from quartz hosted fluid inclusions cluster at ~210°C while vein textures record histories of incremental hydrothermal deposition under low effective stress, probably in the epizonal environment (<1-2 km depth). This regional study demonstrates the existence of a rather uniform stress province, corresponding to an Andersonian regime and initiation of faults in accord with the coulomb failure criterion.

Temporal Changes in Microscale Colonization of the Phylloplane by Aureobasidium pullulans

PubMed Central

McGrath, Molly J.; Andrews, John H.

2006-01-01

Colonization of apple leaves by the yeastlike fungus Aureobasidium pullulans was followed quantitatively and spatially at a microscale level throughout two growing seasons. Ten field leaves were sampled on 11 dates in 2003 and 15 dates in 2004. Using an A. pullulans-specific fluorescence in situ hybridization probe and epifluorescence microscopy, we enumerated total cells, swollen-cells and chlamydospores (SCC), and blastospores/mm2 on leaf features, including the midvein, other (smaller) veins, and the interveinal regions. By 7 July 2003 and 7 June 2004, the total numbers of A. pullulans cells/mm2 were significantly higher (P < 0.05) on the midvein and other veins than in the interveinal regions. This pattern remained consistent thereafter. The primary colonizing morphotype in all regions at all dates was the SCC form, although blastospores always occurred in low numbers. Occupancy was quantified based on the percentage of microscope fields of a particular leaf feature containing ≥1 A. pullulans cell. In general, as seasons progressed, the percent occupancy of features increased and, for most midvein and veinal features, approximated 100% at the end of both growing seasons. Except for early collections, when A. pullulans cell numbers were low, the percent occupancy of interveinal regions was lower than that of the midvein or other veinal regions. A. pullulans was distributed primarily as single cells throughout the seasons in interveinal regions. On the midvein and other veins, colonies of ≥4 cells developed over time, and more cells occurred in colonies than as singletons by August. Our results demonstrate that A. pullulans primarily colonizes veins, where populations appear to increase by growth in situ. This pattern is established early in the growing season and persists. PMID:16957250

Hydrothermal Alteration of the Lower Oceanic Crust: Insight from OmanDP Holes GT1A and GT2A.

NASA Astrophysics Data System (ADS)

Harris, M.; Zihlmann, B.; Mock, D.; Akitou, T.; Teagle, D. A. H.; Kondo, K.; Deans, J. R.; Crispini, L.; Takazawa, E.; Coggon, J. A.; Kelemen, P. B.

2017-12-01

Hydrothermal circulation is a fundamental Earth process that is responsible for the cooling of newly formed ocean crust at mid ocean ridges and imparts a chemical signature on both the crust and the oceans. Despite decades of study, the critical samples necessary to resolve the role of hydrothermal circulation during the formation of the lower ocean crust have remained poorly sampled in the ocean basins. The Oman Drilling Project successfully cored 3 boreholes into the lower crust of the Semail ophiolite (Holes GT1A layered gabbros, GT2A foliated gabbros and GT3A dike/gabbro transition). These boreholes have exceptionally high recovery ( 100%) compared to rotary coring in the oceans and provide an unrivalled opportunity to quantitatively characterise the hydrothermal system in the lower oceanic crust. Hydrothermal alteration in Holes GT1A and GT2A is ubiquitous and manifests as secondary minerals replacing primary igneous phases and secondary minerals precipitated in hydrothermal veins and hydrothermal fault zones. Hole GT1A is characterised by total alteration intensities between 10 -100%, with a mean alteration intensity of 60%, and shows no overall trend downhole. However, there are discrete depth intervals (on the scale of 30 -100 m) where the total alteration intensity increases with depth. Alteration assemblages are dominated by chlorite + albite + amphibole, with variable abundances of epidote, clinozoisite and quartz. Hole GT1A intersected several hydrothermal fault zones, these range from 2-3 cm up to >1m in size and are associated with more complex secondary mineral assemblages. Hydrothermal veins are abundant throughout Hole GT1A, with a mean density of 37 vein/m. Hole GT2A is characterised by total alteration intensities between 6-100%, with a mean alteration intensity of 45%, and is highly variable downhole. Alteration halos and patches are slightly more abundant than in Hole GT1A. The secondary mineral assemblage is similar to Hole GT1A, but Hole GT2A has higher abundances of epidote, clinozoisite, quartz, laumontite and iron-oxydroxides. Vein density in Hole GT2A is 61 veins/m. In both holes, cross cutting vein relationships indicate a relative timing from earliest to latest of: amphibole; epidote + zoisite + qtz; chlorite + prehnite + qtz, calcite-laumontite-anhydrite; gypsum.

Metallogenic and tectonic significance of oxygen isotope data and whole-rock potassium-argon ages of the Nikolai Greenstone, McCarthy Quadrangle, Alaska

USGS Publications Warehouse

Silberman, M.L.; MacKevett, E.M.; Connor, C.L.; Matthews, Alan

1980-01-01

The Middle and (or) Late Triassic Nikolai Greenstone, part of the allochthonous terrane of Wrangellia, is typically altered and locally metamorphosed to prehnite-pumpellyite facies with chlorite and epidote as the most common secondary minerals. Intrinsic copper content averages 155 ppm, and two types of concentrations of copper in the Nikolai are common: (1) native copper fillings of amygdules and rubble zones typically near flow tops, and (2) veins and thin replacement zones that contain native copper and copper-iron sulfides in quartz-epidote or calcite gangue in faults and fractures. Oxygen isotope data from quartz and epidote from three copperbearing veins yield calculated ore fluid temperatures of approximately 200°C and 6180 of approximately +1 per mil in agreement with a metamorphicsegregation origin of these deposits, as suggested by Sinclair (1977). Seven K-Ar ages of chloritized greenstone, including those adjacent to veins fall on an initial argon diagram with a zero intercept and a slope which yields an isochron age of 112 + 11 m.y. The ages define a Cretaceous thermalmetamorphic episode which is responsible for alteration and mineralization. The episode is younger than a major Jurassic progeny, accompanied by granitic intrusion, in the area, and appears to be unaffected by minor granitic intrusion in the middle to late Tertiary. We believe the Cretaceous event is related to accretion of Wrangellia to its present relative position in North America. This age of accretion agrees with stratigraphic and structural evidence cited by other workers. 

Exploration and geology of the Karangahake and Rahu epithermal Au-Ag deposits, Hauraki Goldfield

USGS Publications Warehouse

Simpson, Mark P.; Stevens, Murray R; Mauk, Jeffrey L.; Harris, Matthew C; Stuart, Alistair G J

2016-01-01

Karangahake was the third largest gold producer in the Hauraki goldfield. In 2009, New Talisman Gold mines was granted a mining permit, and plans are underway to commence underground mine development of the Maria vein, which has a maiden Ore Reserve (consistent with the 2012 JORC Code) of 28 800 oz Au and 127 800 oz Ag. Exploration drilling at Rahu, located 2 km north of Karangahake has identified polymictic hydrothermal breccias and quartz veins that are strongly gold anomalous. Some quartz vein clasts within the breccia have up to 8.7 g/t Au, suggesting the presence of higher grade quartz vein(s) either below or directly adjacent to the breccias. A controlled source audio-frequency magnetotelluric (CSAMT) survey at Rahu revealed that strongly resistive zones extend below the Barbara and Eunice anomalies to at least 300 m depth and likely correspond to areas of increased silicification, breccias and/or veins. Future drilling will focus on these targets. Detailed geophysical, alteration and fluid inclusion studies have been undertaken at Karangahake, Rahu and Ascot (c 1 km NW of Rahu). Karangahake and Rahu both occur within a broad demagnetised zone, c 4.2 × 2.7 km, in which magnetite has been destroyed by strong hydrothermal alteration. At Karangahake, andesite and overlying minor rhyolite are replaced by adularia, chlorite, illite, pyrite, plus minor albite, epidote and calcite, which have formed from upwelling chloride waters that at depth were hotter than 280°C. At Rahu, localised adularia coupled with complex distributions of illite and interstratified illite-smectite, suggest cooler (c 180° to 240°C) and more focused fluid flow, as well as inferred cool groundwater influx. Fluid inclusion data suggest veins at Karangahake, Rahu and Ascot formed beneath palaeowater tables at 920 m, 440 m and 430 m relative to current sea level (asl), respectively. At Ascot, the presence of silica sinter at 135 m asl, which formed at the palaeosurface, is shallower compared to the fluid inclusion depth estimate and suggests that the palaeowater table here rose some 300 m during hydrothermal activity due to burial, resulting in overprinting. This overprint may also have occurred at Karangahake and Rahu, but the evidence is inconclusive; although burial during hydrothermal activity could explain the exceptional 700 m vertical range of mineralisation at Karangahake and raises the possibility of concealed mineralisation at depth elsewhere within the Karangahake alteration envelope.

The Gifford Creek Ferrocarbonatite Complex, Gascoyne Province, Western Australia: Associated fenitic alteration and a putative link with the ~ 1075 Ma Warakurna LIP

NASA Astrophysics Data System (ADS)

Pirajno, Franco; González-Álvarez, Ignacio; Chen, Wei; Kyser, Kurt T.; Simonetti, Antonio; Leduc, Evelyne; leGras, Monica

2014-08-01

The Gifford Creek Ferrocarbonatite Complex (GFC), located in the Neoarchean-Palaeoproterozoic Gascoyne Province, Western Australia, comprises sills, dykes, and veins of ferrocarbonatite intruding the Pimbyana Granite and Yangibana Granite of the Durlacher Supersuite and metasedimentary rocks of the Pooranoo Metamorphics. The ferrocarbonatites are associated with complex and irregularly distributed zones of fenitic alteration. These ferrocarbonatites and fenites are also associated with a swarm of ironstone veins, containing magnetite, hematite and goethite. The GFC and associated fenite outcrops are distributed within a ~ 700 km2 area, north of the Lyons River Fault. Ferrocarbonatite sills and dykes are predominant in a northwest-trending belt, along the southern margin of the complex; whereas ferrocarbonatite veins tend to be distributed in a series of sub-parallel west-northwest-trending linear belts, generally associated with the Fe oxide veins with sinuous trends. These veins have margins of Fe-rich carbonates associated with zones of alteration that have a fenitic character. The fenitic haloes are characterised by the presence of Na-K-feldspars and/or Na-amphiboles and magnetite. In some cases monomineralic feldspar zones (orthoclasite) are present. Fenitic alteration is spatially associated with the carbonatites, but it can also form discrete veins and veinlets in basement granitic rocks (Pimbyana and Yangibana Granites). Petrographic, XRD and SEM analyses show that the ferrocarbonatites are dominantly composed of ankerite-dolomite, magnetite, arfvedsonite-riebeckite, and lesser calcite. Alkali amphibole has compositions ranging from potassian magnesio-arfvedsonite to magnesio-riebeckite. Sills and dykes north of the Lyons River, are characterised by a carbonate-rich matrix, containing > 50 vol.% ankerite-dolomite, with accessory quantities of apatite, barite, monazite, and phlogopite. In-situ U-Pb age determination of apatite grains by LA-ICP-MS on a sample of ferrocarbonatite was performed and an average age of 1075 ± 35 Ma was obtained. This age is within the range of ages (~ 1078-1070 Ma) of the Warakurna Large Igneous Province (WLIP) and we suggest that the GFC is related to the mantle plume event that generated the WLIP. This is a significant outcome, because it may lead to the recognition or discovery of other carbonatites within the area covered by the WLIP. In addition, monazite from fenitic rocks associated with the ironstones yielded an age of 1050 ± 25 Ma, suggesting that a second phase of carbonatite magmatism occurred, resulting in the emplacement of the carbonatite-ironstone veins swarm. A model is proposed to explain the formation of the GFC system.

Hydrothermal alteration and mass exchange in the hornblende latite porphyry, Rico, Colorado

USGS Publications Warehouse

Larson, P.B.; Cunningham, C.G.; Naeser, C.W.

1994-01-01

The Rico paleothermal anomaly, southwestern Colorado, records the effects of a large hydrothermal system that was active at 4 Ma. This hydrothermal system produced the deep Silver Creek stockwork Mo deposit, which formed above the anomaly's heat source, and shallower base and precious-metal vein and replacement deposits. A 65 Ma hornblende latite porphyry is present as widespread sills throughout the area and provided a homogenous material that recorded the effects of the hydrothermal system up to 8 km from the center. Hydrothermal alteration in the latite can be divided into a proximal facies which consists of two assemblages, quartz-illite-calcite and chlorite-epidote, and a distal facies which consists of a distinct propylitic assemblage. Temperatures were gradational vertically and laterally in the anomaly, and decreased away from the centra heat source. A convective hydrothermal plume, 3 km wide and at least 2 km high, was present above the stock-work molybdenum deposit and consisted of upwelling, high-temperature fluids that produced the proximal alteration facies. Distal facies alteration was produced by shallower cooler fluids. The most important shallow base and precious-metal vein deposits in the Rico district are at or close to the boundary of the thermal plume. Latite within the plume had a large loss of Na2O, large addition of CaO, and variable SiO2 exchante. Distal propylitized latite samples lost small amounts of Na2O and CaO and exchanged minor variable amounts of SiO2. The edge of the plume is marked by steep Na2O exchange gradients. Na2O exchange throughout the paleothermal anomaly was controlled by the reaction of the albite components in primary plagioclase and alkali feldspars. Initial feldspar alteration in the distal facies was dominated by reaction of the plagioclase, and the initial molar ratio of reactants (alkali feldspar albite component to plagioclase albite component) was 0.35. This ratio of the moles of plagioclase to alkali feldspar albite components that reacted evolved to 0.92 as the reaction progressed. Much of the alkali feldspar albite component in the proximal facies reacted while the, primary plagioclase was still unreacted, but the ratio for these assemblages increased to 1.51 when the plagioclase entered the reaction paragenesis. Plagioclase reaction during distal propylitic alteration resulted in pseudomorphic albite mixed with illite and a loss of Na2O. CaO is lost in the distal facies as hornblende reacts to chlorite, although some calcium may be fixed in calcite. CaO is added to the proximal facies as the quantity of chlorite replacing hornblende increases and epidote and calcite are produced. ?? 1994 Springer-Verlag.

Matrix deformation mechanisms in HP-LT tectonic mélanges — Microstructural record of jadeite blueschist from the Franciscan Complex, California

NASA Astrophysics Data System (ADS)

Wassmann, Sara; Stöckhert, Bernhard

2012-09-01

Exhumed high pressure-low temperature metamorphic mélanges of tectonic origin are believed to reflect high strain accumulated in large scale interplate shear zones during subduction. Rigid blocks of widely varying size are embedded in a weak matrix, which takes up the deformation and controls the rheology of the composite. The microfabrics of a highly deformed jadeite-blueschist from the Franciscan Complex, California, are investigated to help understand deformation mechanisms at depth. The specimen shows a transposed foliation with dismembered fold hinges and boudinage structures. Several generations of open fractures have been sealed to become veins at high-pressure metamorphic conditions. The shape of these veins, frequently restricted to specific layers, indicates distributed host rock deformation during and after sealing. Small cracks in jadeite and lawsonite are healed, with tiny quartz inclusions aligned along the former fracture surface. Large jadeite porphyroblasts show strain caps and strain shadows. Open fractures are sealed by quartz and new jadeite epitactically grown on the broken host. Monophase glaucophane aggregates consist of undeformed needles with a diameter between 0.1 and 2 μm, grown after formation of isoclinal folds. Only quartz microfabrics indicate some stage of crystal-plastic deformation, followed by annealing and grain growth. Aragonite in the latest vein generation shows retrogression to calcite along its rims. The entire deformation happened under HP-LT metamorphic conditions in the stability field of jadeite and quartz, at temperatures between 300 and 450 °C and pressures exceeding 1-1.4 GPa. The microfabrics indicate that dissolution precipitation creep was the predominant deformation mechanism, accompanied by brittle failure and vein formation at quasi-lithostatic pore fluid pressure. This indicates low flow strength and, combined with high strain rates expected for localized deformation between the plates, a very low viscosity of material in the interplate shear zone at a depth > 30-45 km.

Association of deformation and fluid events in the central Brooks Range fold-and-thrust belt, Northern Alaska

USGS Publications Warehouse

Moore, Thomas E.; Potter, Christopher J.; O'Sullivan, Paul B.; Shelton, Kevin L.; Underwood, Michael B.

2003-01-01

Ocentral Brooks Range consists of two superposed north-directed contractional orogens, one formed between 140-120 Ma and the other at ~60-45 Ma. The older orogen was an arc-continent collisional zone characterized by far-traveled allochthons and relatively low structural relief. The younger orogen is a retroarc thrust belt with relatively low amounts of shortening and high structural relief. Folding and thrusting of the younger episode is superimposed on the thin-skinned deformational wedge of the earlier orogen and also produced a frontal triangle zone in a thick sequence of mid-Cretaceous foreland basin sediments to the north. Stable isotope compositions of calcite and quartz veins indicate two fluid events including: (1) an earlier, higher-temperature (~250-300° C) event that produced veins in deformed Devonian clastic rocks, and (2) a younger, lower-temperature (~150° C) event that deposited veins in deformed Mississippian through Albian strata. The fluids in the first event had variable d18O values, but nearly constant d13C values buffered by limestone lithologies. The vein-forming fluids in the second event had similarly variable d18O values, but with distinctly lower d13C values as a result of oxidation of organic matter and/or methane. Zircon fission track ages demonstrate cooling to temperatures below 200° C between 140-120 Ma for the Devonian rocks, whereas zircon and apatite fission track ages show that Mississippian to Albian rocks were never heated above 200° C and cooled below 110-90° C at ~60-45 Ma. These data are interpreted as indicating that the older, high-temperature fluid event was active during thrusting at 120-140 Ma, and the younger fluid event during deformation at ~60-45 Ma. The data and results presented in this poster will be published in early 2004 in Moore and others (in press).

Neogene deformation in the West Antarctic Rift in the McMurdo Sound region from studies of the ANDRILL and Cape Roberts drill cores

NASA Astrophysics Data System (ADS)

Paulsen, T. S.; Wilson, T. J.; Jarrard, R. D.; Millan, C.; Saddler, D.; Läufer, A.; Pierdominici, S.

2010-12-01

Seismic studies indicate that the West Antarctic rift system records at least two distinct periods of Cenozoic rifting (Paleogene and Neogene) within the western Ross Sea. Natural fracture data from ANDRILL and Cape Roberts drill cores are revealing a picture of the geodynamic patterns associated with these rifting episodes. Kinematic indicators along faults recovered in drill cores document dominant normal faulting, although reverse and strike-slip faults are also present. Ongoing studies of mechanically twinned calcite in veins recovered in the drill cores yield predominantly vertical shortening strains with horizontal extension, consistent with a normal fault regime. In the Cape Roberts Project drill core, faults of inferred Oligocene age document a dominant NNE maximum horizontal stress associated with Paleogene rifting within the Victoria Land Basin. The NNE maximum horizontal stress at Cape Roberts is at an oblique angle to Transantarctic Mountain front, and consistent with previous interpretations invoking Cenozoic dextral transtensional shear along the boundary. In the ANDRILL SMS (AND-2A) drill core, faults and veins presumably associated with Neogene rifting document a dominant NNW to NE faulting of an expanded Lower Miocene section, although subsidiary WNW faulting is also present within the upper sections of oriented core. In the ANDRILL MIS (AND-1B) drill core, natural fractures are consistently present through the core below c. 450 mbsf, the estimated depth of the ‘B-clino’ seismic reflector. This is consistent with the presence of seismically-detectable faults below this horizon, which record the major faulting episode associated with Neogene rifting in the Terror Rift. Sedimentary intrusions and steep veins folded by compaction indicate that deformation occurred prior to complete lithification of the strata, suggesting that deformation was at least in part coeval with deposition. Faults and associated veins intersected in the AND-1B drill core also cut Pliocene and Pleistocene strata, suggesting that deformation has continued to the recent or may perhaps ongoing.

A Multi-analytical Approach for the Characterization of Marbles from Lesser Himalayas (Northwest Pakistan)

NASA Astrophysics Data System (ADS)

Fahad, M.; Iqbal, Y.; Riaz, M.; Ubic, R.; Redfern, S. A. T.

2015-12-01

The KP province of Pakistan hosts widespread deposits of thermo-metamorphic marbles that were extensively used as a building and ornamental stones since the time of earliest flourishing civilization in this region known as Indus Valley Civilization (2500 BC). The macroscopic characteristics of 22 marble varieties collected from three different areas of Lesser Himalayas (Northwest Pakistan), its chemical, mineralogical, petrographic features, temperature conditions of metamorphic re-crystallization, and the main physical properties are presented in order to provide a solid basis for possible studies on the provenance and distribution of building stones from this region. The results provide a set of diagnostic parameters that allow discriminating the investigated marbles and quarries. Studied marbles overlap in major phase assemblage, but the accessory mineral content, chemistry, the maximum grain size (MGS) and other petrographic characteristics are particularly useful in the distinction between them. On the basis of macroscopic features, the studied marbles can be classifies into four groups: (i) white (ii) grey-to-brown veined, (iii) brown-reddish to yellowish and (iv) dark-grey to blackish veined marbles. The results show that the investigated marbles are highly heterogeneous in both their geochemical parameters and minero-petrographic features. Microscopically, the white, grey-to-brown and dark-grey to blackish marbles display homeoblastic/granoblastic texture, and the brown-reddish to yellowish marbles display a heteroblastic texture with traces of slightly deformed polysynthetic twining planes. Minero-petrography, XRD, SEM and EPMA revealed that the investigated marbles chiefly consist of calcite along with dolomite, quartz, muscovite, pyrite, K-feldspar, Mg, Ti and Fe-oxides as subordinates. The magnesium content of calcite coexisting with dolomite was estimated by both XRD and EPMA/EDS, indicating the metamorphic temperature of re-crystallization from 414 - 628oC. The multi-analytical approach applied in the present study allows the best possible discrimination. The detailed databank relating to the quarried material, created here for the first time, provides a solid basis for possible studies on the provenance and distribution of building stones from these areas.

The "fault of the Pool" along the Congo River between Kinshasa and Brazzaville, R(D)Congo is no more a myth: Paleostress from small-scale brittle structures

NASA Astrophysics Data System (ADS)

Delvaux, Damien; Ganza, Gloire; Kongota, Elvis; Fukiabantu, Guilain; Mbokola, Dim; Boudzoumou, Florent; Miyouna, Timothée; Gampio, Urbain; Nkodia, Hardy

2017-04-01

Small-scale brittle structures such as shear fractures and tension joints are well developed in the indurated Paleozoic Inkisi red sandstones of the West-Congo Supergroup in the "pool" region of Kinshasa and Brazzaville, along the Congo River. They appear to be related to the evolution of intraplate stresses during the late Cretaceous-Paleogene period, possibly related to the opening of the South Atlantic. However, inferring paleostresses from such structures is difficult due to the lack of clear kinematic indicators, so we used mainly the geometry, architecture and sequence of the joint systems to infer paleostresses. A limited number of kinematic indicators for slip sense (displaced pebbles, irregularities on striated surfaces, slickensides) or extension (plume joints) confirm the general conclusions of the joint architecture analysis. We found evidence for two major brittle deformation systems, leading to almost orthogonal fracture sets. They both started by the development of plume joints, which progressively evolved into open tension joints, isolated shear fractures and long (up to several hundred meters) brittle shear zones. The first system started to develop under NE-SW extension and evolved into strike-slip with NNW-SSE horizontal compression while the second (and later), started to develop under NW-SE extension and evolved into strike-slip with NNE-SSW horizontal compression. The second brittle deformation episode was associated with fluid flow as shown by the presence of palygorskite-calcite veins in the most prominent fractures of the second fracture system. Along the NE-SW brittle shear zones which run parallel to the Congo River, carbonate-rich fault-gauge lenses are filled by sand derived from the crushed adjacent walls and calcite vein fragments injected at a high fluid pressure, with late precipitation of palygorskite. Our study demonstrates the existence of two fault systems between Kinshasa and Brazzaville, the first one orthogonal to the trend of the Congo River and the second one, orthogonal to it. This reconciles the different views on the suspected presence of a major fault in the Pool.

Thorium and rare earth minerals in the Powderhorn district, Gunnison County, Colorado

USGS Publications Warehouse

Olson, Jerry C.; Wallace, Stewart R.

1954-01-01

Thorium has been found since 1949 in at least 33 deposits in an area 6 miles wide and 20 miles long in the Powderhorn district, Gunnison County, Colo. The district is composed largely of pre-Jurassic metamorphic and igneous rocks, which are chiefly if not entirely pre-Cambrian in age. The metamorphic and igneous rocks are overlain by sandstone of the Morrison formation of Jurassic age, and by volcanic rocks of the Alboroto group and Hinsdale formation of Miocene and Pliocene (?) age, respectively. The thorium deposits occur in or near alkalic igneous rocks in which such elements as titanium, rare earths, barium, strontium, and niobium occur in greater-than-average amounts. The greatest mass of the alkalic igneous rocks the Iron Hill composite stoc,- occupies an area of 12 square miles in the southeastern part of the district. The age of the thorium deposits, like that of the alkalic igneous rocks, is not known other than pre-Jurassic. The thorium veins and mineralized shear zones range from a few inches to 18 feet in thickness and from a few feet to 3,500 feet in length. The veins are composed of calcite,.dolomite, siderite, ankerite, quartz, barite, pyrite, sphalerite, galena, goethite,. apatite, alkali feldspar, and many other minerals. The thorium occurs at least partly in thorite or hydrothorite. Sparse xenotime has been tentatively identified in one deposit. Several minerals containing rare earths of the cerium group as major constituents are found in carbonate veins near Iron Hill. Bastnaesite has been identified by X-ray methods, and cerite and synchisite are probably present also.The fluorapatite in some veins and in parts of the carbonate rock mass that occupies 2 square miles in the central part of the Iron Hill complex contains rare earths of the cerium group, generally in amounts of a fraction of a percent of the rock. The radioactivity of the deposits appears to be due almost entirely to thorium and its daughter products The ThO2 content of selected highgrade samples from the Little Johnnie vein is as much as 4 percent. The ThO2 content of the veins is generally less than 1 percent, however, and is only 0.05 to 0.1 percent in many of the veins studied. The little Johnnie vein, which was mapped in detail, can be traced discontinuously for a distance of more than 3,500 feet. The thoriumbearing material occurs as irregular veinlets and thin films introduced into the fault zone. The mineralized shear zone ranges from less than 6 inches to 5 feet in thickness. Near its west end the vein is broken by many faults in a zone that marks the edge of a roughly circular fault block, 11/2.miles in diameter, that has dropped 1,000 feet or more since the deposition of Miocene volcanic-rocks that now floor the Milkranch basin.

The Laramide Caborca orogenic gold belt of northwestern Sonora, Mexico; white mica 40Ar/39Ar geochronology from gold-rich quartz veins

USGS Publications Warehouse

Izaguirre, Aldo; Kunk, Michael J.; Iriondo, Alexander; McAleer, Ryan J.; Caballero-Martinez, Juan Antonio; Espinosa-Arámburu, Enrique

2016-02-12

The COGB is approximately 600 kilometers long and 60 to 80 km wide, trends northwest, and extends from west-central Sonora to southern Arizona and California. The COGB contains mineralized gold-rich quartz veins that contain free gold associated with white mica (sericite), carbonate minerals (calcite and ankerite), and sulfides such as pyrite and galena. Limited geochronologic studies exist for parts of the COGB, and previous work was concentrated in mining districts. These previous studies recorded mineralization ages of approximately 70 to 40 Ma. Therefore, some workers proposed that the orogenic gold mineralization in the region occurred during a single pulse that was associated with the Laramide Orogeny that took place during the Cretaceous to early Eocene in the western margin of North America. However, the geochronologic dataset was quite limited, making any regional interpretations tenuous. Accordingly, one of the objectives of this geochronology study was to get a better representative sampling of the COGB in order to obtain a more complete record of the mineralization history. The 63 samples presented in this work are broadly distributed throughout the area of the COGB and allow us to better test the hypothesis that mineralization occurred in a single pulse.

Geology of the Jabal Riah area, Kingdom of Saudi Arabia

USGS Publications Warehouse

Wells, J.D.

1982-01-01

The Jabal Riah area is in the southern part of the Jibal al Hamdah quadrangle (lat 19?00'00'' to 19?07'S0'' N., long 45?37'30'' to 43?45'00' E.) in the southeastern Precambrian Shield, Asir Province, Kingdom of Saudi Arabia. The Jabal Mahanid group of ancient gold mines, which is part of the Jabal Ishmas-Wadi Tathlith gold belt, is in the west-central part of the area. Rocks in the Jabal Riah area consist of Precambrian layered metasedimentary and metavolcanic rocks intruded by Precambrian igneous rocks. The metamorphic rocks are, from oldest to youngest, interlayered hornblende and biotite schist, quartz-biotite schist, hornblende schist, serpentinite, and chlorite schist. The igneous rocks are, from oldest to youngest, diorite-gabbro including dikes, granodiorite, monzogranite-granodiorite, leucocratic quartz porphyry, rhyolite, and aplite and pegmatite dikes. A large area of jasper replaces serpentinite. On the valley floors, recent alluvium and pediment deposits overlie the bedrock. The structure of the area is dominated by a dome centered over the eastern border of the area; leucocratic quartz porphyry forms the core of the dome. Minor folds and faults are present. The Jabal Mahanid group of ancient gold mines is on a northwest-trending vein system, and major ancient mine areas are found where the system splits or changes direction. The veins consist of zones of brecciated and crushed rock, which are generally less than 0.5 m wide but may be as wide as 1 m. These zones contain quartz and calcite stringers and commonly are along hornblende schist-serpentinite contacts; however, they also cut both units. Most aplite, pegmatite, and quartz dikes in the area are thin and discontinuous and are intruded along the vein trend. Similar veins, at the same stratigraphic interval, have been found beyond the northeastern part of the map area. The veins contain detectable gold and silver (median gold, approximately 0.14 ppm; median silver, approximately 1 ppm). Gold and silver are most abundant in calcium-rich rocks and veins; silver was not detected in igneous rocks. Altered wall-rock zones are mineralized as much as 10 m away from the veins. Away from the Jabal Mahanid vein-system, silver was detected in the jasper. Gold and silver were detected in minor brecciated and sheared structures and in metasedimentary rocks. Gold was detected in sericitized margins of the leucocratic quartz porphyry, in unaltered rhyolite, and in aplite dikes. The presence of unusual amounts of gold and silver over a wide area is indicated by the ancient gold mines along veins at or near the hornblende schist-serpentinite contact in the map area and to the south in the Hajrah-Hamdah area and by the widespread evidence of precious metals in igneous rocks and other vein structures. A domed-shaped area, approximately 30 km in diameter, is outlined by the hornblende schist-serpentinite contact and has leucocratic quartz prophyry in the middle. Additional study of this area might reveal economic concentrations of gold and silver.

Rapid Removal of Atmospheric CO2 by Urban Soils.

PubMed

Washbourne, Carla-Leanne; Lopez-Capel, Elisa; Renforth, Phil; Ascough, Philippa L; Manning, David A C

2015-05-05

The measured calcium carbonate content of soils to a depth of 100 mm at a large urban development site has increased over 18 months at a rate that corresponds to the sequestration of 85 t of CO2/ha (8.5 kg of CO2 m(-2)) annually. This is a consequence of rapid weathering of calcium silicate and hydroxide minerals derived from the demolition of concrete structures, which releases Ca that combines with CO2 ultimately derived from the atmosphere, precipitating as calcite. Stable isotope data confirm an atmospheric origin for carbonate carbon, and 14C dating indicates the predominance of modern carbon in the pedogenic calcite. Trial pits show that carbonation extends to depths of ≥1 m. Work at other sites shows that the occurrence of pedogenic carbonates is widespread in artificially created urban soils containing Ca and Mg silicate minerals. Appropriate management of fewer than 12000 ha of urban land to maximize calcite precipitation has the potential to remove 1 million t of CO2 from the atmosphere annually. The maximal global potential is estimated to be approximately 700-1200 Mt of CO2 per year (representing 2.0-3.7% of total emissions from fossil fuel combustion) based on current rates of production of industry-derived Ca- and Mg-bearing materials.

Lake Level Changes in the Mono Basin During the Last Deglacial Period

NASA Astrophysics Data System (ADS)

Wang, X.; Ali, G.; Hemming, S. R.; Zimmerman, S. R. H.; Stine, S. W.; Hemming, G.

2014-12-01

Mono Basin, located in the southwestern corner of the US Great Basin, has long been known to have experienced large lake level changes, particularly during the last deglaciation. But until recently it was not possible to establish a reliable lake level time series. We discovered many visually clean, white, shiny, dense calcite samples in the basin, associated with tufa deposits from high terraces. Their low thorium, but high uranium contents allow precise and reproducible U/Th age determinations. A highly resolved history of a minimum lake level through the last deglaciation can therefore be inferred based on sample locations and their ages. We found that the lake level reached ~2030 m asl at ~20.4 ka, evidenced by calcite coatings on a tufa mound at the upper Wilson Creek. The lake then rose to ~2075 m by ~19.1 ka, shown by calcite cements on conglomerates from the Hansen Cut terrace. The lake climbed to at least ~2140 m at ~15.9 ka, indicated by beach calcites from the east Sierra slope. Such timing of the highest lake stand, occurring within Heinrich Stadial 1, is reinforced by U/Th dates on calcite coatings from widespread locations in the basin, including the Bodie Hills and Cowtrack Mountains. The lake then dropped rapidly to ~2075 m at ~14.5 ka. It stood near this height over the next ~300 years, evidenced by a few-centimeter thick, laminated calcite rims on the Goat Ranch tufa mounds. It subsequently plunged to ~2007 m at ~13.8 ka, indicated by calcite coatings from cemetery road tufa mounds. The lake level came back to ~2030 m at ~12.9 ka, as seen in upper Wilson Creek tufa mounds. The lake level had a few fluctuations within the Younger Dryas, and even shot up to ~2075 m at ~12.0 ka. It then fell to levels in accord with Holocene climatic conditions. Relative to the present lake level of ~1950 m, Mono Lake broadly stood high during Heinrich Stadial 1 and Younger Dryas, when the climate was extremely cold over the North Atlantic, and the Asian monsoon was much weakened. When the climate shifted from cold to warm, the lake dropped significantly, during the transition between Heinrich Stadial 1 and the Bølling time interval, and then during the Allerød period. The U/Th ages on the tufa samples therefore not only establish a highly resolved chronology of hydroclimate history in the Mono Basin, but also put the lake level oscillations in a global context.

Carbonate pseudotachylite? from a Miocene extensional detachment, W. Cyclades, Greece.

NASA Astrophysics Data System (ADS)

Rice, A. Hugh N.; Grasemann, Bernhard

2016-04-01

Most pseudotachylites, both impact- and fault-related, occur in silicate-rich rocks, typically with 'granitoid' compositions. Examples of melting in carbonate rocks, excluding magmatic sources, are restricted to impact-events, except for a carbonate pseudotachylite in the Canalone Fault, S. Italy (Viganò et al. 2011). Another potential example of carbonate pseudotachylite, shown here, comes from the Miocene-aged W. Cycladic Detachment System, in Greece. Top-SSE ductile to brittle movement on this detachment, with a maximum displacement estimated at tens of kilometers, exhumed of HP-rocks. The carbonate pseudotachylite occurs within an <200 mm thick zone of cataclasites developed between footwall carbonate ultramylonites, containing thin layers and cm-scale boudins of quartzite, and hanging wall breccias; no contacts with the footwall ultramylonites or hanging wall breccias has been found (yet). The cataclasite zone, which can be traced along-strike for at least 90 m, over ~20 m elevation, comprises several distinct layers. In the sample described, five layers occur. The lowest (A; >43 mm thick), consists of dark (hematitic) red, ultra-fine grained unlayered carbonate with up to 40x10 mm rather rounded clasts of earlier generations of cataclasite, many with a quartzite composition. These clasts are fractured and partially separated, with a fine red carbonate matrix. No layering of the matrix or clasts is apparent. The clasts become finer and more abundant towards the boundary with Layer B. Layers B and D (~57 & ~20 mm thick) dominantly comprises protocataclasite with greyish quartz fragments separated by a carbonate matrix along narrow fractures. Zone C and E (~23 m & >15 mm thick) comprise pale pink carbonate-dominated rocks with abundant <30x5 mm-sized red carbonate clasts (+/- quartz fragments) of earlier cataclasite generations. These elongate clasts lie parallel to the overall banding, which is parallel to the ultramylonitic foliation (detachment surface). Smaller clasts are markedly more rounded and comprise carbonate and quartzite material and may have darker (?reaction) rims. No layering is seen in the pale pink groundmass although this is present in some elongate clasts. All layer boundaries are irregular and no principle slip surfaces have been seen. Injection veins from 1 to 9 mm wide and up to at least 100 mm long derive from the central layer (C), cutting the overall layering at a high angle and branching in several places. These veins contain clasts comparable to those in Layer C. Both thick and thin injection-veins are rimmed by impersistent white calcite suggesting that injection was associated with precipitation of calcite. Whether Layer C (and perhaps E also) is a carbonate pseudotachylite is unknown. Although the injection veins are suggestive of this, these also occur in conjunction with ultracataclasites (Craddock et al. 2012). The irregular boundaries between the layers and the lack of any principal slip surfaces might indicate decarbonation and/or fluidization of gouge layer (Rowe and Griffith, 2015). Finally, abundant tubules, with rounded profiles and mostly sub-circular shapes up to 1.2 mm across, occur in Layers C and E, and less so D; these could be interpreted to reflect vents formed by partial carbonate degassing during melting.

Early diagenesis of travertine deposits from the Tibetan Plateau - implications for 230Th/234U dating and palaeoenvironmental reconstruction

NASA Astrophysics Data System (ADS)

Wang, Zhijun; Meyer, Michael; Hoffmann, Dirk; Spötl, Christoph; Aldenderfer, Mark; Sanders, Diethard

2014-05-01

Travertine is calcium carbonate precipitated from hydrothermal springs. These terrestrial carbonate deposits can be used as high-resolution archives for reconstructing palaeoclimatic and palaeoenvironmental change and are also suitable for uranium-series disequilibrium (230Th/234U) dating. In many instances such spring deposits are associated with archaeological remains (e.g. stone artifacts and other traces of prehistoric human activity) and are therefore of interest for palaeoclimatologists and archaeologists alike. However, travertines are often affected by early diagenesis that can impact on the closed-system U-series behavior and on their geochemical signature. Hence, careful evaluation of the travertine microfabrics is required before these types of hot spring deposits can be accurately dated and used for paleoenviromental reconstruction. The Tibetan plateau hosts numerous hydrothermal spring deposits that occur along neotectonic faults. In this study, samples were collected from two archaeological travertine sites, i.e. Chusang and Tirthapuri, located in southern and western Tibet, respectively. Microscopic analysis of thin sections reveals a wide variety of crystal fabrics, including micrite, microspar and sparite, the latter can be composed of columnar or mosaic crystals, respectively. Areas where dendritic crystals are preserved are identified in our micrographs as well. Many of the Chusang and Tirthapuri travertine samples are porous. Drusy sparite is rimming most of the pore walls and a complex succession of secondary calcite phases precipitated in these pore spaces as well. The different generations of pore cement comprise micrite and sparite that can be laminated or fibrous in character and show sometimes evidence of an aragonite precursor. Detrital material like quartz, feldspar and other grains as well as humic and fulvic acids have been washed into the travertine pores too. Based on our microscopic analysis a complex growth history can be reconstructed for these Tibetan travertine samples with evidence for early diagenetic alteration. In particular the dendritic calcite is known to form under hydrothermal conditions and can thus be regarded as a primary hydrothermal fabric. However, this fabric is preserved as a relict in some samples only, suggestive of widespread early diagenesis. In other samples primary - biologically mediated - calcite precipitation can be inferred from microfabrics; however, recrystallization to mosaic sparite took place soon after deposition for most of them, too. Here we combine detailed petrographic investigations with XRD, microprobe as well as stable isotope analysis and a systematic 230Th/234U dating approach. We show that certain fabrics act as closed system with respect to radiogenic isotopes and are thus suitable for U-series dating. For the majority of fabrics encountered in our Tibetan samples, however, early diagenesis can be inferred and these fabrics also suffer from open-system behavior, hence, require and 'isochron' dating approach. Guidelines are established for identifying early diagenesis in these Tibetan travertine samples and implications for palaeoenvironmental reconstruction are discussed.

Resection of tumors of the neck of the pancreas with venous invasion: the "Whipple at the Splenic Artery (WATSA)" procedure.

PubMed

Strasberg, Steven M; Sanchez, Luis A; Hawkins, William G; Fields, Ryan C; Linehan, David C

2012-05-01

Tumors of the neck of the pancreas may involve the superior mesenteric and portal veins as well as the termination of the splenic vein. This presents a difficult problem since the pancreas cannot be transected through the neck as is standard in a Whipple procedure. Here, we present our method of resecting such tumors, which we term "Whipple at the Splenic Artery (WATSA)". The superior mesenteric and portal veins are isolated below and above the pancreas, respectively. The pancreas and splenic vein are divided just to the right of the point that the splenic artery contacts the superior border of the pancreas. This plane of transection is approximately 2 cm to the left of the pancreatic neck and away from the tumor. The superior mesenteric artery is cleared from the left side of the patient. With the specimen remaining attached only by the superior mesenteric and portal veins, these structures are clamped and divided. Reconstruction is performed with or without a superficial femoral vein graft. The splenic vein is not reconstructed. Ten cases have been performed to date without mortality. We have previously shown that the pattern of venous collateral development following occlusion of the termination of the splenic vein in the manner described is not similar to that of cases of sinistral (left sided) portal hypertension. Whipple at the splenic artery (WATSA) is a safe method for resection of tumors of the neck of the pancreas with vein involvement. It should be performed in high-volume pancreatic surgery centers.

Genetic therapy for vein bypass graft disease: current perspectives.

PubMed

Simosa, Hector F; Conte, Michael S

2004-01-01

Although continued progress in endovascular technology holds promise for less invasive approaches to arterial diseases, surgical bypass grafting remains the mainstay of therapy for patients with advanced coronary and peripheral ischemia. In the United States, nearly 400,000 coronary and 100,000 lower extremity bypass procedures are performed annually. The autogenous vein, particularly the greater saphenous vein, has proven to be a durable and versatile arterial substitute, with secondary patency rates at 5 years of 70 to 80% in the extremity. However, vein graft failure is a common occurrence that incurs significant morbidity and mortality, and, to date, pharmacologic approaches to prolong vein graft patency have produced limited results. Dramatic advances in genetics, coupled with a rapidly expanding knowledge of the molecular basis of vascular diseases, have set the stage for genetic interventions. The attraction of a genetic approach to vein graft failure is based on the notion that the tissue at risk is readily accessible to the clinician prior to the onset of the pathologic process and the premise that genetic reprogramming of cells in the wall of the vein can lead to an improved healing response. Although the pathophysiology of vein graft failure is incompletely understood, numerous relevant molecular targets have been elucidated. Interventions designed to influence cell proliferation, thrombosis, inflammation, and matrix remodeling at the genetic level have been described, and many have been tested in animal models. Both gene delivery and gene blockade strategies have been investigated, with the latter reaching the stage of advanced clinical trials.

Fracture permeability in the Matalibong-25 corehole, Tiwi geothermal field, Philippines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nielson, D.L.; Moore, J.N.; Clemente, W.C.

1996-12-31

The Tiwi geothermal field is located in southern Luzon on the northeast flank of Mt. Malinao, an andesitic volcano that was active 0.5 to 0.06 Ma. Matalibong-25 (Mat-25) was drilled through the Tiwi reservoir to investigate lithologic and fracture controls on reservoir permeability and to monitor reservoir pressure. Continuous core was collected from 2586.5 to 8000 feet (789 to 2439 meters) with greater than 95% recovery. The reservoir rocks observed in Mat-25 consist mainly of andesitic and basaltic lavas and volcaniclastic rocks above 6600 feet depth (2012 meters) and andesitic sediments below, with a transition from subaerial to subaqueous (marine)more » deposition at 5250 feet (1601 meters). The rocks in the reservoir interval are strongly altered and veined. Common secondary minerals include chlorite, illite, quartz, calcite rite, epidote, anhydrite, adularia and wairakite. An {sup 39}Ar/{sup 40}Ar age obtained on adularia from a quartz-adularia-cemented breccia at a depth of 6066 feet (2012 meters) indicates that the hydrothermal system has been active for at least 320,000 years. Fractures observed in the core were classified as either veins (sealed) or open fractures, with the latter assumed to represent fluid entries in the geothermal system. Since the core was not oriented, only fracture frequency and dip angle with respect to the core axis could be determined. The veins and open fractures are predominantly steeply dipping and have a measured density of up to 0.79 per foot in the vertical well. Below 6500 feet (1982 meters) there is a decrease in fracture intensity and in fluid inclusion temperatures.« less

Hydrothermal alteration, ore fluid characteristics, and gold depositional processes along a trondhjemite-komatiite contact at Tarmoola, Western Australia

USGS Publications Warehouse

Duuring, P.; Hagemann, S.G.; Cassidy, K.F.; Johnson, C.A.

2004-01-01

Tarmoola is a structurally controlled Archean orogenic gold deposit hosted in greenschist facies metamorphosed komatiite and trondhjemite in the Leonora district of the Eastern Goldfields province, Yilgarn craton. High-grade (>1 g/t Au) orebodies are located in komatiite wall rock adjacent to the eastern and northeastern margins of the asymmetrical, north-south-striking, Tarmoola trondhjemite intrusion. Gold-bearing veins post-date trondhjemite emplacement (ca. 2700 Ma), quartz diorite dikes (ca. 2667 Ma), and regional greenschist facies metamorphism. Textures and crosscutting relationships in gold-bearing veins indicate two stages of hydrothermal fluid infiltration associated with a single gold-related hydrothermal event: a volumetrically dominant, but gold-poor, stage I fluid and a gold-rich stage II fluid. Gold-bearing veins contain stage I milky quartz and pyrite that are overprinted by stage II quartz-ankerite-muscovite-chalcopyrite-sphalerite-galena-gold-tellurides ?? albite ?? chlorite ?? fuchsite ?? epidote ?? scheelite. Stage I hydrothermal alteration assemblages are different in trondhjemite and komatiite due to contrasting reactions between a common ore fluid and disparate wall-rock chemistry. Stage II fluid-wall rock interaction was minor compared to stage I and is indicated by the overprinting of stage I mineral assemblages by stage II microveins. Wall-rock alteration proximal to veins in trondhjemite is characterized by replacement of igneous plagioclase, amphibole, biotite, and metamorphic chlorite by hydrothermal quartz, muscovite, ankerite, calcite, pyrite, chalcopyrite, sphalerite, galena, tellurides, and gold, whereas in proximal alteration in komatiite, metamorphic chlorite and talc are replaced by ankerite, quartz, muscovite, albite, chlorite, fuchsite, pyrite, chalcopyrite, sphalerite, galena, tellurides, and gold. The stage II fluid was enriched in H2O, CO2, Si, Ca, K, Na, S, Au, Ag, Cu, Pb, W, Bi, As, Mo, Zn, and Te. Based on fluid inclusion studies and stage II mineral equilibria, gold deposited from a homogeneous, neutral to slightly alkaline (pH 5.1-5.5), reduced, low-salinity (<5.5 wt % NaCl equiv) fluid that had a bulk composition of 78 mole percent H2O and 21 mole percent CO2, and trace amounts of CH4, C2H6, H2, Ar, H2S, and He. Gold deposition occurred at 300?? ?? 50??C and 0.5 to 3.0 kbars. Assuming lithostatic fluid pressures, gold precipitated at a 2- to 10-km depth. Stage II gray quartz ??18Ofluid values range from 5.9 to 7.5 per mil, whereas ??Dfluid values calculated from the dehydration of muscovite grains and measured directly from bulk fluid inclusion analyses of stage II gray quartz have ranges of -9 to -35 and -27 to -28 per mil, respectively. Hydrothermal ore fluids were transported from greater crustal depths to the site of gold deposition during the district-scale D3 event by shallowly W dipping, reverse brittle-ductile shear zones in supracrustal rock and along the steeply east dipping trondhjemite contact. Associated subhorizontal east-west shortening caused the reactivation of the eastern trondhjemite margin and subparallel foliation, which facilitated the transport of hydrothermal fluids and the generation of gold-bearing veins and hydrothermal alteration zones in komatiite. East-west-striking fractures in trondhjemite aided the lateral migration of ore fluids away from trondhjemite margins and the formation of east-west-striking gold-bearing veins and broad alteration zones. Gold was most likely transported in the stage II fluid as bisulfide complexes. The sulfidation of trondhjemite and komatiite wall rock by the stage II fluid caused the destabilization of An bisulfide complexes and gold deposition. Potassium, Ca, and CO2 metasomatism of komatiite wall rock may have enhanced gold deposition via the acidification of the stage II fluid. The physicochemical characteristics of the Tarmoola ore fluid and relative timing of gold mineralization are consistent with the Yilgarn-wide,

AMS 14C and 230Th/U dating on stalagmites from North Altai Mountain, Siberia, Russia

NASA Astrophysics Data System (ADS)

Li, H. C.; Yin, J. J.; Blyakharchuk, T.; Shen, C. C.

2017-12-01

Three stalagmites, two from Lunnaya Cave (LUN-1 and LUN-2, 52º40.729'N, 88º43.854' E, 481 m a.s.l.), one from Nadezhda Cave (HOP-1, 52º38.872'N, 88º39.194'E, 550 m a.s.l.) located along Mrassy River in the northern Altai Mountains, Siberia, Russia were collected in the summer of 2016 for paleoclimate reconstruction. HOP-1 is a 21-cm long stalagmite which contains very low U content (238U = 70 ppb) and relatively high Th content (232Th = 2 9.3 ppb), resulting in unsuccessful 230Th/U dating (-262 ± 284 yr BP in the top and -19,935 ± 22,246 yr BP). Thirty one AMS 14C dates from 27 horizons of the stalagmite provide a detailed chronology, showing that the stalagmite grew from 6,350 ± 45 yr BP to 490 ± 10 Calib. yr BP. Both LUN-1 and LUN-2 are about 20-cm long. The growth feature of LUN-2 is similar to that of HOP-1 with continuous growth, clear bands of depositional cycles in white non-transparent calcite, whereas LUN-1 has light yellow transparent calcite in the center part with multiple growth hiatuses. The 230Th/U dates show that LUN-1 from 2725 ± 775 yr BP at 193 mm depth to 823 ± 28 yr BP at 12 mm depth with very fast growth rate during 900 1500 yr BP. The AMS 14C dates of LUN-1 provide similar growth pattern with very fast growth between the first hiatus at 12 mm depth and the second hiatus at 155 cm depth. Six 14C dates from this fast growth period are all around 1500 Calib. yr BP without a correct age sequence. Two 14C dates from the top 12 mm exhibit "nuclear bomb signal" (percentage of modern carbon >100%). Similar ages of AMS 14C and 230Th/U dating results in the lower part indicate that dead carbon influence in radiocarbon ages are negligible. 230Th/U dating is not successful for LUN-2. The preliminary AMS 14C dating on LUN-2 shows that the stalagmite continuously deposited from 13335 ± 150 Calib. yr BP. All three stalagmites do not have growth deposition during the Little Ice Age due to cold and dry climates. Further work on stable isotope analyses will provide us high-resolution paleoclimate changes since the deglaciation in the study area.

Genesis of the vein-type tungsten mineralization at Nyakabingo (Rwanda) in the Karagwe-Ankole belt, Central Africa

NASA Astrophysics Data System (ADS)

Dewaele, S.; De Clercq, F.; Hulsbosch, N.; Piessens, K.; Boyce, A.; Burgess, R.; Muchez, Ph.

2016-02-01

The vein-type tungsten deposit at Nyakabingo in the central Tungsten belt of Rwanda is located in the eastern flank of the complex Bumbogo anticlinal structure. The host rock is composed of alternating sequences of sandstones, quartzites, and black pyritiferous metapelitic rocks. Two types of W-mineralized quartz veins have been observed: bedding-parallel and quartz veins that are at high angle to the bedding, which are termed crosscutting veins. Both vein types have been interpreted to have been formed in a late stage of a compressional deformation event. Both vein types are associated with small alteration zones, comprising silicification, tourmalinization, and muscovitization. Dating of muscovite crystals at the border of the veins resulted in a maximum age of 992.4 ± 1.5 Ma. This age is within error similar to the ages obtained for the specialized G4 granites (i.e., 986 ± 10 Ma). The W-bearing minerals formed during two different phases. The first phase is characterized by scheelite and massive wolframite, while the second phase is formed by ferberite pseudomorphs after scheelite. These minerals occur late in the evolution of the massive quartz veins, sometimes even in fractures that crosscut the veins. The ore minerals precipitated from a H2O-CO2-CH4-N2-NaCl-(KCl) fluid with low to moderate salinity (0.6-13.8 eq. wt% NaCl), and minimal trapping temperatures between 247 and 344 °C. The quartz veins have been crosscut by sulfide-rich veins. Based on the similar setting, mineralogy, stable isotope, and fluid composition, it is considered that both types of W-mineralized quartz veins formed during the same mineralizing event. Given the overlap in age between the G4 granites and the mineralized quartz veins, and the typical association of the W deposits in Rwanda, but also worldwide, with granite intrusions, W originated from the geochemically specialized G4 granites. Intense water-rock interaction and mixing with metamorphic fluids largely overprinted the original magmatic-hydrothermal signature.

Subglacial Calcites from Northern Victoria Land: archive of Antarctic volcanism in the Last Glacial Maximum

NASA Astrophysics Data System (ADS)

Frisia, Silvia; Weirich, Laura; Hellstrom, John; Borsato, Andrea; Golledge, Nicholas R.; Anesio, Alexandre M.; Bajo, Petra; Drysdale, Russell N.; Augustinus, Paul C.; Barbante, Carlo; Cooper, Alan

2017-04-01

Subglacial carbonates bear similarities to stalagmites in their fabrics and the potential to obtain precise chronologies using U-series methods. Their chemical properties also reflect those of their parent waters, which, in contrast to stalagmites, are those of subglacial meltwaters. In analogy to speleothems, stable Carbon isotope ratios and trace elements such as Uranium, Iron and Manganese provide the opportunity to investigate ancient extreme environments without the need to drill through thousands of metres of ice. Sedimentological, geochemical and microbial evidence preserved in LGM subglacial calcites from Northern Victoria Land, close to the East Antarctic Ice Sheet margin, allow us to infer that subglacial volcanism was active in the Trans Antarctic Mountain region and induced basal ice melting. We hypothesize that a meltwater reservoir was drained and injected into interconnected basal pore systems where microbial processes enhanced bedrock weathering and, thus, released micronutrients. Volcanic influence is supported by the presence of fluorine (F) and sulphur in sediment-laden calcite layers containing termophilic species. Notably, calcite δ13C points to dissolved inorganic carbon evolved from subglacial metabolic processes. Once transported to the sea, soluble iron likely contributed to fertilizing the Southern Ocean and CO2 drawdown. This is the first well-dated evidence for LGM volcanism in Antarctica, which complements the record of volcanic eruptions retrieved from Talos Dome ice core, and supports the hypothesis of large-scale volcanism as an important driver of climate change. We conclude that subglacial carbonates are equivalent to speleothems in their palaeoclimate potential and may become a most useful source of information of ecosystems and processes at peak glacials in high altitude/high latitude settings.

Large-Scale Experiments in Microbially Induced Calcite Precipitation (MICP): Reactive Transport Model Development and Prediction

NASA Astrophysics Data System (ADS)

Nassar, Mohamed K.; Gurung, Deviyani; Bastani, Mehrdad; Ginn, Timothy R.; Shafei, Babak; Gomez, Michael G.; Graddy, Charles M. R.; Nelson, Doug C.; DeJong, Jason T.

2018-01-01

Design of in situ microbially induced calcite precipitation (MICP) strategies relies on a predictive capability. To date much of the mathematical modeling of MICP has focused on small-scale experiments and/or one-dimensional flow in porous media, and successful parameterizations of models in these settings may not pertain to larger scales or to nonuniform, transient flows. Our objective in this article is to report on modeling to test our ability to predict behavior of MICP under controlled conditions in a meter-scale tank experiment with transient nonuniform transport in a natural soil, using independently determined parameters. Flow in the tank was controlled by three wells, via a complex cycle of injection/withdrawals followed by no-flow intervals. Different injection solution recipes were used in sequence for transport characterization, biostimulation, cementation, and groundwater rinse phases of the 17 day experiment. Reaction kinetics were calibrated using separate column experiments designed with a similar sequence of phases. This allowed for a parsimonious modeling approach with zero fitting parameters for the tank experiment. These experiments and data were simulated using PHT3-D, involving transient nonuniform flow, alternating low and high Damköhler reactive transport, and combined equilibrium and kinetically controlled biogeochemical reactions. The assumption that microbes mediating the reaction were exclusively sessile, and with constant activity, in conjunction with the foregoing treatment of the reaction network, provided for efficient and accurate modeling of the entire process leading to nonuniform calcite precipitation. This analysis suggests that under the biostimulation conditions applied here the assumption of steady state sessile biocatalyst suffices to describe the microbially mediated calcite precipitation.

Geology of the Vienna Mineralized Area, Blaine and Camas Counties, Idaho

USGS Publications Warehouse

Mahoney, J. Brian; Horn, Michael C.

2005-01-01

The Vienna mineralized area of south-central Idaho was an important silver-lead-producing district in the late 1800s and has intermittently produced lead, silver, zinc, copper, and gold since that time. The district is underlain by biotite granodiorite of the Cretaceous Idaho batholith, and all mineral deposits are hosted by the biotite granodiorite. The granodiorite intrudes Paleozoic sedimentary rocks of the Sun Valley Group, is overlain by rocks of the Eocene Challis Volcanic Group, and is cut by numerous northeast-trending Eocene faults and dikes. Two mineralogically and texturally distinct vein types are present in a northwest- and east-trending conjugate shear-zone system. The shear zones postdate granodiorite emplacement and joint formation, but predate Eocene fault and dike formation. Ribbon veins consist of alternating bands of massive vein quartz and silver-sulfide (proustite and pyrargyrite) mineral stringers. The ribbon veins were sheared and brecciated during multiple phases of injection of mineralizing fluids. A quartz-sericite-pyrite-galena vein system was subsequently emplaced in the brecciated shear zones. Both vein systems are believed to be the product of mesothermal, multiphase mineralization. K-Ar dating of shear-zone sericite indicates that sericitization occurred at 80.7?2.8 Ma; thus mineralization in the Vienna mineralized area probably is Late Cretaceous in age.

Modelling the evolution of complex conductivity during calcite precipitation on glass beads

NASA Astrophysics Data System (ADS)

Leroy, Philippe; Li, Shuai; Jougnot, Damien; Revil, André; Wu, Yuxin

2017-04-01

When pH and alkalinity increase, calcite frequently precipitates and hence modifies the petrophysical properties of porous media. The complex conductivity method can be used to directly monitor calcite precipitation in porous media because it is sensitive to the evolution of the mineralogy, pore structure and its connectivity. We have developed a mechanistic grain polarization model considering the electrochemical polarization of the Stern and diffuse layers surrounding calcite particles. Our complex conductivity model depends on the surface charge density of the Stern layer and on the electrical potential at the onset of the diffuse layer, which are computed using a basic Stern model of the calcite/water interface. The complex conductivity measurements of Wu et al. on a column packed with glass beads where calcite precipitation occurs are reproduced by our surface complexation and complex conductivity models. The evolution of the size and shape of calcite particles during the calcite precipitation experiment is estimated by our complex conductivity model. At the early stage of the calcite precipitation experiment, modelled particles sizes increase and calcite particles flatten with time because calcite crystals nucleate at the surface of glass beads and grow into larger calcite grains. At the later stage of the calcite precipitation experiment, modelled sizes and cementation exponents of calcite particles decrease with time because large calcite grains aggregate over multiple glass beads and only small calcite crystals polarize.

An aminostratigraphy for the British Quaternary based on Bithynia opercula

PubMed Central

Penkman, Kirsty E.H.; Preece, Richard C.; Bridgland, David R.; Keen, David H.; Meijer, Tom; Parfitt, Simon A.; White, Tom S.; Collins, Matthew J.

2013-01-01

Aminostratigraphies of Quaternary non-marine deposits in Europe have been previously based on the racemization of a single amino acid in aragonitic shells from land and freshwater molluscs. The value of analysing multiple amino acids from the opercula of the freshwater gastropod Bithynia, which are composed of calcite, has been demonstrated. The protocol used for the isolation of intra-crystalline proteins from shells has been applied to these calcitic opercula, which have been shown to more closely approximate a closed system for indigenous protein residues. Original amino acids are even preserved in bithyniid opercula from the Eocene, showing persistence of indigenous organics for over 30 million years. Geochronological data from opercula are superior to those from shells in two respects: first, in showing less natural variability, and second, in the far better preservation of the intra-crystalline proteins, possibly resulting from the greater stability of calcite. These features allow greater temporal resolution and an extension of the dating range beyond the early Middle Pleistocene. Here we provide full details of the analyses for 480 samples from 100 horizons (75 sites), ranging from Late Pliocene to modern. These show that the dating technique is applicable to the entire Quaternary. Data are provided from all the stratotypes from British stages to have yielded opercula, which are shown to be clearly separable using this revised method. Further checks on the data are provided by reference to other type-sites for different stages (including some not formally defined). Additional tests are provided by sites with independent geochronology, or which can be associated with a terrace stratigraphy or biostratigraphy. This new aminostratigraphy for the non-marine Quaternary deposits of southern Britain provides a framework for understanding the regional geological and archaeological record. Comparison with reference to sites yielding independent geochronology, in combination with other lines of evidence, allows tentative correlation with the marine oxygen isotope record. PMID:23396683

Chemistry and petrography of calcite in the KTB pilot borehole, Bavarian Oberpfalz, Germany

USGS Publications Warehouse

Komor, S.C.

1995-01-01

The KTB pilot borehole in northeast Bavaria, Germany, penetrates 4000 m of gneiss, amphibolite, and subordinate calc-silicate, lamprophyre and metagabbro. There are three types of calcite in the drilled section: 1) metamorphic calcite in calc-silicate and marble; 2) crack-filling calcite in all lithologies; and 3) replacement calcite in altered minerals. Crack-filling and replacement calcite postdate metamorphic calcite. Multiple calcite generations in individual cracks suggest that different generations of water repeatedly flowed through the same cracks. Crack-filling mineral assemblages that include calcite originally formed at temperatures of 150-350??C. Presently, crack-filling calcite is in chemical and isotopic equilibrium with saline to brackish water in the borehole at temperatures of ???120??C. The saline to brackish water contains a significant proportion of meteoric water. Re-equilibration of crack-filling calcite to lower temperatures means that calcite chemistry tells us little about water-rock interactions in the crystal section of temperatures higher than ~120??C. -from Author

Genesis of the Abu Marawat gold deposit, central Eastern Desert of Egypt

NASA Astrophysics Data System (ADS)

Zoheir, Basem A.; Akawy, Ahmed

2010-06-01

Gold mineralisation at the Abu Marawat mine, central Eastern Desert of Egypt, is related to a system of massive and sheared, milky quartz veins cutting a sequence of Neoproterozoic island arc metavolcanic/volcaniclastic rocks and related banded iron formation (BIF). Sulphide-bearing quartz veins and related hydrothermal breccia bodies display a range of textures including sheared, boudinaged and recrystallised quartz, open space filling and microbreccia. These variable textures imply a complex history of crack-seal mechanism characterising the relation between mineral deposition and a major N-S-trending shear zone, during a late brittle-ductile deformation event which affected the area at about 550 Ma. Gold-base metal mineralisation is associated with brecciation and fracturing of the iron ore bands, close to silicified shears and related quartz veins. The auriferous quartz lodes are characterised by the occurrence of visible pyrite-chalcopyrite ± pyrrhotite ± sphalerite ± galena mineralisation. Gold is refractory in pyrite and chalcopyrite, but rare visible gold/electrum and telluride specks were observed in a few samples. Hydrothermal alteration includes pervasive silicification, pyritisation, sericitisation, carbonatisation confined to a delicate set of veins and altered shears, and a more widespread propylitic alteration assemblage (quartz + chlorite + pyrite + calcite ± epidote). Fluid inclusion petrography and microthermometric studies suggest heterogeneous trapping of a low-salinity (1.4-6.7 wt.% eq. NaCl) aqueous solution and a carbonic fluid. Evidence for fluid immiscibility during ore formation includes variable liquid/vapour ratios in inclusions along individual trails and bulk inclusion homogenisation into liquid and occasionally to vapour at comparable temperatures. The trapping conditions of intragranular aqueous-carbonic inclusions approximate 264-378 °C at 700-1300 bar. Similar temperature estimates have been obtained from Al-in-chlorite geothermometry of chlorite associated with sulphides in the mineralised quartz veins. Fracturing enhanced fluid circulation through the wallrock and related BIF, allowing reaction of the S-bearing ore fluid with iron oxides. This caused pyrite formation and concomitant Au precipitation, enhanced by fluid immiscibility as H 2S partitioned preferentially into the carbonic phase. The ore fluids may have originated from granitoid intrusions (likely the post-Hammamat felsites, whereas gold and base metals might have been leached from the Abu Marawat basic metavolcanics.

Boxwork and ferromanganese coatings in hypogenic caves: An example from Sima de la Higuera Cave (Murcia, SE Spain)

NASA Astrophysics Data System (ADS)

Gázquez, Fernando; Calaforra, José-María; Rull, Fernando

2012-12-01

This paper examines the greyish-blue deposits that were recently discovered in the lower levels of the Sima de la Higuera Cave (Murcia, SE Spain) which occur as patinas over the walls and ceilings, as well as coating boxwork formations. Their mineralogy was determined using XRD and micro-Raman spectroscopy, while EDX microanalysis was used to determine their elemental composition. The mineralogical analyses revealed the presence of Mn oxides (todorokite and pyrolusite) and Fe with a low degree of crystallinity, whereas EDX microprobe showed elevated concentrations of Mn (38.2 wt.%), Fe (15.2 wt.%) and Pb (8.1 wt.%). The ferromanganese oxyhydroxides occur as botryoidal aggregates overlying blades of calcite that have a visibly sugary texture. The speleogenetic model proposed describes (1) an initial phase of precipitation of hydrothermal calcite veins (of hypogenic origin) within the fissures of the host rock under phreatic conditions and (2) a subsequent vadose phase involving preferential corrosion of the carbonate host rock caused by lowering of the pH resulting from CO2 diffusion in condensed water and oxidation of Fe and Mn under aerobic conditions, probably mediated by microorganisms. It is this later phase that gave rise to the boxwork. The boxwork of the Sima de la Higuera Cave is a singular example of a formation that is generated by dissolution-corrosion of the rock due to acidification caused by oxidation of iron and manganese.

Timing of porphyry (Cu-Mo) and base metal (Zn-Pb-Ag-Cu) mineralisation in a magmatic-hydrothermal system—Morococha district, Peru

NASA Astrophysics Data System (ADS)

Catchpole, Honza; Kouzmanov, Kalin; Bendezú, Aldo; Ovtcharova, Maria; Spikings, Richard; Stein, Holly; Fontboté, Lluís

2015-12-01

The Morococha district in central Peru is characterised by economically important Cordilleran polymetallic (Zn-Pb-Ag-Cu) vein and replacement bodies and the large Toromocho porphyry Cu-Mo deposit in its centre. U-Pb, Re-Os, and 40Ar/39Ar geochronology data for various porphyry-related hydrothermal mineralisation styles record a 3.5-Ma multi-stage history of magmatic-hydrothermal activity in the district. In the late Miocene, three individual magmatic-hydrothermal centres were active: the Codiciada, Toromocho, and Ticlio centres, each separated in time and space. The Codiciada centre is the oldest magmatic-hydrothermal system in the district and consists of a composite porphyry stock associated with anhydrous skarn and quartz-molybdenite veins. The hydrothermal events are recorded by a titanite U-Pb age at 9.3 ± 0.2 Ma and a molybdenite Re-Os age at 9.26 ± 0.03 Ma. These ages are indistinguishable from zircon U-Pb ages for porphyry intrusions of the composite stock and indicate a time span of 0.2 Ma for magmatic-hydrothermal activity. The small Ticlio magmatic-hydrothermal centre in the west of the district has a maximum duration of 0.3 Ma, ranging from porphyry emplacement to porphyry mineralisation at 8.04 ± 0.14 Ma (40Ar/39Ar muscovite cooling age). The Toromocho magmatic-hydrothermal centre has a minimum of five recorded porphyry intrusions that span a total of 1.3 Ma and is responsible for the formation of the giant Toromocho Cu-Mo deposit. At least two hydrothermal pulses are identified. Post-dating a first pulse of molybdenite mineralisation, wide-spread hydrous skarn covers an area of over 6 km2 and is recorded by five 40Ar/39Ar cooling ages at 7.2-6.8 Ma. These ages mark the end of the slowly cooling and long-lived Toromocho magmatic-hydrothermal centre soon after last magmatic activity at 7.26 ± 0.02 Ma. District-wide (50 km2) Cordilleran base metal vein and replacement bodies post-date the youngest recorded porphyry mineralisation event at Toromocho by more than 0.5 Ma. Polymetallic veins (5.78 ± 0.10 and 5.72 ± 0.18 Ma; 40Ar/39Ar ages) and the Manto Italia polymetallic replacement bodies (6.23 ± 0.12 and 6.0 ± 0.2 Ma; 40Ar/39Ar ages) are interpreted to have been formed by a single hydrothermal pulse. Hydrothermal activity ceased after the formation of the base metal vein and replacement bodies. Overlapping monazite U-Pb (8.26 ± 0.18 Ma) and muscovite 40Ar/39Ar ages (8.1 ± 0.5 Ma) from the early base metal stage of one Cordilleran vein sample in the Sulfurosa area provide evidence that a discrete hydrothermal pulse was responsible for polymetallic vein formation 2.6 Ma prior to the district-wide polymetallic veins. These ages pre-date those of Toromocho porphyry Cu-Mo formation and show that Zn-Pb-Ag-Cu mineralisation formed during several discrete magmatic-hydrothermal pulses in the same district.

Oblique collision and accretion of the Netherlands Leeward Antilles island arc: A structural analysis of the Caribbean-South American plate boundary zone

NASA Astrophysics Data System (ADS)

Beardsley, Amanda Gail

2007-12-01

The Netherlands Leeward Antilles volcanic island arc is an ideal natural laboratory to study the evolution of the Caribbean-South American plate boundary. The Leeward Antilles islands (Aruba, Curacao, and Bonaire) are located offshore western Venezuela, within the obliquely convergent diffuse plate boundary zone. Outcrop analysis, microthermometry, and 2D marine seismic reflection data provide evidence of three generations of regional deformation since the Late Cretaceous. Outcrop analysis of structural features, including faults, joints, and veins, characterizes the kinematic history of the islands. Fluid inclusion analysis of quartz and calcite veins coupled with apatite fission-track dating provides the island exhumation history. Finally, marine reflection seismic data processing and interpretation of newly acquired data elucidates offshore structures to integrate with our onshore results. The oldest regional deformation, resulting in both ductile (D1) and brittle (F 1) structures, is attributed to displacement partitioning along the arcuate Caribbean plate boundary. Associated crustal thinning initiated island exhumation, at a rate of 0.18 km/my, from a maximum burial depth of 6 km in the Late Cretaceous (˜89 Ma). Coeval with D1/F1 deformation and exhumation, stretching of the island arc resulted in extensive basin rifting that separated the island blocks. At ˜55 Ma, a change in the relative motion of the Caribbean plate altered plate boundary dynamics. Displacement along the right-lateral Caribbean transform fault and Oca - San Sebastian - El Pilar strike-slip fault system created a wrench tectonic regime within the diffuse plate boundary zone. A second generation of brittle structures (F2) developed while the islands were at a maximum burial depth of 2 km during the Paleocene/Eocene. Since ˜45 Ma, continued motion along the strike-slip fault systems and oblique plate convergence resulted in the youngest generation of structural features (F3). Regional tectonics control the ongoing steady-state exhumation of the islands at a rate of 0.04 km/my. Most recently, the northeast escape of the Maracaibo block also drives deformation within the diffuse plate boundary zone. Overall, the Caribbean-South American plate boundary geometry has evolved with diachronous deformation, from west to east, accompanied by 135° of clockwise block rotation during collision and accretion of the Leeward Antilles since the Late Cretaceous.

Lower plate deformation structures along the Costa Rica erosive plate boundary - results from IODP Expedition 344 (CRISP 2)

NASA Astrophysics Data System (ADS)

Brandstätter, Jennifer; Kurz, Walter; Micheuz, Peter; Krenn, Kurt

2015-04-01

The primary objective of Integrated Ocean Drilling Program (IODP) Expedition 344 offshore the Osa Peninsula in Costa Rica was to sample and quantify the material entering the seismogenic zone of the Costa Rican erosive subduction margin. Fundamental to this objective is an understanding of the nature of both the subducting Cocos plate crust and of the overriding Caribbean plate. The subducting Cocos plate is investigated trying to define its hydrologic system and thermal state. The forearc structures recorded by the sediment deposited on the forearc, instead, document periods of uplift and subsidence and provide important information about the process of tectonic erosion that characterizes the Costa Rica margin. Offshore the western margin of Costa Rica, the oceanic Cocos plate subducts under the Caribbean plate, forming the southern end of the Middle America Trench. Subduction parameters including the age, convergence rate, azimuth, obliquity, morphology, and slab dip all vary along strike. The age of the Cocos plate at the Middle America Trench decreases from 24 Ma offshore the Nicoya Peninsula to 15 Ma offshore the Osa Peninsula. Subduction rates vary from 70 mm/y offshore Guatemala to 90 mm/y offshore southern Costa Rica. Convergence obliquity across the trench varies from offshore Nicaragua, where it is as much as 25° oblique, to nearly orthogonal southeast of the Nicoya Peninsula. Passage of the Cocos plate over the Galapagos hotspot created the aseismic Cocos Ridge, an overthickened welt of oceanic crust. This ridge is ~25 km thick, greater than three times normal oceanic crustal thickness. During IODP Expedition 344, the incoming Cocos plate was drilled at sites U1381 and U1414. Site U1381 is located ~4.5 km seaward of the deformation front offshore the Osa Peninsula and Caño Island. It is located on a local basement high. Basement relief often focuses fluid flow, so data from this site are likely to document the vigor of fluid flow in this area. Site U1414 is located ~1 km seaward of the deformation front offshore the Osa Peninsula and Caño Island. Primary science goals at Site U1414 included characterization of the alteration state of the magmatic basement. Brittle structures within the incoming plate (sites U1380, U1414) are mineralized extensional fractures and shear fractures. The shear fractures mainly show a normal component of shear. Within the sedimentary sequence both types of fractures dip steeply (vertical to subvertical) and strike NNE-SSW. Deformation bands trend roughly ENE-WSW, sub-parallel to the trend of the Cocos ridge. Structures in the Cocos Ridge basalt mainly comprise mineralized veins at various orientations. A preferred orientation of strike directions was not observed. Some veins show straight boundaries, others are characterized by an irregular geometry characterized by brecciated wall rock clasts embedded within vein precipitates. The vein mineralization was analysed in detail by RAMAN spectroscopy. Precipitation conditions and fluid chemistry were analysed by fluid inclusions entrapped within vein minerals. Vein mineralizations mainly consist of carbonate (fibrous aragonite, calcite), chalcedony, and quartz. Vein mineralization is mainly characterized by zoned antitaxial growth of carbonate fibres including a suture along the central vein domains. Quartz is often characterized by fibre growth of crystals perpendicular to the vein boundaries, too. These zoned veins additinally have wall rock alteration seams consisting of clay minerals. The precipitation sequence basically indicates that fluid chemistry evolved from an CO2-rich towards a SiO2- rich fluid.

Spectroscopic studies of the fish fossils (Cladocyclus gardneri and Vinctifer comptoni) from the Ipubi Formation of the Cretaceous Period

NASA Astrophysics Data System (ADS)

Sousa Filho, F. E.; da Silva, J. H.; Saraiva, G. D.; Abagaro, B. T. O.; Barros, O. A.; Saraiva, A. A. F.; Viana, B. C.; Freire, P. T. C.

2016-03-01

Fossils are mineralized remains or traces from animals, plants and other organisms aged to about 108 years. The chemical processes of fossilization are dated back from old geological periods on Earth. The understanding of these processes and the structure of the fossils are one of the goals of paleontology and geology in the sedimentary environments. Many researches have tried to unveil details about special kinds of biological samples; however, a lack of data is noticed for various other specimens. This study reports the investigations through infrared spectroscopy, X-ray fluorescence and X-ray diffraction measurements for two types of fish fossils from the Cretaceous Period. The sample of Cladocyclus gardneri and Vinctifer comptoni fossils were collected from the Ipubi Formation, being one of the less studied, among the formations that constitute the important Santana group in the Araripe Basin, Brazil. The results obtained through different techniques, showed that the C. gardneri fish fossil contains hydroxyapatite and calcite as constituents whereas its rock matrix was formed by calcite, quartz and pyrite. Regarding the V. comptoni, the measurements confirmed the presence of hydroxyapatite in the fossil and its rock matrix gypsum, pyrite, quartz and calcite. The above scientific data contributed to the understanding the fossil formation in the Ipubi Formation, an important environment of the Cretaceous Period, which is rich in well-preserved fossils from different species.

Mars weathering analogs - Secondary mineralization in Antarctic basalts

NASA Technical Reports Server (NTRS)

Berkley, J. L.

1982-01-01

Alkalic basalt samples from Ross Island, Antarctica, are evaluated as terrestrial analogs to weathered surface materials on Mars. Secondary alteration in the rocks is limited to pneumatolytic oxidation of igneous minerals and glass, rare groundmass clay and zeolite mineralization, and hydrothermal minerals coating fractures and vesicle surfaces. Hydrothermal mineral assemblages consist mainly of K-feldspar, zeolites (phillipsite and chabazite), calcite, and anhydrite. Low alteration rates are attributed to cold and dry environmental factors common to both Antarctica and Mars. It is noted that mechanical weathering (aeolian abrasion) of Martian equivalents to present Antarctic basalts would yield minor hydrothermal minerals and local surface fines composed of primary igneous minerals and glass but would produce few hydrous products, such as palagonite, clay or micas. It is thought that leaching of hydrothermal vein minerals by migrating fluids and redeposition in duricrust deposits may represent an alternate process for incorporating secondary minerals of volcanic origin into Martian surface fines.

Multidisciplinary hydrologic investigations at Yucca Mountain, Nevada

USGS Publications Warehouse

Dudley, William W.

1990-01-01

Future climatic conditions and tectonic processes have the potential to cause significant changes of the hydrologic system in the southern Great Basin, where a nuclear-waste repository is proposed for construction above the water table at Yucca Mountain, Nevada. Geothermal anomalies in the vicinity of Yucca Mountain probably result from the local and regional transport of heat by ground-water flow. Regionally and locally irregular patterns of hydraulic potential, local marsh and pond deposits, and calcite veins in faults and fractures probably are related principally to climatically imposed hydrologic conditions within the geologic and topographic framework. However, tectonic effects on the hydrologic system have also been proposed as the causes of these features, and existing data limitations preclude a full evaluation of these competing hypotheses. A broad program that integrates many disciplines of earth science is required in order to understand the relation of hydrology to past, present and future climates and tectonism.

Fault zone structure and fluid-rock interaction of a high angle normal fault in Carrara marble (NW Tuscany, Italy)

NASA Astrophysics Data System (ADS)

Molli, G.; Cortecci, G.; Vaselli, L.; Ottria, G.; Cortopassi, A.; Dinelli, E.; Mussi, M.; Barbieri, M.

2010-09-01

We studied the geometry, intensity of deformation and fluid-rock interaction of a high angle normal fault within Carrara marble in the Alpi Apuane NW Tuscany, Italy. The fault is comprised of a core bounded by two major, non-parallel slip surfaces. The fault core, marked by crush breccia and cataclasites, asymmetrically grades to the host protolith through a damage zone, which is well developed only in the footwall block. On the contrary, the transition from the fault core to the hangingwall protolith is sharply defined by the upper main slip surface. Faulting was associated with fluid-rock interaction, as evidenced by kinematically related veins observable in the damage zone and fluid channelling within the fault core, where an orange-brownish cataclasite matrix can be observed. A chemical and isotopic study of veins and different structural elements of the fault zone (protolith, damage zone and fault core), including a mathematical model, was performed to document type, role, and activity of fluid-rock interactions during deformation. The results of our studies suggested that deformation pattern was mainly controlled by processes associated with a linking-damage zone at a fault tip, development of a fault core, localization and channelling of fluids within the fault zone. Syn-kinematic microstructural modification of calcite microfabric possibly played a role in confining fluid percolation.

40Ar/39Ar mica ages from marble mylonites: a cautionary tale

NASA Astrophysics Data System (ADS)

Rogowitz, Anna; Huet, Benjamin; Schneider, David; Grasemann, Bernhard

2014-05-01

40Ar/39Ar geochronology on white mica is a popular method to date deformation under moderate (brittle-ductile) temperatures. In particular, deformation events preserved in greenschist facies shear zones have been successfully dated with this method. A consequence of strain localization in many tectonic settings that bear calcitic marbles is the formation of marble mylonites and ultramylonites. Little is known, however, about the behaviour of the K/Ar systems and the influence of deformation on the ages in such rocks. We studied an extremely localized shear zone (2 cm thick) in marble from Syros (Cyclades, Greece) and performed microstructural, chemical and isotopic analysis on samples from the host rock and the shear zone. The host rock is composed of coarse-grained (300 µm) calcite with only minor undulatory extinction and slightly curved grain boundaries. This initial large grain size is likely to have formed during the Eocene high-pressure - low-temperature event that is well documented in the Cyclades. In contrast, the marble within the shear zone shows evidence of strong intracrystalline deformation and recrystallization resulting in grain size reduction and the formation of an ultramylonite. Both microstructures and kinematics are consistent with the low grade evolution described on Syros. White mica (100's microns in size) are preferentially orientated parallel to the foliation. In both samples there is no clear evidence for crystal plastic deformation of the mica grains. Bigger grains behave brittle resulting in grain size reduction. A deformation mechanism map for calcite at 300 °C indicates that the host rock deformed at strain rates of around 10-12.5 s-1 whereas within the shear zone strain rates of up to 10-9.5 s-1 are attained. We performed laser-heating 40Ar/39Ar analysis on white mica located in the host rock and the shear zone. The low-strain host rock yielded a ca. 40 Ma age, and the shear zone recorded a ca. 37 Ma age; both ages are statistically indistinguishable when errors are considered. These dates correspond to the regional Eocene high-pressure - low-temperature event and not the later low grade deformation event that is responsible for the formation of the studied shear zone. Although the marble within the shear zone was deformed at extremely fast strain rates, we observe no resetting in the isotopic system. Moreover, mineral chemistry demonstrates that (1) white mica is homogeneous and (2) there is no compositional difference between the host rock and the shear zone. This is in agreement with thermodynamical modelling, which indicates that the observed assemblage (calcite + dolomite + quartz + white mica) is stable without any composition change along the pressure-temperature path followed by the metamorphic rocks of Syros. Our case study emphasizes it is not the amount of strain the rock suffered but the degree of mica recrystallization that is important for resetting of the K/Ar system at low temperatures.

Renal vein thrombosis

MedlinePlus

... Chertow GM, Marsden PA, Taal MW, Yu ASL, et al, eds. Brenner and Rector's The Kidney . 10th ed. Philadelphia, PA: Elsevier Saunders; 2016:chap 35. Review Date 4/14/2017 Updated by: Walead Latif, MD, Nephrologist and Clinical Associate Professor, Rutgers Medical ...

Calcite growth-rate inhibition by fulvic acid and magnesium ion—Possible influence on biogenic calcite formation

NASA Astrophysics Data System (ADS)

Reddy, Michael M.

2012-08-01

Increases in ocean surface water dissolved carbon dioxide (CO2) concentrations retard biocalcification by reducing calcite supersaturation (Ωc). Reduced calcification rates may influence growth-rate dependent magnesium ion (Mg) incorporation into biogenic calcite modifying the use of calcifying organisms as paleoclimate proxies. Fulvic acid (FA) at biocalcification sites may further reduce calcification rates. Calcite growth-rate inhibition by FA and Mg, two common constituents of seawater and soil water involved in the formation of biogenic calcite, was measured separately and in combination under identical, highly reproducible experimental conditions. Calcite growth rates (pH=8.5 and Ωc=4.5) are reduced by FA (0.5 mg/L) to 47% and by Mg (10-4 M) to 38%, compared to control experiments containing no added growth-rate inhibitor. Humic acid (HA) is twice as effective a calcite growth-rate inhibitor as FA. Calcite growth rate in the presence of both FA (0.5 mg/L) and Mg (10-4 M) is reduced to 5% of the control rate. Mg inhibits calcite growth rates by substitution for calcium ion at the growth site. In contrast, FA inhibits calcite growth rates by binding multiple carboxylate groups on the calcite surface. FA and Mg together have an increased affinity for the calcite growth sites reducing calcite growth rates.

Calcite growth-rate inhibition by fulvic acid and magnesium ion—Possible influence on biogenic calcite formation

USGS Publications Warehouse

Reddy, Michael M.

2012-01-01

Increases in ocean surface water dissolved carbon dioxide (CO2) concentrations retard biocalcification by reducing calcite supersaturation (Ωc). Reduced calcification rates may influence growth-rate dependent magnesium ion (Mg) incorporation into biogenic calcite modifying the use of calcifying organisms as paleoclimate proxies. Fulvic acid (FA) at biocalcification sites may further reduce calcification rates. Calcite growth-rate inhibition by FA and Mg, two common constituents of seawater and soil water involved in the formation of biogenic calcite, was measured separately and in combination under identical, highly reproducible experimental conditions. Calcite growth rates (pH=8.5 and Ωc=4.5) are reduced by FA (0.5 mg/L) to 47% and by Mg (10−4 M) to 38%, compared to control experiments containing no added growth-rate inhibitor. Humic acid (HA) is twice as effective a calcite growth-rate inhibitor as FA. Calcite growth rate in the presence of both FA (0.5 mg/L) and Mg (10−4 M) is reduced to 5% of the control rate. Mg inhibits calcite growth rates by substitution for calcium ion at the growth site. In contrast, FA inhibits calcite growth rates by binding multiple carboxylate groups on the calcite surface. FA and Mg together have an increased affinity for the calcite growth sites reducing calcite growth rates.

A 150-ka-long record for the volcano-tectonic deformation of Central Anatolian Volcanic Province

NASA Astrophysics Data System (ADS)

Karabacak, Volkan; Tonguç Uysal, I.; Ünal-İmer, Ezgi; Mutlu, Halim; Zhao, Jian-xin

2017-04-01

The Anatolian Block represents one of the most outstanding examples of intra-plate deformation related to continental collision. Deformation related to the convergence of the Afro-Arabian continent toward north gives rise to widespread and intense arc volcanism in the Central Anatolia. All the usual studies on dating the volcano-tectonic deformation of the region are performed entirely on volcanic events of the geological record resulted in eruptions. However, without volcanic eruption, magma migration and related fluid pressurization also generate crustal deformation. In the current study has been funded by the Scientific and Technological Research Council of Turkey with the project no. 115Y497, we focused on fracture systems and their carbonate veins around the Ihlara Valley (Cappadocia) surrounded by well-known volcanic centers with latest activities of the southern Central Anatolian Volcanic Province. We dated 37 samples using the Uranium-series technique and analyzed their isotope systematics from fissure veins, which are thought to be controlled by the young volcanism in the region. Our detailed fracture analyses in the field show that there is a regional dilatation as a result of a NW-SE striking extension which is consistent with the results of recent GPS studies. The Uranium-series results indicate that fracture development and associated carbonate vein deposition occurred in the last 150 ka. Carbon and oxygen isotope systematics have almost remained unchanged in the studied time interval. Although veins in the region were precipitated from fluids primarily of meteoric origin, fluids originating from water-rock interaction also contribute for the deposition of carbonate veins. The age distribution indicates that the crustal deformation intensified during 7 different period at about 4.7, 34, 44, 52, 83, 91, 149 ka BP. Four of these periods (4.7, 34, 91, 149 ka BP) correspond to the volcanic activities suggested in the previous studies. The three crustal deformation periods occurred at 44, 52, and 83 ka BP were dated in addition to the known. They are interpreted to have possibly occurred without any eruption in the late Pleistocene and were controlled by magma movements and/or associated fluid pressure. Such crustal deformation controlled by volcanism is dated for the first time in the literature with a sampling other than extrusive material. The obtained age data revealed that crustal deformation linked to the young volcanism in the Central Anatolian Volcanic Province was repeated in short-term strain cycles of 8-10 ka and that the duration of activity lasted approximately 1100 ± 1000 years in each period, possibly triggered fracture development without any eruption in some periods.

Relantionships between gold mineralization and granite - Discussion with the support of a pluridisciplinary study of the Passa Tres gold deposit (South Brazil)

NASA Astrophysics Data System (ADS)

Dressel, Bárbara; Chauvet, Alain; Trzaskos, Barbara; Biondi, Joao Carlos; Bruguier, Olivier; Monie, Patrick; Villanova, Sandro; Bazille, Jose

2016-04-01

The Passa Três Granite, located at East of the Paraná State is elongated following a NNE-SSW direction. This sienogranite is emplaced within metapelites of the meso to neoproterozoic Açungui Group, between the Morro Agudo and Lancinha transcurrent faults, comprising the N040°E trending Lancinha Transcurrent Fault System. Gold mineralization within the Passa Três Granite is constituted by huge quartz veins with sulfides, variable quantities of fluorite and carbonates, forming orebodies with different internal textures, including massive, banded, sheared and brecciated. Structural data indicate the existence of two major fault systems, one N-S and the other E-W, with dips of 15-45°W and 20-75°S, respectively. Both NS and EW systems are interpreted to be contemporaneous and conjugate. Normal motions are everywhere suspected and main mineralized veins are located at opening sites at these fault systems, such as pull-aparts. The structural model suggests that the normal motion can be initiated by shearing along a "guide" level, in which sulfides and clay minerals are concentrated. This configuration can be observed at several scales, such as field, hand samples and thin section. Mineralized veins mainly contain, in addition to the quartz of the gangue, sulphides (pyrite, chalcopyrite, galena, molybdenite), fluorite, chlorite, muscovite, sericite, and carbonate. The presence of sericite, kaolinite and chlorite indicate the occurrence of, at least, propylitic and phyllic-type alterations, both in core of the granite and best-expressed at the rim of quartz-rich orebodies. Gold occurs as native grains in core of the quartz veins, within fractures that affect pyrite and frequently exhibiting normal motions consistent with the one observed at larger scale and systematically associated with chalcopyrite and galena. Quartz veins are sometimes bordered by aplitic dike. Additionally, some of the veins can exhibit a very thin margin of adularia minerals that seems to represent the early stage of vein formation. These observations favor the link between late-magmatic fluids and veins formation. In order to constrain this assumption, a campaign of absolute dating has been undertaken. Zircons from granite and aplite for the magmatic feature and adularia, muscovite, sericite and molybdenite grains for the hydrothermal ones were selected and will be dated by, respectively U-Pb, Ar-Ar and Re-Os methods. Preliminary field results may suggest that gold-quartz veins may formed during the magmatic-hydrothermal transition and that mineralizing fluids possibly represent the late stages of magmatic fluid. Their mode of formation looks to be consistent with an extensional setting. With the help of all these new data, a discussion will be initiated about the genetic model of granite-hosted gold deposits and particularly on this specific case represented by the Passa Três deposit in which huge quartz veins, and no stockwork, are only formed inside the granite and not in surrounding rocks.

Tectono-metallogenetic evolution of the Fe-Cu deposit of Dominga, northern Chile

NASA Astrophysics Data System (ADS)

Veloso, E.; Cembrano, J.; Arancibia, G.; Heuser, G.; Neira, S.; Siña, A.; Garrido, I.; Vermeesch, P.; Selby, D.

2017-04-01

The Dominga district in northern Chile (2082 Mt at 23.3 % Fe, 0.07 % Cu) shows a spatial and genetic affinity among distinctive structural elements and Fe-Cu-rich paragenetic mineral assemblages. Deep seated, NE-to-E striking structural elements form a right-lateral duplex-like structural system (early structural system, ESS) that cuts a regionally extensive alteration (stage I) zone. The EES system served as a locus and as path for the emplacement of biotite-magnetite alteration/mineralization (stage IIa) as veins and Fe-bearing layers following altered volcano sedimentary strata. NW-striking actinolite-magnetite hydrothermal breccias, coeval with and part of the ESS, include apatite (stage IIb) crystallized at 127 ± 15 Ma (U-Pb, 2σ). The ESS was also the locus of subsequent alteration/mineralization represented by K-feldspar, epidote, and albite (stage IIIa) and Fe-Cu-rich (vermiculite-anhydrite-chalcopyrite, stage IIIb) mineral associations. Shallowly developed, NNE-striking, left-lateral structural elements defining the El Tofo Structural System (ETSS)—probably part of the Atacama Fault System—clearly crosscut the ESS. Minerals associated with alteration/mineralization stage IIIb also occur as veins and as part of hydrothermal breccias of the ETSS, marking the transition from the ESS to ETSS. Molybdenite associated with alteration/mineralization stage IIIb yielded a Re-Os age of 127.1 ± 0.7 Ma (2σ). Both the ESS and ETSS were cut by left-lateral, NW- to E-striking shallowly developed structural elements (Intermediate Structural System, ISS) on which a hematite-calcite assemblage (stage IV) occurs mostly as infill material of veins and fault veins. The ISS is cut by N-striking, left-lateral, and shallowly developed structural elements (Late Structural System, LSS) showing no evidence of alteration/mineralization. Estimated strain and stress fields indicate an overall NW-trending shortening/compression and NE-trending stretching/tension strike-slip regime probably due to oblique subduction during the Mesozoic. However, the orientations of the stress and strain fields calculated for each structural system suggest a back-and-forth rotation pattern during transition from one structural system to the other—as they change between transtension and transpression—and between alteration/mineralization stages.

Application of the FINDER system to the search for epithermal vein gold-silver deposits : Kushikino, Japan, a case study

USGS Publications Warehouse

Singer, Donald A.; Kouda, Ryoichi

1991-01-01

The FINDER system employs geometric probability, Bayesian statistics, and the normal probability density function to integrate spatial and frequency information to produce a map of probabilities of target centers. Target centers can be mineral deposits, alteration associated with mineral deposits, or any other target that can be represented by a regular shape on a two dimensional map. The size, shape, mean, and standard deviation for each variable are characterized in a control area and the results applied by means of FINDER to the study area. The Kushikino deposit consists of groups of quartz-calcite-adularia veins that produced 55 tonnes of gold and 456 tonnes of silver since 1660. Part of a 6 by 10 km area near Kushikino served as a control area. Within the control area, data plotting, contouring, and cluster analysis were used to identify the barren and mineralized populations. Sodium was found to be depleted in an elliptically shaped area 3.1 by 1.6 km, potassium was both depleted and enriched locally in an elliptically shaped area 3.0 by 1.3 km, and sulfur was enriched in an elliptically shaped area 5.8 by 1.6 km. The potassium, sodium, and sulfur content from 233 surface rock samples were each used in FINDER to produce probability maps for the 12 by 30 km study area which includes Kushikino. High probability areas for each of the individual variables are over and offset up to 4 km eastward from the main Kushikino veins. In general, high probability areas identified by FINDER are displaced from the main veins and cover not only the host andesite and the dacite-andesite that is about the same age as the Kushikino mineralization, but also younger sedimentary rocks, andesite, and tuff units east and northeast of Kushikino. The maps also display the same patterns observed near Kushikino, but with somewhat lower probabilities, about 1.5 km east of the old gold prospect, Hajima, and in a broad zone 2.5 km east-west and 1 km north-south, centered 2 km west of the old gold prospect, Yaeyama.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Basavatia, A; Kalnicki, S; Garg, M

Purpose: To implement a clinically useful palm vein pattern recognition biometric system to treat the correct treatment plan to the correct patient each and every time and to check-in the patient into the department to access the correct medical record. Methods: A commercially available hand vein scanning system was paired to Aria and utilized an ADT interface from the hospital electronic health system. Integration at two points in Aria, version 11 MR2, first at the appointment tracker screen for the front desk medical record access and second at the queue screen on the 4D treatment console took place for patientmore » daily time-out. A test patient was utilized to check accuracy of identification as well as to check that no unintended interactions take place between the 4D treatment console and the hand vein scanning system. This system has been in clinical use since December 2013. Results: Since implementation, 445 patients have been enrolled into our biometric system. 95% of patients learn the correct methodology of hand placement on the scanner in the first try. We have had two instances of patient not found because of a bad initial scan. We simply erased the scanned metric and the patient enrolled again in those cases. The accuracy of the match is 100% for each patient, we have not had one patient misidentified. We can state this because we still use patient photo and date of birth as identifiers. A QA test patient is run monthly to check the integrity of the system. Conclusion: By utilizing palm vein scans along with the date of birth and patient photo, another means of patient identification now exits. This work indicates the successful implementation of technology in the area of patient safety by closing the gap of treating the wrong plan to a patient in radiation oncology. FOJP Service Corporation covered some of the costs of the hardware and software of the palm vein pattern recognition biometric system.« less

Mechanochemical endovenous ablation of saphenous veins using the ClariVein: A systematic review.

PubMed

Witte, Marianne E; Zeebregts, Clark J; de Borst, Gert Jan; Reijnen, Michel M P J; Boersma, Doeke

2017-12-01

Objective To systematically review all available English literature on mechanochemical endovenous ablation and to report on the anatomical, technical, and clinical success. Methods A systematic literature search was performed in PubMed, EMBASE, and the Cochrane Library on mechanochemical endovenous ablation for the treatment of insufficient great and/or small saphenous vein. Methodological quality of the included studies was evaluated using the MINORS score. The primary outcome measure was anatomical success, defined as closure of the treated vein on follow-up duplex ultrasound imaging. Secondary outcomes were technical and clinical success, and major complications defined as deep venous thrombosis, pulmonary embolisms or paresthesia. Results The literature search identified 759 records, of which 13 were included, describing 10 unique cohorts. A total of 1521 veins (1267 great saphenous vein and 254 small saphenous vein) were included, with cohort sizes ranging from 30 to 570 veins. The pooled anatomical success rate after short-term follow up was 92% (95% CI 90-94%) ( n = 1314 veins). After 6 and 12 months these numbers were 92% (95% CI 88-95%) ( n = 284) and 91% (95% CI 86-94%) ( n = 228), respectively. The long-term anatomical success rates at 2 and 3 years were 91% (95% CI 85-95%) ( n = 136) and 87% (95% CI 75-94%) ( n = 48), respectively. Major complications and especially nerve injury were very rare (≤ 0.2%). All studies were of moderate or good quality using the MINORS scoring scale. Conclusions Mechanochemical endovenous ablation using the ClariVein in combination with liquid sclerosant is associated with an anatomical success rate ranging from 87% to 92% and good clinical success. To date, no randomized controlled trials are available studying the anatomical success after mechanochemical ablation, compared to the endothermal ablation. The risk of major complications is very low after the procedure.

Isotopic studies of authigenic sulfides, silicates and carbonates, and calcite and pyrite veinlets in the Creede Formation, San Juan Mountains, Southwest Colorado

USGS Publications Warehouse

Bethke, Philip M.; Rye, Robert O.; Finkelstein, David B.

2000-01-01

Sulfur isotope analysis of authigenic pyrite in the Creede Formation documents its precipitation by the reaction between iron in the volcaniclastic sediments and H2S formed through bacteriogenic reduction of sulfate added to the lake during and immediately following repeated volcanic eruptions during sedimentation. Pyrite veinlets in the underlying Snowshoe Mountain Tuff were formed by the percolation of H2S-bearing pore waters into fractures in the tuff. Conventional analyses of bulk samples of authigenic pyrite range from -20.4% to 34.5% essentially equivalent to the range of -30% to 40% determined using SHRIMP microprobe techniques. Conventional analyses of bulk samples of pyrite from veinlets in the Snowshow Mountain Tiff range from -3.5% to 17.6% much more limited than the ranges of -23% to 111% and -15.6% to 67.0% determined by SHRIMP and laser ablation microbeam techniques, respectively. The extreme range of δ34S for the veinlets is interpreted to be the result of continued fractionation of the already 34S-depleted pore water. Oxygen isotope analysis of authigenic smectite, kaolinite, and K-feldspar together with fluid-inclusion temperatures and oxygen isotope analysis of calcite coexisting with kaolinite indicate that the smectites formed early during burial diagenesis, in accord with petrographic observations. The 40Ar/39Ar dating of K-feldspar, concorfance of K-feldspar, kaolinite, and calcite δ18O values, and fluid-inclusion temperatures in calcite, indicate that the sediments at core hole CCM-1 were subjected to a hydrothermal event at 17.6 Ma. The minerals formed oxygen-shifted meteoric waters with δ18O values of ~-9% Smecities at CCM-1 at least partially exchanged with these waters. Carbon and oxygen isotope analysis of authigenic calcites in the Creede Formation show that they formed over a wide range of temperatures from fluids having a wide range of isotopic composition, presumably over an extended period time. Some of the cements apparently formed very late from unexchanged meteoric water. Concretions and possibly some cements at CCM-1 appear to have exchanged with the 17.6 Ma oxygen-shifted hydrothermal fluids. Such exchange is consistent with evidence that lacustrine carbonates at CCM-1 exchanged with low 18O waters, whereas those at CCM-2 underwent little, if any, exchange. The δ13C-δ18O values for calcite veinlets in the Creede Formation are similar to those for authegenic calcites. Fluid-inclusion temperatures and δ18O indicate that some were deposited during the 17.6 Ma hydrothermal event and others from unexchanged meteoric water at a later date. The isotope studies confirm that part of the model of Rye et al., proposing that the barites in the southern end of the Creede Mining District were formed by mixing of the Creede hydrotermal system with Lake Creede pore of lake waters. The silicate and carbonate isotope data indicate that the pores of the Creede Formation were occupied by at least three isotopically distinct water since the time of deposition. The original pore fluids were probably shifted to lower δ18O values during burial diagensis as a result of the hydrolysis of the volcanic glass to for smectites and other hydrous silicates. During or prior to a 17.6 Ma hydrothermal event in the vicinity of CCM-1, the Creede Formation was flushed with oxygen-shifted meteoric water, possibly related to the breaching of the east side of the caldera wall sometime between 20 and 22 Ma. Later, the Creede Formation was again flushed, this time with unexchanged meteoric water with δD-δ18O values of present-day waters, possibly during the incision of the Rio Grande drainage during uplifting of the southern Rocky Mountains beginning about 5 Ma.

Geological and geochemical implications of the genesis of the Qolqoleh orogenic gold mineralisation, Kurdistan Province (Iran)

NASA Astrophysics Data System (ADS)

Taghipour, Batoul; Ahmadnejad, Farhad

2015-03-01

The Qolqoleh gold deposit is located in the northwestern part of the Sanandaj-Sirjan Zone (SSZ), within the NE-SW trending Qolqoleh shear zone. Oligocene granitoids, Cretaceous meta-limestones, schists and metavolcanics are the main lithological units. Chondrite-normalised REE patterns of the ore-hosting metavolcanics indicate REE enrichment relative to hanging wall (chlorite-sericite schist) and footwall (meta-limestone) rocks. The pattern also reflects an enrichment in LREE relative to HREE. It seems that the LREE enrichment is related to the circulation of SO42- and CO2-bearing fluids and regional metamorphism in the Qolqoleh shear zone. Both positive and negative Eu anomalies are observed in shear-zone metavolcanics. These anomalies are related to the degree of plagioclase alteration during gold mineralisation and hydrothermal alteration. In progressing from a metavolcanic protomylonite to an ultramylonite, significant changes occurred in the major/trace element and REE concentration. Utilising an Al-Fe-Ti isocon for the ore-hosting metavolcanics shows that Sc, Y, K, U, P, and M-HREE (except Eu) are relatively unchanged; S, As, Ag, Au, Ca, LOI, Rb and LREE are enriched, and Sr, Ba, Eu, Cr, Co and Ni decrease with an increasing degree of deformation. Based on geochemical features and comparison with other well-known shear zones in the world, the study area is best classified as an Isovolume-Gain (IVG) type shear zone and orogenic type gold mineralisation. Based on the number of phases observed at room temperature and their microthermometric behaviour, three fluid inclusion types have been recognised in quartz-sulphide and quartz-calcite veins: Type I monophase aqueous inclusions, Type II two-phase liquid-vapour (L-V) inclusions which are subdivided into two groups based on the homogenisation temperature (Th): a) L-V inclusions with Th from 205 to 255°C and melting temperature of last ice (Tm) from -3 to -9°C. b) L-V inclusions with higher Th from 335 to 385°C and Tm from -11 to -16°C. Type III three-phase carbonic-liquid inclusions (liquid water-liquid CO2-vapour CO2) with Th of 345-385°C. The mean values of the density of ore-forming fluids, pressure and depth of mineralisation have been calculated to be 0.79-0.96 gr/cm3, 2 kbar and 7 km, respectively. The δ18Owater and δD values of the gold-bearing quartz-sulphide veins vary from 7.2‰ to 8‰ and -40.24‰ to -35.28‰, respectively, which are indicative of an isotopically heavy crustal fluid and likely little involvement of meteoric fluid. The δ18Owater values of the quartz-calcite veins have a range of -5.31‰ to -3.35‰, and the δD values of -95.65‰ to -75.31‰, which are clearly lower than those of early-stage quartz-sulphide-gold veins, and are close to the meteoric water line. Based on comparisons of the D-O isotopic systematics, the Qolqoleh ore-mineralising fluids originated from metamorphic devolatilisation of Cretaceous volcano-sedimentary piles. Devolatilisation of these units occurred either synchronously with, or postdates, the development of penetrative (ductile) structures such as shear zones and during overprinting brittle deformation

Suitability of biogenic carbonate of Lithospermum fruits for 14C dating

NASA Astrophysics Data System (ADS)

Pustovoytov, Konstantin; Riehl, Simone

2006-05-01

Lithospermum (Boraginaceae) belongs to a small group of plant taxa that accumulate biogenic carbonate in their fruits. In this genus, carbonate incrustations form in the cells of the epidermis and sclerenchyma of the pericarp. Fossil Lithospermum fruits (nutlets) with well-preserved calcified tissues commonly occur in Quaternary sediments and cultural layers. We tested the suitability of biogenic carbonate of Lithospermum fruits for radiocarbon dating using a total of 15 AMS measurement results from four modern and 11 fossil samples. The 14C data from modern samples suggest that Lithospermum utilises only atmospheric carbon to synthesise calcite in the nutlets. In general, the ages determined through 14C dating of fossil fruitscorresponded well with the absolute-age intervals for archaeological sites over the last 5000 yr. Biogenic carbonate of Lithospermum fruits, like that of Celtis, represents a new source of chronological information for late Quaternary studies.

U-series dating of Paleolithic art in 11 caves in Spain.

PubMed

Pike, A W G; Hoffmann, D L; García-Diez, M; Pettitt, P B; Alcolea, J; De Balbín, R; González-Sainz, C; de las Heras, C; Lasheras, J A; Montes, R; Zilhão, J

2012-06-15

Paleolithic cave art is an exceptional archive of early human symbolic behavior, but because obtaining reliable dates has been difficult, its chronology is still poorly understood after more than a century of study. We present uranium-series disequilibrium dates of calcite deposits overlying or underlying art found in 11 caves, including the United Nations Educational, Scientific, and Cultural Organization (UNESCO) World Heritage sites of Altamira, El Castillo, and Tito Bustillo, Spain. The results demonstrate that the tradition of decorating caves extends back at least to the Early Aurignacian period, with minimum ages of 40.8 thousand years for a red disk, 37.3 thousand years for a hand stencil, and 35.6 thousand years for a claviform-like symbol. These minimum ages reveal either that cave art was a part of the cultural repertoire of the first anatomically modern humans in Europe or that perhaps Neandertals also engaged in painting caves.

A Synthetic Calcite Standard for Determination of Relative Mn/Cr Sensitivity Factor

NASA Astrophysics Data System (ADS)

Fujiya, W.; Ichimura, K.; Takahata, N.; Sugiura, N.; Sano, Y.

2009-12-01

Primitive chondrites which suffered from aqueous alteration often contain carbonates such as calcites, dolomites and breunnerites. 53Mn-53Cr decay system (half-life: 3.7 Myr) is applicable to dating their precipitation and many authors have measured their Mn-Cr ages using the SIMS. However, the relative Mn/Cr sensitivity factor: RSF (measured Mn+/Cr+ ratio divided by the true ratio) is not well established due to the absence of suitable standards, therefore the ages have systematic uncertainties. We prepared a synthetic Mn and Cr bearing calcite to evaluate the Mn/Cr RSF. Here we report the technical details of preparation for the standard and its Mn/Cr RSF. We also measured the Mn/Cr RSF of San Carlos olivine which is often assumed to be the same as that of a carbonate, and compared it with that of our synthetic calcite. The Cr-bearing calcite was produced in a N2 filled closed system by the reaction Ca2+ + CO32- = CaCO3 in an aqueous solution. The reaction proceeded by continuous addition of ammonium carbonate vapor to the solution. The crystal size of the calcite was ~300 μm. A small amount of hydrazine was added to the solution in order to keep chromous ion from oxidation. Mn and Cr concentrations in the calcite grains were determined by the SEM-EDS. A weak, defocused beam was used due to prevent electron beam damage. In a spherical grain, radial zoning of Mn and Cr concentrations occur and they decrease towards the periphery. At the center of the grains, Mn and Cr concentrations are ~0.5 atomic % and the values of the Mn/Cr ratios are relatively constant. The Mn/Cr RSF was determined with the CAMECA NanoSIMS 50 at Ocean Research Institute of Univ. of Tokyo. A primary O- beam of ~1 nA and 5 μm diameter was used. 43Ca+, 52Cr+, 53Cr+ and 55Mn+ ions were analyzed in a combined peak-jumping/multi-detection mode. The total measurement time was typically ~20 minutes. The measurements were started after presputtering of 15 minutes. The mass resolution power was ~3500, sufficient to resolve all relevant isobaric interferences. Several points near the center of calcite grains with constant Mn and Cr concentrations were measured. As for San Carlos olivine, a primary beam was rastered over 20 x 20 μm2 areas. Signals of all ions decreased with time during the measurements. The 55Mn/52Cr RSF also decreased with time. Initially it was ~0.7-0.8, and approached to a nearly constant value of ~0.5-0.6 after ~20 minutes. 53Cr+/52Cr+ isotopic ratio was 0.1105 ± 0.0002 (1σ), not dependent on time and space. This value corresponds to ~-26 permil fractionation from the reference value. On the other hand, the RSF of San Carlos olivine was found to be ~0.9, consistent with previous studies. The RSF of our calcite is significantly lower than the values used in previous studies and the RSF of San Carlos olivine measured in this study. This implies that Mn-Cr ages for carbonates obtained in previous studies may have systematic biases (~3 Myr).

The Submarine 4-km diameter Corossol Crater, Eastern Canada: Evidence for an impact origin

NASA Astrophysics Data System (ADS)

Higgins, Michael D.; Lajeunesse, Patrick; St-Onge, Guillaume; Locat, Jacques; Sanfacon, Richard; Duchesne, Mathieu J.

2014-05-01

The newly-discovered Corossol Crater lies in the northwestern Gulf of St. Lawrence (Eastern Canada; 50°3'N, 66°23'W) and was found in 40-185 metres of water using high-resolution multibeam sonar. It is a 4 km in diameter complex circular structure with a central uplift and concentric rings. Glacial resurfacing indicates that it predates the last phase of glaciation in this area. Dredging on the central uplift recovered many angular clasts of hard grey limestone, which forms the bedrock in much of this area. One 4 cm clast of limestone breccia is somewhat different from the other blocks and has characteristics that suggest that it is an impact breccia. The block comprises fragments of calcite limestone up to 2 mm long. In many parts of the block these fragments have thin black rims. At the edges of the block these rims are brown, presumably reflecting aqueous alteration. Mineral grains in the rims are too small to characterize, but the fact that the ensemble can be oxidized suggests that it contains sulfides. In places the block is cut by veins of fine-grained calcite with euhedral dolomite crystals. The most unusual component is rare droplets up to 2 mm long, commonly fragmented. The droplets comprise a glassy matrix with a composition very close to fluorapatite and opaque crystals that have a composition close to pyrite. A few droplets have up to 5% vesicles. Fluorapatite requires fusion temperatures of about 1600 C, which cannot be achieved at the surface of the Earth by endogenous processes. A single fragmented quartz crystal with planar features was found close to one droplet. Universal stage measurements of the orientation of the planar features give an angle of 42 degrees which is close to that of {10-13} planes. This is the most common set of deformation planes produced during shock metamorphism of quartz. Unfortunately no other grains were found with similar planes. The glassy droplets and shocked quartz together suggest that the clast was produced by an impact, and hence that it is very likely that the Corossol Crater in which the clast was found is an astrobleme. The absolute age of this structure is unknown, but its geological setting indicates that it was formed long after the Mid-Ordovician and possibly before regional pre-Quaternary sea-level lowstand. We are now attempting to obtain a U-Th helium age for the droplets which will date the impact event.

Kinetic and thermodynamic factors controlling the distribution of SO32- and Na+ in calcites and selected aragonites

USGS Publications Warehouse

Busenberg, E.; Plummer, Niel

1985-01-01

Significant amounts of SO42-, Na+, and OH- are incorporated in marine biogenic calcites. Biogenic high Mg-calcites average about 1 mole percent SO42-. Aragonites and most biogenic low Mg-calcites contain significant amounts of Na+, but very low concentrations of SO42-. The SO42- content of non-biogenic calcites and aragonites investigated was below 100 ppm. The presence of Na+ and SO42- increases the unit cell size of calcites. The solid-solutions show a solubility minimum at about 0.5 mole percent SO42- beyond which the solubility rapidly increases. The solubility product of calcites containing 3 mole percent SO42- is the same as that of aragonite. Na+ appears to have very little effect on the solubility product of calcites. The amounts of Na+ and SO42- incorporated in calcites vary as a function of the rate of crystal growth. The variation of the distribution coefficient (D) of SO42- in calcite at 25.0??C and 0.50 molal NaCl is described by the equation D = k0 + k1R where k0 and k1 are constants equal to 6.16 ?? 10-6 and 3.941 ?? 10-6, respectively, and R is the rate of crystal growth of calcite in mg??min-1??g-1 of seed. The data on Na+ are consistent with the hypothesis that a significant amount of Na+ occupies interstitial positions in the calcite structure. The distribution of Na+ follows a Freundlich isotherm and not the Berthelot-Nernst distribution law. The numerical value of the Na+ distribution coefficient in calcite is probably dependent on the number of defects in the calcite structure. The Na+ contents of calcites are not very accurate indicators of environmental salinities. ?? 1985.

Surface Forces Apparatus Measurements of Interactions between Rough and Reactive Calcite Surfaces.

PubMed

Dziadkowiec, Joanna; Javadi, Shaghayegh; Bratvold, Jon E; Nilsen, Ola; Røyne, Anja

2018-06-26

nm-Range forces acting between calcite surfaces in water affect macroscopic properties of carbonate rocks and calcite-based granular materials and are significantly influenced by calcite surface recrystallization. We suggest that the repulsive mechanical effects related to nm-scale surface recrystallization of calcite in water could be partially responsible for the observed decrease of cohesion in calcitic rocks saturated with water. Using the surface forces apparatus, we simultaneously followed the calcite reactivity and measured the forces in water in two surface configurations: between two rough calcite surfaces (CC) and between rough calcite and a smooth mica surface (CM). We used nm-scale rough, polycrystalline calcite films prepared by atomic layer deposition. We measured only repulsive forces in CC in CaCO 3 -saturated water, which was related to roughness and possibly to repulsive hydration effects. Adhesive or repulsive forces were measured in CM in CaCO 3 -saturated water depending on calcite roughness, and the adhesion was likely enhanced by electrostatic effects. The pull-off adhesive force in CM became stronger with time, and this increase was correlated with a decrease of roughness at contacts, the parameter which could be estimated from the measured force-distance curves. That suggested a progressive increase of real contact areas between the surfaces, caused by gradual pressure-driven deformation of calcite surface asperities during repeated loading-unloading cycles. Reactivity of calcite was affected by mass transport across nm- to μm-thick gaps between the surfaces. Major roughening was observed only for the smoothest calcite films, where gaps between two opposing surfaces were nm-thick over μm-sized areas and led to force of crystallization that could overcome confining pressures of the order of MPa. Any substantial roughening of calcite caused a significant increase of the repulsive mechanical force contribution.

Two-stage fluid flow and element transfers in shear zones during collision burial-exhumation cycle: Insights from the Mont Blanc Crystalline Massif (Western Alps)

NASA Astrophysics Data System (ADS)

Rolland, Y.; Rossi, M.

2016-11-01

The Mont-Blanc Massif was intensely deformed during the Alpine orogenesis: in a first stage of prograde underthrusting at c. 30 Ma and in a second stage of uplift and exhumation at 22-11 Ma. Mid-crustal shear zones of 1 mm-50 m size, neighbouring episyenites (quartz-dissolved altered granite) and alpine veins, have localised intense fluid flow, which produced substantial changes in mineralogy and whole-rock geochemistry. Four main metamorphic zones are oriented parallel to the strike of the massif: (i) epidote, (ii) chlorite, (iii) actinolite-muscovite ± biotite and (iv) muscovite ± biotite. In addition, phlogopite-bearing shear zones occur in the chlorite zone, and calcite-bearing shear zones are locally found in the muscovite zone. The initial chemical composition of the granitic protolith is relatively constant at massif scale, which allows investigating compositional changes related to shear zone activity, and subsequent volume change and elements mobility. The variations of whole-rock composition and mineral chemistry in shear zones reflect variations in fluid/rock ratios and fluid's chemistry, which have produced specific mineral reactions. Estimated time-integrated fluid fluxes are of the order of 106 m3/m2. The mineral assemblages that crystallised upon these fluid-P-T conditions are responsible for specific major and trace element enrichments. The XFe (Fe/Fe + Mg) pattern of shear zone phyllosilicates and the δ13C pattern of vein calcite both show a bell-type pattern across the massif with high values on the massif rims and low values in the centre of the massif. These low XFe and δ13C values are explained by down temperature up-flow of a Fe-Mg-CO2-rich and silica-depleted fluid during stage 1, while the massif was underthrusting. These produced phlogopite, chlorite and actinolite precipitation and quartz hydrolysis, resulting in strong volume losses. In contrast, during stage 2 (uplift), substantial volume gains occurred on the massif rims due to the precipitation of quartz, epidote and muscovite from a local fluid hosted in the Helvetic cover. These two fluids advocate for the presence of an upper-crustal scaled fluid convection cell, with up-going fluids through the lower crust and likely down-going fluids in the 15 km upper crust.

Characterization of Fluid Transfer Properties in a Transpressive Fault System: Chaîne des Matheux Fold-and-Thrust Belt and Enriquillo-Plantain Garden Fault Zone - Haiti

NASA Astrophysics Data System (ADS)

Wessels, R.; Ellouz-Zimmermann, N.; Rosenberg, C.; Hamon, Y.; Battani, A.; Bellahsen, N.; Deschamps, R.; Leroy, S. D.; Momplaisir, R.

2016-12-01

The NW - SE trending Chaîne des Matheux (CdM) comprises the onshore frontal thrust sheet of the SW-verging Haitian fold-and-thrust belt (HFTB). The HFTB's active deformation front is covered by sediments of the Cul-de-Sac plain and is bounded on the south by the E - W trending left-lateral Enriquillo-Plantain Garden fault zone (EPGFZ). Seismicity down to the junction between the two systems has been recorded during the 12 January 2010 Mw 7.0 Léogâne earthquake. Stratigraphic, structural and kinematic field data on a transect from the CdM to the EPGFZ indicate (N)NE - (S)SW oriented shortening, which is partitioned over 1) (N)NE-dipping oblique thrusts rooted in Cretaceous basement, 2) decollement levels in both latest Cretaceous and Paleogene limestones, and 3) by strike-slip and positive flower structures along the EPGFZ. We investigated the geometry and kinematics of both fault and fracture systems, which was coupled with sampling and analysis of fluid-derived mineralizations to constrain the timing and geological evolution. C & O isotope and whole-rock analyses have been performed to characterize the geochemistry of the source of these fluids. Raman spectroscopy and fluid-inclusion analyses has been applied to selected samples to comprehend the local burial history. Fluid and gas seepages along fault planes are qualitative indicators for transfer properties between different fault segments and their connectivity with deeper crustal or mantle reservoirs. Relative timing of structures in the CdM coupled with cathodoluminescence (CL) microscopy reveals three deformation phases, characterized by associated calcite veins that precipitated from oxidizing meteoric fluids. The deeply rooted frontal CdM thrust lacks mineralization, but fluids expelled from along-strike natural springs registered He and Ne isotope ratios suggesting a strong mantle-derived component. CL microscopy results on calcite veins from the EPGFZ's fault core imply fluid circulation in an episodically `open' system under a reducing environment. He and Ne isotope ratios from fluids derived along the EPGFZ suggest a significant, but less pronounced, mantle-derived component compared to the frontal thrust of the CdM. The above results indicate a change in fluid transfer properties over time for this transpressive system.

Non-Reductive Strategies for U Sequestration: Natural Analogues and Practical Application

NASA Astrophysics Data System (ADS)

Maher, K.; Bethke, C. M.; Massey, M. S.

2011-12-01

A number of strategies have been proposed for the in situ remediation of U contaminated zones, including bioreduction, permeable reactive barriers, and incorporation into secondary phases such as phosphates. An alternative approach is to sequester U within amorphous Si phases such as opaline silica. We have investigated the isotopic and major element composition and structure of naturally occurring U-rich opaline silica in semi-arid soil environments across the western United States. These phases constitute a large natural reservoir of sequestered U. By combining these observations with geochemical considerations, we propose a remedial strategy for sequestering U in amorphous silica. The U-rich opal occurs as laminations, veins, and coatings on clasts in soils developed on a range of parent materials. U-rich opal deposits are also found as speleothems in caves, as silica-rich spring deposits, and as cavity fillings and hydrothermal veins in volcanic tuffs. Measurements of U, Th and Pb isotopes reveal the age of the opaline silica, demonstrating the long-term stability of U sequestration in open chemical environments. The isotopic data also suggest that opaline silica will retain the majority of the initial U over millions of years. U in naturally occurring opal generally ranges between 200 to 1000 ppm. In contrast, co-existing calcite contains less than 100 ppb U. From pore water chemistry, the distribution coefficient for U incorporation into opaline silica is approximately 20, whereas the coefficient for calcite is typically between 0.2 and 1. X-ray absorption spectroscopy investigations confirm that hexavalent U is incorporated in amorphous silica as the UO22+ ion. Coexisting Fe-oxides provide a further sink for sequestering UO22+ from the pore water. However, preliminary calculations suggest that incorporation of U into amorphous silica may be a dominant mechanism for isolating UO22+from groundwater over long time scales. Nature's mechanism for sequestering UO22+ from the environment might be profitably incorporated into groundwater remediation strategies. We consider a remedial strategy in which Na2SiO3 is amended into the subsurface. The silicate flood reacts with the surface acidity in the sediments to lower pH and precipitate amorphous silica. Hexavalent uranium is partitioned strongly into the silica, as well as complexed with the sediment surfaces.

Microstructures and deformation mechanisms in Opalinus Clay: insights from scaly clay from the Main Fault in the Mont Terri Rock Laboratory (CH)

NASA Astrophysics Data System (ADS)

Laurich, Ben; Urai, Janos L.; Nussbaum, Christophe

2017-01-01

The Main Fault in the shaly facies of Opalinus Clay is a small reverse fault formed in slightly overconsolidated claystone at around 1 km depth. The fault zone is up to 6 m wide, with micron-thick shear zones, calcite and celestite veins, scaly clay and clay gouge. Scaly clay occurs in up to 1.5 m wide lenses, providing hand specimens for this study. We mapped the scaly clay fabric at 1 m-10 nm scale, examining scaly clay for the first time using broad-ion beam polishing combined with scanning electron microscopy (BIB-SEM). Results show a network of thin shear zones and microveins, separating angular to lensoid microlithons between 10 cm and 10 µm in diameter, with slickensided surfaces. Our results show that microlithons are only weakly deformed and that strain is accumulated by fragmentation of microlithons by newly formed shear zones, by shearing in the micron-thick zones and by rearrangement of the microlithons.The scaly clay aggregates can be easily disintegrated into individual microlithons because of the very low tensile strength of the thin shear zones. Analyses of the microlithon size by sieving indicate a power-law distribution model with exponents just above 2. From this, we estimate that only 1 vol % of the scaly clay aggregate is in the shear zones.After a literature review of the hypotheses for scaly clay generation, we present a new model to explain the progressive formation of a self-similar network of anastomosing thin shear zones in a fault relay. The relay provides the necessary boundary conditions for macroscopically continuous deformation. Localization of strain in thin shear zones which are locally dilatant, and precipitation of calcite veins in dilatant shear fractures, evolve into complex microscale re-partitioning of shear, forming new shear zones while the microlithons remain much less deformed internally and the volume proportion of the µm-thick shear zones slowly increases. Grain-scale deformation mechanisms are microfracturing, boudinage and rotation of mica grains, pressure solution of carbonate fossils and pore collapse during ductile flow of the clay matrix. This study provides a microphysical basis to relate microstructures to macroscopic observations of strength and permeability of the Main Fault, and extrapolating fault properties in long-term deformation.

Age of Zhoukoudian Homo erectus determined with (26)Al/(10)Be burial dating.

PubMed

Shen, Guanjun; Gao, Xing; Gao, Bin; Granger, Darryl E

2009-03-12

The age of Zhoukoudian Homo erectus, commonly known as 'Peking Man', has long been pursued, but has remained problematic owing to the lack of suitable dating methods. Here we report cosmogenic (26)Al/(10)Be burial dating of quartz sediments and artefacts from the lower strata of Locality 1 in the southwestern suburb of Beijing, China, where early representatives of Zhoukoudian Homo erectus were discovered. This study marks the first radioisotopic dating of any early hominin site in China beyond the range of mass spectrometric U-series dating. The weighted mean of six meaningful age measurements, 0.77 +/- 0.08 million years (Myr, mean +/- s.e.m.), provides the best age estimate for lower cultural layers 7-10. Together with previously reported U-series dating of speleothem calcite and palaeomagnetic stratigraphy, as well as sedimentological considerations, these layers may be further correlated to S6-S7 in Chinese loess stratigraphy or marine isotope stages (MIS) 17-19, in the range of approximately 0.68 to 0.78 Myr ago. These ages are substantially older than previously supposed and may imply early hominin's presence at the site in northern China through a relatively mild glacial period corresponding to MIS 18.

Isotope and fluid inclusion studies of geological and hydrothermal processes, northern Peru

DOE Office of Scientific and Technical Information (OSTI.GOV)

MacFarlane, A.W.; Prol-Ledesma, R.M.; Conrad, M.E.

1994-07-01

Mineralization in the Hualgayoc district of northern Peru occurs in altered Miocene felsic intrusions and in mid-Cretaceous platform sedimentary rocks of the Goyllarisquizga, Inca, and Chulec formations. The ores occur both as stratiform and stratabound pyritiferous base-metal deposits (mantos), and as steeply dipping, sedimentary and intrusive rock-hosted base-metal veins. Igneous rocks in the district are affected by propylytic, sericitic-argillic, sericitic, potassic, and acid-sulfate alteration. K-Ar and Rb-Sr dating and geological evidence indicate multiple stages of intrusive activity and hydrothermal alteration, including close spatial emplacement of two or more separate Miocene magmatic-hydrothermal systems. K-Ar dates on sericite, hydrothermal biotite, and alunitemore » indicate that the most important hydrothermal episodes in the district took place {approx}13.24 and 12.4 Ma. Other K-Ar dates on altered rocks in the district may reflect various amounts of resetting by the emplacement of the 9.05 {+-} 0.2 Ma Hualgayoc rhyodacite. A five-point Rb-Sr isochron for the San Miguel intrusion at Cerro Coymolache yields an age of 45 {+-} 3.4 Ma, which indicates much earlier magmatic activity in this area than recognized previously. Fluid inclusion and paragenetic studies reveal a clear temporal evolution of fluid temperature and chemistry in the San Agustin area at Hualgayoc. Gradually, ore formation shifted to precipitation of vein minerals in the brittle fractures as the mantos became less permeable and were sealed off. Vein formation continued from progressively cooler and more diluted fluids (down to {approx}150{degrees}C and 4.3 wt% NaCl equivalent) as the system waned. No evidence for phase separation is observed in the fluids until the very last paragenetic stage, which contributed no economic mineralization. 53 refs., 15 figs., 7 tabs.« less

Calcite growth-rate inhibition by fulvic acids isolated from Big Soda Lake, Nevada, USA, The Suwannee River, Georgia, USA and by polycarboxylic acids

USGS Publications Warehouse

Reddy, Michael M.; Leenheer, Jerry

2011-01-01

Calcite crystallization rates are characterized using a constant solution composition at 25°C, pH=8.5, and calcite supersaturation (Ω) of 4.5 in the absence and presence of fulvic acids isolated from Big Soda Lake, Nevada (BSLFA), and a fulvic acid from the Suwannee River, Georgia (SRFA). Rates are also measured in the presence and absence of low-molar mass, aliphatic-alicyclic polycarboxylic acids (PCA). BSLFA inhibits calcite crystal-growth rates with increasing BSLFA concentration, suggesting that BSLFA adsorbs at growth sites on the calcite crystal surface. Calcite growth morphology in the presence of BSLFA differed from growth in its absence, supporting an adsorption mechanism of calcite-growth inhibition by BSLFA. Calcite growth-rate inhibition by BSLFA is consistent with a model indicating that polycarboxylic acid molecules present in BSLFA adsorb at growth sites on the calcite crystal surface. In contrast to published results for an unfractionated SRFA, there is dramatic calcite growth inhibition (at a concentration of 1 mg/L) by a SRFA fraction eluted by pH 5 solution from XAD-8 resin, indicating that calcite growth-rate inhibition is related to specific SRFA component fractions. A cyclic PCA, 1, 2, 3, 4, 5, 6-cyclohexane hexacarboxylic acid (CHXHCA) is a strong calcite growth-rate inhibitor at concentrations less than 0.1 mg/L. Two other cyclic PCAs, 1, 1 cyclopentanedicarboxylic acid (CPDCA) and 1, 1 cyclobutanedicarboxylic acid (CBDCA) with the carboxylic acid groups attached to the same ring carbon atom, have no effect on calcite growth rates up to concentrations of 10 mg/L. Organic matter ad-sorbed from the air onto the seed crystals has no effect on the measured calcite crystal-growth rates.

The Transfiguration continental red-bed Cu-Pb-Zn-Ag deposit, Quebec Appalachians, Canada

NASA Astrophysics Data System (ADS)

Cabral, Alexandre Raphael; Beaudoin, Georges; Taylor, Bruce E.

2009-04-01

The Transfiguration Cu-Pb-Zn-Ag deposit, enclosed within reduced grey sandstone, is associated with continental red beds of the Lower Silurian Robitaille Formation in the Quebec Appalachians, Canada. The Robitaille Formation rests unconformably on foliated Cambro-Ordovician rocks. The unconformity is locally cut by barite veins. The basal unit of the Robitaille Formation comprises green wacke and pebble conglomerate, which locally contain calcite nodules. The latter have microstructures characteristic of alpha-type calcretes, such as “floating” fabrics, calcite-filled fractures (crystallaria) and circumgranular cracks. Massive, grey sandstone overlies the basal green wacke and pebble conglomerate unit, which is overlain, in turn, by red, fine-grained sandstone. Mineralisation occurred underneath the red sandstone unit, chiefly in the grey sandstone unit, as disseminated and veinlet sulphides. Chalcopyrite, the most abundant Cu sulphide, replaced early pyrite. Calcrete, disseminated carbonate and vein carbonate have stable isotope ratios varying from -7.5‰ to -1.1‰ δ13C and from 14.7‰ to 21.3‰ δ18O. The negative δ13C values indicate the oxidation of organic matter in a continental environment. Sulphur isotope ratios for pyrite, chalcopyrite and galena vary from -19‰ to 25‰ δ34S, as measured on mineral concentrates by a conventional SO2 technique. Laser-assisted microanalyses (by fluorination) of S isotopes in pyrite show an analogous range in δ34S values, from -21‰ to 25‰. Negative and positive δ34S values are compatible with bacterial sulphate reduction (BSR) in systems open and closed with respect to sulphate. We interpret similarly high δ34S values for sulphide concentrates (25.1‰) and for vein barite (26.2‰) to result from rapid and complete thermochemical reduction of pore-water sulphate. Two early to late diagenetic stages of mineralisation best explain the origin of the Transfiguration deposit. The first stage was characterised by the ponding of groundwater over the Taconian unconformity, recorded by calcrete and early pyrite formation via BSR in grey sandstone. Early pyrite contains up to 2 wt.% Pb, which is consistent with Pb fixation by sulphate-reducing bacteria. The second stage (II) is defined by the replacement of early pyrite by chalcopyrite, as well as by sulphide precipitation via either BSR or thermochemical sulphate reduction (TSR) in grey sandstone. This event resulted from the synsedimentary fault-controlled percolation and mixing of (1) an oxidising, sulphate-bearing cupriferous fluid migrating per descensum from the red-bed sequence and (2) a hydrocarbon-bearing fluid migrating per ascensum from the Cambro-Ordovician basement. Mixing between the two fluids led to sulphate reduction, causing Cu sulphide precipitation. The positive correlation between Cu and Fe3+/Fe2+ bulk rock values suggests that Fe acted as a redox agent during sulphate reduction. Stage II diagenetic fluid migration is tentatively attributed to the Late Silurian Salinic extensional event.

Time-Series Radiocarbon Measurements Indicate Carbon Turnover Across Soil Fractions is Correlated With Productivity in a Long-Term Agricultural Experiment

NASA Astrophysics Data System (ADS)

Sanderman, J.; Baisden, W. T.; Creamer, C.; Farrell, M.; Fallon, S.

2016-12-01

Carbonatites and alkaline intrusions are important sources of REEs. Environmental risks related to these deposit types have been assessed through literature review and evaluation of the geochemical properties of representative samples of mill tailings and their leachates. The main ore mineral in carbonatite deposits is bastnasite [(Ce,La)(CO3)F], which is found with dolomite and calcite ( 65 %), barite (20 - 25 %), plus a number of minor accessory minerals including sulfides such as galena and pyrite. Generally, alkaline intrusion-related REE deposits either occur in layered complexes or with dikes and veins cutting alkaline intrusions. Such intrusions have a more diverse group of REE ore minerals that include fluorcarbonates, oxides, silicates, and phosphates. Ore also can include minor calcite and iron (Fe), lead (Pb), and zinc (Zn) sulfides. The acid-generating potential of both deposit types is low because of a predominance of carbonate minerals in the carbonatite deposits, the presence of feldspars and minor calcite in alkaline intrusion-related deposits, and to only minor to trace occurrence of potentially acid-generating sulfide minerals. Both deposit types, however, are produced by igneous and hydrothermal processes that enrich high-field strength, incompatible elements, which typically are excluded from common rock-forming minerals. Elements such as yttrium (Y), niobium Nb), zirconium (Zr), hafnium (Hf), tungsten (W), titanium (Ti), tantalum (Ta), scandium (Sc), thorium (Th), and uranium (U) can be characteristic of these deposits and may be of environmental concern. Most of these elements, including the REEs, but with the exception of U, have low solubilities in water at the near-neutral pH values expected around these deposits. Mill tailings from carbonatite deposits can exceed residential soil and sediment criteria for Pb, and leachates from mill tailings can exceed drinking water guidelines for Pb. The greatest environmental challenges, however, are linked to the presence of Th and U, although mineral hosts for these elements are moderately unreactive in the environment. Both deposit types can have mill tailings that exceed residential soil criteria for U. Uranium can be recovered as a byproduct to mitigate its environmental effects, but Th remains a waste product that requires management.

Environmental Characteristics of Carbonatite and Alkaline Intrusion-related Rare Earth Element (REE) Deposits

NASA Astrophysics Data System (ADS)

Seal, R. R., II; Piatak, N. M.

2017-12-01

Carbonatites and alkaline intrusions are important sources of REEs. Environmental risks related to these deposit types have been assessed through literature review and evaluation of the geochemical properties of representative samples of mill tailings and their leachates. The main ore mineral in carbonatite deposits is bastnasite [(Ce,La)(CO3)F], which is found with dolomite and calcite ( 65 %), barite (20 - 25 %), plus a number of minor accessory minerals including sulfides such as galena and pyrite. Generally, alkaline intrusion-related REE deposits either occur in layered complexes or with dikes and veins cutting alkaline intrusions. Such intrusions have a more diverse group of REE ore minerals that include fluorcarbonates, oxides, silicates, and phosphates. Ore also can include minor calcite and iron (Fe), lead (Pb), and zinc (Zn) sulfides. The acid-generating potential of both deposit types is low because of a predominance of carbonate minerals in the carbonatite deposits, the presence of feldspars and minor calcite in alkaline intrusion-related deposits, and to only minor to trace occurrence of potentially acid-generating sulfide minerals. Both deposit types, however, are produced by igneous and hydrothermal processes that enrich high-field strength, incompatible elements, which typically are excluded from common rock-forming minerals. Elements such as yttrium (Y), niobium Nb), zirconium (Zr), hafnium (Hf), tungsten (W), titanium (Ti), tantalum (Ta), scandium (Sc), thorium (Th), and uranium (U) can be characteristic of these deposits and may be of environmental concern. Most of these elements, including the REEs, but with the exception of U, have low solubilities in water at the near-neutral pH values expected around these deposits. Mill tailings from carbonatite deposits can exceed residential soil and sediment criteria for Pb, and leachates from mill tailings can exceed drinking water guidelines for Pb. The greatest environmental challenges, however, are linked to the presence of Th and U, although mineral hosts for these elements are moderately unreactive in the environment. Both deposit types can have mill tailings that exceed residential soil criteria for U. Uranium can be recovered as a byproduct to mitigate its environmental effects, but Th remains a waste product that requires management.

The Influence of Grain Boundary Fluids on the Recrystallization Behavior in Calcite: A Comparison of "dry" and "wet" Marble Mylonites

NASA Astrophysics Data System (ADS)

Schenk, O.; Urai, J.; Evans, B.

2003-12-01

Carbonate rocks are able to accumulate large amounts of strain and deform crystal-plastically even at low p-T conditions and thus, marble sequences are often the site of strain localization in the upper crust during late-stage deformation in mountain building processes. In this study we sought to identify the effect of fluids on grain boundary morphology and recrystallization processes in marble mylonites during shear zone evolution, as fluids play a major role in the flow behavior of many rock materials during deformation (e.g. quartz, olivine, halite, feldspar). We compared calcite marble mylonites from two geological settings: (a) Schneeberg Complex, Southern Tyrole, Italy and (b) Naxos Metamorphic Core Complex, Greece. The shear zones of the selected areas are suitable for comparison, because they consist of similar lithology and the marble mylonites resemble each other in chemical composition. In addition, calcite-dolomite solvus geothermometry and TEM observations indicate similar p-T conditions for the shear zones formation. However, the two settings are different in the availability of fluids during the shear zone evolution: In the Schneeberg mylonites, both the alteration of minerals during retrograde metamorphism of neighboring micaschists and the existence of veins suggest that fluids were present during mylonitization. The absence of these features in the Naxos samples indicates that fluids were not present during deformation of these mylonites. This difference is also supported by the signature of stable isotopes. Microstructural investigations using optical and scanning electron microscopes on broken and planar surfaces did not indicate major differences between wet and dry mylonites: Grain boundaries of both types of samples display pores with shapes controlled by crystallography, and pore morphologies that are similar to observations from crack and grain-boundary healing experiments. Grain size reduction was predominantly the result of subgrain rotation recrystallization. However, the coarse grains inside the wet protomylonites (Schneeberg) are characterized by intracrystalline shear zones. With the exception of the intracrystalline shear zones, there were no obvious microstructural signatures that were obvious indicators of the presence of fluids, at least for these two field examples.

The carbonaceous phyllite rock-hosted Pedra Verde copper mine, Borborema Province, Brazil: Stable isotope constraints, structural controls and metallogenic evolution

NASA Astrophysics Data System (ADS)

da Silva Nogueira de Matos, José Henrique; Saraiva dos Santos, Ticiano José; Virgínia Soares Monteiro, Lena

2017-12-01

The Pedra Verde Copper Mine is located in the Viçosa do Ceará municipality, State of Ceará, NE Brazil. The copper mineralization is hosted by the Pedra Verde Phyllite, which is a carbonaceous chlorite-calcite phyllite with subordinate biotite. It belongs to the Neoproterozoic Martinópole Group of the Médio Coreaú Domain, Borborema Province. The Pedra Verde deposit is stratabound and its ore zoning is conspicuous, according to the following sequence, from bottom to top: marcasite/pyrite, native silver, chalcopyrite, bornite, chalcocite, native copper and hematite. Barite and carbonaceous material are reported in ore zones. Zoning reflects the ore formation within a redox boundary developed due to the interaction between oxidized copper- and sulfate-bearing fluids and the reduced phyllite. Structural control on mineralization is evidenced by the association of the ore minerals with veins, hinge folds, shadow pressures, and mylonitic foliation. It was mainly exercised by a dextral transcurrent shear zone developed during the third deformational stage identified in the Médio Coreaú Domain between 590 Ma and 570 Ma. This points to the importance of epigenetic, post-metamorphic deformational events for ore formation. Oxygen isotopic composition (δ18OH2O = 8.94 to 11.28‰, at 250 to 300 °C) estimated for the hydrothermal fluids in equilibrium with calcite indicates metamorphic or evolved meteoric isotopic signatures. The δ13CPDB values (-2.60 to -9.25‰) obtained for hydrothermal calcite indicate mixing of carbon sources derived from marine carbonate rocks and carbonaceous material. The δ34SCDT values (14.88 to 36.91‰) of sulfides suggest evaporites as sulfate sources or a closed system in relation to SO42- availability to form H2S. Carbonaceous matter had a key role in thermochemical sulfate processes and sulfide precipitation. The Pedra Verde Copper Mine is considered the first stratabound meta-sedimentary rock-hosted copper deposit described in Brazil and shares similarities with the syn-orogenic copper deposits of the Congo-Zambian Copperbelt formed during the Gondwana amalgamation.

Mineral chemistry and shrimp U-Pb Geochronology of mesoproterozoic polycrase-titanite veins in the sullivan Pb-Zn-Ag Deposit, British Columbia

USGS Publications Warehouse

Slack, J.F.; Aleinikoff, J.N.; Belkin, H.E.; Fanning, C.M.; Ransom, P.W.

2008-01-01

Small polycrase-titanite veins 0.1-2 mm thick cut the tourmalinite feeder zone in the deep footwall of the Sullivan Pb-Zn-Ag deposit, southeastern British Columbia. Unaltered, euhedral crystals of polycrase and titanite 50-100 ??m in diameter are variably replaced by a finer-grained alteration-induced assemblage composed of anhedral polycrase and titanite with local calcite, albite, epidote, allanite, and thorite or uranothorite (or both). Average compositions of the unaltered and altered polycrase, as determined by electron-microprobe analysis, are (Y0.38 REE0.49 Th0.10 Ca0.04 Pb0.03 Fe0.01U0.01) (Ti1.48 Nb0.54 W0.04 Ta0.02)O6 and (Y0.42 REE0.32 Th0.15 U0.06 Ca0.04 Pb0.01 Fe0.01) (Ti1.57 Nb0.44 W0.04 Ta0.02)O6, respectively. The unaltered titanite has, in some areas, appreciable F (to 0.15 apfu), Y (to 0.40 apfu), and Nb (to 0.13 apfu). SHRIMP U-Pb geochronology of eight grains of unaltered polycrase yields a weighted 207Pb/206Pb age of 1413 ?? 4 Ma (2??) that is interpreted to be the age of vein formation. This age is 50-60 m.y. younger than the ca. 1470 Ma age of synsedimentary Pb-Zn-Ag mineralization in the Sullivan deposit, which is based on combined geological and geochronological data. SHRIMP ages for altered polycrase and titanite suggest later growth of minerals during the ???1370-1320 Ma East Kootenay and ???1150-1050 Ma Grenvillian orogenies. The 1413 ?? 4 Ma age for the unaltered polycrase in the veins records a previously unrecognized post-ore (1370 Ma) mineralizing event in the Sullivan deposit and vicinity. The SHRIMP U-Pb age of the polycrase and high concentrations of REE, Y, Ti, Nb, and Th in the veins, together with elevated F in titanite and the absence of associated sulfides, suggest transport of these high-field-strength elements (HFSE) by F-rich and S-poor hydrothermal fluids unrelated to the fluids that formed the older Fe-Pb-Zn-Ag sulfide ores of the Sullivan deposit. Fluids containing abundant REE, HFSE, and F may have been derived from a geochemically specialized magma such as those that form alkaline granites, pegmatites, or carbonatites. In an alternative model. preferred here, these fluids were associated with a rift-related, crustal metasomatic event in the region. Determination of a Mesoproterozoic age for the polycrase-titanite veins establishes the first known occurrence of pre-Grenvillian REE-rich mineralization in the Belt-Purcell basin.

Mechanochemical endovenous ablation versus radiofrequency ablation in the treatment of primary small saphenous vein insufficiency (MESSI trial): study protocol for a randomized controlled trial.

PubMed

Boersma, Doeke; van Eekeren, Ramon R J P; Kelder, Hans J C; Werson, Debora A B; Holewijn, Suzanne; Schreve, Michiel A; Reijnen, Michel M P J; de Vries, Jean Paul P M

2014-10-29

Minimally invasive endothermal techniques, for example, radiofrequency ablation (RFA), have revolutionized the treatment of insufficient truncal veins and are associated with an excellent outcome. The use of thermal energy requires the instillation of tumescent anesthesia around the vein. Mechanochemical endovenous ablation (MOCA™) combines mechanical endothelial damage, using a rotating wire, with simultaneous infusion of a liquid sclerosans. Tumescent anesthesia is not required as no heat is used. Prospective studies using MOCA™ in both great and small saphenous veins showed good anatomical and clinical results with fast postoperative recovery. The MESSI trial (Mechanochemical Endovenous ablation versus radiofrequency ablation in the treatment of primary Small Saphenous vein Insufficiency) is a multicenter randomized controlled trial in which a total of 160 patients will be randomized (1:1) to MOCA™ or RFA. Consecutive patients with primary small saphenous vein incompetence, who meet the eligibility criteria, will be invited to participate in this trial. The primary endpoint is anatomic success, defined as occlusion of the treated veins objectified with duplex ultrasonography at 1 year follow-up. Secondary endpoints are post-procedural pain, initial technical success, clinical success, complications and the duration of the procedure. Initial technical success is defined as the ability to position the device adequately, treat the veins as planned and occlude the treated vein directly after the procedure has been proven by duplex ultrasonography. Clinical success is defined as an objective improvement of clinical outcome after treatment, measured with the Venous Clinical Severity Score (VCSS). Power analyses are conducted for anatomical success and post-procedural pain.Both groups will be evaluated on an intention-to-treat principle. The hypothesis of the MESSI trial is that the anatomic success rate of MOCA™ is not inferior to RFA. The second hypothesis is that post-procedural pain is significantly less after MOCA compared to RFA. NTR4613 Date of trial registration: 28 May 2014.

[SERV clinical practice guidelines: management of retinal vein occlusion. Sociedad Española de Retina y Vitreo].

PubMed

Gómez-Ulla, F; Abraldes, M J; Basauri, E; Fernández, M; García-Layana, A; Gili, P; Montero, J; Nadal, J; Morales, V; Saravia, M; Cabrera, F; Cervera, E

2010-09-01

A guidelines for the management of retinal vein occlusion is presented. This is necessary because at this moment several therapeutic alternatives have been developed although their role is not yet sufficiently defined. Review of the literature for evidence published up to date. Relevant literature was identified and the level of evidence graded. Evidence was then assessed for consistency, applicability and clinical impact. The information was contrasted with those guides published in other countries. Taking into account the different options of treatment that are currently used, several modes of action are suggested. The role of the various complementary examinations are discussed and it is recommended that criteria for the treatment are based on clinical, angiographic, and tomographic findings. Although there is no overall consensus, these guidelines promote a good standard of clinical practise and provide an update of the management of retinal vein occlusion. Copyright © 2010. Published by Elsevier Espana.

Orogenesis of the Oman Mountains - a new geodynamic model based on structural geology, plate reconstructions and thermochronology

NASA Astrophysics Data System (ADS)

Grobe, Arne; Virgo, Simon; von Hagke, Christoph; Ralf, Littke; Urai, Janos L.

2017-04-01

Ophiolite obduction is an integral part of mountain building in many orogens. However, because the obduction stage is usually overprinted by later tectonic events, obduction geodynamics and its influence on orogenesis are often elusive. The best-preserved ophiolite on Earth is the Semail Ophiolite, Oman Mountains. 350 km of ophiolite and the entire overthrusted margin sequence are exposed perpendicular to the direction of obduction along the northeastern coast of the Sultanate of Oman. Despite excellent exposure, it has been debated whether early stages of obduction included formation of a micro-plate, or if the Oman Mountains result from collision of two macro-plates (e.g. Breton et al., 2004). Furthermore, different tectonic models for the Oman Mountains exist, and it is unclear how structural and tectonic phases relate to geodynamic context. Here we present a multidisciplinary approach to constrain orogenesis of the Oman Mountains. To this end, we first restore the structural evolution of the carbonate platform in the footwall of the Semail ophiolite. Relative ages of nine structural generations can be distinguished, based on more than 1,500 vein and fault overprintings. Top-to-S overthrusting of the Semail ophiolite is witnessed by three different generations of bedding confined veins in an anticlockwise rotating stress field. Rapid burial induced the formation of overpressure cells, and generation and migration of hydrocarbons (Fink et al., 2015; Grobe et al., 2016). Subsequent tectonic thinning of the ophiolite took place above a top-to-NNE crustal scale, ductile shear zone, deforming existing veins and forming a cleavage in clay-rich layers. Ongoing extension formed normal- to oblique-slip faults and horst-graben structures. This was followed by NE-SW oriented ductile shortening, the formation of the Jebel Akhdar anticline, potentially controlled by the positions of the horst-graben structures. Exhumation in the Cenozoic was associated with low angle normal faults on the northern flank of the anticline. We link these results with the geodynamic framework of the area, constrained by plate tectonic reconstructions. Furthermore, we constrain the exhumation history of the mountain belt using zircon (U-Th-Sm)/He dating. Geodynamic and exhumation events can be linked to structural generations. This results in a new tectonic model of the Oman Mountains. We find a remarkable along-strike consistency of mountain building phases and argue involvement of a micro-plate is not required. Breton, J.P., Béchennec, F., Le Métour, J., Moen-Maurel, L., Razin, P., 2004. Eoalpine (Cretaceous) evolution of the Oman Tethyan continental margin: Insights from a structural field study in Jabal Akhdar (Oman Mountains). GeoArabia 9, 41-58. Fink, R., Virgo, S., Arndt, M., Visser, W., Littke, R., Urai, J.L.L., 2015. Solid bitumen in calcite veins from the Natih Formation in the Oman Mountains: Multiple phases of petroleum migration in a changing stress field. Int. J. Coal Geol. 157, 39-51. doi:10.1016/j.coal.2015.07.012 Grobe, A., Urai, J.L.L., Littke, R., Lünsdorf, N.K.K., 2016. Hydrocarbon generation and migration under a large overthrust: The carbonate platform under the Semail Ophiolite, Jebel Akhdar, Oman. Int. J. Coal Geol. 1-17. doi:10.1016/j.coal.2016.02.007

Molybdenite tricks with titanite give history of the Central Indian Tectonic Zone

NASA Astrophysics Data System (ADS)

Stein, Holly J.; Hannah, Judith L.; Pandit, Manoj K.; Mohanty, Saradaprasad; Corfu, Fernando; Zimmerman, Aaron

2014-05-01

The time that the cratonic blocks joined to form peninsular India creating the E-W-trending Central Indian Tectonic Zone (CITZ) is important for tectonic reconstructions and Paleoproterozoic glaciations, and fundamental to understanding how sutures behave through time. An abundance of recent literature highlights ~1.0 Ga as the time of suturing. This late 1.0 Ga meeting of the two cratons, however, is increasingly difficult to reconcile. One of the well-studied and well-mapped terranes in the southern part of the CITZ is the Sausar Belt [1]. The metasedimentary and metavolcanic rocks comprising the extensive Paleoproterozoic Sausar Group are multiply deformed. To examine the history of the Sausar Belt from a new vantage, we employed Re-Os dating of molybdenite, a sulfide that serves faithfully as a single-mineral radiometric clock in both magmatic and metamorphic environments [2]. Molybdenite is rare in the Sausar belt. Samples containing a 1-cm molybdenite patch and coarse-grained, euhedral, clear brown titanite were acquired from two different varieties of calc-silicate rocks near the village of Umri in central India. The molybdenite occurs in a calcite-quartz vein that clearly cross-cuts a strongly deformed calc-silicate host with quartz-biotite and quartz bands at the cm scale. This vein, metamorphic in character, is about 1-cm-wide and slightly deformed. The molybdenite was contained wholly within the vein. To check for possible Re-Os decoupling [2], we split the molybdenite patch into seven subsamples, analyzing each fraction separately; in sum, these seven fractions account for the entire molybdenite crystal. We obtained extremely disparate ages for the individual fractions, ranging from 1.4 to 3.1 Ga. These data were recombined on an atomic basis to calculate the Re-Os age for the entire crystal, a trick we employed after affirming there was no additional sulfide and no additional molybdenite that might compete for Re and Os in our hand-sample of 10 x 15 cm. This circumstance provided us the opportunity to turn Re-Os decoupling to our advantage. The whole-crystal Re-Os molybdenite age on combining data from individual separates is between 2.41 and 2.45 Ga, depending on estimates of very minor silicate dilution as the crystal was extracted piecemeal from the vein. The U-Pb age for euhedral titanite crystals in a dense massive calc-silicate host, not unexpectedly, is ~1.0 Ga. The molybdenite and titanite record two different episodes of metamorphism. These results suggest that the Sausar Group calc-silicate rocks we analyzed are earliest Paleoproterozoic, >2.41 Ga. Shortly after deposition these rocks were metamorphosed - the first event in a long history of metamorphism and deformation continually focused along an ancient suture. These results have implications for the CITZ, and are similar to ages found in terranes on either side of this continental scale collisional belt [3,4]. This study was funded by the U.S. National Science Foundation (EAR-1119655). References Cited [1] Mohanty, S. (2010) Journal of Asian Earth Sciences 39: 516-526. [2] Stein et al. (2003) Geochimica et Cosmochimica Acta 67: 3673-3686. [3] Stein et al. (2004) Precambrian Research 134: 189-226. [4] Radhakrishna et al. (2013) Precambrian Research 226: 91-104.

Evolution of fracture and fault-controlled fluid pathways in carbonates of the Albanides fold-thrust belt

USGS Publications Warehouse

Graham, Wall B.R.; Girbacea, R.; Mesonjesi, A.; Aydin, A.

2006-01-01

The process of fracture and fault formation in carbonates of the Albanides fold-thrust belt has been systematically documented using hierarchical development of structural elements from hand sample, outcrop, and geologic-map scales. The function of fractures and faults in fluid migration was elucidated using calcite cement and bitumen in these structures as a paleoflow indicator. Two prefolding pressure-solution and vein assemblages were identified: an overburden assemblage and a remote tectonic stress assemblage. Sheared layer-parallel pressure-solution surfaces of the overburden assemblage define mechanical layers. Shearing of mechanical layers associated with folding resulted in the formation of a series of folding assemblage fractures at different orientations, depending on the slip direction of individual mechanical layers. Prefolding- and folding-related fracture assemblages together formed fragmentation zones in mechanical layers and are the sites of incipient fault localization. Further deformation along these sites was accommodated by rotation and translation of fragmented rock, which formed breccia and facilitated fault offset across multiple mechanical layers. Strike-slip faults formed by this process are organized in two sets in an apparent conjugate pattern. Calcite cement and bitumen that accumulated along fractures and faults are evidence of localized fluid flow along fault zones. By systematic identification of fractures and faults, their evolution, and their fluid and bitumen contents, along with subsurface core and well-log data, we identify northeast-southwest-trending strike-slip faults and the associated structures as dominant fluid pathways in the Albanides fold-thrust belt. Copyright ?? 2006. The American Association of Petroleum Geologists. All rights reserved.

Spectroscopic studies of the fish fossils (Cladocyclus gardneri and Vinctifer comptoni) from the Ipubi Formation of the Cretaceous Period.

PubMed

Sousa Filho, F E; da Silva, J H; Saraiva, G D; Abagaro, B T O; Barros, O A; Saraiva, A A F; Viana, B C; Freire, P T C

2016-03-15

Fossils are mineralized remains or traces from animals, plants and other organisms aged to about 10(8)years. The chemical processes of fossilization are dated back from old geological periods on Earth. The understanding of these processes and the structure of the fossils are one of the goals of paleontology and geology in the sedimentary environments. Many researches have tried to unveil details about special kinds of biological samples; however, a lack of data is noticed for various other specimens. This study reports the investigations through infrared spectroscopy, X-ray fluorescence and X-ray diffraction measurements for two types of fish fossils from the Cretaceous Period. The sample of Cladocyclus gardneri and Vinctifer comptoni fossils were collected from the Ipubi Formation, being one of the less studied, among the formations that constitute the important Santana group in the Araripe Basin, Brazil. The results obtained through different techniques, showed that the C. gardneri fish fossil contains hydroxyapatite and calcite as constituents whereas its rock matrix was formed by calcite, quartz and pyrite. Regarding the V. comptoni, the measurements confirmed the presence of hydroxyapatite in the fossil and its rock matrix gypsum, pyrite, quartz and calcite. The above scientific data contributed to the understanding the fossil formation in the Ipubi Formation, an important environment of the Cretaceous Period, which is rich in well-preserved fossils from different species. Copyright © 2015 Elsevier B.V. All rights reserved.

Carbonate microbialites and hardgrounds from Manito Lake, an alkaline, hypersaline lake in the northern Great Plains of Canada

NASA Astrophysics Data System (ADS)

Last, Fawn M.; Last, William M.; Halden, Norman M.

2010-03-01

Manito Lake is a large, perennial, Na-SO 4 dominated saline to hypersaline lake located in the northern Great Plains of western Canada. Significant water level decrease over the past several decades has led to reduction in volume and surface area, as well as an increase in salinity. The salinity has increased from 10 ppt to about 50 ppt TDS. This decrease in water level has exposed large areas of nearshore microbialites. These organogenic structures range in size from several cm to over a meter and often form large bioherms several meters high. They have various external morphologies, vary in mineralogical composition, and show a variety of internal fabrics from finely laminated to massive. In addition to microbiolities and bioherms, the littoral zone of Manito Lake contains a variety of carbonate hardgrounds, pavements, and cemented clastic sediments. Dolomite and aragonite are the most common minerals found in these shoreline structures, however, calcite after ikaite, monohydrocalcite, magnesian calcite, and hydromagnesite are also present. The dolomite is nonstoichiometric and calcium-rich; the magnesian calcite has about 17 mol% MgCO 3. AMS radiocarbon dating of paired organic matter and endogenic carbonate material confirms little or no reservoir affect. Although there is abundant evidence for modern carbonate mineral precipitation and microbialite formation, most of the larger microbialites formed between about 2300 and 1000 cal BP, whereas the hardgrounds, cements, and laminated crusts formed about 1000-500 cal BP.

Radiocarbon dating of dissolved inorganic carbon in groundwater from confined parts of the Upper Floridan aquifer, Florida, USA

USGS Publications Warehouse

Plummer, Niel; Sprinkle, C.L.

2001-01-01

Geochemical reaction models were evaluated to improve radiocarbon dating of dissolved inorganic carbon (DIC) in groundwater from confined parts of the Upper Floridan aquifer in central and northeastern Florida, USA. The predominant geochemical reactions affecting the 14C activity of DIC include (1) dissolution of dolomite and anhydrite with calcite precipitation (dedolomitization), (2) sulfate reduction accompanying microbial degradation of organic carbon, (3) recrystallization of calcite (isotopic exchange), and (4) mixing of fresh water with as much as 7% saline water in some coastal areas. The calculated cumulative net mineral transfers are negligibly small in upgradient parts of the aquifer and increase significantly in downgradient parts of the aquifer, reflecting, at least in part, upward leakage from the Lower Floridan aquifer and circulation that contacted middle confining units in the Floridan aquifer system. The adjusted radiocarbon ages are independent of flow path and represent travel times of water from the recharge area to the sample point in the aquifer. Downgradient from Polk City (adjusted age 1.7 ka) and Keystone Heights (adjusted age 0.4 ka), 14 of the 22 waters have adjusted 14C ages of 20-30 ka, indicating that most of the fresh-water resource in the Upper Floridan aquifer today was recharged during the last glacial period. All of the paleowaters are enriched in 18O and 2H relative to modern infiltration, with maximum enrichment in ??18O of approximately 2.0%o.

Raman spectroscopic study of calcite III to aragonite transformation under high pressure and high temperature

NASA Astrophysics Data System (ADS)

Liu, Chuanjiang; Zheng, Haifei; Wang, Duojun

2017-10-01

In our study, a series of Raman experiments on the phase transition of calcite at high pressure and high temperature were investigated using a hydrothermal diamond anvil cell and Raman spectroscopy technique. It was found that calcite I transformed to calcite II and calcite III at pressures of 1.62 and 2.12 GPa and room temperature. With increasing temperature, the phase transition of calcite III to aragonite occurred. Aragonite was retained upon slowly cooling of the system, indicating that the transition of calcite III to aragonite was irreversible. Based on the available data, the phase boundary between calcite III and aragonite was determined by the following relation: P(GPa) = 0.013 × T(°C) + 1.22 (100°C ≤ T ≤ 170°C). It showed that the transition pressure linearly rose with increasing temperature. A better understanding of the stability of calcite III and aragonite is of great importance to further explore the thermodynamic behavior of carbonates and carbon cycling in the mantle.

Study of reverse flotation of calcite from scheelite in acidic media

NASA Astrophysics Data System (ADS)

Deng, Rongdong; Huang, Yuqing; Hu, Yuan; Ku, Jiangang; Zuo, Weiran; Yin, Wanzhong

2018-05-01

A new coated-reactive reverse flotation method based on the generation of CO2 bubbles at a calcite surface in acidic solution was used to separate calcite from scheelite. The dissolution kinetics of coated and uncoated calcite were studied in sulfuric acid. The CO2 bubbles generated on the uncoated calcite particle surface are enough to float the particle. However, most of these bubbles left the surface quickly, preventing calcite from floating. Here, a mixture of polyvinyl alcohol polymer and sodium dodecyl sulfonate was used to coat the mineral particles and form a stable membrane, resulting in the formation of a stable foam layer on the calcite surface. After the calcite is coated, the generated bubbles could be successfully captured on the calcite surface, and calcite particles could float to the air-water interface and remain there for more than one hour. Flotation tests indicated that a high-quality tungsten concentrate with a grade of more than 75% and a recovery of more than 99% could be achieved when the particle size was between 0.3 and 1.5 mm. The present results provide theoretical support for the development of a highly efficient flotation separation for carbonate minerals.

Reconstructing water level in Hoyo Negro, Quintana Roo, Mexico, implications for early Paleoamerican and faunal access

NASA Astrophysics Data System (ADS)

Collins, S. V.; Reinhardt, E. G.; Rissolo, D.; Chatters, J. C.; Nava Blank, A.; Luna Erreguerena, P.

2015-09-01

The skeletal remains of a Paleoamerican (Naia; HN5/48) and extinct megafauna were found at -40 to -43 mbsl in a submerged dissolution chamber named Hoyo Negro (HN) in the Sac Actun Cave System, Yucatan Peninsula, Mexico. The human remains were dated to between 12 and 13 Ka, making these remains the oldest securely dated in the Yucatan. Twelve sediment cores were used to reconstruct the Holocene flooding history of the now phreatic cave passages and cenotes (Ich Balam, Oasis) that connect to HN. Four facies were found: 1. bat guano and Seed (SF), 2. lime Mud (MF), 3. Calcite Rafts (CRF) and 4. Organic Matter/Calcite Rafts (OM/CRF) which were defined by their lithologic characteristics and ostracod, foraminifera and testate amoebae content. Basal radiocarbon ages (AMS) of aquatic sediments (SF) combined with cave bottom and ceiling height profiles determined the history of flooding in HN and when access was restricted for human and animal entry. Our results show that the bottom of HN was flooded at least by 9850 cal yr BP but likely earlier. We also found, that the pit became inaccessible for human and animal entry at ≈8100 cal yr BP, when water reaching the cave ceiling effectively prevented entry. Water level continued to rise between ≈6000 and 8100 cal yr BP, filling the cave passages and entry points to HN (Cenotes Ich Balam and Oasis). Analysis of cave facies revealed that both Holocene sea-level rise and cave ceiling height determined the configuration of airways and the deposition of floating and bat derived OM (guano and seeds). Calcite rafts, which form on the water surface, are also dependent on the presence of airways but can also form in isolated air domes in the cave ceiling that affect their loci of deposition on the cave bottom. These results indicated that aquatic cave sedimentation is transient in time and space, necessitating extraction of multiple cores to determine a limit after which flooding occurred.

REE Incorporation into Calcite Individual Crystals as One Time Spike Addition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gabitov, Rinat; Sadekov, Aleksey; Migdisov, Artas

Experiments on the incorporation of trace elements into calcite were performed, and rare earth elements (REE) were used to mark the growth zones of individual crystals. Experiments were conducted at different pH (7.7 to 8.8) and temperatures (2 °C to 24.6 °C) in NH 4Cl + CaCl 2 solutions, where REE were rapidly consumed by growing calcite. LA-ICP-MS line-scans yielded the distribution of (REE/Ca) calcite within individual crystals in a manner consistent with the addition of REE into fluid. A sharp decrease of (REE/Ca) calcite toward the crystal edge suggests the fast depletion of (REE/Ca) fluid due to strong REEmore » consumption by growing calcite. An attempt was made to estimate the lower limit of the partition coefficients between calcite and fluid using selected REE/Ca data within individual calcite crystals and the amount of REE added into fluid.« less

REE Incorporation into Calcite Individual Crystals as One Time Spike Addition

DOE PAGES

Gabitov, Rinat; Sadekov, Aleksey; Migdisov, Artas

2017-10-26

Experiments on the incorporation of trace elements into calcite were performed, and rare earth elements (REE) were used to mark the growth zones of individual crystals. Experiments were conducted at different pH (7.7 to 8.8) and temperatures (2 °C to 24.6 °C) in NH 4Cl + CaCl 2 solutions, where REE were rapidly consumed by growing calcite. LA-ICP-MS line-scans yielded the distribution of (REE/Ca) calcite within individual crystals in a manner consistent with the addition of REE into fluid. A sharp decrease of (REE/Ca) calcite toward the crystal edge suggests the fast depletion of (REE/Ca) fluid due to strong REEmore » consumption by growing calcite. An attempt was made to estimate the lower limit of the partition coefficients between calcite and fluid using selected REE/Ca data within individual calcite crystals and the amount of REE added into fluid.« less

Exploration for gold mineralization in the Arabo Nubian Shield: Using remote sensing Approach

NASA Astrophysics Data System (ADS)

Ramadan, Talaat

2013-04-01

In the southern part of the Eastern Desert of Egypt, Landsat Thematic Mapper (ETM+) data and fieldwork was combined with mineralogical and geochemical investigations in order to detect and characterize alteration zones within Pan-African rocks. The processing of Landsat ETM+ data using ratioing (bands 5/7,5/1,4/3 in Red, Green, Blue) showed two different types of alteration zones (type l and 2). Type 1 is close to the ophiolitic ultramafic rocks and type 2 is located within island-arc related metavolcanic rocks at the study areas. Both of these alteration zones are concordant with the main NW-SE structural trend. Mineralogical studies indicate that the alteration zones of type 1 consist mainly of calcite, ankerite, magnesite, dolomite and quartz. Chromian spinel, pyrite, and Ni-bearing sulphides (gersdorffite, pentlandite and polydymite) are the main ore minerals within this zone. Alteration zones of type 2 are strongly potassium-enriched and pyrophyllite, kaolinite, illite, gypsum and quartz occur. The brecciated quartz-veins associated with theses alteration zones consist of quartz, Fe-hydroxides, hematite and native gold. The gold content reaches up to 5 g/t in the alteration zone, while it extends up to 50 g/t in the quartz veins. This study presents a mineralogical characterization of such zones and demonstrates the utility of orbital remote sensing for finding unknown alteration zones in the Eastern Desert and other arid areas with similar host rock lithologies.

Late-Hercynian intrusion-related gold deposits: An integrated model on the Tighza polymetallic district, central Morocco

NASA Astrophysics Data System (ADS)

Éric, Marcoux; Khadija, Nerci; Yannick, Branquet; Claire, Ramboz; Gilles, Ruffet; Jean-Jacques, Peucat; Ross, Stevenson; Michel, Jébrak

2015-07-01

Gold have been recently recognized in the Tighza (formerly Jebel Aouam) district, in the Hercynian belt of central Morocco. This district has long been known for its W mineralization, as well as major Pb-Ag-Zn, and minor Sb-Ba deposits, all geographically associated with late-Hercynian calc-alkaline magmatism. Gold mineralization in the district is mainly hosted by thick W-Au quartz veins located around the "Mine granite" small granitic plug. Within the veins, gold grade is highest (up to 70 g/t) close to the granite but rapidly decreases going outward from the granite, defining a perigranitic zoning. Anomalous gold grades have also been measured in hydrothermal skarn layers close to two other granitic plugs (Kaolin granite and Mispickel granite), associated with disseminated As-Fe sulfides. The paragenetic sequence for the W-Au quartz veins shows three stages: (1) an early oxidized stage with wolframite-scheelite associated with early quartz (Q1), (2) an intermediate Bi-As-Te-Mo-Au sulfide stage with loellingite, bismuth minerals and native gold with a later quartz (Q2), restricted to a narrow distance from the granite, and (3) a late lower temperature As-Cu-Zn-(Pb) stage with abundant massive pyrrhotite, arsenopyrite and sphalerite, locally forming independent veins ("pyrrhotite vein"). Both Q1 hyaline and Q2 saccharoidal gold-bearing quartz display aqua-carbonic fluids with minor H2S and Cu and an homogeneous composition (81 mole% H2O, 18 mole% CO2 and about 1 mole% NaCl). The trapping pressure is estimated to 1.5-2 kbar with temperature ranging from 300 to 350 °C. Q1 inclusions have exploded indicating an uplift of the Tighza block, that lead to saccharoidal Q2 quartz deposition with multiphase NaCl-saturated fluid inclusions. 40Ar/39Ar dating demonstrates that the "Mine granite", tungsten skarnoid, scheelite-molybdenite veins, and very likely gold-bearing veins are coeval, emplaced at 286 ± 1 Ma. Multiple and widespread metal sources are indicated by radiogenic isotope studies. Nd and Sr isotope compositions of scheelite and granites suggest the participation of a juvenile component while lead isotopes demonstrate a major participation of the basement. Both gold mineralization and zoning suggest that the system developed at the end of the magmatic activity, accompanying a major transition in magmatic fluid composition. The morphology of the gold-bearing mineralization is dependent of the permeability and the reactivity of host-rocks: focus circulation of fluids through pre-existing tectonic corridors, reactivated by late-Hercynian intrusions favor the formation of large W-type gold veins, while infiltration of fluid within reactive stratigraphic layers gives rise to skarn mineralization. A 40Ar/39Ar date (W1 north vein: 291.8 ± 0.3 Ma) indicates that hydrothermal circulation predates gold and tungsten deposition in open fractures as well as Mine granite emplacement. The W-Au mineralization preceded the onset of a large convective hydrothermal cell around the intrusion that led to the formation of the Pb-Ag-Zn mined veins. The Tighza polymetallic district displays numerous similarities with the R-IRG model that was defined in the American Cordillera, such as thermal and zonation patterns, carbonic hydrothermal fluids and chronology of intrusion and related deposits, but also provides new insight to the R-IRG model such as wide Au-quartz veins instead of sheeted Au-veins, oxidation state of the magma, and Sr-Nd isotopic data. These results establish a major magmatic contribution and discard a direct genetic relationship between gold mineralization and major neighboring Pb-Ag-Zn veins. A large number of classic Pb-Zn district of the Western Hercynides belong to the same clan.

Evidence for solar cycles in a late Holocene speleothem record from Dongge Cave, China

PubMed Central

Duan, Fucai; Wang, Yongjin; Shen, Chuan-Chou; Wang, Yi; Cheng, Hai; Wu, Chung-Che; Hu, Hsun-Ming; Kong, Xinggong; Liu, Dianbing; Zhao, Kan

2014-01-01

The association between solar activity and Asian monsoon (AM) remains unclear. Here we evaluate the possible connection between them based on a precisely-dated, high-resolution speleothem oxygen isotope record from Dongge Cave, southwest China during the past 4.2 thousand years (ka). Without being adjusted chronologically to the solar signal, our record shows a distinct peak-to-peak correlation with cosmogenic nuclide 14C, total solar irradiance (TSI), and sunspot number (SN) at multi-decadal to centennial timescales. Further cross-wavelet analyses between our calcite δ18O and atmospheric 14C show statistically strong coherence at three typical periodicities of ~80, 200 and 340 years, suggesting important roles of solar activities in modulating AM changes at those timescales. Our result has further indicated a better correlation between our calcite δ18O record and atmospheric 14C than between our record and TSI. This better correlation may imply that the Sun–monsoon connection is dominated most likely by cosmic rays and oceanic circulation (both associated to atmospheric 14C), instead of the direct solar heating (TSI). PMID:24894978

Thermodynamics of magnesian calcite solid-solutions at 25°C and 1 atm total pressure

USGS Publications Warehouse

Busenberg, Eurybiades; Plummer, Niel

1989-01-01

The stability of magnesian calcites was reexamined, and new results are presented for 28 natural inorganic, 12 biogenic, and 32 synthetic magnesian calcites. The magnesian calcite solid-solutions were separated into two groups on the basis of differences in stoichiometric solubility and other physical and chemical properties. Group I consists of solids of mainly metamorphic and hydrothermal origin, synthetic calcites prepared at high temperatures and pressures, and synthetic solids prepared at low temperature and very low calcite supersaturations () from artificial sea water or NaClMgCl2CaCl2solutions. Group I solids are essentially binary s of CaCO2 and MgCO2, and are thought to be relatively free of structural defects. Group II solid-solutions are of either biogenic origin or are synthetic magnesian calcites and protodolomites (0–20 and ∼ 45 mole percent MgCO3) prepared at high calcite supersaturations () from NaClNa2SO4MgCl2CaCl2 or NaClMgCl2CaCl2 solutions. Group II solid-solutions are treated as massively defective solids. The defects include substitution foreign ions (Na+ and SO42−) in the magnesian calcite lattice (point defects) and dislocations (~2 · 109 cm−2). Within each group, the excess free energy of mixing, GE, is described by the mixing model , where x is the mole fraction of the end-member Ca0.5Mg0.5CO3 in the solid-solution. The values of A0and A1 for Group I and II solids were evaluated at 25°C. The equilibrium constants of all the solids are closely described by the equation ln , where KC and KD are the equilibrium constants of calcite and Ca0.5Mg0.5CO3. Group I magnesian calcites were modeled as sub-regular solid-solutions between calcite and dolomite, and between calcite and “disordered dolomite”. Both models yield almost identical equilibrium constants for these magnesian calcites. The Group II magnesian calcites were modeled as sub-regular solid-solutions between defective calcite and protodolomite. Group I and II solid-solutions differ significantly in stability. The rate of crystal growth and the chemical composition of the aqueous solutions from which the solids were formed are the main factors controlling stoichiometric solubility of the magnesian calcites and the density of crystal defects. The literature on the occurrence and behavior of magnesian calcites in sea water and other aqueous solutions is also examined.

Diagenesis of the Lisburne Group, northeastern Brooks Range, Alaska

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carlson, R.C.; Goldstein, R.H.; Enos, P.

1995-05-01

Petrographic cathodoluminescence studies of the cement stratigraphy of the Lisburne Group yield insights on its diagenetic history. Crosscutting relationships between features of subaerial exposure and calcite cements show that early generations of nonferroan, nonluminescent and multibanded-luminescent calcites are synchronous with or postdated by subaerial exposure surfaces within the Lisburne. Surfaces of subaerial exposure occur at 18 horizons within the Lisburne and are distinguished by features as laminated crusts, rhizoliths, autoclastic breccia, fissure fills, mud cracks, and erosional surfaces. Crosscutting relationships also occur between calcite cements and clasts in karst breccias and conglomerates that formed along the sub-Permian unconformity at themore » top of the Lisburne. The sub-Permian unconformity postdates later generations of calcite cement. These cements formed in the following sequence: nonferroan to low-ferroan, dully luminescent calcite; ferroan, very-dully luminescent calcite; and second generation of nonferroan, multibanded calcite. The crosscutting relationships not only constrain the timing of cement precipitation, but also suggest that the cements probably were precipitated from meteoric groundwaters introduced during subaerial exposure of the Lisburne platform. Late cements in the Lisburne postdate the Permian Echooka Formation. These cements are low-ferroan, moderately-bright to dully luminescent calcite, followed by a second generation of ferroan, very-dully luminescent calcite. Features of compaction and pressure solution are coincident with the precipitation of the late ferroan calcite and further constrain its timing to deep burial of the Lisburne. The youngest phase of calcite cement precipitated in the Lisburne Group is nonferroan, very-dully luminescent calcite. It commonly fills tectonically-induced shear fractures, indicating precipitation after the onset of Cretaceous (and/or Cenozoic) tectonism in the northeastern Brooks Range.« less

SIMS analyses of minor and trace element distributions in fracture calcite from Yucca Mountain, Nevada, USA

NASA Astrophysics Data System (ADS)

Denniston, Rhawn F.; Shearer, Charles K.; Layne, Graham D.; Vaniman, David T.

1997-05-01

Fracture-lining calcite samples from Yucca Mountain, Nevada, obtained as part of the extensive vertical sampling in studies of this site as a potential high-level waste repository, have been characterized according to microbeam-scale (25-30 μm) trace and minor element chemistry, and cathodoluminescent zonation patterns. As bulk chemical analyses are limited in spatial resolution and are subject to contamination by intergrown phases, a technique for analysis by secondary ion mass spectrometry (SIMS) of minor (Mn, Fe, Sr) and trace (REE) elements in calcite was developed and applied to eighteen calcite samples from four boreholes and one trench. SIMS analyses of REE in calcite and dolomite have been shown to be quantitative to abundances < 1 × chondrite. Although the low secondary ion yields associated with carbonates forced higher counting times than is necessary in most silicates, Mn, Fe, Sr, and REE analyses were obtained with sub-ppm detection limits and 2-15% analytical precision. Bulk chemical signatures noted by Vaniman (1994) allowed correlation of minor and trace element signatures in Yucca Mountain calcite with location of calcite precipitation (saturated vs. unsaturated zone). For example, upper unsaturated zone calcite exhibits pronounced negative Ce and Eu anomalies not observed in calcite collected below in the deep unsaturated zone. These chemical distinctions served as fingerprints which were applied to growth zones in order to examine temporal changes in calcite crystallization histories; analyses of such fine-scale zonal variations are unattainable using bulk analytical techniques. In addition, LREE (particularly Ce) scavenging of calcite-precipitating solutions by manganese oxide phases is discussed as the mechanism for Ce-depletion in unsaturated zone calcite.

YouTube as a potential source of information on deep venous thrombosis.

PubMed

Bademci, Mehmet Ş; Yazman, Serkan; Güneş, Tevfik; Ocakoglu, Gokhan; Tayfur, Kaptanderya; Gokalp, Orhan

2017-09-01

Background No work has been reported on the use of video websites to learn about deep vein thrombosis and the value of education using them. We examined the characteristics and scientific accuracy of videos related to deep vein thrombosis on YouTube. Methods YouTube was surveyed using no filter and the key words 'deep vein thrombosis' and 'leg vein clot' in June 2016. The videos evaluated were divided into three groups in terms of their scientific content, accuracy, and currency: useful, partly useful, and useless. Results Of the 1200 videos watched, 715 (59.58%) were excluded with the exclusion criteria. Although most of the videos uploaded (22.9%, n = 111) were created by physicians, the number of views for website-based videos was significantly higher (p = 0.002). When the uploaded videos were assessed in terms of their usefulness, videos from physicians and hospitals were statistically more useful than other videos (p < 0.001). Conclusions For videos created by medical professionals to be of higher quality, we believe they should be more up-to-date and comprehensive, and contain animations about treatment modalities and early diagnosis in particular.

The ubiquitous nature of accessory calcite in granitoid rocks: Implications for weathering, solute evolution, and petrogenesis

USGS Publications Warehouse

White, A.F.; Schulz, M.S.; Lowenstern, J. B.; Vivit, D.V.; Bullen, T.D.

2005-01-01

Calcite is frequently cited as a source of excess Ca, Sr and alkalinity in solutes discharging from silicate terrains yet, no previous effort has been made to assess systematically the overall abundance, composition and petrogenesis of accessory calcite in granitoid rocks. This study addresses this issue by analyzing a worldwide distribution of more than 100 granitoid rocks. Calcite is found to be universally present in a concentration range between 0.028 to 18.8 g kg-1 (mean = 2.52 g kg-1). Calcite occurrences include small to large isolated anhedral grains, fracture and cavity infillings, and sericitized cores of plagioclase. No correlation exists between the amount of calcite present and major rock oxide compositions, including CaO. Ion microprobe analyses of in situ calcite grains indicate relatively low Sr (120 to 660 ppm), negligible Rb and 87Sr/86Sr ratios equal to or higher than those of coexisting plagioclase. Solutes, including Ca and alkalinity produced by batch leaching of the granitoid rocks (5% CO2 in DI water for 75 d at 25??C), are dominated by the dissolution of calcite relative to silicate minerals. The correlation of these parameters with higher calcite concentrations decreases as leachates approach thermodynamic saturation. In longer term column experiments (1.5 yr), reactive calcite becomes exhausted, solute Ca and Sr become controlled by feldspar dissolution and 87Sr/ 86Sr by biotite oxidation. Some accessory calcite in granitoid rocks is related to intrusion into carbonate wall rock or produced by later hydrothermal alteration. However, the ubiquitous occurrence of calcite also suggests formation during late stage (subsolidus) magmatic processes. This conclusion is supported by petrographic observations and 87Sr/86Sr analyses. A review of thermodynamic data indicates that at moderate pressures and reasonable CO2 fugacities, calcite is a stable phase at temperatures of 400 to 700??C. Copyright ?? 2005 Elsevier Ltd.

Calcite precipitation on glass substrates and active stalagmites in Katerloch Cave (Austria): Constraints from environmental monitoring

NASA Astrophysics Data System (ADS)

Sakoparnig, Marlene; Boch, Ronny; Wang, Xianfeng; Lin, Ke; Spötl, Christoph; Leis, Albrecht; Gollowitsch, Anna; Dietzel, Martin

2016-04-01

Located near Graz at the SE-rim of the Alps Katerloch is well-known for its impressive dripstone decoration, e.g. several metres tall and relatively fast growing (0.2-0.7 mm/yr on average) candle-stick-type stalagmites. In the course of an ongoing multi-annual and partially high-resolution cave monitoring program we study modern (active) sites of carbonate deposition focusing on the site-specific growth dynamics and connection of modern regional and cave environmental conditions with petrographic, chemical and stable isotopic information captured in the speleothems. Fresh calcite precipitates on artificial (glass) substrates underneath active drip sites were collected continuously from 2006 to 2014 (eight years!). The samples (up to 7 mm thick) represent cave sections of different temperature and drip sites of partially different characteristics (e.g. drip rate). We also recovered short drill cores (up to 3 cm length, 1 cm diameter) from the top of active stalagmites probably representing the last decades to centuries of calcite crystallization. Moreover, an actively growing stalagmite (K10) comprising both modern and past calcite deposition was collected. 238U-234U-230Th dating using MC-ICP-MS of K10 (71 cm long) revealed several distinct growth intervals (separated by growth interruptions) starting at 129.1 ±1.2 kyr BP (Last Interglacial) up to now, mostly reflecting warm and humid climate intervals. High-resolution (100 μm) isotope profiles micromilled from the multi-annual modern calcite precipitates on artificial substrates revealed low δ13C values of -12.8 to -8.3 ‰ (VPDB) and relatively high δ18O of -6.9 to -4.9 ‰Ṫhe δ18O curves from all collection sites (different growth rate) record a pronounced decrease during their most recent growth period most likely corresponding to a significant decrease towards lower oxygen isotope values observed in drip waters collected in the year 2014 compared with samples from 2005 to 2007. Drip water δ2H /δ18O values plot between the Western Mediterranean Meteoric Water Line and Global MWL indicating a significant contribution of Mediterranean moisture to regional precipitation. The prominent shifts could also be explained by changes in seasonality of precipitation and water infiltration. Geochemical and petrographic results from the modern stalagmite calcite are therefore compared to new and published (Boch et al., 2011) hydrochemical and cave air data, as well as regional meteorological data. The modern datasets are further compared to data from Katerloch stalagmites of older time intervals. BOCH, R., SPÖTL, C., FRISIA, S. (2011): Sedimentology, 58, 508-531

Radiocarbon dates for lava flows and pyroclastic deposits on Sao Miguel, Azores

USGS Publications Warehouse

Moore, R.B.; Rubin, M.

1991-01-01

We report 63 new radiocarbon analyses of samples from Sao Miguel, the largest island in the Azores archipelago. The samples are mainly carbonized tree roots and other plant material collected from beneath 20 mafic lava flows and spatter deposits and from within and beneath 42 trachytic pyroclastic flow, pyroclastic surge, mudflow, pumice-fall and lacustrine deposits and lava flows. One calcite date is reported. These dates establish ages for 48 previously undated lava flows and pyroclastic deposits, and revise three ages previously reported. These data are critical to deciphering the Holocene and late Pleistocene eruptive history of Sao Miguel and evaluating its potential volcanic hazards. Average dormant intervals during the past 3000 years are about 400 years for Sete Cidades volcano, 145 years for volcanic Zone 2, 1150 years for Agua de Pau volcano and 320 years for Furnas volcano. No known eruptions have occurred in volcanic Zone 4 during the past 3000 years. -from Authors

Geology, S-Pb isotopes, and 40Ar/39Ar geochronology of the Zhaxikang Sb-Pb-Zn-Ag deposit in Southern Tibet: implications for multiple mineralization events at Zhaxikang

NASA Astrophysics Data System (ADS)

Sun, Xiang; Zheng, Youye; Pirajno, Franco; McCuaig, T. Campbell; Yu, Miao; Xia, Shenlan; Song, Qingjie; Chang, Huifang

2018-03-01

Several Au, Sb, Sb-Au, Pb-Zn, and Sb-Pb-Zn-Ag deposits are present throughout the North Himalaya in southern Tibet, China. The largest Sb-Pb-Zn-Ag deposit is Zhaxikang (18 Mt at 0.6 wt% Sb, 2.0 wt% Pb, 3.5 wt% Zn, and 78 g/t Ag). Zhaxikang veins are hosted within N-S trending faults, which crosscut the Early-Middle Jurassic Ridang Formation consisting of shale interbedded with sandstone and limestone deposited on a passive continental margin. Ore paragenesis indicates that Zhaxikang mineralization occurred in two main phases composed of six total stages. The initial phase was characterized by assemblages of fine-grained Mn-Fe carbonate + arsenopyrite + pyrite + sphalerite (stage 1), followed by relatively coarse-grained Mn-Fe carbonate + Fe-rich sphalerite + galena + pyrite (stage 2). The second phase was marked by assemblages of quartz + pyrite + Fe-poor sphalerite and Ag-rich galena + tetrahedrite + sericite (stage 3), quartz + Sb-Pb sulfosalt minerals mainly composed of boulangerite and jamesonite (stage 4), quartz + stibnite ± cinnabar (stage 5), and quartz ± calcite (stage 6). Sulfides of stage 2 have δ34SV-CDT of 8.4-12.0‰, 206Pb/204Pb ratios of 19.648 to 19.659, 207Pb/204Pb ratios of 15.788 to 15.812, and 208Pb/204Pb ratios of 40.035 to 40.153. Sulfides of stage 3 have similar δ34SV-CDT of 6.1-11.2‰ and relatively more radiogenic lead isotopes (206Pb/204Pb = 19.683-19.792). Stage 4 Sb-Pb sulfosalt minerals have δ34SV-CDT of 5.0-7.2‰ and even more radiogenic lead (206Pb/204Pb = 19.811-19.981). By contrast, stibnite of stage 5 has δ34SV-CDT of 4.5-7.8‰ and less radiogenic lead (206Pb/204Pb = 18.880-18.974). Taken together with the geological observations that the Pb-Zn-bearing Mn-Fe carbonate veins were crosscut by various types of quartz veins, sphalerite and galena of stage 2 underwent dissolution and remobilization, and that Sb-Pb(-Fe) sulfosalts formed at the expense of Pb from stage 2 galena and of Fe from stage 2 sphalerite, we argue that the early Pb-Zn veins were overprinted by later Sb-rich fluids. Stage 2 fluids were likely acidic and oxidized and leached lead from high-grade metamorphic rocks of the Greater Himalayan crystalline complex (GHC) and sulfur from reduced rocks, such as slate of the Ridang Formation, along N-S trending faults, leading to precipitation of Pb-Zn sulfides and Mn-Fe carbonate and formation of solution collapse breccias. Later Sb-rich fluids leached Pb from the GHC and the pre-existing sulfides and deposited Fe-poor sphalerite, Ag-rich galena, tetrahedrite, Sb-Pb sulfosalts, and stibnite in quartz veins that cut pre-existing Pb-Zn-bearing Mn-Fe carbonate veins. The Sb-rich fluids also likely leached Pb from Early Cretaceous gabbro and formed stibnite at shallow levels where early Pb-Zn-bearing Mn-Fe carbonate veins are absent. A sericite 40Ar-39Ar plateau age of 17.9 ± 0.5 Ma from stage 3 veins represents the timing of the onset of stage 3 mineralization.

The effect of sulfated polysaccharides on the crystallization of calcite superstructures

NASA Astrophysics Data System (ADS)

Fried, Ruth; Mastai, Yitzhak

2012-01-01

Calcite with unique morphology and uniform size has been successfully synthesized in the presence of classes of polysaccharides based on carrageenans. In the crystallization of calcite, the choice of different carrageenans, (iota, lambda and kappa), as additives concedes systematic study of the influence of different chemical structures and particularly molecular charge on the formation of CaCO 3 crystals. The uniform calcite superstructures are formed by assemblies and aggregation of calcite crystals. The mechanism for the formation of calcite superstructures was studied by a variety of techniques, SEM, TEM, XRD, time-resolved conductivity and light scattering measurements, focusing on the early stages of crystals' nucleation and aggregation.

Effect of acidified water glass on the flotation separation of scheelite from calcite using mixed cationic/anionic collectors

NASA Astrophysics Data System (ADS)

Dong, Liuyang; Jiao, Fen; Qin, Wenqing; Zhu, Hailing; Jia, Wenhao

2018-06-01

In this paper, the effect of acidified water glass (AWG) on the flotation separation of scheelite from calcite using mixed collector of dodecylamine (DDA) and sodium oleate (NaOL) was investigated. The flotation results show that AWG could selectively depress the flotation of calcite at pH 7. A series of mechanism experiments confirm that the chemisorption of AWG on calcite surface is more intense than scheelite. Although the chemisorption of NaOL on calcite surface is almost unaffected by the presence of AWG, the chemisorption of AWG hinders the adsorption of DDA on calcite surface.

Dissolution of coccolithophorid calcite by microzooplankton and copepod grazing

NASA Astrophysics Data System (ADS)

Antia, A. N.; Suffrian, K.; Holste, L.; Müller, M. N.; Nejstgaard, J. C.; Simonelli, P.; Carotenuto, Y.; Putzeys, S.

2008-01-01

Independent of the ongoing acidification of surface seawater, the majority of the calcium carbonate produced in the pelagial is dissolved by natural processes above the lysocline. We investigate to what extent grazing and passage of coccolithophorids through the guts of copepods and the food vacuoles of microzooplankton contribute to calcite dissolution. In laboratory experiments where the coccolithophorid Emiliania huxleyi was fed to the rotifer Brachionus plicatilis, the heterotrophic flagellate Oxyrrhis marina and the copepod Acartia tonsa, calcite dissolution rates of 45-55%, 37-53% and 5-22% of ingested calcite were found. We ascribe higher loss rates in microzooplankton food vacuoles as compared to copepod guts to the strongly acidic digestion and the individual packaging of algal cells. In further experiments, specific rates of calcification and calcite dissolution were also measured in natural populations during the PeECE III mesocosm study under differing ambient pCO2 concentrations. Microzooplankton grazing accounted for between 27 and 70% of the dynamic calcite stock being lost per day, with no measurable effect of CO2 treatment. These measured calcite dissolution rates indicate that dissolution of calcite in the guts of microzooplankton and copepods can account for the calcite losses calculated for the global ocean using budget and model estimates.

Biotic Control of Skeletal Growth by Scleractinian Corals in Aragonite–Calcite Seas

PubMed Central

Higuchi, Tomihiko; Fujimura, Hiroyuki; Yuyama, Ikuko; Harii, Saki; Agostini, Sylvain; Oomori, Tamotsu

2014-01-01

Modern scleractinian coral skeletons are commonly composed of aragonite, the orthorhombic form of CaCO3. Under certain conditions, modern corals produce calcite as a secondary precipitate to fill pore space. However, coral construction of primary skeletons from calcite has yet to be demonstrated. We report a calcitic primary skeleton produced by the modern scleractinian coral Acropora tenuis. When uncalcified juveniles were incubated from the larval stage in seawater with low mMg/Ca levels, the juveniles constructed calcitic crystals in parts of the primary skeleton such as the septa; the deposits were observable under Raman microscopy. Using scanning electron microscopy, we observed different crystal morphologies of aragonite and calcite in a single juvenile skeleton. Quantitative analysis using X-ray diffraction showed that the majority of the skeleton was composed of aragonite even though we had exposed the juveniles to manipulated seawater before their initial crystal nucleation and growth processes. Our results indicate that the modern scleractinian coral Acropora mainly produces aragonite skeletons in both aragonite and calcite seas, but also has the ability to use calcite for part of its skeletal growth when incubated in calcite seas. PMID:24609012

Infrared spectroscopy and density functional theory investigation of calcite, chalk, and coccoliths--do we observe the mineral surface?

PubMed

Andersson, M P; Hem, C P; Schultz, L N; Nielsen, J W; Pedersen, C S; Sand, K K; Okhrimenko, D V; Johnsson, A; Stipp, S L S

2014-11-13

We have measured infrared spectra from several types of calcite: chalk, freshly cultured coccoliths produced by three species of algae, natural calcite (Iceland Spar), and two types of synthetic calcite. The most intense infrared band, the asymmetric carbonate stretch vibration, is clearly asymmetric for the coccoliths and the synthetic calcite prepared using the carbonation method. It can be very well fitted by two peaks: a narrow Lorenzian at lower frequency and a broader Gaussian at higher frequency. These two samples both have a high specific surface area. Density functional theory for bulk calcite and several calcite surface systems allows for assignment of the infrared bands. The two peaks that make up the asymmetric carbonate stretch band come from the bulk (narrow Lorenzian) and from a combination of two effects (broad Gaussian): the surface or near surface of calcite and line broadening from macroscopic dielectric effects. We detect water adsorbed on the high surface area synthetic calcite, which permits observation of the chemistry of thin liquid films on calcite using transmission infrared spectroscopy. The combination of infrared spectroscopy and density functional theory also allowed us to quantify the amount of polysaccharides associated with the coccoliths. The amount of polysaccharides left in chalk, demonstrated to be present in other work, is below the IR detection limit, which is 0.5% by mass.

Replacement of Calcite (CaCO 3) by Cerussite (PbCO 3)

DOE PAGES

Yuan, Ke; Lee, Sang Soo; De Andrade, Vincent; ...

2016-10-21

The mobility of toxic elements, such as lead (Pb) can be attenuated by adsorption, incorporation, and precipitation on carbonate minerals in subsurface environments. Here in this paper, we report a study of the bulk transformation of single-crystal calcite (CaCO 3) into polycrystalline cerussite (PbCO 3) through reaction with acidic Pb-bearing solutions. This reaction began with the growth of a cerussite shell on top of calcite surfaces followed by the replacement of the remaining calcite core. The external shape of the original calcite was preserved by a balance between calcite dissolution and cerussite growth controlled by adjusting the Pb 2+ concentration and pH. The relation between the rounded calcite core and the surrounding lath-shaped cerussite aggregates was imaged by transmission X-ray microscopy, which revealed preferentially elongated cerussite crystals parallel to the surface and edge directions of calcite. The replacement reaction involved concurrent development ~100 nm wide pores parallel to calcite c-glide or (1more » $$\\overline{20}$$) planes, which may have provided permeability for chemical exchange during the reaction. X-ray reflectivity measurements showed no clear epitaxial relation of cerussite to the calcite (104) surface. These results demonstrate Pb sequestration through mineral replacement reactions and the critical role of nanoporosity (3% by volume) on the solid phase transformation through a dissolution-recrystallization mechanism.« less

Dolomitization and over-dolomitization in the Vajont limestone (Dolomiti Bellunesi, Italy) controlled by Mesozoic normal faults: a microstructural and diagenesis study

NASA Astrophysics Data System (ADS)

Cortinovis, Silvia; Swennen, Rudy; Bistacchi, Andrea

2015-04-01

The Vajont Gorge (Dolomiti Bellunesi, Italy) provides spectacular outcrops of Jurassic limestones (Vajont Limestone Formation) in which Mesozoic faults and fracture corridors are continuously exposed. Some of these faults acted as conduits for Mg-enriched hydrothermal fluids resulting in structurally-controlled dolomitization of the limestone. The dolomitization resulted in several dolomite bodies (100-200 m thick and several hundreds of meters along fault strike) that are particularly interesting as reservoir analogues for hydrocarbon, CO2, or water-bearing systems. The dolomitization process occurred after deposition and compaction of the oolitic limestone (dolomitization post-dates a dissolution event that affected the internal parts of the oolites), but before the Alpine contractional deformation. In fact, the meso-structural data collected in the Vajont Gorge allowed the reconstruction of a 3D model showing that the circulation of the dolomitizing fluids into the limestone host rock, but also the late stage of porosity reduction (strong pore filling due to over-dolomitization) were controlled by normal faults and fracture corridors interpreted as Pre-Alpine (Jurassic or Cretaceous). Later on, the influence of Alpine (Tertiary) deformation have been very limited in the studied volume. For instance dolomite veins are sometimes overprinted by bed-inclined stylolites consistent with Alpine shortening axes, but no large Alpine fault is present in the studied outcrops. Cathodoluminescence microscopy allowed recognizing different growth stages saddle dolomite crystals, which point to varying precipitation conditions during three main stages of dolomitization. Dolomite and calcite crystal twinning suggests deformation under increasing temperature conditions, consistent with intracrystalline plasticity deformation mechanisms. The presence of cataclasites composed of hydrothermal dolostone clasts, in turn cemented by dolomite, or of dolomite veins and compaction/deformation bands in high porosity dolomite bodies, is an additional argument pointing to the close interaction between tectonic deformation and fluid circulation. Particularly, it shows how tectonics controlled fluid circulation both in the first stages of dolomitization, when porosity was created, and in later stages, when porosity was strongly reduced due to over-dolomitization. The microstructure of fault breccia suggests a high-pressure of injected fluids and is useful to reconstruct the chronology of events involved in the formation and evolution of dolostone bodies. A study of quasi-steady-state (e.g. crack and seal) vs. episodic/seismic (mass precipitation, cavitation) deformation processes is under way to investigate the possible correlation between fluid injection events and the progressive slip on faults.

Microbially Induced Calcite Precipitation Employing Environmental Isolates

PubMed Central

Kim, Gunjo; Youn, Heejung

2016-01-01

In this study, five microbes were employed to precipitate calcite in cohesionless soils. Four microbes were selected from calcite-precipitating microbes isolated from calcareous sand and limestone cave soils, with Sporosarcina pasteurii ATCC 11859 (standard strain) used as a control. Urease activities of the four microbes were higher than that of S. pasteurii. The microbes and urea–CaCl2 medium were injected at least four times into cohesionless soils of two different relative densities (60% and 80%), and the amount of calcite precipitation was measured. It was found that the relative density of cohesionless soils significantly affects the amount of calcite precipitation and that there is a weak correlation between urease activity and calcite precipitation. PMID:28773600

Microbially Induced Calcite Precipitation Employing Environmental Isolates.

PubMed

Kim, Gunjo; Youn, Heejung

2016-06-15

In this study, five microbes were employed to precipitate calcite in cohesionless soils. Four microbes were selected from calcite-precipitating microbes isolated from calcareous sand and limestone cave soils, with Sporosarcina pasteurii ATCC 11859 (standard strain) used as a control. Urease activities of the four microbes were higher than that of S. pasteurii . The microbes and urea-CaCl₂ medium were injected at least four times into cohesionless soils of two different relative densities (60% and 80%), and the amount of calcite precipitation was measured. It was found that the relative density of cohesionless soils significantly affects the amount of calcite precipitation and that there is a weak correlation between urease activity and calcite precipitation.

Repulsive hydration forces between calcite surfaces and their effect on the brittle strength of calcite-bearing rocks

NASA Astrophysics Data System (ADS)

Røyne, Anja; Dalby, Kim N.; Hassenkam, Tue

2015-06-01

The long-term mechanical strength of calcite-bearing rocks is highly dependent on the presence and nature of pore fluids, and it has been suggested that the observed effects are due to changes in nanometer-scale surface forces near fracture tips and grain contacts. In this letter, we present measurements of forces between two calcite surfaces in air and water-glycol mixtures using the atomic force microscope. We show a time- and load-dependent adhesion at low water concentrations and a strong repulsion in the presence of water, which is most likely due to hydration of the strongly hydrophilic calcite surfaces. We argue that this hydration repulsion can explain the commonly observed water-induced decrease in strength in calcitic rocks and single calcite crystals. Furthermore, this relatively simple experimental setup may serve as a useful tool for analyzing surface forces in other mineral-fluid combinations.

Nickel adsorption on chalk and calcite

NASA Astrophysics Data System (ADS)

Belova, D. A.; Lakshtanov, L. Z.; Carneiro, J. F.; Stipp, S. L. S.

2014-12-01

Nickel uptake from solution by two types of chalk and calcite was investigated in batch sorption studies. The goal was to understand the difference in sorption behavior between synthetic and biogenic calcite. Experiments at atmospheric partial pressure of CO2, in solutions equilibrated with calcite and chalk and pH ranging from 7.7 to 8.8, explored the influence of initial concentration and the amount and type of sorbent on Ni uptake. Adsorption increases with increased surface area and pH. A surface complexation model describes the data well. Stability constants for the Ni surface complex are log KNi = - 1.12 on calcite and log KNi = - 0.43 and - 0.50 on the two chalk samples. The study confirms that synthetic calcite and chalk both take up nickel, but Ni binds more strongly on the biogenic calcite than on inorganically precipitated, synthetic powder, because of the presence of trace amounts of polysaccharides and clay nanoparticles on the chalk surface.

Ocean chemistry controls trends in foraminiferal mineralogy

NASA Astrophysics Data System (ADS)

de Nooijer, Lennart; van Dijk, Inge; Reichart, Gert-Jan

2014-05-01

Foraminifera are unicellular marine protists of which many produce a calcium carbonate shell of either aragonite or calcite. Since they are responsible for a large part of open ocean calcium carbonate precipitation, it is necessary to understand their response to changes in ocean chemistry. On geological time scales, the ratio of Mg over Ca in seawater played an important role in controlling marine aragonite versus calcite mineralogy. Here we reconstructed occurrences of aragonite and low- and high-Mg calcite producing foraminifera through the Phanerozoic. We discovered a two-step impact of seawater chemistry and mass extinction events on the evolution of foraminifera. Seawater Mg to Ca ratios favor production of either calcite, or of high magnesium carbonate and aragonite shells. However, mass extinction events controlled the timing of shifts in dominance from one mineralogy to the other. This observation suggests that ongoing ocean acidification may have important consequences for foraminiferal calcification. Although reduced carbonate saturation state increases dissolution rates of high-Mg calcite and aragonite compared to low-Mg calcite, the current high Mg/Ca of the ocean kinetically favors precipitation of high-Mg calcite and aragonite. Contrary to the differential effects of dissolution, we argue that ongoing ocean acidification is likely to particularly impact calcite producers (e.g. planktonic foraminifera, coccolithophores) compared to those precipitating high-Mg calcite and aragonite (e.g. corals).

Morphology Controls on Calcite Recrystallization.

PubMed

Heberling, Frank; Paulig, Leonie; Nie, Zhe; Schild, Dieter; Finck, Nicolas

2016-11-01

Environmental scientists and geoscientists working in different fields regard the reactivity of calcite and corresponding changes in its trace elemental- or isotopic composition from diametrically opposed points of view. As one extreme, calcite based environmental remediation strategies rely on the fast recrystallization of calcite and the concurrent uptake and immobilization of pollutants. Paleo-ecological investigations denote the other extreme, and rely on the invariability of calcite composition over geological periods of time. We use long-term radiotracer experiments to quantify recrystallization rates of seven types of calcite powder with diverse morphology and particle size distribution. On the one hand our results demonstrate the long-term metastability of calcite with equilibrated crystal surfaces even at isotopic dis-equilibrium. On the other hand, we document the extremely high reactivity and interfacial free energy of freshly ground, rough calcite. Our results indicate that bulk calcite recrystallization is an interfacial free energy driven Ostwald-ripening process, in which particle roughness effects dominate over the effect of crystal habitus and particle size. We confirm that the dynamic equilibrium exchange of crystal constituents between kink sites involves an activation barrier of about 25 kJ/mol. At room temperature the equilibrium exchange is limited to a near surface region and proceeds at a rate of (3.6 ± 1.4)·10 -13 mol/(m 2 ·s).

High surface area calcite

NASA Astrophysics Data System (ADS)

Schultz, L. N.; Andersson, M. P.; Dalby, K. N.; Müter, D.; Okhrimenko, D. V.; Fordsmand, H.; Stipp, S. L. S.

2013-05-01

Calcite (CaCO3) is important in many fields—in nature, because it is a component of aquifers, oil reservoirs and prospective CO2 storage sites, and in industry, where it is used in products as diverse as paper, toothpaste, paint, plastic and aspirin. It is difficult to obtain high purity calcite with a high surface area but such material is necessary for industrial applications and for fundamental calcite research. Commercial powder is nearly always contaminated with growth inhibitors such as sugars, citrate or pectin and most laboratory synthesis methods deliver large precipitates, often containing vaterite or aragonite. To address this problem, we (i) adapted the method of carbonating a Ca(OH)2 slurry with CO2 gas to develop the first simple, cheap, safe and reproducible procedure using common laboratory equipment, to obtain calcite that reproducibly had a surface area of 14-17 m2/g and (ii) conducted a thorough characterization of the product. Scanning electron microscopy (SEM) revealed nanometer scale, rhombohedral crystals. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (IR) confirmed highly crystalline, pure calcite that more closely resembles the dimensions of the biogenic calcite produced by algae in coccoliths than other methods for synthesizing calcite. We suggest that this calcite is useful when purity and high surface area are important.

Fluid circulations in response to mantle exhumation at the passive margin setting in the north Pyrenean zone, France

NASA Astrophysics Data System (ADS)

Corre, B.; Boulvais, P.; Boiron, M. C.; Lagabrielle, Y.; Marasi, L.; Clerc, C.

2018-02-01

Sub-continental lithospheric mantle rocks are exhumed in the distal part of magma-poor passive margins. Remnants of the North Iberian paleo-passive margin are now exposed in the North-Pyrenean Zone (NPZ) and offers a field analogue to study the processes of continental crust thinning, subcontinental mantle exhumation and associated fluid circulations. The Saraillé Massif which belongs to the `Chaînons Béarnais' range (Western Pyrenees), displays field, petrographic and stable isotopic evidence of syn-kinematic fluid circulations. Using electron probe micro-analyses on minerals, O, C, Sr isotopes compositions and micro thermometry/Raman spectrometry of fluid inclusions, we investigate the history of fluid circulations along and in the surroundings of the Saraillé detachment fault. The tectonic interface between the pre-rift Mesozoic sedimentary cover and the mantle rocks is marked by a metasomatic talc-chlorite layer. This layer formed through the infiltration of a fluid enriched in chemical elements like Cr leached from the exhuming serpentinized mantle rocks. In the overlying sediments (dolomitic and calcitic marbles of Jurassic to Aptian age), a network of calcitic veins, locally with quartz, formed as a consequence of the infiltration of aqueous saline fluids (salinities up to 34 wt% NaCl are recorded in quartz-hosted fluid inclusions) at moderate temperatures ( 220 °C). These brines likely derived from the dissolution of the local Triassic evaporites. In the upper part of the metasomatic system, upward movement of fluids is limited by the Albian metasediments, which likely acted as an impermeable layer. The model of fluid circulation in the Saraillé Massif sheds light onto other synchronous metasomatic systems in the Pyrenean realm.

Fluid mixing and the deep biosphere of a fossil Lost City-type hydrothermal system at the Iberia Margin.

PubMed

Klein, Frieder; Humphris, Susan E; Guo, Weifu; Schubotz, Florence; Schwarzenbach, Esther M; Orsi, William D

2015-09-29

Subseafloor mixing of reduced hydrothermal fluids with seawater is believed to provide the energy and substrates needed to support deep chemolithoautotrophic life in the hydrated oceanic mantle (i.e., serpentinite). However, geosphere-biosphere interactions in serpentinite-hosted subseafloor mixing zones remain poorly constrained. Here we examine fossil microbial communities and fluid mixing processes in the subseafloor of a Cretaceous Lost City-type hydrothermal system at the magma-poor passive Iberia Margin (Ocean Drilling Program Leg 149, Hole 897D). Brucite-calcite mineral assemblages precipitated from mixed fluids ca. 65 m below the Cretaceous paleo-seafloor at temperatures of 31.7 ± 4.3 °C within steep chemical gradients between weathered, carbonate-rich serpentinite breccia and serpentinite. Mixing of oxidized seawater and strongly reducing hydrothermal fluid at moderate temperatures created conditions capable of supporting microbial activity. Dense microbial colonies are fossilized in brucite-calcite veins that are strongly enriched in organic carbon (up to 0.5 wt.% of the total carbon) but depleted in (13)C (δ(13)C(TOC) = -19.4‰). We detected a combination of bacterial diether lipid biomarkers, archaeol, and archaeal tetraethers analogous to those found in carbonate chimneys at the active Lost City hydrothermal field. The exposure of mantle rocks to seawater during the breakup of Pangaea fueled chemolithoautotrophic microbial communities at the Iberia Margin, possibly before the onset of seafloor spreading. Lost City-type serpentinization systems have been discovered at midocean ridges, in forearc settings of subduction zones, and at continental margins. It appears that, wherever they occur, they can support microbial life, even in deep subseafloor environments.

Fluid mixing and the deep biosphere of a fossil Lost City-type hydrothermal system at the Iberia Margin

PubMed Central

Klein, Frieder; Humphris, Susan E.; Guo, Weifu; Schubotz, Florence; Schwarzenbach, Esther M.; Orsi, William D.

2015-01-01

Subseafloor mixing of reduced hydrothermal fluids with seawater is believed to provide the energy and substrates needed to support deep chemolithoautotrophic life in the hydrated oceanic mantle (i.e., serpentinite). However, geosphere-biosphere interactions in serpentinite-hosted subseafloor mixing zones remain poorly constrained. Here we examine fossil microbial communities and fluid mixing processes in the subseafloor of a Cretaceous Lost City-type hydrothermal system at the magma-poor passive Iberia Margin (Ocean Drilling Program Leg 149, Hole 897D). Brucite−calcite mineral assemblages precipitated from mixed fluids ca. 65 m below the Cretaceous paleo-seafloor at temperatures of 31.7 ± 4.3 °C within steep chemical gradients between weathered, carbonate-rich serpentinite breccia and serpentinite. Mixing of oxidized seawater and strongly reducing hydrothermal fluid at moderate temperatures created conditions capable of supporting microbial activity. Dense microbial colonies are fossilized in brucite−calcite veins that are strongly enriched in organic carbon (up to 0.5 wt.% of the total carbon) but depleted in 13C (δ13CTOC = −19.4‰). We detected a combination of bacterial diether lipid biomarkers, archaeol, and archaeal tetraethers analogous to those found in carbonate chimneys at the active Lost City hydrothermal field. The exposure of mantle rocks to seawater during the breakup of Pangaea fueled chemolithoautotrophic microbial communities at the Iberia Margin, possibly before the onset of seafloor spreading. Lost City-type serpentinization systems have been discovered at midocean ridges, in forearc settings of subduction zones, and at continental margins. It appears that, wherever they occur, they can support microbial life, even in deep subseafloor environments. PMID:26324888

Alteration mineralogy, mineral chemistry and stable isotope geochemistry of the Eocene pillow lavas from the Trabzon area, NE Turkey

NASA Astrophysics Data System (ADS)

Abdioğlu Yazar, Emel

2018-02-01

The Eocene subaqueous volcanic units in NE Turkey developed as pillow, closely packed pillow, isolated pillow, pillow breccia, hyaloclastite breccia and rare peperitic facies with red micritic limestones. They are locally set on volcaniclastic sandstone and claystone alternations and gradually pass to tuffs and volcanic breccias. The pillow lava samples generally exhibit intersertal, intergranular, microlitic porphyritic, variolitic, vesicular and glomeroporphyritic and glassy textures with clinopyroxene (Wo47-52En40-45Fs6-8), plagioclase (An10 to An96), olivine (Fo79-87) and Fe-Ti oxides (Usp0-0.27). Saponite, interlayered chlorite/saponite, rare beidellite and calcite were determined after olivine, rarely after plagioclase as well as in the glassy groundmass. Illite was restricted to plagioclase and the glassy groundmass. Na-Ca zeolites, chlorites/saponites, beidellite, dolomite and calcite occur as void infillings and in the glassy groundmass. Mineralogical, lithochemical and isotopic interpretations as well as thermometric calculations reveal a low-temperature seawater alteration in a semi-closed environment for the alteration of primary minerals and volcanic glass in addition to sealed vesicles and open systems for crosscutting veins. Due to the short exposure time intervals of seawater to rocks, the total chemistry of the rocks is not fully changed and most of the elements seem to be immobile, remaining in the system as a result of precipitation in voids and cracks. Thermometric estimations indicate that, the temperature of heated seawater is approximately 160 °C at the highest point especially in the vesicles, and decreases to approximately 85 °C due to circulation, resulting in alterations of the primary phases and volcanic glass.

Fault zone architecture of a major oblique-slip fault in the Rawil depression, Western Helvetic nappes, Switzerland

NASA Astrophysics Data System (ADS)

Gasser, D.; Mancktelow, N. S.

2009-04-01

The Helvetic nappes in the Swiss Alps form a classic fold-and-thrust belt related to overall NNW-directed transport. In western Switzerland, the plunge of nappe fold axes and the regional distribution of units define a broad depression, the Rawil depression, between the culminations of Aiguilles Rouge massif to the SW and Aar massif to the NE. A compilation of data from the literature establishes that, in addition to thrusts related to nappe stacking, the Rawil depression is cross-cut by four sets of brittle faults: (1) SW-NE striking normal faults that strike parallel to the regional fold axis trend, (2) NW-SE striking normal faults and joints that strike perpendicular to the regional fold axis trend, and (3) WNW-ESE striking normal plus dextral oblique-slip faults as well as (4) WSW-ENE striking normal plus dextral oblique-slip faults that both strike oblique to the regional fold axis trend. We studied in detail a beautifully exposed fault from set 3, the Rezli fault zone (RFZ) in the central Wildhorn nappe. The RFZ is a shallow to moderately-dipping (ca. 30-60˚) fault zone with an oblique-slip displacement vector, combining both dextral and normal components. It must have formed in approximately this orientation, because the local orientation of fold axes corresponds to the regional one, as does the generally vertical orientation of extensional joints and veins associated with the regional fault set 2. The fault zone crosscuts four different lithologies: limestone, intercalated marl and limestone, marl and sandstone, and it has a maximum horizontal dextral offset component of ~300 m and a maximum vertical normal offset component of ~200 m. Its internal architecture strongly depends on the lithology in which it developed. In the limestone, it consists of veins, stylolites, cataclasites and cemented gouge, in the intercalated marls and limestones of anastomosing shear zones, brittle fractures, veins and folds, in the marls of anastomosing shear zones, pressure solution seams and veins and in the sandstones of coarse breccia and veins. Later, straight, sharp fault planes cross-cut all these features. In all lithologies, common veins and calcite-cemented fault rocks indicate the strong involvement of fluids during faulting. Today, the southern Rawil depression and the Rhone Valley belong to one of the seismically most active regions in Switzerland. Seismogenic faults interpreted from earthquake focal mechanisms strike ENE-WSW to WNW-ESE, with dominant dextral strike-slip and minor normal components and epicentres at depths of < 15 km. All three Neogene fault sets (2-4) could have been active under the current stress field inferred from the current seismicity. This implies that the same mechanisms that formed these fault zones in the past may still persist at depth. The Rezli fault zone allows the detailed study of a fossil fault zone that can act as a model for processes still occurring at deeper levels in this seismically active region.

A model for microbially induced precipitation of vadose-zone calcites in fractures at LOS Alamos, New Mexico, USA

NASA Astrophysics Data System (ADS)

Newman, Brent D.; Campbell, Andrew R.; Norman, David I.; Ringelberg, David B.

1997-05-01

Fractures are unique environments that can concentrate the flow of water, nutrients, and contaminants. As such, fractures play an important role in controlling the flux of various substances into and through the vadose zone. Calcite fracture fillings are present in the near surface in the Bandelier Tuff Formation at Los Alamos, New Mexico, and provide a record of the geochemical and hydrologic processes that have occurred in fractures. The objective of this study was to examine calcite fracture fills in order to improve understanding of processes within fractures, and in particular those that lead to precipitation of calcite. Samples of calcite fillings were collected from vertical and horizontal fractures exposed in a shallow waste-burial pit. Scanning electron microscopy show morphologies which suggest that plants, fungi, and bacteria were important in the precipitation process. Quadrupole mass spectrometric analyses of fluid inclusion gases show predominantly methane (17-99%) and little to no oxygen (0-8%), suggesting the development of anaerobic conditions in the fractures. Ester-linked phospholipid biomarkers are evidence for a diverse microbial community in the fractures, and the presence of di-ether lipids indicate that the methane was generated by anaerobic bacteria. The calcite fillings apparently resulted from multiple biological and chemical processes in which plant roots in the fractures were converted to calcite. Roots grew into the fractures, eventually died, and were decomposed by bacteria and fungi. Anaerobic gases were generated from encapsulated organic material within the calcite via microbial decomposition, or were generated by microbes simultaneously with calcite precipitation. It is likely that the biological controls on calcite formation that occurred in the Los Alamos fractures also occurs in soils, and may explain the occurrence of other types of pedogenic calcites.

Investigating calcite growth rates using a quartz crystal microbalance with dissipation (QCM-D)

NASA Astrophysics Data System (ADS)

Cao, Bo; Stack, Andrew G.; Steefel, Carl I.; DePaolo, Donald J.; Lammers, Laura N.; Hu, Yandi

2018-02-01

Calcite precipitation plays a significant role in processes such as geological carbon sequestration and toxic metal sequestration and, yet, the rates and mechanisms of calcite growth under close to equilibrium conditions are far from well understood. In this study, a quartz crystal microbalance with dissipation (QCM-D) was used for the first time to measure macroscopic calcite growth rates. Calcite seed crystals were first nucleated and grown on sensors, then growth rates of calcite seed crystals were measured in real-time under close to equilibrium conditions (saturation index, SI = log ({Ca2+}/{CO32-}/Ksp) = 0.01-0.7, where {i} represent ion activities and Ksp = 10-8.48 is the calcite thermodynamic solubility constant). At the end of the experiments, total masses of calcite crystals on sensors measured by QCM-D and inductively coupled plasma mass spectrometry (ICP-MS) were consistent, validating the QCM-D measurements. Calcite growth rates measured by QCM-D were compared with reported macroscopic growth rates measured with auto-titration, ICP-MS, and microbalance. Calcite growth rates measured by QCM-D were also compared with microscopic growth rates measured by atomic force microscopy (AFM) and with rates predicted by two process-based crystal growth models. The discrepancies in growth rates among AFM measurements and model predictions appear to mainly arise from differences in step densities, and the step velocities were consistent among the AFM measurements as well as with both model predictions. Using the predicted steady-state step velocity and the measured step densities, both models predict well the growth rates measured using QCM-D and AFM. This study provides valuable insights into the effects of reactive site densities on calcite growth rate, which may help design future growth models to predict transient-state step densities.

Post-deformational relocation of mica grains in calcite-dolomite marbles identified by cathodoluminescence microscopy

NASA Astrophysics Data System (ADS)

Kuehn, Rebecca; Duschl, Florian; Leiss, Bernd

2017-04-01

Hot-cathodoluminescence-microscopy (CL) reveals micas which are rotated or shifted within a calcite fabric from a foliation parallel to a random orientation. This feature has been recognized in calcite-dolomite marble samples from the locations Hammerunterwiesenthal, Erzgebirge, Germany and the Alpi Apuane, Italy. As obtained from petrographic thin section analysis, the micas either moved totally within a single calcite grain or from a grain boundary position, and then the calcite grain growth was dragged with the movement of the mica grain. In the moved-through grain, features like fluid-inclusions, twins or cleavage faces are erased and a new, clear calcite phase developed. This indicates dissolution-precipitation as process which led to the new calcite phase. As former deformation features are erased it can be assumed that the mica relocation is a fluid-driven, post-deformational equilibration process. In CL the new calcite mineral phase shows a zonation indicating a polycyclic process. Calcite CL gradually changes from a very dark purple, exactly as the surrounding grains, to a bright orange CL and supports the idea of fluid-induced deformation relocation. We suppose a specific lattice relationship between mica and calcite as initial driving factor for mica relocation. This recrystallization mechanism is probably supported by fluids - either from an external source or developed during retrograde metamorphosis fluid inclusion studies shall identify formation temperatures and origin of involved fluids and thereby clarify the timing of the post-deformational mica rotation. EBSD analysis of involved calcite and mica grains shall reveal a possible systematic relationship between the orientation of the hosting grains, the orientation of the mica and the final position of the mica. It will be interesting to learn in the future, if this kind of calcite-mica microstructure is a general phenomenon and how it can contribute to the understanding of fabric development.

Heterogeneous alternation of fractured rock driven by preferential carbonate dissolution

NASA Astrophysics Data System (ADS)

Wen, H.; Zhi, W.; Li, L.

2016-12-01

Understanding the alternation of fractured rock induced by geochemical reactions is critical for predicting the flow, solute transport and energy production in geosystems. Most existing studies on fracture alterations focus on rocks with single minerals where reactions occur at the fracture wall resulting in fracture aperture alteration while ignoring rock matrix properties (e.g. the formation and development of altered zones). In this work, we aimed to mechanistically understand the role of preferential calcite dissolution in the long-term evolution of fracture and rock matrix. We use direct simulation of physics-based reactive transport processes in an image of fractured rock at the resolution of tens of micrometers. Three numerical experiments were carried out with the same initial physical properties however different calcite content. Simulation results show that the formation and development of altered zones in the rock matrix is highly related to the abundance of fast-dissolving calcite. Abundant calcite (50% (v/v), calcite50) leads to a localized, thick zone of large porosity increase while low calcite content (10% (v/v), calcite10) creates an extended and narrow zone of small porosity increase resulting in surprisingly larger change in effective transport property. After 300 days of dissolution, although with relatively similar dissolved calcite mass and matrix porosity increase, effective matrix diffusion coefficients increase by 9.9 and 19.6 times in calcite50 and calcite10, respectively. In turn, calcite dissolution rates are directly limited by diffusive transport in the altered matrix and the shape of the altered zone. This work sheds light on the unique characteristics of reactive transport in fractured, mineralogically complex rocks that are different from those with single minerals (Wen et al., 2016). Reference: Wen, H., Li, L., Crandall, D. and Hakala, J.A. (2016) Where Lower Calcite Abundance Creates More Alteration: Enhanced Rock Matrix Diffusivity Induced by Preferential Carbonate Dissolution. Energy & Fuels.

Seawater Mg/Ca controls polymorph mineralogy of microbial CaCO3: a potential proxy for calcite-aragonite seas in Precambrian time.

PubMed

Ries, J B; Anderson, M A; Hill, R T

2008-03-01

A previously published hydrothermal brine-river water mixing model driven by ocean crust production suggests that the molar Mg/Ca ratio of seawater (mMg/Ca(sw)) has varied significantly (approximately 1.0-5.2) over Precambrian time, resulting in six intervals of aragonite-favouring seas (mMg/Ca(sw) > 2) and five intervals of calcite-favouring seas (mMg/Ca(sw) < 2) since the Late Archaean. To evaluate the viability of microbial carbonates as mineralogical proxy for Precambrian calcite-aragonite seas, calcifying microbial marine biofilms were cultured in experimental seawaters formulated over the range of Mg/Ca ratios believed to have characterized Precambrian seawater. Biofilms cultured in experimental aragonite seawater (mMg/Ca(sw) = 5.2) precipitated primarily aragonite with lesser amounts of high-Mg calcite (mMg/Ca(calcite) = 0.16), while biofilms cultured in experimental calcite seawater (mMg/Ca(sw) = 1.5) precipitated exclusively lower magnesian calcite (mMg/Ca(calcite) = 0.06). Furthermore, Mg/Ca(calcite )varied proportionally with Mg/Ca(sw). This nearly abiotic mineralogical response of the biofilm CaCO3 to altered Mg/Ca(sw) is consistent with the assertion that biofilm calcification proceeds more through the elevation of , via metabolic removal of CO2 and/or H+, than through the elevation of Ca2+, which would alter the Mg/Ca ratio of the biofilm's calcifying fluid causing its pattern of CaCO3 polymorph precipitation (aragonite vs. calcite; Mg-incorporation in calcite) to deviate from that of abiotic calcification. If previous assertions are correct that the physicochemical properties of Precambrian seawater were such that Mg/Ca(sw) was the primary variable influencing CaCO3 polymorph mineralogy, then the observed response of the biofilms' CaCO3 polymorph mineralogy to variations in Mg/Ca(sw), combined with the ubiquity of such microbial carbonates in Precambrian strata, suggests that the original polymorph mineralogy and Mg/Ca(calcite )of well-preserved microbial carbonates may be an archive of calcite-aragonite seas throughout Precambrian time. These results invite a systematic evaluation of microbial carbonate primary mineralogy to empirically constrain Precambrian seawater Mg/Ca.

Influence of lysozyme on the precipitation of calcium carbonate: a kinetic and morphologic study

NASA Astrophysics Data System (ADS)

Jimenez-Lopez, Concepcion; Rodriguez-Navarro, Alejandro; Dominguez-Vera, Jose M.; Garcia-Ruiz, Juan M.

2003-05-01

Several mechanisms have been proposed to explain the interactions between proteins and mineral surfaces, among them a combination of electrostatic, stereochemical interactions and molecular recognition between the protein and the crystal surface. To identify the mechanisms of interaction in the lysozyme-calcium carbonate model system, the effect of this protein on the precipitation kinetics and morphology of calcite crystals was examined. The solution chemistry and morphology of the solid were monitored over time in a set of time-series free-drift experiments in which CaCO 3 was precipitated from solution in a closed system at 25°C and 1 atm total pressure, in the presence and absence of lysozyme. The precipitation of calcite was preceded by the precipitation of a metastable phase that later dissolved and gave rise to calcite as the sole phase. With increasing lysozyme concentration, the nucleation of both the metastable phase and calcite occurred at lower Ω calcite, indicating that lysozyme favored the nucleation of both phases. Calcite growth rate was not affected by the presence of lysozyme, at least at protein concentrations ranging from 0 mg/mL to 10 mg/mL. Lysozyme modified the habit of calcite crystals. The degree of habit modification changed with protein concentration. At lower concentrations of lysozyme, the typical rhombohedral habit of calcite crystals was modified by the expression of {110} faces, which resulted from the preferential adsorption of protein on these faces. With increasing lysozyme concentration, the growth of {110}, {100}, and finally {001} faces was sequentially inhibited. This adsorption sequence may be explained by an electrostatic interaction between lysozyme and calcite, in which the inhibition of the growth of {110}, {100}, and {001} faces could be explained by a combined effect of the density of carbonate groups in the calcite face and the specific orientation (perpendicular) of these carbonate groups with respect to the calcite surface. Overgrowth of calcite in the presence of lysozyme demonstrated that the protein favored and controlled the nucleation on the calcite substrate. Overgrowth crystals nucleated epitaxially in lines which run diagonal to rhombohedral {104} faces.

The character and evolution of fault rocks from the Phase 3 SAFOD core and potential weakening mechanisms along the San Andreas Fault

NASA Astrophysics Data System (ADS)

Holdsworth, Robert; van Diggelen, E. W. E.; Spiers, C. J.; de Bresser, H.; Smith, S. A. F.; Bowen, L.

2010-05-01

In the region of the SAFOD borehole, the San Andreas Fault (SAF) separates two very different geological terranes referred to here as the Salinian and Great Valley blocks (SB, SVB). Whilst material was not collected from the SB-GVB terrane boundary, the cores preserve a diverse range of fault rocks. Not all of these necessarily formed at the same depth, although the amount of exhumation is likely fairly limited. The distribution of deformation is asymmetric, with a broad (200m wide) intensely deformed region developed in the GVB located NE of the terrane boundary; this includes two narrow zones of active creep that have deformed the borehole casing. Microstructurally, low strain domains (most of Core 1, significant parts of Core 3) preserve clear protolith structures, with highly localised evidence for classic upper crustal cataclastic brittle faulting processes and associated fluid flow. The GVB in particular shows clear geological evidence for both fluid pressure and differential stress cycling (variable modes of hydrofacture associated with faults) during seismicity. There is also evidence in all minor faults for the operation of solution-precipitation creep. High strain domains (much of Core 2, parts of Core 3) are characterised by the development of foliated cataclasites and gouge, with variable new growth of fine-grained, interconnected phyllosilicate networks (predominantly smectite-bearing mixed layer clays). Many of the gouges are characterised by the development of S-C fabrics and asymmetric folds. Reworking and reactivation is widespread manifested by: i) the preservation of one or more earlier generations of gouge preserved as clasts; and ii) by the development of later interconnected, polished and striated slip surfaces at low angles or sub-parallel to the foliation. These are coated with thin smectitic phyllosilicate films and are closely associated with the development of lozenge, arrow-head and triangular mineral veins (mostly calcite) precipitated in dilation sites during slip. Outwith of the actively creeping sections, mineral veins (mainly calcite, locally anhydrite) are widespread, with evidence for hydrofracturing events prior to, during and after local gouge-forming deformation episodes. Disseminated pyrite mineralisation is widespread and locally produces highly indurated sections of black, hard gouge. The gouges in the active creeping segments are different in three important respects: 1) mineral veins only occur as (or within) clasts; 2) pyrite mineralisation is limited; and 3) they carry numerous serpentinite clasts, some quite large (metre scale). The actively creeping gouges are also characterised by the most intense development of smectitic phyllosilicates. The SAFOD core fault rocks highlight the fundamental role played by fluid-rock interactions in upper crustal fault zones. There is clear evidence for the development of high pore fluid pressures (hydrofracture development), reaction weakening (phyllosilicate growth following cataclasis) and geometric weakening due to the development of weak interconnected layers (foliations, polished striated slip surfaces). There are also very significant similarities between the fault rocks seen here and those preserved along other deeply exhumed weak faults elsewhere in the world.

Microfractures in bed-parallel veins (beef) as predictors of vertical macrofractures in shale: Vaca Muerta Formation, Agrio Fold-and-Thrust Belt, Argentina

NASA Astrophysics Data System (ADS)

Ukar, Estibalitz; Lopez, Ramiro G.; Laubach, Stephen E.; Gale, Julia F. W.; Manceda, René; Marrett, Randall

2017-11-01

Shales of the Upper Jurassic-Lower Cretaceous Vaca Muerta Formation are the main source rock for petroleum in the Neuquén Basin, Argentina and an important unconventional exploration target. Folded Vaca Muerta Formation is well exposed in the Agrio Fold-and-Thrust belt where an arid climate and rapid erosion reveal relatively unweathered shale strata accessible along creek beds at Arroyo Mulichinco and in 10+ m-tall cliffs at Puesto. Widespread within these organic-rich shales are several cm-thick, prominent bed-parallel veins (BPVs) of fibrous calcite (beef) that are cut by multiple sets of vertical calcite lined or filled fractures having apertures unaffected by near-surface stress release. Similar, and probably contemporaneous fractures are present within horizons of interbedded dolomitic rock. Evidence that vertical fractures in BPVs and dolomitic horizons continue into shale beds suggests that in-depth analysis of vertical fractures within BPVs and dolomitic horizons allows fracture set and orientation identification and size population measurements-primarily aperture distributions-that circumvent some of the limitations of shale outcrops. At Arroyo Mulichinco, four main fracture sets are present separable by orientation and crosscutting relations. An E-W set is oldest, followed by successively younger NE-SW, NW-SE, and N-S sets. At Puesto, the E-W and N-S sets are the most prominent and show opposite cross-cutting relationships (E-W set is youngest) indicating a possible episode of younger E-W fractures. The E-W set shows the highest micro-and macrofracture intensity at both localities. The intensity of N-S micro- and macrofractures is similar at both outcrops away from faults, but macrofracture intensity increases closer to faults. While macrofracture abundance is similar in BPVs and in shale, microfractures having apertures smaller than ∼0.1 mm are mostly absent in shale and dolomitic layers but are abundant cutting BPVs. Thus, microfractures are BPV-bounded and only fractures wider than ∼0.05 mm are tall enough to cut into shale. Nevertheless, using size distributions of microfractures in BPVs that are absent in shale accurately predicts the abundance of macrofractures in nearby shale, either because microfractures in organic shale have annealed, or because of only small differences in fracture strain for fractures of different sizes across different rocks types. Microfractures in readily sampled BPVs may be a practical way to diagnose or predict attributes of macrofractures in adjacent shale.

Current achievements and challenges of a multiple dating approach (14C, 230Th/U and 36Cl) to infer tsunami transport age(s) of reef-top boulders on Bonaire (Leeward Antilles)

NASA Astrophysics Data System (ADS)

Rixhon, Gilles; May, Simon Matthias; Engel, Max; Mechernich, Silke; Schroeder-Ritzrau, Andrea; Frank, Norbert; Fohlmeister, Jens; Boulvain, Frédéric; Dunai, Tibor; Brückner, Helmut

2017-04-01

The deposition of supratidal coarse-clast deposits is difficult to date, limiting their value for inferring frequency-magnitude patterns of high-energy wave events. On Bonaire (Leeward Antilles, Caribbean), these deposits form prominent landforms, and transport by one or several Holocene tsunamis is assumed at least for the largest clasts. Although a large dataset of 14C and electron spin resonance (ESR) ages is available for major coral rubble ridges and ramparts, it is still debated whether these data reflect the timing of major events, and how these datasets are biased by the reworking of coral fragments. As an attempt to overcome the current challenges for dating the dislocation of singular boulders, three distinct dating methods are implemented and compared: (i) 14C dating of boring bivalves attached to the boulders; (ii) 230Th/U dating of post-depositional, secondary calcite flowstone and subaerial microbialites at the underside of the boulders; and (iii) surface exposure dating of overturned boulders via 36Cl concentration measurements in corals. Approaches (ii) and (iii) have never been applied to coastal boulder deposits so far. The three 14C age estimates are older than 37 ka, i.e. most probably beyond the applicability of the method, which is attributed to post-depositional diagenetic processes, shedding doubt on the usefulness of this method in the local context. The remarkably convergent 230Th/U ages, all pointing to the Late Holocene period (1.0-1.6 ka), are minimum ages for the transport event(s). The microbialite sample yields an age of 1.23±0.23 ka and both flowstone samples are in stratigraphic order: the older (onset of carbonate precipitation) and younger flowstone layers yield ages of 1.59±0.03 and 1.23±0.03 ka, respectively. Four coral samples collected from the topside of overturned boulders yielded similar 36Cl concentration measurements. However, the computed ages are affected by large uncertainties, mostly due to the high natural chlorine concentration resulting in low AMS ratios. After correction for the inherited component and chemical denudation since platform emergence (inducing additional uncertainty), the calculated 36Cl ages cluster between 2.5±1.3 and 3.0±1.3 ka for three of four boulders whilst the fourth one yields an age of 6.1±1.8 ka, probably related to a higher inheritance. These 230Th/U and 36Cl age estimates are coherent with a suggested tsunami age of <3.3 ka obtained from the investigation of allochthonous shell horizons in sediment cores of northwestern Bonaire. While 230Th/U dating of post-depositional calcite flowstone appears to be the most robust and/or accurate approach, these results illustrate the potential and current limitations of the applied methods for dating the dislocation of supralittoral boulders in carbonate-reef settings.

An XRPD and EPR spectroscopy study of microcrystalline calcite bioprecipitated by Bacillus subtilis

NASA Astrophysics Data System (ADS)

Perito, B.; Romanelli, M.; Buccianti, A.; Passaponti, M.; Montegrossi, G.; Di Benedetto, F.

2018-05-01

We report in this study the first XRPD and EPR spectroscopy characterisation of a biogenic calcite, obtained from the activity of the bacterium Bacillus subtilis. Microcrystalline calcite powders obtained from bacterial culture in a suitable precipitation liquid medium were analysed without further manipulation. Both techniques reveal unusual parameters, closely related to the biological source of the mineral, i.e., to the bioprecipitation process and in particular to the organic matrix observed inside calcite. In detail, XRPD analysis revealed that bacterial calcite has slightly higher c/a lattice parameters ratio than abiotic calcite. This correlation was already noticed in microcrystalline calcite samples grown by bio-mineralisation processes, but it had never been previously verified for bacterial biocalcites. EPR spectroscopy evidenced an anomalously large value of W 6, a parameter that can be linked to occupation by different chemical species in the next nearest neighbouring sites. This parameter allows to clearly distinguish bacterial and abiotic calcite. This latter achievement was obtained after having reduced the parameters space into an unbiased Euclidean one, through an isometric log-ratio transformation. We conclude that this approach enables the coupled use of XRPD and EPR for identifying the traces of bacterial activity in fossil carbonate deposits.

Dating native gold by noble gas analyses

NASA Technical Reports Server (NTRS)

Niedermann, S.; Eugster, O.; Hofmann, B.; Thalmann, CH.; Reimold, W. U.

1993-01-01

Our recent work on He, Ne, and Ar in Alpine gold samples has demonstrated that gold is extremely retentive for He and could thus, in principle, be used for U/Th-He-4 dating. For vein-type gold from Brusson, Northern Italy, we derived a U/Th-He-4 age of 36 Ma, in agreement with the K-Ar formation age of associated muscovites and biotites. However, in placer gold from the Napf area, Central Switzerland, we observed large excesses of both He-4 and radiogenic Ar-40 (Ar-40 sub rad, defined as Ar-40-295.5-Ar-.36). The gas release systematics indicate two distinct noble gas components, one of which is released below about 800 C and the other one at the melting point of gold (1064 C). We now present results of He and Xe measurements in a 1 g placer gold sample from the river Kruempelgraben, as well as He and Ar data for Brusson vein-type gold and for gold from the Lily Gold Mine, South Africa. We calculate reasonable U/Th-He-4 as well as U-Xe ages based on those gases which are released at approximately 800 C. Probably the low-temperature components represent in-situ-produced radiogenic He and fission Xe, whereas the gases evolving when gold melts have been trapped during gold formation. Therefore, only the low-temperature components are relevant for dating purposes.

Nickel adsorption on chalk and calcite.

PubMed

Belova, D A; Lakshtanov, L Z; Carneiro, J F; Stipp, S L S

2014-12-01

Nickel uptake from solution by two types of chalk and calcite was investigated in batch sorption studies. The goal was to understand the difference in sorption behavior between synthetic and biogenic calcite. Experiments at atmospheric partial pressure of CO2, in solutions equilibrated with calcite and chalk and pH ranging from 7.7 to 8.8, explored the influence of initial concentration and the amount and type of sorbent on Ni uptake. Adsorption increases with increased surface area and pH. A surface complexation model describes the data well. Stability constants for the Ni surface complex are log KNi=-1.12 on calcite and log KNi=-0.43 and -0.50 on the two chalk samples. The study confirms that synthetic calcite and chalk both take up nickel, but Ni binds more strongly on the biogenic calcite than on inorganically precipitated, synthetic powder, because of the presence of trace amounts of polysaccharides and clay nanoparticles on the chalk surface. Copyright © 2014 Elsevier B.V. All rights reserved.

An enigmatic source of hematitic carbonate beds containing vast amounts of iron oxidizers in a paleozoic metamorphic complex, South Hungary, Geresd-Hills, Ófalu.

NASA Astrophysics Data System (ADS)

Jáger, Viktor; Dabi, Gergely; Menyhárt, Adrienn

2013-04-01

Near the village of Ófalu, in the Geresd Hills, South Hungary, within the "Mecsekalja tectonic belt", low and intermediate grade paleozoic metamorphic complex (phyllite, gneiss) contains vein-like hematitic carbonate beds, up to 30 cm in thickness. The carbonate mineral is calcite. These hematitic carbonate beds cross-cut the foliation of the phyllite, and show no signs of any metamorphic alteration. In the studied section the red carbonate beds are associated with a vein system filled with multiple generations of vein carbonates(Dabi et al., 2011). The red carbonate beds contain a vaste number of twisted stalks of the iron oxidizing taxon of Gallionella. Rarely in some siliceous parts, Leptothrix-like microbial fossils can be found and these beds also contain numerous unidentifiable, hematitic foraminifers. According to ICP-AES measurements, the hematitic carbonate beds contains 8 % Fe, 0.86 % Mn and 0.12 % Ba. XRD and Raman measurements proved that the iron phase is hematite. The SEM observations revealed that the bacterial microfossils and foraminifers are built up of micron-submicron sized pseudohexagonal platy hematite. The bacterial microfossils of the Gallionella iron oxidizer are very well preserved and reaches about 80 µm length and about 2-3 µm width. The above observations raise the following issues: 1. how did these non metamorphic hematitic-carbonatic beds get inside into the metamorphic complex?, 2. what is the age of the formation of these beds?, and 3. what was the source of the iron? If we consider that the hematitic beds contain foraminifers and iron oxidizing bacteria, and no signs of metamorphic alteration nor foliations can be observed in these beds, the only answer for the first question is that the formations are fractures filled with lime-mud, i.e. neptunian dykes, which penetrated into the cracks of the phyllite. The presence of foraminifers and the geotectonic situation of the unit imply marine origin. Considering that these beds are neptunian dykes, their age must be younger than the paleozoic metamorphic event. They must be older than the Early Cretaceous dyke emplacement in the region, based on cross-cutting relation with limonite stained calcite veins, related to the volcanic activity (Dabi et al., 2011) In this region (Tisza-megaunit) continental rift-related alkali basaltic submarine volcanism was widespread during the Early Cretaceous epoch, when hypabyssal basaltic bodies (intrusive pillow basalts) intruded into unconsolidated sediments. Along these magmatic bodies low temperature hydrothermal circulation of seawater hydrolyzed basaltic glass and mafic minerals, and huge amount of Fe(II) was released and got into the lime mud that was saturated with anaerobic water, where iron oxidizing microorganisms thrived (Jáger et al., 2012).We propose a very similar paleoenvironmental model for Ófalu occurence, where low temperature, reductive iron-rich hydrothermal fluids penetrated soft sediments and contributed to the flourishing of iron-oxidizers. Due to subsequent tectonic events, these iron-rich sediments got into the fissures of the Ófalu metamorphic complex. This model is strenghtened by some borehole and outcrops where the Lower Cretaceous interpillow sediments and hyaloclastites rich in iron oxydes and intrusive pillow basalt can be found close to our investigated section. (Hetényi et al., 1976) This study was supported by the Developing Competitiveness of Universities in the South Transdanubian Region (SROP-4.2.1.B-10/2/KONV-2010-0002). Dabi, G., Siklósy, Z., Schubert, F., Bajnóczi, B., M. Tóth, T., 2011. The relevance of vein texture in understanding the past hydraulic behaviour of a crystalline rock mass: reconstruction of the palaeohydrology of the Mecsekalja Zone, South Hungary. Geofluids, 11, 309-327. Hetényi, R., Földi, M., Hámor, G., Nagy, I., Bilik, I., Jantsky, B. 1976. Magyarázó a Mecsek hegység földtani térképéhez 10 000-es sorozat. MÁFI Budapest (in hungarian). Jáger, V., Molnár, F., Buchs, D. & Koděra, P. 2012: The connection between iron ore formations and "mud-shrimp" colonizations around sunken wood debris and hydrothermal sediments in a Lower Cretaceous continental rift basin, Mecsek Mts., Hungary. — Earth-Science Reviews 114/3-4, 250-278.

Trace metal distribution and isotope variations in low-temperature calcite and groundwater in granitoid fractures down to 1 km depth

NASA Astrophysics Data System (ADS)

Drake, Henrik; Tullborg, Eva-Lena; Hogmalm, K. Johan; Åström, Mats E.

2012-05-01

Studies of low-temperature fracture calcite in Proterozoic or Archaean crystalline rocks are very limited, mainly because this calcite usually is, first, not very abundant and second, very fine-grained or forms rims on older (and much more abundant) hydrothermal calcite and is thus difficult to distinguish. Knowledge of chemical characteristics and the correlation with groundwater chemistry is thus scarce for low-temperature calcite in these settings, and consequently, knowledge of the recent palaeohydrogeological history is limited. Boreholes drilled with triple-tube technique in the upper 1 km of the Palaeoproterozoic crystalline crust at Laxemar, SE Sweden, have enabled preservation of fragile and potentially recently formed fracture minerals. Earlier investigations of these boreholes have resulted in an extensive set of groundwater chemistry data from various depths, and in detailed knowledge of the fracture mineral assemblages (ranging from 1.8 Ga to present). This has made it possible to identify and sample low-temperature, potentially recently formed, calcite from water-flowing fractures for which representative groundwater chemical data exists. This, in turn, provides an opportunity to detailed comparisons of fracture calcite (age span in the order of million years, with possibility of post-glacial contributes) and groundwater (age in the order of decades to more than a million year depending on depth) in terms of both isotopic and geochemical properties, giving input to the understanding of groundwater history, partition coefficients derived in laboratory experiment, and reliability of calcite geochemistry in terms of representing the actual source fluid composition. In this study, the focus is on trace elements (Fe, Mg, Mn and Sr), stable isotopes and Sr isotopes and, for the groundwater data set, also aquatic speciation with Visual MINTEQ. An optimised step-by-step sample specific analytical procedure was used for the collection of calcite coatings. The methods used depended on the crystal homogeneity (one or several calcite generations), discerned by detailed SEM-investigations (back-scatter and cathodo-luminescence). 87Sr/86Sr ratios as well as δ18O signatures in calcite are in the range expected for the precipitates from present-day groundwater, or older groundwater with similar composition (except in sections with a considerable portion of glacial water, where calcite definitely is older than the latest glaciation). Stable carbon isotopes in calcite generally show values typically associated with HCO3- originating from soil organic matter but at intermediate depth frequently with HCO3- originating from in situ microbial anaerobic oxidation of methane (highly depleted δ13C). For one of the studied metals - manganese - there was a strong correlation between the sampled calcite coatings and hypothetical calcite predicted by applying laboratory-based partition coefficients (literature data) on groundwater chemistry for sections corresponding to those where the calcites were sampled. This points to temporal and spatial stability in groundwater Mn/Ca ratios over millions of years, or even more, and show that it is possible to assess, based on laboratory-derived data on Mn partitioning, past groundwater Mn-composition from fracture calcites. For other metals - Fe, Sr, and Mg - which are expected to interact with co-precipitating minerals to a higher degree than Mn, the correlations between measured and predicted calcite were weaker for various reasons.

Stratigraphy, Hydrothermal Alteration and Evolution of the Mangakino Geothermal System, Taupo Volcanic Zone, New Zealand

NASA Astrophysics Data System (ADS)

Fagan, C. J.; Wilson, C. J.; Spinks, K. D.; Browne, P. R.; Simmons, S. F.

2006-12-01

A major part of the ca. 1.6 Myr history of the Taupo Volcanic Zone (TVZ) is represented by buried and hydrothermally altered rocks penetrated by geothermal exploration wells. The geothermal field at Mangakino is sited in the oldest TVZ caldera on the western edge of the TVZ. Four exploration wells into the field reveal a thick sequence of flat-lying ignimbrites. Basement Mesozoic greywacke metasediments were not reached by the deepest well, MA2 (3192 m), implying the presence of a thick caldera infill. Ignimbrites exposed at the surface nearby have distinct mineralogies and crystal contents, which enable correlation with down-hole lithologies. Five ignimbrites are identified in the wells: the 0.32 Ma Whakamaru, 0.93 Ma Marshall, 1.0 Ma Rocky Hill, 1.18 Ma Ahuroa and 1.25 Ma Ongatiti ignimbrites, two of which are >800m thick. The Whakamaru and Marshall units are separated by a thick sequence of lacustrine and volcaniclastic deposits related to infilling of the Mangakino caldera. The ignimbrite sequence is continuous between all wells, with no fault offset, and only well MA3 intersects two rhyolite intrusions at 1190 m and 1850 m that are thought to be feeder dikes to post-0.32 Ma rhyolite domes to the east of Mangakino. Alteration assemblages include epidote and wairakite in MA2 below 2200 m. Adularia occurs in MA2 and MA3 where it replaces, wholly or in part, primary andesine. Adularia is also locally replaced by illite, indicating a shift in hydrothermal conditions. Other minerals present are chlorite, quartz, calcite, titanite and pyrite. Secondary quartz and calcite veins are seen in thin section, with a first appearance in the lacustrine sediments at 550 m in both MA2 and MA3. Fluid inclusions in secondary calcite show high temperatures (300 and 315 °C) while inclusions in primary quartz show ca. 165 °C (the current temperature at the sampled depth), recording current conditions. The modern maximum temperature is 250 °C at 3000 m in MA2. Evidence for two different temperatures in the fluid inclusion data and a shift in alteration mineralogy may reflect an earlier thermal event, possibly related to dike intrusion nearby.

Geochemistry, mineralization, structure, and permeability of a normal-fault zone, Casino mine, Alligator Ridge district, north central Nevada

NASA Astrophysics Data System (ADS)

Hammond, K. Jill; Evans, James P.

2003-05-01

We examine the geochemical signature and structure of the Keno fault zone to test its impact on the flow of ore-mineralizing fluids, and use the mined exposures to evaluate structures and processes associated with normal fault development. The fault is a moderately dipping normal-fault zone in siltstone and silty limestone with 55-100 m of dip-slip displacement in north-central Nevada. Across-strike exposures up to 180 m long, 65 m of down-dip exposure and 350 m of along-strike exposure allow us to determine how faults, fractures, and fluids interact within mixed-lithology carbonate-dominated sedimentary rocks. The fault changes character along strike from a single clay-rich slip plane 10-20 mm thick at the northern exposure to numerous hydrocarbon-bearing, calcite-filled, nearly vertical slip planes in a zone 15 m wide at the southern exposure. The hanging wall and footwall are intensely fractured but fracture densities do not vary markedly with distance from the fault. Fault slip varies from pure dip-slip to nearly pure strike-slip, which suggests that either slip orientations may vary on faults in single slip events, or stress variations over the history of the fault caused slip vector variations. Whole-rock major, minor, and trace element analyses indicate that Au, Sb, and As are in general associated with the fault zone, suggesting that Au- and silica-bearing fluids migrated along the fault to replace carbonate in the footwall and adjacent hanging wall rocks. Subsequent fault slip was associated with barite and calcite and hydrocarbon-bearing fluids deposited at the southern end of the fault. No correlation exists at the meter or tens of meter scale between mineralization patterns and fracture density. We suggest that the fault was a combined conduit-barrier system in which the fault provides a critical connection between the fluid sources and fractures that formed before and during faulting. During the waning stages of deposit formation, the fault behaved as a localized conduit to hydrocarbon-bearing calcite veins. The results of this study show that fault-zone character may change dramatically over short, deposit- or reservoir-scale distances. The presence of damage zones may not be well correlated at the fine scale with geochemically defined regions of the fault, even though a gross spatial correlation may exist.

Crystal growth of calcite from calcium bicarbonate solutions at constant PCO2 and 25°C: a test of a calcite dissolution model

USGS Publications Warehouse

Reddy, Michael M.; Plummer, Niel; Busenberg, E.

1981-01-01

A highly reproducible seeded growth technique was used to study calcite crystallization from calcium bicarbonate solutions at 25°C and fixed carbon dioxide partial pressures between 0.03 and 0.3 atm. The results are not consistent with empirical crystallization models that have successfully described calcite growth at low PCO2 (< 10−3 atm). Good agreement was found between observed crystallization rates and those calculated from the calcite dissolution rate law and mechanism proposed by Plummer et al. (1978).

Caves in caves: Post depositional holes in stalagmites

NASA Astrophysics Data System (ADS)

Shtober Zisu, Nurit; Schwarcz, Henry P.; Chow, Tom; Konyer, Norman B.; Noseworthy, Michael D.

2010-05-01

Previous studies of speleothems for the purposes of isotopic analysis and U-series dating have resulted in preparation of stalagmites by sectioning longitudinally along the growth axis. We frequently observe holes in such sections, both along the growth axis, and laterally to it, ranging in size up to several mm in diameter. Our initial supposition was that these holes are produced during the growth of the stalagmite under constant dripping conditions, but it was found that two kinds of holes exist within the stalagmites. "Axial holes" were formed syngenetically as is shown by the depression of growth layers into the holes and the persistence of the axial hole over many cm of the growth history. Some cut the active growth surface of the stalagmite. "Off-axis holes" are seen in many stalagmites (as well as stalactites); they cut discordantly through growth layers, and never terminate at a growth surface. They range in size from a few mm to several cm in maximum dimension, and may not be coaxially oriented. They are lined with micron-sized, randomly oriented calcite crystals and under which lies an organic-rich coating. We used CT (Computed Tomography) and MRI (Magnetic Resonance Imaging) scanning in order to locate holes, and to search for water trapped in these macro-inclusions. These methods, allow us to visualize the holes without destruction of the stalagmite, the holes and the surrounding calcite. To our best knowledge, the present paper is the first to combine CT and MRI methods in the study of fluid inclusions in rocks, or in visualizing the distribution of holes in speleothems. CT scans reveal abundant off-axis holes in some speleothems, while most display at least a few holes. MRI scans shows that, in uncut speleothems, these holes never contain water (although Genty et al. [2002] found water-filled holes in some stalagmites). Off-axis holes may be a result of bioerosion, possibly bacterial, followed by partial refilling of the hole with calcite which is prevented from growing epitaxially on the host calcite.

Geology of the world-class Kiaka polyphase gold deposit, West African Craton, Burkina Faso

NASA Astrophysics Data System (ADS)

Fontaine, Arnaud; Eglinger, Aurélien; Ada, Koumangdiwè; André-Mayer, Anne-Sylvie; Reisberg, Laurie; Siebenaller, Luc; Le Mignot, Elodie; Ganne, Jérôme; Poujol, Marc

2017-02-01

The Kiaka gold deposit is a major resource in West Africa, with measured and indicated resources of 124 Mt at 1.09 g/t Au (3.9 Moz) and inferred resources of 27 Mt at 0.83 g/t Au (0.8 Moz). Located within the Manga-Fada N'Gourma greenstone and plutonic belt in south of the Burkina Faso, the deposit is hosted by a metamorphosed volcano-sedimentary sequence of lithic-, quartz-biotite metagreywackes, aluminosilicate-bearing metapelites and garnet-orthopyroxene-bearing schists and volcanic units. Structural observations indicate four local deformation events: DK1, DK2 and DK3 and DK4. Respectively, these events are linked to regional D1 E-W compression, D2 NW-SE compression and lastly, D3- and D4-related reactivations along D2 shear zones. The S2 foliation and D2 shear zones are developed during lower amphibolite facies metamorphism whereas retrogression occurs during D3-4 reactivations along these shear zones at upper greenschist facies conditions. The emplacement of a dioritic intrusion, dated at 2140 ± 7 Ma (Concordia U-Pb age on magmatic zircon), is interpreted to be contemporaneous with sinistral displacement along mineralized, NE-trending D2 shear zones. The intersection of these shears zones and the Markoye shear zone (dextral-reverse D1 and sinistral-reverse D2 reactivations) controlled the final geometry of the host rocks and the ore zones. Four subparallel elongated ore bodies are mainly hosted within D2-related shear zones and some are developed in an apparent axial plane of a F2 isoclinal fold. Detailed petrographic studies have identified two main types of hydrothermal alteration associated with two stages of gold mineralization. The stage (1) corresponds to replacement zones with biotite and clinozoisite during the D2 event associated with pyrrhotite ± pyrite, chalcopyrite (disseminated gold stage). The stage (2) occurs during reactivations of the D2-related auriferous shear zones (vein stage) and is characterized by diopside ± actinolite D3 veins and veinlets and D4 pervasive muscovite, ± chlorite, ± calcite in quartz-carbonate vein selvages and associated with pyrrhotite + arsenopyrite ± electrum, ± native gold and tellurobismuthite. The latter stage (2) could be divided into two sub-stages based on mineralogy and crosscutting relationship. A weighted average Re-Os pyrrhotite age at 2157 ± 24 Ma (Re-Os age based on 3 replicates) constraints the timing of the disseminated gold stage and represents the first absolute age for gold mineralization in the Manga Fada N'Gourma area. The timing of gold at Kiaka may be also coeval with one of the two lode gold event at ∼ ca. 2.16-2.15 Ga and occurred concomitant with tectono-thermal activity during Eo-Eburnean orogeny. The study of the Kiaka gold deposit emphasizes the importance of a multi-scale and multidisciplinary approach (field observations, petrography geothermobarometry and geochronology) to decipher the polyphase character of some Paleoproterozoic gold deposits.

Distribution of Minor Elements in Calcite From the Unsaturated Zone at Yucca Mountain, Nevada

NASA Astrophysics Data System (ADS)

Marshall, B. D.; Whelan, J. F.

2001-12-01

Calcite is sporadically distributed in fractures and cavities in the volcanic rocks that form the 500- to 700-m-thick unsaturated zone at Yucca Mountain. Previous work has shown that the calcite precipitated from water moving downward through the unsaturated zone since the volcanic rocks were emplaced approximately 13 Ma. Calcite thus serves as a proxy for the chemistry and amounts of past percolation, two parameters that are important in predictions of the future behavior of the potential radioactive waste repository at Yucca Mountain. Latest calcite, which began forming between approximately 5 and 2 Ma, typically displays fine-scale growth zoning defined by distributions of Mn (inferred from cathodoluminescence), Mg, and Sr. Electron microprobe (EPMA) mapping of outermost calcite reveals Mg growth zoning1 and higher overall concentrations of Mg in late calcite than in older calcite. Micro X-ray fluorescence (micro-XRF) maps were obtained by slow rastering of the samples over a 100-watt X-ray source collimated through a final aperture of 100 μ m. Although the spatial resolution of the micro-XRF mapping is much less than that of EPMA, this technique reveals distributions of some elements to which EPMA is less sensitive. Micro-XRF maps show that Sr is spatially correlated with Mg; Sr concentrations range to 500 μ g/g at the resolution of the 100-μ m collimator. Because both Mg and Sr have similar calcite-water distribution coefficients much less than one, the Mg/Sr in calcite reflects the Mg/Sr of the water that precipitated the calcite. The distribution coefficient for Mn is greater than one and variations in Mn are not correlated with Mg and Sr. Covariation of Mg and Sr in the percolating water may be explained by reactions that affect the rate of uptake of chemical constituents from the overlying rock and soil, and/or evaporation. Late calcite has lower δ 13C values, probably due to a regional change from wetter to drier climate conditions. The higher Mg and Sr concentrations in the late calcite may record lower deposition rates and decreased percolation fluxes due to the drier climate. 1 Wilson, N.S.F., Cline, J.S., and Lundberg, S.A.W., 2000, Paragenesis and chemical composition of secondary mineralization at Yucca Mountain, Nevada, Geol. Soc. Am. Abs. Prog., v. 32, p. A260.

Recent sediment remolding on a deep shelf, Ross Sea: implications for radiocarbon dating of Antarctic marine sediments

NASA Astrophysics Data System (ADS)

Domack, Eugene W.; Taviani, Marco; Rodriguez, Anthonio

1999-11-01

Coarse, bioclastic rich sands have been widely reported from the banks of the Antarctic continental shelf but their origin is still poorly known. We report on a suite of coarse sediments recovered from the top of the Mawson Bank in the northwestern Ross Sea. Radiocarbon ages of biogenic calcite, for modern and apparently late Pleistocene deposits, range from 1085±45 to 20,895±250 yr B.P.. Discovery of soft tissue (Ascidian) preserved as an incrustation on a pebble at 2 m depth indicates aggregation of the sediment within several months or a year of core recovery. Radiocarbon ages of acid insoluble organic matter (aiom) are less than those of the foraminifera calcite. The aiom ages are also reversed in sequence, indicating reworking of the sediment during deposition. These observations and a review of recently published literature suggest that much of the bank top sediment in Antarctica is presently undergoing remobilization, under the influence of strong currents and/or icebergs even under interglacical (high-stand) sea levels. These observations point out the need for careful, integrated studies on high latitude marine sediment cores before resultant "ages" alone are used as the foundation for paleoglacial reconstructions.

Calcite Formation in Soft Coral Sclerites Is Determined by a Single Reactive Extracellular Protein*

PubMed Central

Rahman, M. Azizur; Oomori, Tamotsu; Wörheide, Gert

2011-01-01

Calcium carbonate exists in two main forms, calcite and aragonite, in the skeletons of marine organisms. The primary mineralogy of marine carbonates has changed over the history of the earth depending on the magnesium/calcium ratio in seawater during the periods of the so-called “calcite and aragonite seas.” Organisms that prefer certain mineralogy appear to flourish when their preferred mineralogy is favored by seawater chemistry. However, this rule is not without exceptions. For example, some octocorals produce calcite despite living in an aragonite sea. Here, we address the unresolved question of how organisms such as soft corals are able to form calcitic skeletal elements in an aragonite sea. We show that an extracellular protein called ECMP-67 isolated from soft coral sclerites induces calcite formation in vitro even when the composition of the calcifying solution favors aragonite precipitation. Structural details of both the surface and the interior of single crystals generated upon interaction with ECMP-67 were analyzed with an apertureless-type near-field IR microscope with high spatial resolution. The results show that this protein is the main determining factor for driving the production of calcite instead of aragonite in the biocalcification process and that –OH, secondary structures (e.g. α-helices and amides), and other necessary chemical groups are distributed over the center of the calcite crystals. Using an atomic force microscope, we also explored how this extracellular protein significantly affects the molecular-scale kinetics of crystal formation. We anticipate that a more thorough investigation of the proteinaceous skeleton content of different calcite-producing marine organisms will reveal similar components that determine the mineralogy of the organisms. These findings have significant implications for future models of the crystal structure of calcite in nature. PMID:21768106

A reaction-transport model for calcite precipitation and evaluation of infiltration fluxes in unsaturated fractured rock.

PubMed

Xu, Tianfu; Sonnenthal, Eric; Bodvarsson, Gudmundur

2003-06-01

The percolation flux in the unsaturated zone (UZ) is an important parameter addressed in site characterization and flow and transport modeling of the potential nuclear-waste repository at Yucca Mountain, NV, USA. The US Geological Survey (USGS) has documented hydrogenic calcite abundances in fractures and lithophysal cavities at Yucca Mountain to provide constraints on percolation fluxes in the UZ. The purpose of this study was to investigate the relationship between percolation flux and measured calcite abundances using reactive transport modeling. Our model considers the following essential factors affecting calcite precipitation: (1) infiltration, (2) the ambient geothermal gradient, (3) gaseous CO(2) diffusive transport and partitioning in liquid and gas phases, (4) fracture-matrix interaction for water flow and chemical constituents, and (5) water-rock interaction. Over a bounding range of 2-20 mm/year infiltration rate, the simulated calcite distributions capture the trend in calcite abundances measured in a deep borehole (WT-24) by the USGS. The calcite is found predominantly in fractures in the welded tuffs, which is also captured by the model simulations. Simulations showed that from about 2 to 6 mm/year, the amount of calcite precipitated in the welded Topopah Spring tuff is sensitive to the infiltration rate. This dependence decreases at higher infiltration rates owing to a modification of the geothermal gradient from the increased percolation flux. The model also confirms the conceptual model for higher percolation fluxes in the fractures compared to the matrix in the welded units, and the significant contribution of Ca from water-rock interaction. This study indicates that reactive transport modeling of calcite deposition can yield important constraints on the unsaturated zone infiltration-percolation flux and provide useful insight into processes such as fracture-matrix interaction as well as conditions and parameters controlling calcite deposition.

Mineralogy and geochemistry of triassic carbonatites in the Matcha alkaline intrusive complex (Turkestan-Alai Ridge, Kyrgyz Southern Tien Shan), SW Central Asian orogenic belt

NASA Astrophysics Data System (ADS)

Vrublevskii, V. V.; Morova, A. A.; Bukharova, O. V.; Konovalenko, S. I.

2018-03-01

Postorogenic intrusions of essexites and alkaline and nepheline syenites in the Turkestan-Alai segment of the Kyrgyz Southern Tien Shan coexist with dikes and veins of carbonatites dated at ∼220 Ma by the Ar-Ar and Rb-Sr age methods. They are mainly composed of calcite and dolomite (60-85%), as well as sodic amphibole, phlogopite, clinopyroxene, microcline, albite, apatite, and magnetite, with accessory niobate, ilmenite, Nb-rutile, titanite, zircon, baddeleyite, monazite-(Ce), barite, and sulfides. The rocks share mineralogical and geochemical similarity with carbonatites that originated by liquid immiscibility at high temperatures above 500 °C. Alkaline silicate and salt-carbonate melts are derived from sources with mainly negative bulk εNd(t) ∼ from -11 to 0 and high initial 87Sr/86Sr ratios (∼0.7061-0.7095) which may be due to mixing of PREMA and EM-type mantle material. Pb isotopic ratios in accessory pyrrhotite (206Pb/204Pb = 18.38; 207Pb/204Pb = 15.64; 208Pb/204Pb = 38.41) exhibit an EM2 trend. The intrusions bear signatures of significant crustal contamination as a result of magma genesis by syntexis and hybridism. Concordant isotope composition changes of δ13C (-6.5 to -1.9‰), δ18O (9.2-23‰), δD (-58 to -41‰), and δ34S (12.6-12.8‰) in minerals and rocks indicate inputs of crustal material at the stage of melting and effect of hot fluids released during dehydration of metamorphosed oceanic basalts or sediments. The observed HFSE patterns of the oldest alkaline gabbro may be due to interaction of the primary mafic magma with IAB-type material. The isotope similarity of alkaline rocks with spatially proximal basalts of the Tarim large igneous province does not contradict the evolution of the Turkestan-Alai Triassic magmatism as the "last echo" of the Tarim mantle plume.

Origin of carbonatites of the Matcha alkaline pluton from Turkestan-Alai ridge, Kyrgyz Southern Tien Shan

NASA Astrophysics Data System (ADS)

Vrublevskii, V. V.

2017-12-01

Postorogenic alkaline intrusions in the Turkestan-Alai segment of the Southern Tien Shan coexist with dikes and veins of carbonatites dated at ˜220 Ma. They are primarily composed of calcite and dolomite (60-85 %), as well as sodic amphibole, phlogopite, clinopyroxene, microcline, albite, apatite, and magnetite, with accessory niobate, ilmenite, Nb-rutile, titanite, zircon, baddeleyite, monazite-(Ce), barite, and sulfides. The rocks share mineralogical and geochemical similarity with carbonatites that originated by liquid immiscibility at high temperatures above 500°C. Silicate and salt-carbonate melts are derived from sources with mainly negative bulk ɛND(t) ˜ from -11 to 0 and high initial 87Sr/86Sr ratios (˜ 0.7061-0.7095) which may be due to mixing of PREMA and EM-type mantle material. Pb isotopic ratios in accessory pyrrhotite (206Pb/204Pb = 18.38; 207Pb/204Pb = 15.64; 208Pb/204Pb = 38.41) exhibit an EM 2 trend. The intrusions bear signatures of significant crustal contamination as a result of magma genesis by syntexis and hybridism. Concordant isotope composition changes of δ 13C (-6.5 to -1.9 ‰), δ 18O (9.2-23 %„), δD (-58 to -41 %„), and δ 34S (12.6-12.8 ‰) in minerals and rocks indicate inputs of crustal material at the stage of melting and effect of hot fluids released during dehydration of metamorphosed oceanic basalts or sediments. The observed HFSE patterns of the oldest alkaline gabbro may be due to interaction of the primary mafic magma with IAB-type material. The isotope similarity of alkaline rocks with spatially proximal basalts of the Tarim large igneous province does not contradict the evolution of the Turkestan-Alai Triassic magmatism as the «last echo» of the Tarim mantle plume.

Cold-seep-driven carbonate deposits at the Central American forearc: contrasting evolution and timing in escarpment and mound settings

NASA Astrophysics Data System (ADS)

Liebetrau, V.; Augustin, N.; Kutterolf, S.; Schmidt, M.; Eisenhauer, A.; Garbe-Schönberg, D.; Weinrebe, W.

2014-10-01

Continuous surface cores of cold-seep carbonates were recovered offshore Pacific Nicaragua and Costa Rica from 800 to 1,500-m water depths (Meteor 66/3) in order to decipher their evolution and methane enriched fluid emanation in contrasting geological settings. Cores from the mounds Iguana, Perezoso, Baula V and from the Jaco Scarp escarpment were used for a multi-method approach. For both settings aragonite was revealed as dominant authigenic carbonate phase in vein fillings and matrix cementation, followed by Mg-calcite as second most abundant. This common precipitation process of CaCO3 polymorphs could be ascribed as indirectly driven by chemical changes of the advecting pore water due to anaerobic oxidation of methane. A more direct influence of seep-related microbial activity on the authigenic mineral assemblage in both settings is probably reflected by the observed minor amounts of dolomite and a dolomite-like CaMg carbonate (MgCO3 ~ 42 %). δ13C data of Jaco Scarp samples are significantly lower (-43 to -56 ‰ PDB) than for mound samples (-22 to -36 ‰ PDB), indicating differences in fluid composition and origin. Noteworthy, δ18O values of Scarp samples correlate most closely with the ocean signature at their time of formation. Documenting the archive potential, a high resolution case study of a mound core implies at least 40 changes in fluid supply within a time interval of approximately 14 ky. As most striking difference, the age data indicate a late-stage downward-progressing cementation front for all three mound cap structures (approx. 2-5 cm/ky), but a significantly faster upward carbonate buildup in the bulging sediments on top of the scarp environment (approx. 120 cm/ky). The latter data set leads to the hypothesis of chemoherm carbonate emplacement in accord with reported sedimentation rates until decompression of the advective fluid system, probably caused by the Jaco Scarp landslide and dating this to approximately 13,000 years ago.

The fossil hydrothermal rootzone from the Northern Apennine ophiolites (Italy)

NASA Astrophysics Data System (ADS)

Tribuzio, R.; Zanetti, A.; Dallai, L.

2003-04-01

The Northern Apennine ophiolites are lithosphere remnants of the Late Jurassic -- Early Cretaceous Ligurian Tethys, which is considered to have developed in conjunction with the opening of the Central Atlantic Ocean. In the Bonassola area, a km-scale gabbroic body permits the study of the magmatic-hydrothermal transition. The body mostly consists of coarse-grained gabbros of cumulus origin that exhibit granulite-facies recrystallization along ductile shear zones, which most likely occurred in the absence of seawater-derived fluids. These shear zones are crosscut at high angle by parallel swarms of hornblende (± plagioclase) veins. The development of these veins is correlated with coronal hornblende growth at the expenses of igneous clinopyroxene in the host gabbro. Scattered, elongated bodies of hornblende-bearing albitites also crop out. In particular, two different generations of albitite bodies have been recognized. The albitite (1) bodies show irregular contacts against the host gabbro, which are characterized by hornblende-rich reaction zones. These albitites are inferred to have developed when the gabbro was not completely solidified. The albitite (2) bodies has sharp contacts, post-date the granulite-facies foliation in the host gabbros, and show the same elongation direction of hornblende veins. The albitite (2) bodies are therefore related to the same brittle deformation event that gave rise to the hornblende veins. Major, trace, halogen and oxygen isotope analyses of hornblende from both veins and albitite bodies have been carried out. The geochemical signature of hornblende from albitite (1) bodies and related contact reaction zones is similar to that of accessory titanian pargasite of igneous origin in the host gabbro, thus indicating that these albitites were derived by extreme differentiation of basaltic liquid. Two different chemical fingerprints have been recognized for the vein hornblendes. The first type indicates a formation by local reaction between migrating seawater-derived fluids and the gabbros. The development of these veins can be ascribed to a high-temperature, amphibolite-facies hydrothermal event. On the other hand, the hornblende from the less diffuse, thickest and fibrous veins has intermediate geochemical features, similar to the hornblende from albitite (2) bodies. These hornblendes provide evidence for interaction between magmatic and hydrothermal systems.

Quantitative single molecule measurements on the interaction forces of poly(L-glutamic acid) with calcite crystals.

PubMed

Sonnenberg, Lars; Luo, Yufei; Schlaad, Helmut; Seitz, Markus; Cölfen, Helmut; Gaub, Hermann E

2007-12-12

The interaction between poly(L-glutamic acid) (PLE) and calcite crystals was studied with AFM-based single molecule force spectroscopy. Block copolymers of poly(ethylene oxide) (PEO) and PLE were synthesized and covalently attached to the tip of an AFM cantilever. In desorption measurements the molecules were allowed to adsorb on the calcite crystal faces and afterward successively desorbed. The corresponding desorption forces were detected with high precision, showing for example a force transition between the two blocks. Because of its importance in the crystallization process in biominerals, the PLE-calcite interaction was investigated as a function of the pH as well as the calcium concentration of the aqueous solution. The sensitivity of the technique was underlined by resolving different interaction forces for calcite (104) and calcite (100).

Trace metal (Mg/Ca and Sr/Ca) analyses of single coccoliths by Secondary Ion Mass Spectrometry

NASA Astrophysics Data System (ADS)

Prentice, Katy; Jones, Tom Dunkley; Lees, Jackie; Young, Jeremy; Bown, Paul; Langer, Gerald; Fearn, Sarah; EIMF

2014-12-01

Here we present the first multi-species comparison of modern and fossil coccolith trace metal data obtained from single liths. We present both trace metal analyses (Sr, Ca, Mg and Al) and distribution maps of individual Paleogene fossil coccoliths obtained by Secondary Ion Mass Spectrometry (SIMS). We use this data to determine the effects of variable coccolith preservation and diagenetic calcite overgrowths on the recorded concentrations of strontium and magnesium in coccolith calcite. The analysis of coccoliths from deep-ocean sediments spanning the Eocene/Oligocene transition demonstrates that primary coccolith calcite is resistant to the neomorphism that is common in planktonic foraminifera from similar depositional environments. Instead, where present, diagenetic calcite forms distinct overgrowths over primary coccolith calcite rather than replacing this calcite. Diagenetic overgrowths on coccoliths are easily distinguished in SIMS analyses on the basis of relatively higher Mg and lower Sr concentrations than co-occurring primary coccolith calcite. This interpretation is confirmed by the comparable SIMS analyses of modern cultured coccoliths of Coccolithus braarudii. Further, with diagenetic calcite overgrowth being the principle source of bias in coccolith-based geochemical records, we infer that lithologies with lower carbonate content, deposited below the palaeo-lysocline, are more likely to produce geochemical records dominated by primary coccolith calcite than carbonate-rich sediments where overgrowth is ubiquitous. The preservation of primary coccolith carbonate in low-carbonate lithologies thus provides a reliable geochemical archive where planktonic foraminifera are absent or have undergone neomorphism.

The calcite → aragonite transformation in low-Mg marble: Equilibrium relations, transformations mechanisms, and rates

USGS Publications Warehouse

Hacker, Bradley R.; Rubie, David C.; Kirby, Stephen H.; Bohlen, Steven R.

2005-01-01

Experimental transformation of a rather pure natural calcite marble to aragonite marble did not proceed via the expected straightforward polymorphic replacement. Instead, the small amount of Mg in the starting material (0.36 wt %) was excluded from the growing aragonite and diffused preferentially into the remaining calcite grains, producing Mg-rich calcite rods that persisted as relicts. Nucleation of aragonite occurred exclusively on grain boundaries, with aragonite [001] oriented subparallel to calcite [0001]. The aragonite crystals preferentially consumed the calcite crystal on which they nucleated, and the reaction fronts developed preferentially along the {010} and {110} planes of aragonite. Each aragonite neoblast that grew was nearly free of Mg (typically <0.1 wt %). The excess Mg was taken up by the calcite grains in between, stabilizing them and causing a few volume percent rodlike relicts of Mg-enriched calcite (up to 10 wt % MgO) to be left behind by the advancing reaction front. The aragonite growth rates are approximately linear and range from ∼3 × 10−11 m s−1 at 600°C to ∼9 × 10−9 m s−1 at 850°C, with an apparent activation enthalpy of 166 ± 91 kJ mol−1. This reaction mechanism and the resultant texture are akin to cellular precipitation reactions in metals. Similar transformation textures have been reported from high-Mg marbles in Japan and China that disproportionated to low-Mg calcite and dolomite.

Multiple dating approach (14C, U/Th and 36Cl) of tsunami-transported reef-top megaclasts on Bonaire (Leeward Antilles) - potential and current limitations

NASA Astrophysics Data System (ADS)

Rixhon, Gilles; May, Simon Matthias; Engel, Max; Mechernich, Silke; Keulertz, Rebecca; Schroeder-Ritzrau, Andrea; Fohlmeister, Jens; Frank, Norbert; Dunai, Tibor; Brueckner, Helmut

2016-04-01

Coastal hazard assessment depends on reliable information on the magnitude and frequency of past high-energy wave events (EWE: tsunamis, storms). For this purpose onshore sedimentary records represent promising geo-archives for the mid- and late-Holocene EWE history. In comparison to fine-grained sediments which have been extensively studied in the recent past, supralittoral megaclasts are less investigated, essentially due to the difficulties related to the dating of corresponding depositional events, and thus their limited value for inferring the timing of major events. On Bonaire (Leeward Antilles, Caribbean), supratidal coarse-clast deposits form prominent landforms all around the island. Fields of large boulders (up to 150 t) are among the best-studied reef-top megaclasts worldwide. Transport by Holocene tsunamis is assumed at least for the largest boulders (Engel and May, 2012). Although a large dataset of 14C and electron spin resonance (ESR) ages is available for major coral rubble ridges and ramparts, showing some age clusters during the Late Holocene, it is still debated whether these data reflect the timing of major depositional/transport event(s), and how these data sets are biased by reworking of coral fragments. In addition, different processes may be responsible for the deposition of the coral rubble ridges and ramparts (storm) and the solitary megaclasts (tsunami). As an attempt to overcome the current challenges for dating the dislocation of the megaclasts, three distinct dating methods were implemented: (i) 14C dating of boring bivalves (Lithophaga) attached to the boulders; (ii) uranium-series (U/Th) dating of post-depositional, secondary calcitic flowstone at the underside of the boulders; and (iii) surface exposure dating of overturned boulders via 36Cl concentration measurements in corals. The three 14C datings yield age estimates >37 ka, i.e. most probably beyond the applicability of the method, which sheds doubt on the usefulness of this method in the current context. It seems that the bivalves had incorporated the old CaCO3 from the MIS 5.5 mother rock. A U/Th age of the calcitic flowstone points to the Late Holocene period (1.3 ka); it represents a minimum age for boulder transport. Further U/Th dating is in progress. Four coral samples collected from three overturned boulders yielded similar 36Cl concentration measurements, also pointing to a late Holocene dislocation of the clasts. However, it remains unclear whether this concentration cluster mostly results from nuclide accumulation at the "blank" side, subsequent to their overturning during the depositional event, or already from pre-exposure at depth in the MIS 5.5 coral reef platform prior to the EWE. Further analysis is in progress to disentangle the problematic role of inheritance. These preliminary results show the potential and the current limitations of the applied methods for dating the dislocation of supralittoral megaclasts. Reference: Engel, M., May, S.M.: Bonaire's boulder fields revisited: evidence for Holocene tsunami impact on the Leeward Antilles. Quat. Sci. Rev., 54, 126-141, 2012.

Influence of surface conductivity on the apparent zeta potential of calcite.

PubMed

Li, Shuai; Leroy, Philippe; Heberling, Frank; Devau, Nicolas; Jougnot, Damien; Chiaberge, Christophe

2016-04-15

Zeta potential is a physicochemical parameter of particular importance in describing the surface electrical properties of charged porous media. However, the zeta potential of calcite is still poorly known because of the difficulty to interpret streaming potential experiments. The Helmholtz-Smoluchowski (HS) equation is widely used to estimate the apparent zeta potential from these experiments. However, this equation neglects the influence of surface conductivity on streaming potential. We present streaming potential and electrical conductivity measurements on a calcite powder in contact with an aqueous NaCl electrolyte. Our streaming potential model corrects the apparent zeta potential of calcite by accounting for the influence of surface conductivity and flow regime. We show that the HS equation seriously underestimates the zeta potential of calcite, particularly when the electrolyte is diluted (ionic strength ⩽ 0.01 M) because of calcite surface conductivity. The basic Stern model successfully predicted the corrected zeta potential by assuming that the zeta potential is located at the outer Helmholtz plane, i.e. without considering a stagnant diffuse layer at the calcite-water interface. The surface conductivity of calcite crystals was inferred from electrical conductivity measurements and computed using our basic Stern model. Surface conductivity was also successfully predicted by our surface complexation model. Copyright © 2016 Elsevier Inc. All rights reserved.

Technical note: An empirical method for absolute calibration of coccolith thickness

NASA Astrophysics Data System (ADS)

González-Lemos, Saúl; Guitián, José; Fuertes, Miguel-Ángel; Flores, José-Abel; Stoll, Heather M.

2018-02-01

As major calcifiers in the open ocean, coccolithophores play a key role in the marine carbon cycle. Because they may be sensitive to changing CO2 and ocean acidification, there is significant interest in quantifying past and present variations in their cellular calcification by quantifying the thickness of the coccoliths or calcite plates that cover their cells. Polarized light microscopy has emerged as a key tool for quantifying the thickness of these calcite plates, but the reproducibility and accuracy of such determinations has been limited by the absence of suitable calibration materials in the thickness range of coccoliths (0-4 µm). Here, we describe the fabrication of a calcite wedge with a constant slope over this thickness range, and the independent determination of calcite thickness along the wedge profile. We show how the calcite wedge provides more robust calibrations in the 0 to 1.55 µm range than previous approaches using rhabdoliths. We show the particular advantages of the calcite wedge approach for developing equations to relate thickness to the interference colors that arise in calcite in the thickness range between 1.55 and 4 µm. The calcite wedge approach can be applied to develop equations relevant to the particular light spectra and intensity of any polarized light microscope system and could significantly improve inter-laboratory data comparability.

Unusual carbon and oxygen isotropic ratios of ostracodal calcite from last interglacial (Sangamon episode) lacustrine sediment in Raymond Basin, Illinois, USA

USGS Publications Warehouse

Curry, B. Brandon; Anderson, T.F.; Lohmann, K.C.

1997-01-01

The stable isotopic records of ostracode valves deposited during the last interglaciation in Raymond Basin, Illinois, have ??13C and ??18O values as high as +16.5??? and +9.2??? respectively, the highest values yet reported from continental ostracodal calcite. Located in south-central Illinois, Raymond, Pittsburgh, Bald Knob, and Hopwood Farm basins collectively have yielded important long pollen and ostracode records that date from about 130 000 years ago to the present. Although fossils from the present-day interglaciation are not well preserved, these records constitute the only described, conformable, fossiliferous successions of this age from the interior of glaciated North America. The high ??13C values from Raymond Basin are attributed to the residual effects of methane loss either by ebullition or by emission through the stems of senescent emergent aquatic vegetation. A mass balance model suggests that an increase in ??13C of dissolved inorganic carbon on the order of +15??? is possible within a few hours given modest rates of methanogenesis of about 0.02 mol m-2 d-1. The ??13C records from other studies of ostracode valves have values approaching, but not exceeding about +14??? suggesting a limiting value to ???13C enrichment due to simultaneous inputs and outputs of dissolved inorganic carbon. Values of ??18O in ostracodal calcite are quite variable (-4 to +9???) in sediment from the late Sangamon subepisode. A model of isotopic enrichment in a desiccating water body implies that a reduction in reservoir volume of 20% could produce this range of isotopic values. High humidity and evaporation probably account for most of the ??18O variability.

δ13C signal of earthworm calcite granules: A new proxy for palaeoprecipitation reconstructions during the Last Glacial in western Europe

NASA Astrophysics Data System (ADS)

Prud'homme, Charlotte; Lécuyer, Christophe; Antoine, Pierre; Hatté, Christine; Moine, Olivier; Fourel, François; Amiot, Romain; Martineau, François; Rousseau, Denis-Didier

2018-01-01

Quantification of paleoprecipitation during the Last Glacial is a key element to reconstruct palaeoclimates. Recently, fossil calcite granules have been identified in loess sequences with high contents in specific horizons. In this study, we explored for the first time the potential of this new bio-indicator as a climatic proxy for precipitation in western Europe during the Last Glacial. We extracted 30 granules from eleven samples belonging to three tundra gleys and two brown soils from the Nussloch loess sequence previously dated between 50 and 20 ka. Stable carbon isotope measurements were performed on each granule and duplicated. Throughout the studied section, δ13C values range from -15.4 to -10.3‰ for tundra gleys and from -14.9 to -9.5‰ for brown soils. By taking into account the fractionation factor between the carbon ingested by the earthworm and the carbon output of the granules, the δ13C values of these granules reflect the composition of the C3 plant vegetation cover. Thus, we estimated the δ13C of the plants with a mean value of -24.3 ± 0.9‰ for tundra gleys and -24.1 ± 0.9‰ for brown soils, which are in agreement with values obtained from organic matter preserved in sediments. Palaeoprecipitation range over both tundra gley horizons and brown soils were estimated at about 333[159-574] mm/yr by using an empirical relationship determined between present-day plant leaf isotopic discrimination and the mean annual precipitation. This original preliminary study highlights the potential of earthworm calcite granule δ13C measurements as a new proxy for paleoprecipitation during the Last Glacial interstadials in continental environments.

Calcite raft geochemistry as a hydrological proxy for Holocene aquifer conditions in Hoyo Negro and Ich Balam (Sac Actun Cave System), Quintana Roo, Mexico

NASA Astrophysics Data System (ADS)

Kovacs, Shawn E.; Reinhardt, Eduard G.; Chatters, James C.; Rissolo, Dominique; Schwarcz, Henry P.; Collins, Shawn V.; Kim, Sang-Tae; Nava Blank, Alberto; Luna Erreguerena, Pilar

2017-11-01

Two cores from calcite rafts deposits located in Cenote Ich Balam and Hoyo Negro were dated and analyzed for 87Sr/86Sr, δ18O, δ13C, Sr/Ca and Cl/Ca. The geochemical records show changing aquifer salinity spanning the last ∼ 8.5 cal kyrs BP and interrelationships with Holocene climate trends (wet and dry periods). During the wet mid-Holocene, the salinity of the meteoric Water Mass (WM; at 7.8-8.3 cal kyrs BP) was relatively high at 1.5-2.7 ppt and then became less saline (1.0-1.5 ppt) during the last ∼ 7000 yrs as climate became progressively drier. High salinity of the meteoric WM during the wet mid-Holocene is attributed to increased turbulent mixing between the meteoric and underlying marine WM. Increased precipitation, in terms of amount, frequency, and intensity (e.g. hurricanes) causes higher flow of meteoric water towards the coast and mixing at the halocline, a phenomenon recorded with recent instrumental monitoring of the aquifer. Conversely, during dry periods reduced precipitation and flow in the meteoric WM would result in lower salinity. Karst properties and Holocene sea-level rise also seem to have an effect on the aquifer. When the regionally extensive network of shallow cave passages (∼ 10-12 m water depth) are flooded at ∼ 8000 cal yrs BP, there is a rapid shift in salinity. This study demonstrates that calcite raft deposits can be used as paleo-environmental recorders documenting the effects of sea level and climate change on aquifer condition.

Stochastic and cyclic deposition of multiple subannual laminae in an urban lake (Twin Lake, Golden Valley, Minnesota, USA)

NASA Astrophysics Data System (ADS)

Myrbo, A.; Ustipak, K.; Demet, B.

2013-12-01

Twin Lake, a small, deep, meromictic urban lake in Minneapolis, Minnesota, annually deposits two to 10 laminae that are distinguished from one another by composition and resulting color. Sediment sources are both autochthonous and allochthonous, including pure and mixed laminae of authigenic calcite, algal organic matter, and diatoms, as well as at least three distinct types of sediment gravity flow deposits. Diagenetic iron sulfide and iron phosphate phases are minor components, but can affect color out of proportion to their abundance. We used L*a*b* color from digital images of a freeze core slab, and petrographic smear slides of individual laminae, to categorize 1080 laminae deposited between 1963 and 2010 CE (based on lead-210 dating). Some causal relationships exist between the ten categories identified: diatom blooms often occur directly above the debris of gravity flows that probably disrupt the phosphate-rich monimolomnion and fertilize the surface waters; calcite whitings only occur after diatom blooms that increase calcite saturation. Stochastic events, as represented by laminae rich in siliciclastics and other terrigenous material, or shallow-water microfossils and carbonate morphologies, are the dominant sediment source. The patterns of cyclic deposition (e.g., summer and winter sedimentation) that produce 'normal' varve couplets in some lakes are continually interrupted by these stochastic events, to such an extent that spectral analysis finds only a weak one-year cycle. Sediments deposited before about 1900, and extending through the entire Holocene sequence (~10m) are varve couplets interrupted by thick (20-90 cm) debris layers, indicating that gravity flows were lower in frequency but greater in magnitude before the historical period, probably due to an increased frequency of disturbance under urban land-use.

Carbonates in mantle xenoliths from French Massif Central: inference for carbonatite-related metasomatism.

NASA Astrophysics Data System (ADS)

Wagner, Christiane; Deloule, Etienne

2016-04-01

Mantle xenoliths from the sub-continental lithospheric mantle (SCLM) frequently display evidence of metasomatism by melts or fluids of variable composition, e.g. alkali-basaltic, alkali-carbonate or carbonate melts. Carbonate-bearing mantle xenoliths are particularly interesting as highly mobile carbonate melts are likely prominent metasomatic agents of the mantle. This study presents detailed petrographic descriptions and major and trace element compositions of minerals in protogranular spinel lherzolites from the Mont Coupet occurrence (Devès province, French Massif Central), with focus on the carbonate phases to discuss their possible link to carbonatite melt. Two representative samples are described here. MC9 shows no evidence for infiltration of the host basanitic magma. Carbonates occur (1) as large (100 μm - 200 μm) anhedral crystals in interstitial pockets at triple point of primary olivine grains, (2) in a few cross-cutting veins (up to 200 μm width), (3) along grain boundaries and (4) in composite carbonate-silicate pockets from well-developed reaction zones, in which carbonates fill globular vesicles. The reaction zone contains secondary subhedral to euhedral phases: Al- and Ti-rich clinopyroxene, Ca-rich olivine, Cr-rich spinel and quenched plagioclase and relict sieved-textured primary spinel. MC2 shows carbonate-bearing thin (< 50 μm width) interconnected veinlets and only a few poorly-developed reaction zones around primary spinel. Large carbonate crystals (1), as in sample MC9, occur associated with (2) fibrous carbonate with a well-formed meniscus at the boundary between the two carbonate types. In some reaction zones the carbonate patches (3) show well-developed concentric carbonate structures, similar to those observed in the globular vesicles from the host basanite. In sample MC9, the carbonate is an alkali-free Mg-poor calcite (XCa = 0.95 - 0.98; with 0.5 - 1.8 wt. % MgO) whatever the occurrence. In sample MC2, carbonates are Mg-richer, particularly the type 2 and 3 carbonates (XCa = 0.88 - 0.91; 3 - 5 wt. % MgO), a composition similar to that of the carbonates from the vesicles in the basanite (XCa = 0.86 - 0.88; 4 - 5 wt. % MgO). In both xenoliths, the carbonates have low REE abundances (mostly below the detection limit except La and Ce), similar to those reported for carbonates from mantle xenoliths. Moreover, the carbonate globules in the basanite have the same REE composition. Although the presence of rounded vesicles of calcite was originally interpreted as an evidence for silicate-carbonate liquid immiscibility, experimental studies have shown that alkali-free immiscible carbonates cannot be almost pure calcite. Textural features and composition (high XCa, low alkali contents and low REE abundances) of carbonates rule out their origin as quenched carbonatitic melts or immiscible carbonate liquids and favor, thus, an origin as crystal cumulates from mantle-derived carbonate-rich melts (e.g. alkali-carbonate melts). A possible scenario is the injection of small amounts of a carbonate-rich melt at mantle level shortly before the eruption to preserve the calcite crystals. Carbonate-rich melt or emanated fluids may have permeated the xenoliths (MC2) during the ascent and precipitated calcite crystals in the xenolith as well as in the entraining basanitic magma.

Oxygen-Carbon and Strontium Isotope Evidence for the Origin and Evolution of CO2-rich Volatiles from Oligocene to Miocene Mantle Magmas, Southwestern Colorado and Northwestern New Mexico

NASA Astrophysics Data System (ADS)

Gonzales, D. A.; Zbrozek, M.

2012-12-01

Oligocene to Miocene, alkaline mafic to ultramafic, rocks that are exposed in the Navajo volcanic field and dikes on the northern San Juan basin (NVSJ) contain calcite in vugs, veins, and breccias. Oxygen-carbon and Sr isotope signatures of bulk carbonate samples from these rocks were used to test hypotheses on the history of volatiles related to this pulse of mantle magmatism. Elevated fluorine in rocks, and fluorite-calcite breccias in some outcrops, indicate that magmatic volatiles were released by NVSJ melts. Oxygen and carbon isotope data for carbonate samples record a complex paragenetic history. δ13C values are mostly -8‰ to -4‰ with a mean value of -5.3 ± 2.0‰, similar to δ13C for primary mantle-derived carbonate. A subset of δ18O values are +5‰ to +10‰ which are within the accepted range of δ18O values for magmatic carbonate in carbonatite and kimberlite. A majority of δ18O values, however, range from +10‰ to +24‰ revealing that low-δ18O magmatic volatiles were overprinted by processes that caused enrichment of 18O at some stage during melt generation and emplacement. A subset of 87Sr/86Sri data from carbonate samples are nearly identical to 87Sr/86Sri for related rocks, hinting that the melts and volatiles came from the same source. Generally, NVSJ calcite samples have higher 87Sr/86Sri ratios than those of rocks, reflecting different melt-volatile sources or crustal contamination from Paleozoic limestone. Field and petrologic evidence does not lend convincing support for crustal contamination. Limestone fragments comprise less than 1% of xenoliths in NVSJ rocks. Also, rock samples do not show elevated CaO, MgO, FeO, Ba or Sr with increasing δ18O calcite which is expected for contamination of magmas with limestone. We propose that CO2-H2O-F volatiles in NVSJ magmas came from distinct melt-volatile sources, similar to the interpretation of Nowell (1993). Our assertion is that CO2-rich volatiles that exsolved from low δ18O mafic melts interacted with volatiles and melts from carbonate-bearing metasomatized lithospheric mantle. This is consistent with the subtle increase of 87Sr/86Sri rock and fluorine over the +6‰ to +24‰ range of δ18Ocalcite values recorded in minette samples. This hypothesis is supported by other studies that document +21‰ to +25‰ δ18O for carbonate in mantle xenoliths from Pliocene alkaline basalts in the region. Incipient to extensive alteration of olivine and phlogopite phenocrysts in NVSJ rocks reveals that deuteric isotopic exchange with H2O-CO2 magmatic fluids was a plausible factor for some of the variation in δ18O of calcite samples. In addition, melt contamination with limestone cannot be ruled out, but it requires nearly complete digestion of xenoliths in feeder dikes that had relatively low volumes of magma and cooled quickly. Overall, the isotope data combined with field and petrologic results are not consistent with models that invoke groundwater as the main source of volatiles in NVSJ magmas.

Estimation of past seepage volumes from calcite distribution in the Topopah Spring Tuff, Yucca Mountain, Nevada

USGS Publications Warehouse

Marshall, B.D.; Neymark, L.A.; Peterman, Z.E.

2003-01-01

Low-temperature calcite and opal record the past seepage of water into open fractures and lithophysal cavities in the unsaturated zone at Yucca Mountain, Nevada, site of a proposed high-level radioactive waste repository. Systematic measurements of calcite and opal coatings in the Exploratory Studies Facility (ESF) tunnel at the proposed repository horizon are used to estimate the volume of calcite at each site of calcite and/or opal deposition. By estimating the volume of water required to precipitate the measured volumes of calcite in the unsaturated zone, seepage rates of 0.005 to 5 liters/year (l/year) are calculated at the median and 95th percentile of the measured volumes, respectively. These seepage rates are at the low end of the range of seepage rates from recent performance assessment (PA) calculations, confirming the conservative nature of the performance assessment. However, the distribution of the calcite and opal coatings indicate that a much larger fraction of the potential waste packages would be contacted by this seepage than is calculated in the performance assessment.

Fabrication of microporous calcite block from calcium hydroxide compact under carbon dioxide atmosphere at high temperature.

PubMed

Otsu, Akihiro; Tsuru, Kanji; Maruta, Michito; Munar, Melvin L; Matsuya, Shigeki; Ishikawa, Kunio

2012-01-01

Effects of carbonation temperature and compacting pressure on basic properties of calcite block were studied using Ca(OH)2 compact made with 0.2-2.0 MPa and their carbonation at 200-800ºC for 1 h. Microporous calcite was obtained only when carbonated at 600ºC using Ca(OH)2 compact made with 0.2 MPa even though thermogravimetry analysis showed that calcite powder was stable up to 920ºC under CO2 atmosphere. CaO formed by carbonation at 700ºC and 800ºC is thought to be caused by the limited CO2 diffusion interior to the Ca(OH)2 compact. Also, unreacted Ca(OH)2 was found for Ca(OH)2 compact prepared with 0.5 MPa or higher pressure even when carbonated at 600ºC. As a result of high temperature carbonation, crystallite size of the calcite, 58.0 nm, was significantly larger when compared to that of calcite prepared at room temperature, 35.5 nm. Porosity and diametral tensile strength of the microporous calcite were 39.5% and 6.4 MPa.

Correcting for initial Th in speleothems to obtain the age of calcite nucleation after a growth hiatus

NASA Astrophysics Data System (ADS)

Richards, D. A.; Nita, D. C.; Moseley, G. E.; Hoffmann, D. L.; Standish, C. D.; Smart, P. L.; Edwards, R.

2013-12-01

In addition to the many U-Th dated speleothem records (δ18O δ13C, trace elements) of past environmental change based on continuous phases of calcite growth, discontinuous records also provide important constraints for a wide range of past states of the Earth system, including sea levels, permafrost extent, regional aridity and local cave flooding. Chronological information about human activity or faunal evolution can also be obtained where calcite can be seen to overlie cave art or mammalian bones, for example. Among the important considerations when determining the U-Th age of calcite that nucleates on an exposed surface are (1) initial 230Th/232Th, which can be elevated and variable in some settings, and (2) growth rate and sub-sample density, where extrapolation is required. By way of example, we present sea level data based on U-Th ages of vadose speleothems (i.e. formed above the water table and distinct from 'phreatic' examples) from caves of the circum-Caribbean , where calcite growth was interrupted by rising sea levels and then reinitiated after regression. These estimates demand large corrections and derived sea level constraints are compared with alternative data from coral reef terraces, phreatic overgrowths on speleothems or indirect, proxy evidence from oxygen isotopes to constrain rates of ice volume growth. Flowstones from the Bahamas provide useful sea level constraints because they present the longest and most continuous records in such settings (a function of preservation potential in addition to hydrological routing) and also earliest growth post-emergence after sea level fall. We revisit estimates for sea level regression at the end of MIS 5 at ~ 80 ka (Richards et al, 1994; Lundberg and Ford, 1994) and make corrections for non-Bulk Earth initial Th contamination (230Th/232Th activity ratio > 10), based on isochron analysis of alternative stalagmites from the same settings and recent high resolution analysis. We also present new U-Th ages for contiguous layers sub-sampled from the first 2-3 mm of flowstone growth after the MIS 5 hiatus, using a sub-sample milling strategy that matches spatial resolution with maximum achievable precision (ThermoFinnigan Neptune MC-ICPMS methodology; 20-30 mg calcite, U = ~ 300 ng.g-1, 2σ age uncertainty is × 600 a at ~80 ka). Isochron methods are used to estimate the range of initial 230Th/232Th ratio and are compared with elevated values obtained from stalagmites from the same cave (Beck et al, 2001; Hoffmann et al, 2010). A similar strategy is presented for a stalagmite with much faster axial growth data, and the data are combined with additional sea level information from the same region to estimate the rate and uncertainty of sea level regression at the MIS stage 5/4 boundary. Elevated initial 230Th/232Th values have also been observed in a stalagmite from 6 m below present sea level in a cenote from the Yucatan, Mexico, where 5 phases of calcite between 10 and 5.5 ka are separated by serpulid worm tubes formed during periods of submergence. The transition between each phase provides constraints on age and elevation of relative sea level, but the former is hampered by the uncertainty of the high initial 230Th/232Th correction. We consider the possible sources of elevated Th ratios: hydrogenous, colloidal and carbonate or other detrital components.

A Laboratory Study Investigating the Feasibility of Applying Calcite-Type Coatings to Segregated Ballast Tanks

DTIC Science & Technology

1981-08-01

A LABORATORY STUDY INVESTIGATIING THE FEASIBILITY OF APPLYING CALCITE -TYPE COATINGS TO SEGREGATED BALLAST TANKS AUGUST, 1981 Prepared by: Ocean City...Laboratory Study Investigating The Feasibility of Applying Calcite -Type Coatings to Segregated Ballast Tanks 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c...Executive Summary List of Figures I. Conclusions II. Introduction III. Background-The Development and Use of Calcite -Type Coatings IV. Experimental

Effect of molding pressure on fabrication of low-crystalline calcite block.

PubMed

Lin, Xin; Matsuya, Shigeki; Nakagawa, Masaharu; Terada, Yoshihiro; Ishikawa, Kunio

2008-02-01

We have reported that low-crystalline porous calcite block, which is useful as a bone substitute or a source material to prepare apatite-type bone fillers could be fabricated by exposing calcium hydroxide compact to carbon dioxide gas saturated with water vapor. In the present study, we investigated the effect of molding pressure on the transformation of calcium hydroxide into calcite and the mechanical strength of the carbonated compact. Transformation into calcite was almost completed within 72 h, however, a small amount of Ca(OH)(2) still remained unreacted at higher molding pressure because of incomplete penetration of CO(2) gas into the interparticle space due to dense packing of Ca(OH)(2) particles. On the other hand, high molding pressure resulted in an increase in diametral tensile strength (DTS) of the calcite compact formed. Critical porosity of the calcite block was calculated as approximately 68%.

Regulation of calcite crystal morphology by intracrystalline acidic proteins and glycoproteins.

PubMed

Albeck, S; Addadi, I; Weiner, S

1996-01-01

Many biologically formed calcite crystals contain intracrystalline macromolecules. The ways in which they interact with growing calcite crystals were evaluated by monitoring changes in the morphology of calcite crystals grown in vitro in their presence. Macromolecules were extracted from within isolated prisms from the prismatic layer of the shell of the mollusk Atrina rigida and from spines of the sea urchin Paracentrotus lividus. Two modes of interaction were identified; the interaction of highly acidic proteins with calcite planes perpendicular to the c crystallographic axis and the interaction of glycoproteins with planes roughly parallel to the c axis. By different preparative procedures we demonstrated that the polysaccharide moieties of the sea urchin spine glycoproteins are directly involved in the latter mode of interactions. We suggest that organisms utilize the abilities of these macromolecules to interact in different ways with calcite crystals, and in so doing fine-tune aspects of the control of crystal growth in vivo.

Upper crustal emplacement and deformation of granitoids inside the Uppermost Unit of the Cretan nappe stack: constraints from U-Pb zircon dating, microfabrics and paleostress analyses

NASA Astrophysics Data System (ADS)

Kneuker, Tilo; Dörr, Wolfgang; Petschick, Rainer; Zulauf, Gernold

2015-03-01

The present study is dealing with the emplacement and deformation of diorite and quartz diorite exposed along new road cuts between Agios Nikolaos and Sitia (Uppermost Unit, eastern Crete). Mingling of both melt types is indicated by enclaves of diorite inside quartz diorite and vice versa. The diorite and quartz diorite intruded into coarse-grained white marble, which is in lateral contact to, but also forms the roof of, the intrusive body. Evidence for contact metamorphism is indicated by increasing grain size of calcite in the marble with decreasing distance from the diorite. U-Pb (TIMS) dating of zircons, separated from quartz diorite, yielded a concordant age at 74.0 ± 0.25 Ma, which is interpreted as emplacement age. As this age is close to published K-Ar cooling ages of hornblende and biotite, the melt should have intruded and cooled down rapidly at upper structural levels, which is not common for granitoids of the Uppermost Unit of Crete. Upper crustal melt emplacement is also documented by stoped blocks and by the lack of any ductile (viscous) deformation. The diorite and quartz diorite, however, are affected by strong post-Oligocene brittle faulting. Paleostress analysis, based on these faults, revealed a change in stress field from N-S and NNW-SSE shortening by thrusting (convergence between African and European plates) to NNE-SSW and NE-SW shortening accommodated by strike-slip (SW-ward extrusion of the Anatolian microplate). Calcite-twin density indicates high differential stress (260 ± 20 MPa) related to these phases of crustal shortening.

An integrated magnetic and geological study of cataclasite- dominated pseudotachylytes in the Chiapas Massif, Mexico: a snapshot of stress orientation following slip

NASA Astrophysics Data System (ADS)

Garza, Roberto S. Molina; Geissman, John; Wawrzyniec, Tim; Weber, Bodo; Martínez, Margarita López; Aranda-Gómez, Jorge

2009-06-01

The Permian age Chiapas Massif in southeast Mexico is locally host to well-exposed pseudotachylyte vein networks. The veins are black to dark grey and aphanitic in appearance, and consist mostly of microbreccia of angular fragments of plagioclase, K-feldspar, biotite and quartz, in a cryptocrystalline (microscopically irresolvable) matrix. Evidence of melting is present in the form of glass seams, dikelets, glass clasts included in cataclasite and a distinct chemistry in the pseudotachylite veins; pristine glass represents a relatively small volume of the pseudotachylite veins. At an exposure along the Tablón River valley, where the host rock is a medium to coarse-grained equigranular quartz diorite, individual veins are consistently oriented about 280°, are up to 16 mm wide, tens of cm apart, display a consistent left-lateral offset and can be traced for several metres. Individual pseudotachylyte veins rarely cross each other, and they cannot be directly linked to a regional-scale fault. Pseudotachylytes are apparently formed by a combination of crushing, comminution and frictional melting, but they are cataclasite dominated. Textures indicate that cataclasis continued after frictional melting had ceased. A 40Ar/39Ar age determination from whole rock chips of one vein shows a climbing Ar release spectrum with a date of ~114 Ma as the most reliable age estimate for Ar retention. This result is interpreted in the context of pseudotachylyte formation, recrystallization and resetting of K-bearing minerals for the K-Ar system in the late Early Cretaceous. Ten veins were sampled for palaeomagnetic and magnetic fabric studies, with samples collected from both the veins and their host rock. Remanence data give moderate natural remanent magnetization (NRM) intensities for both the veins (e.g. NRM mean 6.6 × 10-3 A m-1 σ = 5.5) and host rock (mean 7.7 × 10-3 A m-1 σ = 10.8). Many samples of host rock yield an ill-defined east-west directed and shallow magnetization, which we interpret as a Late Permian magnetization based on previous studies of the Chiapas Massif. This magnetization resides in haematite. Veins, as well as immediately adjacent host rock, typically have well-defined, single polarity magnetizations of north-northwest declination and moderate positive inclination and these resemble the Cretaceous expected field direction. The overall mean of the veins is of Dec = 348.7° and Inc = 33.6° (k = 30.5 and α95 = 12.3° n = 6 site means). Rock magnetic parameters suggest that the remanence in the veins principally resides in low-Ti pseudo-single domain magnetite and maghemite grains, but haematite, coarse-grained magnetite, rutile, Fe-Cr-Ni oxides and ilmenite are also present in the veins. Bulk magnetic susceptibility values range between ~0.3 and 1.1 * 10-3 SI volume units, and host rock values do not differ significantly from vein values. The orientations of the principal susceptibility axes in the host rock and the veins are indistinguishable. In both, magnetic foliations are near vertical and are essentially parallel to the nearly east-west orientation of the veins. Nonetheless, host rock fabrics are predominantly prolate, whereas vein fabrics are oblate. The mean susceptibility tensors of host rocks and pseudotachylyte are characterized by P'/T values of 1.041/-0.327 and 1.033/+0.302, respectively. This result suggests that the fabric reflected by magnetic susceptibility anisotropy in the veins was formed under pure shear stress, during cooling of the veins. The lack of evidence of fabric rotation supports models that associate partial melt with viscous break during fault slip.

Effect of organic ligands on Mg partitioning and Mg isotope fractionation during low-temperature precipitation of calcite in the absence of growth rate effects

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; Immenhauser, Adrian; Buhl, Dieter; Purgstaller, Bettina; Baldermann, Andre; Dietzel, Martin

2017-06-01

Calcite growth rate has been previously shown to be the dominating parameter controlling both Mg partitioning and Mg isotope fractionation during calcite growth. In natural calcite precipitation environments - characterized by abundant organic material - the presence of dissolved organic molecules may affect these two parameters. In order to assess the role of organic molecules, steady state calcite growth experiments have been performed at 25 °C, 1 bar pCO2 and constant, within analytical uncertainty growth rate (rp = 10-7.4 mol m-2 s-1) in the presence of aqueous Mg and six organic ligands in the concentration range from 0.01 to 10 mM. The organic ligands used in this study are: (i) acetic acid, (ii) citric acid, (iii) glutamic acid, (iv) salycilic acid, (v) glycine, and (vi) ethylenediaminetetraacetic acid (EDTA). These contain one or more carboxyl- and amino-groups that are commonly present in natural organic substances found in lacustrine, fluvial, soil, cave, as well as in marine and earliest diagenetic porewater environments. Results shown here indicate that the presence of these carboxyl- and amino-groups promotes an increase in the partition coefficient of Mg in calcite (DMg = (Mg/Ca)calcite/(Mg/Ca)fluid) that can be attributed to their adsorption onto the calcite surfaces and the subsequent reduction of the active sites of growth. This increase of DMg values as a function of the supersaturation degree of calcite in the fluid phase can be described by the linear equation:

Fi Investigations On Hp-Rocks From The Lower Engadine Window New Insights On Its Late Tectono-Metamorphic Evolution

NASA Astrophysics Data System (ADS)

Bertle, R. J.; Götzinger, M. A.; Koller, F.

2003-04-01

Fluid inclusions studies in metamorphic rocks allow to reconstruct not only the chemistry of the fluids enabling and/or supporting metamorphic reactions but also the late metamorphic evolution of orogenesis. Therefore late, discordant quarz-calcite veins were investigated using FI-techniques. The Engadine Window which is exposed at the Swiss-Austrian-border exposes the penninic units of the Western Alps as a tectonic window within the Austroalpine nappes of the Eastern Alps. The nappes of the Engadine window underwent metamorphism and deformation during Tertiary times (THÖNI 1981, BERTLE 2000). The highest unit (Fimber unit) and the core of the window (= Zone of Pfunds) suffered HP-LT-metamorphism. P-T-conditions for parts of the Zone of Pfunds at the region of Piz Mundin are at 13-15 kbar at 380^oC (BOUSQUET et al. 2002) indicated by the occurrence of carpholite and glaucophane. The late metamorphic history is not very well constrained. There exist only a few FI-data published in an abstract by STÖCKHERT et al. 1990 and some unpublished data in RING 1989. During the ongoing mapping campaign of the first author samples from the Fimber unit and the Zone of Pfunds were collected and investigated using a LINKHAM freezing-cooling-stage. The investigated veins are discordant in respect to the main-foliation of the rocks and show nice cristalls of quarz, calcite and sometimes feldspar (adularia). Structural data implie that the investigated veins correspond to a set of ac-joints that correlate to the late updoming of the large "Engadiner Gewölbe" (Engadin anticlinal structure, MATTMÜLLER 1996). All investigated veins (from all tectonic units) show the same relationship to the anticlinal structure. FI-investigations show, that a large amount of the primary FI are decrepitated, however it was possible to find enough to provide a serious statistical data set. FI from Piz Mundin in the core of the Engadine window exhibit at the base of the vein quarz at the contact to the host rock (blueschist) epidote-clinozoisite cristalls. Futheron amphibole is visible. It is common at the base of the vein quarz and decreases towards the middle of the vein. FI are H2O-rich and indicate high pressure of trapping. Quarzes from the upper most part of the Zone of Pfunds from S of Zeblasjoch (W of Samnaun Dorf) show two main groups of primary FI which could be differentiated at room temperature: homogenous FI and such with a bubble. All FI were frozen at max. temperatures of ca. -56 ^oC. Bigger FI show cracking due to cristallisation pressure (build up of "wings"), the cracks however closed again during heating, so that the FI remained closed. Initial melting started between -20 ^oC (first recristallisation signs) and -9 ^oC, final melting was observable at -1 ^oC to 0 ^oC. Then the FI was a.) homogenous or b.) showed a bubble. Homogenisation Temp. of the inclusions with bubble were in the range of 70 to 150 ^oC , most of them between 70 and 80 ^oC and 110 - 125 ^oC. The data indicate a more or less pure H_2O-system for the FI under high pressure. Assuming a cristallisation temperature of the cristalls of about 200 to 250 ^oC and a density of the FI between 0,97 and 1,0 g/cm^3 pressures of 2,5 to 4,5 Kbar are indicated. The same P-T-conditions (same chemistry and melting & homog. Temp.) could be derived from FI in quarz from the Salaaser Kopf (Idalpe) for the late metamorphic evolution of the Fimber unit, indicating that the late metamorphic history of both units is the same. It is concluded that opening of the veins and first cristallisation of vein quarz corresponds to the first signs of updoming of the Engadine anticlinal structure. Updoming of the anticline started when the whole nappe stack was covered by the Austroalpine nappes. Therefore FI show such high pressures for trapping of the fluid. Acknowledgements: Data partly result from FWF-project P. 15278 "Bündnerschieferakkretion in the westlichen Ostalpen". Financal support is greatly acknowledged. References: BERTLE, R. J. 2000: Zur Geologie und Geochronologie um Alp Trida (Samnaun/Schweiz) einschließlich ingenieurgeologischer Fragen der Gebirgsauflösung und des Permafrosts. - Unpubl. Msc-Thesis. Univ. Wien, 395 S. BOUSQUET, R., GOFFÉ, B., VIDAL, O., OBERHÄNSLI, R. & PATRIAT, M. 2002: The tectono-metamorphic history of the Valaisan domain from the Western to the Central Alps: new constraints on the evolution of the Alps. - Geol. Soc. America Bull., 114/2, S. 207-225. KÜSTER, M. &STÖCKHERT, B. 1997: Density changes of fluid inclusions in high-pressure low-temperature metamorphic rocks from Crete: A thermobarometric approach based on the creep strength of the host minerals. Lithos, 41, S. 151-167. MATTMÜLLER, C. R. 1996: Geometrische Untersuchung des Inntalgewölbes. - Jahrb. Geol. B.-A., 139/1, S. 45-69, Wien 1996. RING, U. 1989: Tectonogenesis of the Penninic/Austroalpine Boundary Zone: The Arosa Zone (Grisons Rätikon area, Swiss-Austrian Alps). - Unpubl. Phd.-Thesis., 177 p., Tübingen. STOECKHERT, B., RÖSSNER, G., KÜSTER, M., HEIDER, M., GUNDLACH, K. &RICHTER, D.K. 1990: High-Pressure Metamorphism of the Mesozoic Sediments in the Lower Engadine Window, Eastern Alps. - Terra Abstracts, 2, S. 34, 1990. THÖNI, M. 1981: Degree and Evolution of the Alpine Metamorphism in the Austroalpine Unit W of the Hohe Tauern in the light of K/Ar and Rb/Sr Age Determinations on Micas. - Jahrb. Geol. B.-A., 124/1, S. 111-174, Wien 1981.

Relative Abundances of Calcite and Silica in Fracture Coatings as a Possible Indicator of Evaporation in a Thick Unsaturated Zone, Yucca Mountain, Nevada

NASA Astrophysics Data System (ADS)

Marshall, B. D.; Moscati, R. J.

2005-12-01

Yucca Mountain, a ridge of shallowly dipping, Miocene-age volcanic rocks in southwest Nevada, is the proposed site for a nuclear waste repository to be constructed in the 500- to 700-m-thick unsaturated zone (UZ). At the proposed repository, the 300-m-thick Topopah Spring Tuff welded unit (TSw) is overlain by approximately 30 m of nonwelded tuffs (PTn); the Tiva Canyon Tuff welded unit (TCw) overlies the PTn with a range in thickness from 0 to approximately 130 m at the site. The amount of water percolation through the UZ is low and difficult to measure directly, but local seepage into mined tunnels has been observed in the TCw. Past water seepage in the welded tuffs is recorded by widespread, thin (0.3 cm) coatings of calcite and silica on fracture surfaces and within cavities. Abundances of calcite and silica in the coatings were determined by X-ray microfluorescence mapping and subsequent multispectral image analysis of over 200 samples. The images were classified into constituent phases including opal-chalcedony-quartz (secondary silica) and calcite. In the TCw samples, the median calcite/silica ratio is 8; in the TSw samples within 35 m below the PTn, median calcite/silica falls to 2, perhaps reflecting an increase in soluble silica from the presence of glass in the nonwelded tuffs. In the deeper parts of the TSw, median calcite/silica reaches 100 and many samples contain no detectable secondary silica phase. Evaporation and changing pCO2 control precipitation of calcite from water percolating downward in the UZ, but precipitation of opal requires only evaporation. Calcite/silica ratios, therefore, can constrain the relative importance of evaporation in the UZ. Although calcite/silica values scatter widely within the TSw, reflecting the spatial variability of gas and water flow, average calcite/silica ratios increase with stratigraphic depth, indicating less evaporation at the deeper levels of the UZ. Coupled with the much smaller calcite/silica ratios observed in coatings from the TCw, these data indicate that evaporation decreases with depth in the UZ. Evaporation at the repository horizon and in the overlying units is an important process that reduces the amount of seepage at the repository horizon.

Intrahepatic venous anastomoses with a focus on the middle hepatic vein anastomoses in normal human livers: anatomical study on liver corrosion casts.

PubMed

Hribernik, Marija; Trotovšek, Blaž

2014-04-01

The aim of this study is to present the anatomical data about intrahepatic venous anastomoses found in normal human livers. The focus is on the middle hepatic vein (MHV) anastomoses, because their existence or non-existence could be of crucial importance in tumour resections as well as in split or living donor liver transplantations. The frequency of livers with intrahepatic venous anastomoses was determined on 164 corrosion casts and the diameter of each anastomosis was measured. Additionally, the type of connection and the position within the liver (liver segment) was determined for each MHV anastomosis. Intrahepatic venous anastomoses were found in 46 % (75/164), whereas MHV anastomoses were found in 28 % (44/164) of liver casts. Most commonly (39/44), MHV had anastomotic connections with the right hepatic vein (RHV), and also with the inferior RHV, the left hepatic vein and the short subhepatic vein. In more than three quarters of liver casts, MHV-RHV anastomoses were found in liver segment 8; in 45 % of cases, there was more than one anastomosis in this liver segment. The diameter of MHV-RHV anastomoses found in segment 8 was ≥1 mm in 90.6 % of cases. As MHV anastomoses were present in more than a quarter of all examined liver casts, we believe that detailed anatomical data presented in this article, together with up to date radiologic technics which enable even 3D reconstruction of venous anastomoses in the liver, could contribute to the clinician's decisions when planning surgical procedures.

Direct observation of the transition from calcite to aragonite growth as induced by abalone shell proteins.

PubMed Central

Thompson, J B; Paloczi, G T; Kindt, J H; Michenfelder, M; Smith, B L; Stucky, G; Morse, D E; Hansma, P K

2000-01-01

The mixture of EDTA-soluble proteins found in abalone nacre are known to cause the nucleation and growth of aragonite on calcite seed crystals in supersaturated solutions of calcium carbonate. Past atomic force microscope studies of the interaction of these proteins with calcite crystals did not observe this transition because no information about the crystal polymorph on the surface was obtained. Here we have used the atomic force microscope to directly observe changes in the atomic lattice on a calcite seed crystal after the introduction of abalone shell proteins. The observed changes are consistent with a transition to (001) aragonite growth on a (1014) calcite surface. PMID:11106633

Scaly fabrics and veins of tectonic mélanges in the Shimanto Belt, SW Japan

NASA Astrophysics Data System (ADS)

Ramirez, G. E.; Fisher, D. M.; Smye, A.; Hashimoto, Y.; Yamaguchi, A.

2017-12-01

Mélanges in ancient subduction fault zones provide a microstructural record of the plate boundary deformation associated with underthrusting. These rocks exhibit many of the characteristics associated with exposed ancient subduction fault zones worldwide, including: 1) σ1 is near orthogonal to the deformation fabric, 2) microstructurally pervasive quartz and calcite filled veins concentrated in coarser blocks and along extensional jogs on slip surfaces, 3) evidence for local diffusion of silica sourced from web-like arrays of slip surfaces (i.e., scaly fabrics), and 4) repeated cracking and sealing that record cyclic variations in stress. We present XRD, XRF, and EPMA observations of scaly fabrics from five ancient subduction-related shear zones (Yokonami, Mugi, Kure, Okitsu, and Makimine mélanges) from the Shimanto Belt in Japan that exemplify these characteristics and represent the full temperature range of the seismogenic zone ( 150-340 °C). The scaly fabrics associated with these shear zones display significantly different microstructural and geochemical characteristics. Individual slip surfaces in the scaly fabrics of Mugi mélange, underplated at the updip limit of the seismogenic zone, are characterized by broader (50-300 µm) anastomosing shear zones while the Makimine mélange, underplated at the downdip limit of the seismogenic zone, exhibits thinner (10-20 µm) anastomosing shear zones. XRD analyses also imply geochemical differences such as a decrease in albite concentration and an increase in illite concentration with increasing temperature/depth of underthrusting. Scaly fabrics are sites of silica redistribution in which silica is depleted on the slip surfaces and precipitated as mostly quartz in crack-seal veins. The time to seal, or heal, fractures is mainly temperature-dependent but can also be significantly quickened by fluid salinity, degree of fluid-rock interactions, and geochemical reactions (i.e. incongruent pressure solution). Microstructural and geochemical characteristics that show differences with temperature/depth of underthrusting highlight the importance of establishing the geochemical processes and activation energies that contribute to slip, fracturing, and healing of rocks that underthrust the subduction interface.

Scaly fabrics and veins of the Mugi and Makimine mélanges in the Shimanto belt, SW Japan

NASA Astrophysics Data System (ADS)

Ramirez, G. E.; Fisher, D. M.; Yamaguchi, A.; Kimura, G.

2016-12-01

Two regionally extensive ancient subduction fault zones provide a microstructural record of the plate boundary deformation associated with underthrusting. These rocks exhibit many of the characteristics associated with exposed ancient subduction fault zones worldwide, including: (1) σ1 is near orthogonal to the deformation fabric (2) there are microstructurally pervasive quartz and calcite filled veins concentrated in coarser blocks and along extensional jogs on slip surfaces, (3) evidence for local diffusion of silica sourced from web-like arrays of slip surfaces (i.e., scaly fabrics), and (4) evidence for cycles of cracking and sealing that record cyclic variations in stress. We present new backscatter SEM observations of scaly fabrics from two ancient subduction-related shear zones from the Shimanto Belt in Japan that exemplify these characteristics and represent the full temperature range of the seismogenic zone: 1) the Mugi mélange (lower ( 130-150 °C) and upper ( 170-200 °C) sections) and 2) Makimine mélange (peak temperatures of 340 °C). The Mugi mélange is an underplated duplex consisting of two horses separated by an OOST. The upper section is bounded at the top by a pseudotachylite-bearing paleodécollement. The Makimine mélange was underplated at the downdip limit of the seismogenic zone. The scaly fabrics associated with these shear zones display significantly different microstructural characteristics. A slip surface from along the upper Mugi is characterized by broader ( 20-30 μm), zones of quartz-poor, anastomosing shear zones composed of fine-grained (0.5-2 μm in length) phyllosilicates. The Makimine mélange exhibits thinner (10-20 μm), anastomosing shear zones with coarser (1-4 μm in length) phyllosilicate grains that are more strongly oriented into parallelism with slip surfaces. Quartz veins are pervasively developed in more competent blocks and are oriented at near perpendicular angles to the slip surfaces. Microstructural analyses of ancient subduction-related faults show differences with temperature that highlight the importance of establishing the geochemical processes and activation energies that contribute to slip, fracturing, and healing of rocks that underthrust the subduction interface.

Production Engineering for Growth of Synthetic Calcite Polarizer Material

DTIC Science & Technology

1974-08-01

AD-A008 043 PRODUCTION ENGINEERING FOR GROWTH OF SYNTHETIC CALCITE POLARIZER MATERIAL Roger F. Belt, et al Litton Systems...Production Bngin««ring for Growth of Synthetic Calcit « Polarizer Material I. RCCIPItNT’tCATALOO NUMMN i. T.vpc or ncpoMT • rtmoo covtnto Final Report...VOKOt (CanlliMit en »xift •id« II ntffrt Kid Idtnlllr br block iwmbmr) Crystal Growth Hydrothermal Growth Calcite Polarizers 30. AtSTHACT

Arsenic uptake in bacterial calcite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Catelani, Tiziano; Perito, Brunella; Bellucci, Francesco

Bio-mediated processes for arsenic (As) uptake in calcite were investigated by means of X-ray Diffraction (XRD) and Xray Absorption Spectroscopy (XAS) coupled with X-ray Fluorescence measurements. The environmental bacterial strain Bacillus licheniformis BD5, sampled at the Bullicame Hot Springs (Viterbo, Central Italy), was used to synthesize calcite from As-enriched growth media. Both liquid and solid cultures were applied to simulate planktonic and biofilm community environments, respectively. Bacterial calcite samples cultured in liquid media had an As enrichment factor (Kd) 50 times higher than that from solid media. The XRD analysis revealed an elongation of the crystal lattice along the cmore » axis (by 0.03Å) for biogenic calcite, which likely resulted from the substitution of larger arsenate for carbonate in the crystal. The XAS data also showed a clear difference in the oxidation state of sorbed As between bacterial and abiotic calcite. Abiotic chemical processes yielded predominantly As(V) uptake whereas bacterial precipitation processes led to the uptake of both As(III) and As(V). The presence of As(III) in bacterial calcite is proposed to result from subsequent reduction of arsenate to arsenite by bacterial activities. To the best of our knowledge, this is the first experimental observation of the incorporation of As(III) in the calcite crystal lattice, revealing a critical role of biochemical processes for the As cycling in nature.« less

Fabrication of porous calcite using chopped nylon fiber and its evaluation using rats.

PubMed

Ishikawa, Kunio; Tram, Nguyen Xuan Thanh; Tsuru, Kanji; Toita, Riki

2015-02-01

Although porous calcite has attracted attention as bone substitutes, limited studies have been made so far. In the present study, porous calcite block was fabricated by introducing chopped nylon fiber as porogen. Ca(OH)2 powder containing 10 wt% chopped nylon fiber was compacted at 150 MPa, and sintered to burn out the fiber and to carbonate the Ca(OH)2 under stream of 1:2 O2-CO2. Sintering of Ca(OH)2 at 750 °C or lower temperature resulted in incomplete burning out of the fiber whereas sintering at 800 °C or higher temperature resulted in the formation of CaO due to the thermal decomposition of Ca(OH)2. However, sintering at 770 °C resulted in complete burning out of the fiber and complete carbonation of Ca(OH)2 to calcite without forming CaO. Macro- and micro-porosities of the porous calcite were approximately 23 and 16%, respectively. Diameter of the macropores was approximately 100 μm which is suitable for bone tissue penetration. Porous calcite block fabricated by this method exhibited good tissue response when implanted in the bone defect in femur of 12-weeks-old rat. Four weeks after implantation, bone bonded on the surface of calcite. Furthermore, bone tissue penetrated interior to the macropore at 8 weeks. These results demonstrated the good potential value of porous calcite as artificial bone substitutes.

Arsenic uptake in bacterial calcite

NASA Astrophysics Data System (ADS)

Catelani, Tiziano; Perito, Brunella; Bellucci, Francesco; Lee, Sang Soo; Fenter, Paul; Newville, Matthew; Rimondi, Valentina; Pratesi, Giovanni; Costagliola, Pilario

2018-02-01

Bio-mediated processes for arsenic (As) uptake in calcite were investigated by means of X-ray Diffraction (XRD) and X-ray Absorption Spectroscopy (XAS) coupled with X-ray Fluorescence measurements. The environmental bacterial strain Bacillus licheniformis BD5, sampled at the Bullicame Hot Springs (Viterbo, Central Italy), was used to synthesize calcite from As-enriched growth media. Both liquid and solid cultures were applied to simulate planktonic and biofilm community environments, respectively. Bacterial calcite samples cultured in liquid media had an As enrichment factor (Kd) 50 times higher than that from solid media. The XRD analysis revealed an elongation of the crystal lattice along the c axis (by 0.03 Å) for biogenic calcite, which likely resulted from the substitution of larger arsenate for carbonate in the crystal. The XAS data also showed a clear difference in the oxidation state of sorbed As between bacterial and abiotic calcite. Abiotic chemical processes yielded predominantly As(V) uptake whereas bacterial precipitation processes led to the uptake of both As(III) and As(V). The presence of As(III) in bacterial calcite is proposed to result from subsequent reduction of arsenate to arsenite by bacterial activities. To the best of our knowledge, this is the first experimental observation of the incorporation of As(III) in the calcite crystal lattice, revealing a critical role of biochemical processes for the As cycling in nature.

Resetting of Mg isotopes between calcite and dolomite during burial metamorphism: Outlook of Mg isotopes as geothermometer and seawater proxy

NASA Astrophysics Data System (ADS)

Hu, Zhongya; Hu, Wenxuan; Wang, Xiaomin; Lu, Yizhou; Wang, Lichao; Liao, Zhiwei; Li, Weiqiang

2017-07-01

Magnesium isotopes are an emerging tool to study the geological processes recorded in carbonates. Calcite, due to its ubiquitous occurrence and the large Mg isotope fractionation associated with the mineral, has attracted great interests in applications of Mg isotope geochemistry. However, the fidelity of Mg isotopes in geological records of carbonate minerals (e.g., calcite and dolomite) against burial metamorphism remains poorly constrained. Here we report our investigation on the Mg isotope systematics of a dolomitized Middle Triassic Geshan carbonate section in eastern China. Magnesium isotope analysis was complemented by analyses of Sr-C-O isotopic compositions, major and trace element concentrations, and petrographic and mineralogical features. Multiple lines of evidence consistently indicated that post-depositional diagenesis of carbonate minerals occurred to the carbonate rocks. Magnesium isotope compositions of the carbonate rocks closely follow a mixing trend between a high δ26Mg dolomite end member and a low δ26Mg calcite end member, irrespective of sample positions in the section and calcite/dolomite ratio in the samples. By fitting the measured Mg isotope data using a two-end member mixing model, an inter-mineral Δ26Mgdolomite-calcite fractionation of 0.72‰ was obtained. Based on the experimentally derived Mg isotope fractionation factors for dolomite and calcite, a temperature of 150-190 °C was calculated to correspond to the 0.72‰ Δ26Mgdolomite-calcite fractionation. Such temperature range matches with the burial-thermal history of the local strata, making a successful case of Mg isotope geothermometry. Our results indicate that both calcite and dolomite had been re-equilibrated during burial metamorphism, and based on isotope mass balance of Mg, the system was buffered by dolomite in the section. Therefore, burial metamorphism may reset Mg isotope signature of calcite, and Mg isotope compositions in calcite should be dealt with caution in studies of carbonate rocks with thermal history. By contrast, Mg isotopes of dolomite are less prone to post-depositional resetting due to a number of properties including high Mg abundance and high thermodynamic stability, and Mg isotopes in dolomite may be a more robust recorder for original carbonate precipitates.

Effect of organic ligands on Mg partitioning and Mg isotope fractionation during low-temperature precipitation of calcite

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; Immenhauser, Adrian; Buhl, Dieter; Purgstaller, Bettina; Baldermann, Andre; Dietzel, Martin

2016-04-01

Calcite growth experiments have been performed at 25 oC and 1 bar pCO2 in the presence of aqueous Mg and six organic ligands in the concentration range from 10-5 to 10-3 M. These experiments were performed in order to quantify the effect of distinct organic ligands on the Mg partitioning and Mg stable isotope fractionation during its incorporation in calcite at similar growth rates normalized to total surface area. The organic ligands used in this study comprise of (i) acetate acid, (ii) citrate, (iii) glutamate, (iv) salicylate, (v) glycine and (vi) ethylenediaminetetraacetic acid (EDTA), containing carboxyl- and amino-groups. These fuctional groups are required for bacterial activity and growth as well as related to biotic and abiotic mineralization processes occurring in sedimentary and earliest diagenetic aquatic environments (e.g. soil, cave, lacustrine, marine). The results obtained in this study indicate that the presence of organic ligands promotes an increase in the partition coefficient of Mg in calcite (DMg = (Mg/Ca)calcite (Mg/Ca)fluid). This behaviour can be explained by the temporal formation of aqueous Mg-ligand complexes that are subsequently adsorbed on the calcite surfaces and thereby reducing the active growth sites of calcite. The increase of DMg values as a function of the supersaturation degree of calcite in the fluid phase can be described by the linear equation LogDMg =0.3694 (±0.0329)×SIcalcite - 1.9066 (±0.0147); R2=0.92 In contrast, the presence of organic ligands, with exception of citrate, does not significantly affect the Mg isotope fractionation factor between calcite and reactive fluid (Δ26Mgcalcite-fluid = -2.5 ±0.1). Citrate likely exhibits larger fractionation between the Mg-ligand complexes and free aqueous Mg2+, compared to the other organic ligands studied in this work, as evidenced by the smaller Δ26Mgcalcite-fluid values. These results indicate that in Earth's surface calcite precipitating environments that are characterized by low dissolved organic carbon levels, the presence of organic ligands is rather unlikely to significantly affect the Mg isotope composition of precipitated calcite.

The role of disseminated calcite in the chemical weathering of granitoid rocks

USGS Publications Warehouse

White, A.F.; Bullen, T.D.; Vivit, D.V.; Schulz, M.S.; Clow, D.W.

1999-01-01

Accessory calcite, present at concentrations between 300 and 3000 mg kg-1, occurs in fresh granitoid rocks sampled from the Merced watershed in Yosemite National Park, CA, USA; Loch Vale in Rocky Mountain National Park CO USA; the Panola watershed, GA USA; and the Rio Icacos, Puerto Rico. Calcite occurs as fillings in microfractures, as disseminated grains within the silicate matrix, and as replacement of calcic cores in plagioclase. Flow-through column experiments, using de-ionized water saturated with 0.05 atm. CO2, produced effluents from the fresh granitoid rocks that were dominated by Ca and bicarbonate and thermodynamically saturated with calcite. During reactions up to 1.7 yr, calcite dissolution progressively decreased and was superceded by steady state dissolution of silicates, principally biotite. Mass balance calculations indicate that most calcite had been removed during this time and accounted for 57-98% of the total Ca released from these rocks. Experimental effluents from surfically weathered granitoids from the same watersheds were consistently dominated by silicate dissolution. The lack of excess Ca and alkalinity indicated that calcite had been previously removed by natural weathering. The extent of Ca enrichment in watershed discharge fluxes corresponds to the amounts of calcite exposed in granitoid rocks. High Ca/Na ratios relative to plagioclase stoichiometries indicate excess Ca in the Yosemite, Loch Vale, and other alpine watersheds in the Sierra Nevada and Rocky Mountains of the western United States. This Ca enrichment correlates with strong preferential weathering of calcite relative to plagioclase in exfoliated granitoids in glaciated terrains. In contrast, Ca/Na flux ratios are comparable to or less than the Ca/Na ratios for plagioclase in the subtropical Panola and tropical Rio Icacos watersheds, in which deeply weathered regoliths exhibit concurrent losses of calcite and much larger masses of plagioclase during transport-limited weathering. These results indicate that the weathering of accessory calcite may strongly influence Ca and alkalinity fluxes from silicate rocks during and following periods of glaciation and tectonism but is much less important for older stable geomorphic surfaces.

Linking natural microstructures with numerical modeling of pinch-and-swell structures

NASA Astrophysics Data System (ADS)

Peters, Max; Berger, Alfons; Herwegh, Marco; Regenauer-Lieb, Klaus

2016-04-01

For a variety of geological problems, the change from homogeneous to localized deformation and the establishment of steady-state conditions are equally important. Here, we show that pinch-and-swell structures are ideal candidates for the study of the switch in deformation style and mechanism during ductile creep. We present an interdisciplinary approach to the onset of pinch-and-swell structures and to the flow conditions during pre- to post-localization stages in ductile rocks. For this reason, naturally boudinaged calcite veins, embedded in a calc-mylonite, and their microfabrics were investigated quantitatively. Remnants of slightly deformed calcite hosts build up the swells, showing twinning and minor dislocation glide as crystal plastic deformation mechanisms which are accompanied by subgrain rotation recrystallization (SGR). Towards the pinches, we find a gradient of severe grain size reduction through progressive SGR, developing a characteristic dislocation creep crystallographic preferred orientation (CPO). Along this gradient, the finest recrystallized calcite grains appear randomly oriented, expressed by a "smearing-out" of the CPO and missing systematics of misorientation angles in the most extended areas. We interpret this microstructure as a switch from dislocation dominated creep to grain boundary sliding processes. Further, we show that the onset of boudinage is independent on both the original orientation and grain size of calcite hosts. We implemented these microstructural observations into a layered elasto-visco-plastic finite element framework, tracing variations in grain size (Peters et al., 2015). We base the microstructural evolution on thermo-mechanical-chemical principles and end-member flow laws (Herwegh et al., 2014). The simulated pinch-and-swell structures indicate that low strain rates in the swells favor dislocation creep, whereas accelerated rates provoke continuous grain size reduction allowing strain accommodation by diffusion creep dominated deformation at relatively high extensional strains in the pinches. The numerical simulations indicate that viscosity weakening due to dissipated heat from grain size reduction marks the onset of localization, resulting in continuous necking of the layer. Interestingly, there exist multiple steady states, i.e. a first homogeneous state out of which localization arises, steady states of the stable end-member structure, expressed by homogeneous conditions in both pinches and swells, and in the surrounding matrix, the latter obeying a linear rheology. Based on our microstructural and numerical results, we suggest that the onset of localization represents a fundamental material bifurcation. This implies that the studied structures can be described as ductile instabilities. Finally, we discuss the profound role of the energy theory of localization described here, which allows deriving the paleo-deformation conditions, as well as fundamental material properties in a self-consistent manner. REFERENCES Herwegh, M., Poulet, T., Karrech, A. and Regenauer-Lieb, K. (2014): Journal of Geophysical Research 119, doi:10.1002/2013JB010701 Peters, M., Veveakis, M., Poulet, T., Karrech, A., Herwegh, M. and Regenauer-Lieb, K. (2015): Journal of Structural Geology 78, doi:10.1016/j.jsg.2015.06.005

Stable isotope studies of metasomatic Ca-Fe-Al-Si skarns and associated metamorphic and igneous rocks, Osgood Mountains, Nevada

USGS Publications Warehouse

Taylor, B.E.; O'Neil, J.R.

1977-01-01

Garnet-pyroxene skarns were formed 90 m.y. B.P. in the Osgood Mountains at or near contacts of grandiorite with calcareous rocks of the Cambrian Preble Formation. The metasomatic replacement followed contact metamorphic recrystallization of the Preble. The sources, temperature, and variation in H2O/CO2 ratios of the metasomatic fluid are interpreted from 269 analyses of oxygen, carbon, hydrogen, and sulfur isotopes in whole rocks, minerals and inclusion fluids. Skarns formed in three mineralogical stages. Oxygen isotope data indicate that temperatures during the crystallization of garnet, pyroxene and wollastonite (Stage I) were least 550 ?? C, and that the metasomatic fluid had an {Mathematical expression} ??? 0.035 in the massive skarns, and ??? 0.12 in vein skarns up to 3 cm thick. Pore fluids in isotopic equilibrium with garnet in calc-silicate metamorphic rocks, on the other hand, had {Mathematical expression} ??? 0.15. The metasomatic fluids of Stage I were derived primarily from the crystallizing magma. The isotopic composition of magmatic water was ??18O =+9.0, ??D= -30 to -45. Oxygen isotope temperatures of greater than 620 ?? C were determined for the granodiorite. Isotopic and chemical equilibria between mineral surfaces and the metasomatic fluid were approached simultaneously in parts of the skarn several meters or more apart, while isotopic and chemical disequilibria (i.e. zoning) have been preserved between 20 to 40 ??m-thick zones in grandite garnet. More Fe-, or andradite-rich garnet crystallized in more H2O-rich C-O-H fluids ( {Mathematical expression} ??? 0.01) than present with grossularite-rich garnet ( {Mathematical expression}??? 0.035). Stage II was marked by the replacement of garnet and pyroxene by quartz, amphibole, plagioclase, epidote, magnetite, and calcite. Many of the replacement reactions took place over a relatively narrow range in temperature (480-550 ?? C), as indicated by 18O fractionations between quartz and amphibole. Meteoric water comprised 20 to 50% of the metasomatic fluid during Stage II. Calcite was formed along with pyrite, minor pyrrhotite, and chalcopyrite during Stage III, although the crystallization of pyrite and calcite had begun earlier, during Stages I and II, respectively. Carbon and sulfur isotope compositions of calcite and pyrite indicate a magmatic source for most of the C and S in the metasomatic fluids of Stage III. By the end of Stage III, meteoric water constituted as much as 100% of the metasomatic fluid. Minerals from grandiorite and skarn do not show large depletions in 18O because the oxygen isotope composition of the metasomatic fluid was buffered by the calcareous wall rocks and the grandiorite. Meteoric water in the vicinity of the Osgood Mountains during the Late Crectaceous (??18Ocale. ??? -14.0, ??D = - 107) was slightly enriched in 18O and D relative to present-day meteoric water (??18O = 15.9, ??D = - 117) ?? 1977 Springer-Verlag.

The Incidence of Deep Vein Thrombosis in Asian Patients With Chronic Obstructive Pulmonary Disease.

PubMed

Chen, Chung-Yu; Liao, Kuang-Ming

2015-11-01

Most studies have focused on the prevalence of deep vein thrombosis (DVT) and pulmonary embolism in patients with chronic obstructive pulmonary disease (COPD) and acute exacerbation in Caucasian populations. DVT is supposedly less likely to occur among Asians than Caucasians, and the primary purpose of this study was to determine the actual incidence of DVT in patients with COPD in Asian populations.We enrolled patients over the age of 40 with a diagnosis of COPD (International Classification of Diseases, Ninth Revision [ICD-9]: 490-492, 496; A-code: A323 and A325) between 1998 and 2008. The index date was the date of first-time COPD diagnosis. We excluded the patients who had been diagnosed with COPD and DVT (The International Classification of Diseases, Ninth Revision, Clinical Modification [ICD-9-CM]: 453.8) before index date. The control group was frequency-matched according to age (3-year stratum), sex, and the year of admission, at a 2:1 ratio. Patients were followed from index date to when either a diagnosis of DVT was made, death occurred, December 31, 2009 was reached, or when the patients withdrew from the National Health Insurance program.The overall incidence rate of DVT was 18.78 per 10,000 person-years in patients with COPD, and the adjusted hazard ration of DVT in patients with COPD was 1.38 (95% confidence interval 1.06-1.80), which was greater than patients without COPD after adjusting for age, sex, atrial fibrillation, hypertension, diabetes, hyperlipidemia, cerebrovascular accident, congestive heart failure, lower leg fracture or surgery, and cancer.Asian patients with COPD had a higher incidence of DVT than non-COPD patients.

Unusual calcite cementing of quartz grains on Chandeleur Island Beach, offshore Louisiana

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mitchell-Tapping, H.J.

1983-09-01

A very unusual calcite cement was found in some beachchips from an unconsolidated beach surface of Chandeleur Island offshore approximately 35 nmi (65 km) south of Mississippi in the Gulf of Mexico. The beachchips are irregularly shaped and are well cemented by this unusual calcite. This calcite crystal structure has not been reported previously as existing in a marine environment. A similar cement has been found in freshwater lake beachrock and in some travertine samples. The calcite crystals are elongate parallel to the c-optic axis, and are composed of bunches of crystallite blades. The crystallite blades of each crystal bunchmore » are pointed and are more bladed than freshwater cement crystals. The intercrystallite pore space contains no fine calcite silt as was observed in the lake samples. Fresh water provided by rainfall may be held in the pore spaces and bounded to the quartz-grain surfaces by ionic attraction. Marine spray above and saline water concentrated underneath from a sandwich effect at the micropore level, allowing rapid growth and precipitation of these very unusual calcite crystals in a single-phase low-salinity fluid.« less

Petrography of Mayan mortar, Isla Mujeres, Quintana Roo, Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bain, R.J.

1985-01-01

Along coastal regions of the Yucatan Peninsula Mayan builders used a mixture of beach sand, shell fragments, and clasts of rock as mortar for construction. With exposure to subaerial conditions, the aragonitic sand was converted into a semi-lithified mortar. Petrographic analysis of mortar samples collected from Mayan ruins on the south end of Isla Mujeres indicates that the mortar is cemented by blocky, meniscus style, low Mg calcite. In addition to the cement, low Mg calcite also occurs as blocky equant crystals either replacing grains or filling grain-moldic porosity. X-ray analysis of both modern beach sand and mortar shows themore » sand is composed of aragonite and high Mg calcite but lacks low Mg calcite. Mortar, on the other hand, consists of low Mg calcite, high Mg calcite, and aragonite however aragonite is much less abundant than in the sand. Aragonitic ooids, pellets and bioclasts of beach sand used in mortar were dissolved producing moldic porosity. At the same time, CaCO/sub 3/ derived from this process was precipitated as low Mg calcite which formed meniscus cement and filled moldic porosity within the walls of Mayan structures producing a remarkably hard mortar.« less

An Investigation of Possible Ways to Enhance the Deposition of Calcite-Type Coatings

DTIC Science & Technology

1984-01-01

AN INVESTIGATION OF POSSIBLE WAYS TO ENHANCE THE DEPOSITION OF CALCITE -TYPE COATINGS JANUARY 1984 Prepared by: OCEAN CITY RESEARCH CORP. in...Enhance The Deposition of Calcite -Type Coatings 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER 5e...City, New Jersey under the direction of Mr. The research study continued of applying calcite -type coatings George A. Gehring, Jr. an to investigation

Functionalization of biomineral reinforcement in crustacean cuticle: Calcite orientation in the partes incisivae of the mandibles of Porcellio scaber and the supralittoral species Tylos europaeus (Oniscidea, Isopoda).

PubMed

Huber, Julia; Griesshaber, Erika; Nindiyasari, Fitriana; Schmahl, Wolfgang W; Ziegler, Andreas

2015-05-01

In arthropods the cuticle forms an exoskeleton with its physical and chemical properties adapted to functions of distinct skeletal elements. The cuticle of the partes incisivae (PI) in mandibles of terrestrial isopods is a composite of chitin-protein fibrils/fibres and minerals. It consists of an unmineralized tip, a middle region with organic fibrils reinforced mainly with amorphous calcium phosphate and a base region mineralized with amorphous calcium carbonate and calcite. In this study we extend our work on the structure and material properties of the incisive cuticle employing electron backscatter diffraction (EBSD), and investigate calcite orientation patterns in the PI of two terrestrial isopod species from different habitats. We trace small-scale differences in texture sharpness and calcite microstructure, and compare calcite organization and orientation patterns in the PI with those in the tergites of the same isopod species. We observe that in the PI calcite orientation, the degree of crystal alignment, and mode of crystalline domain assemblage is highly varied within short length scales. This contrasts to calcite organization in the tergite cuticle, where calcite has only one specific texture pattern. Such a large range in the variation of calcite organization has not been observed in other carbonate biological hard tissues, such as shells and teeth, where one specific texture and microstructure prevails. Thus, the investigated isopod species are able to control crystallization of the amorphous carbonate precursor in a differential way, most probably related to the function of the individual skeletal element and the animals' behavior. Copyright © 2015 Elsevier Inc. All rights reserved.

Review of calcium carbonate polymorph precipitation in spring systems

NASA Astrophysics Data System (ADS)

Jones, Brian

2017-05-01

Many spring deposits throughout the world are characterized by spectacular deposits of calcium carbonate that are formed of various combinations of aragonite and calcite, and in very rare cases vaterite. The factors that control the precipitation of the aragonite and calcite have been the subject of considerable debate that has been based on natural precipitates and information gained from numerous laboratory experiments. Synthesis of this information indicates that there is probably no single universal factor that controls calcite and aragonite precipitation in all springs. Instead, the reason for aragonite as opposed to calcite precipitation should be ascertained by considering the following ordered series of possibilities for each system. First, aragonite, commonly with calcite as a co-precipitate, will form from spring water that has a high CO2 content and rapid CO2 degassing, irrespective of the Mg:Ca ratio and scale of precipitation. Second, aragonite can be precipitated from waters that have low levels of CO2 degassing provided that the Mg:Ca ratio is high enough to inhibit calcite precipitation. Third, the presence of biofilms may lead to the simultaneous precipitation of aragonite and calcite (irrespective of CO2 degassing or Mg:Ca ratio) either within the different microdomains that develop in the biofilm or because of diurnal changes in various geochemical parameters associated with the biofilm. Although the precipitation of calcite and aragonite has commonly been linked directly to water temperature, there is no clear evidence for this proposition. It is possible, however, that temperature may be influencing another parameter that plays a more direct role in the precipitation of these CaCO3 polymorphs. Despite the advances that have been made, the factors that ultimately control calcite and aragonite are still open to debate because this long-standing problem has still not been fully resolved.

Identifying the optical phenomena responsible for the blue appearance of veins

NASA Astrophysics Data System (ADS)

Van Leeuwen, Spencer R.; Baranoski, Gladimir V. G.

2017-09-01

Blue in nature is often associated with beauty. It can be observed all around us, from captivating blue eyes to iridescent blue butterfly wings. While colours in nature are often the result of pigmentation, the majority of natural blue is produced by structural coloration. The colour of the sky, for example, is primarily caused by Rayleigh scattering. In this paper, we examine a single occurrence of blue in nature, specifically the blue appearance of veins near the surface of human skin. The most comprehensive investigation of this coloration to date showed that it arises from a combination of the scattering properties of skin and the absorptance of venous blood. However, that work only considered broad optical properties of these mediums and did not identify the source of the colour. In this paper, we employ in silico experiments, performed using first-principles light interaction models for skin and blood, to investigate the net effect of skin and vein optical properties on their aggregate reflectance across the visible range. We show that the contribution of skin to the distinct appearance of veins primarily results from Rayleigh scattering occurring within the papillary dermis, a sublayer of the skin. The results of this paper, in addition to addressing an old open scientific question, may have practical implications for performing non-invasive measurements of the physiological properties of skin and blood.

Mapping alteration using imagery from the Tiangong-1 hyperspectral spaceborne system: Example for the Jintanzi gold province, China

NASA Astrophysics Data System (ADS)

Liu, Lei; Feng, Jilu; Rivard, Benoit; Xu, Xinliang; Zhou, Jun; Han, Ling; Yang, Junlu; Ren, Guangli

2018-02-01

The Tiangong-1 Hyperspectral Imager (HSI) is a relatively new spaceborne hyperspectral remote sensing system that was launched by the Chinese government on September 29th 2011. The system has 64 shortwave infrared (SWIR) spectral bands (1000-2500 nm) and imagery is at a spatial resolution of 20 m. This study represents an evaluation of Tiangong-1 data for the production of alteration mineral maps. Alteration mineral maps resulting from the analysis of Tiangong-1 HSI data and airborne SASI (Shortwave infrared Airborne Spectrographic Imager) data are compared for the Jintanzi area, Beishan, Gansu province, northwest China where gold bearing veins are documented. The results illustrate the detection of muscovite, kaolinite, chlorite, epidote, calcite and dolomite from Tiangong-1 HSI data and most anomalies seen in the airborne SASI data are captured. The Tiangong-1 data appears to be well suited for the detection of surface mineralogy in support of regional mapping and exploration. The data complements that which will be offered by the Chinese GF-5 Hyperspectral Imager and the German EnMAP system, both scheduled for launch in 2018.

Carbonaceous structures in the Tissint Martian Meteorite: evidence of a biogenetic origin

NASA Astrophysics Data System (ADS)

Wallis, Jamie; Wickramasinghe, N. C.; Wallis, Daryl H.; Miyake, Nori; Wallis, M. K.; Hoover, Richard B.

2015-09-01

We report for the first time in situ observations of 5-50μm spherical carbonaceous structures in the Tissint Martian meteorite comprising of pyrite (FeS2) cores and carbonaceous outer coatings. The structures are characterized as smooth immiscible spheres with curved boundaries occasionally following the contours of the pyrite inclusion. The structures bear striking resemblance to similar-sized immiscible carbonaceous spheres found in hydrothermal calcite vein deposits in the Mullaghwornia Quarry in central Ireland. Similar structures have been reported in Proterozoic and Ordovician sandstones from Canada as well as in a variety of astronomical sources including carbonaceous chondrites, chondritic IDPs and primitive chondritic meteorites. SEM and X-Ray elemental mapping confirmed the presence of organic carbon filling the crack and cleavage space in the pyroxene substrate, with further evidence of pyrite acting as an attractive substrate for the collection of organic matter. The detection of precipitated carbon collecting around pyrite grains is at variance with an igneous origin as proposed for the reduced organic component in Tissint, and is more consistent with a biogenetic origin.

Introduction to the hydrogeochemical investigations within the International Stripa Project

USGS Publications Warehouse

Nordstrom, D. Kirk; Olsson, T.; Carlsson, L.; Fritz, P.

1989-01-01

The International Stripa Project (1980-1990) has sponsored hydrogeochemical investigations at several subsurface drillholes in the granitic portion of an abandoned iron ore mine, central Sweden. The purpose has been to advance our understanding of geochemical processes in crystalline bedrock that may affect the safety assessment of high-level radioactive waste repositories. More than a dozen investigators have collected close to a thousand water and gas samples for chemical and isotopic analyses to develop concepts for the behavior of solutes in a granitic repository environment. The Stripa granite is highly radioactive and has provided an exceptional opportunity to study the behavior of natural radionuclides, especially subsurface production. Extensive microfracturing, low permeability with isolated fracture zones of high permeability, unusual water chemistry, and a typical granitic mineral assemblage with thin veins and fracture coatings of calcite, chlorite, seriate, epidote and quartz characterize the site. Preliminary groundwater flow modeling indicates that the mine has perturbed the flow environment to a depth of about 3 km and may have induced deep groundwaters to flow into the mine. ?? 1989.

Teneur en uranium et datation U-Th des tissus osseux et dentaires fossiles de la grotte du Lazaret

NASA Astrophysics Data System (ADS)

Michel, Véronique; Falguères, Christophe; Yokoyama, Yuji

1997-09-01

Fossil bone and dental tissues from Lazaret cave and modern ones are here the subject of a comparative microscopical study. Porous tissues such as dentine and bone have retained their Haversian and Tomes canals respectively. However, cracked areas with calcite were detected, indicating a water percolation within porous tissues and an alteration of tissue in places. In addition, compact fossil enamel is particularly well preserved. These results are essential for U-Th and ESR dating application. Uranium contents, U-Th ages of two fossil mandibular tissues, two tibias and of six burnt fossil bones are presented and discussed.

The quantitative determination of calcite associated with the carbonate-bearing apatites

USGS Publications Warehouse

Silverman, Sol R.; Fuyat, Ruth K.; Weiser, Jeanne D.

1951-01-01

The CO2 combined as calcite in carbonate-bearing apatites as been distinguished from that combined as carbonate-apatite, or present in some form other than calcite, by use of X-ray powder patterns, differential thermal analyses, and differential solubility tests. These methods were applied to several pure apatite minerals, to one fossil bone, and to a group of phosphorites from the Phosphoria formation of Permian age from Trail Canyon and the Conda mine, Idaho, and the Laketown district, Utah. With the exceptions of pure fluorapatite, pure carbonate-flueorapatite, and one phosphorite from Trail Canyon, these substances contain varying amounts of calcite, but in all the samples an appreciable part of the carbonite content is not present as calcite. The results of solubility tests, in which the particle size of sample and the length of solution time were varied, imply that the carbonate content is not due to shielded calcite entrapped along an internal network of surfaces.

Low grade metamorphism fluid circulation in a sedimentary environment thrust fault zone: properties and modeling

NASA Astrophysics Data System (ADS)

Trincal, Vincent; Lacroix, Brice; Buatier, Martine D.; Charpentier, Delphine; Labaume, Pierre; Lahfid, Abdeltif

2014-05-01

In fold-and-thrust belts, shortening is mainly accommodated by thrust faults that can constitute preferential pathways for fluid circulation. The present study focuses on the Pic de Port Vieux thrust, a second-order thrust related to major Gavarnie thrust in the Axial Zone of the Pyrenees. The fault juxtaposes lower Triassic red siltstones and sandstones in the hanging-wall and Upper Cretaceous limestone in the footwall. A dense network of synkinematic quartz-chlorite veins is present in outcrop and allows to unravel the nature of the fluid that circulated in the fault zone. The hanging wall part of fault zone comprises a core which consists of intensely foliated phyllonite; the green color of this shear zone is related to the presence of abundant newly-formed chlorite. Above, the damage zone consists of red pelites and sandstones. Both domains feature kinematic markers like S-C type shear structures associated with shear and extension quartz-chlorite veins and indicate a top to the south displacement. In the footwall, the limestone display increasing mylonitization and marmorization when getting close to the contact. In order to investigate the mineralogical and geochemical changes induced by deformation and subsequent fluid flow, sampling was conducted along a complete transect of the fault zone, from the footwall limestone to the red pelites of the hanging wall. In the footwall limestone, stable isotope and Raman spectroscopy analyzes were performed. The strain gradient is strongly correlated with a high decrease in δ18OV PDB values (from -5.5 to -14) when approaching the thrust (i.e. passing from limestone to marble) while the deformation temperatures estimated with Raman spectroscopy on carbon remain constant around 300° C. These results suggest that deformation is associated to a dynamic calcite recrystallization of carbonate in a fluid-open system. In the hanging wall, SEM observations, bulk chemical XRF analyses and mineral quantification from XRD analyses were conducted in order to compare the green phyllonites from the fault core zone with the red pelites from the damage zone. Quartz, muscovite 2M1, chlorite (clinochlore), calcite and rutile are present in all samples. Hematite occurs in the damage zone but is absent in the core zone. Synkinematic chlorites are abundant in the core and damage zones and are mainly located in veins, sometimes in association with quartz. The temperature of formation of these newly-formed chlorites is 300-350° C according to Inoue (2009) geothermometer. Mössbauer spectroscopic analyses were performed on bulk rock samples. In the damage zone, Fe3+/Fetotal vary between 0.7 and 0.8, whereas in the core zone Fe3+/Fetotal is about 0.35. This decrease in Fe3+ from the damage zone to the core zone can be related to the dissolution of hematite. In contrast, Fe3+/Fetotal in phyllosilicates is clearly related to the chlorite content relative to mica, as Fe2+ increases with chlorite content. All these data allow us to propose a model of fluid circulation in relation with the Pic de Port Vieux thrust activity. The origin of the fluid, its interactions with host-rock and the consequences on fault zone mineralizations will be discussed. Inoue, A., Meunier, A., Patrier-Mas, P., Rigault, C., Beaufort, D., Vieillard, P., 2009. Application of chemical geothermometry to low-temperature trioctahedral chlorites. Clay Clay Min. 57, 371-382.

ENVIRONMENTALMANAGEMENT SCIENCE PROGRAM PROJECT NUMBER 87016 CO-PRECIPITATION OF TRACEMETALS INGROUNDWATER AND VADOSE ZONE CALCITE: IN SITU CONTAINMENT AND STABILIZATION OF STRONTIUM-90 ANDOTHER DIVALENT METALS AND RADIONUCLIDES AT ARIDWESTERN DOE SITES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferris, F. Grant; Fujita, Yoshiko; Smith, Robert W.

2004-06-15

Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) weapons complex. In situ containment and stabilization of these contaminants in vadose zones or groundwater is a cost-effective treatment strategy. Our facilitated approach relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal coprecipitation) by increasing groundwater pH and alkalinity (Fujita et al., 2000; Warren et al., 2001). Subsurface urea hydrolysis is catalyzed by the urease enzyme, which may be either introduced with the urea or produced in situ by ubiquitous subsurface ureamore » hydrolyzing microorganisms. Because the precipitation processes are irreversible and many western aquifers are saturated with respect to calcite, the co-precipitated metals and radionuclides will be effectively removed from groundwater. The rate at which trace metals are incorporated into calcite is a function of calcite precipitation kinetics, adsorption interactions between the calcite surface and the trace metal in solution (Zachara et al., 1991), solid solution properties of the trace metal in calcite (Tesoriero and Pankow, 1996), and also the surfaces upon which the calcite is precipitating. A fundamental understanding of the coupling of calcite precipitation and trace metal partitioning, and how this occurs in aquifers and vadose environments is lacking. This report summarizes work undertaken during the second year of this project.« less

The impact of Last Glacial climate variability in west-European loess revealed by radiocarbon dating of fossil earthworm granules.

PubMed

Moine, Olivier; Antoine, Pierre; Hatté, Christine; Landais, Amaëlle; Mathieu, Jérôme; Prud'homme, Charlotte; Rousseau, Denis-Didier

2017-06-13

The characterization of Last Glacial millennial-timescale warming phases, known as interstadials or Dansgaard-Oeschger events, requires precise chronologies for the study of paleoclimate records. On the European continent, such chronologies are only available for several Last Glacial pollen and rare speleothem archives principally located in the Mediterranean domain. Farther north, in continental lowlands, numerous high-resolution records of loess and paleosols sequences show a consistent environmental response to stadial-interstadial cycles. However, the limited precision and accuracy of luminescence dating methods commonly used in loess deposits preclude exact correlations of paleosol horizons with Greenland interstadials. To overcome this problem, a radiocarbon dating protocol has been developed to date earthworm calcite granules from the reference loess sequence of Nussloch (Germany). Its application yields a consistent radiocarbon chronology of all soil horizons formed between 47 and 20 ka and unambiguously shows the correlation of every Greenland interstadial identified in isotope records with specific soil horizons. Furthermore, eight additional minor soil horizons dated between 27.5 and 21 ka only correlate with minor decreases in Greenland dust records. This dating strategy reveals the high sensitivity of loess paleoenvironments to Northern Hemisphere climate changes. A connection between loess sedimentation rate, Fennoscandian ice sheet dynamics, and sea level changes is proposed. The chronological improvements enabled by the radiocarbon "earthworm clock" thus strongly enhance our understanding of loess records to a better perception of the impact of Last Glacial climate changes on European paleoenvironments.

The impact of Last Glacial climate variability in west-European loess revealed by radiocarbon dating of fossil earthworm granules

PubMed Central

Moine, Olivier; Antoine, Pierre; Hatté, Christine; Landais, Amaëlle; Mathieu, Jérôme; Prud’homme, Charlotte

2017-01-01

The characterization of Last Glacial millennial-timescale warming phases, known as interstadials or Dansgaard–Oeschger events, requires precise chronologies for the study of paleoclimate records. On the European continent, such chronologies are only available for several Last Glacial pollen and rare speleothem archives principally located in the Mediterranean domain. Farther north, in continental lowlands, numerous high-resolution records of loess and paleosols sequences show a consistent environmental response to stadial–interstadial cycles. However, the limited precision and accuracy of luminescence dating methods commonly used in loess deposits preclude exact correlations of paleosol horizons with Greenland interstadials. To overcome this problem, a radiocarbon dating protocol has been developed to date earthworm calcite granules from the reference loess sequence of Nussloch (Germany). Its application yields a consistent radiocarbon chronology of all soil horizons formed between 47 and 20 ka and unambiguously shows the correlation of every Greenland interstadial identified in isotope records with specific soil horizons. Furthermore, eight additional minor soil horizons dated between 27.5 and 21 ka only correlate with minor decreases in Greenland dust records. This dating strategy reveals the high sensitivity of loess paleoenvironments to Northern Hemisphere climate changes. A connection between loess sedimentation rate, Fennoscandian ice sheet dynamics, and sea level changes is proposed. The chronological improvements enabled by the radiocarbon “earthworm clock” thus strongly enhance our understanding of loess records to a better perception of the impact of Last Glacial climate changes on European paleoenvironments. PMID:28559353

Cap rock efficiency of geothermal systems in fold-and-thrust belts: Evidence from paleo-thermal and structural analyses in Rosario de La Frontera geothermal area (NW Argentina)

NASA Astrophysics Data System (ADS)

Maffucci, R.; Corrado, S.; Aldega, L.; Bigi, S.; Chiodi, A.; Di Paolo, L.; Giordano, G.; Invernizzi, C.

2016-12-01

Cap rock characterization of geothermal systems is often neglected despite fracturing may reduce its efficiency and favours fluid migration. We investigated the siliciclastic cap rock of Rosario de La Frontera geothermal system (NW Argentina) in order to assess its quality as a function of fracture patterns and related thermal alteration. Paleothermal investigations (XRD on fine-grained fraction of sediments, organic matter optical analysis and fluid inclusions on veins) and 1D thermal modelling allowed us to distinguish the thermal fingerprint associated to sedimentary burial from that related to fluid migration. The geothermal system is hosted in a Neogene N-S anticline dissected by high angle NNW- and ENE-striking faults. Its cap rock can be grouped into two quality categories: rocks acting as good insulators, deformed by NNW-SSE and E-W shear fractures, NNE-SSW gypsum- and N-S-striking calcite-filled veins that developed during the initial stage of anticline growth. Maximum paleo-temperatures (< 60 °C) were experienced during deposition to folding phases. rocks acting as bad insulators, deformed by NNW-SSE fault planes and NNW- and WNW-striking sets of fractures associated to late transpressive kinematics. Maximum paleo-temperatures higher than about 115 °C are linked to fluid migration from the reservoir to surface (with a reservoir top at maximum depths of 2.5 km) along fault damage zones. This multi-method approach turned out to be particularly useful to trace the main pathways of hot fluids and can be applied in blind geothermal systems where either subsurface data are scarce or surface thermal anomalies are lacking.

The Krásná Hora, Milešov, and Příčovy Sb-Au ore deposits, Bohemian Massif: mineralogy, fluid inclusions, and stable isotope constraints on the deposit formation

NASA Astrophysics Data System (ADS)

Němec, Matěj; Zachariáš, Jiří

2018-02-01

The Krásná Hora-Milešov and Příčovy districts (Czech Republic) are the unique examples of Sb-Au subtype orogenic gold deposits in the Bohemian Massif. They are represented by quartz-stibnite veins and massive stibnite lenses grading into low-grade, disseminated ores in altered host rocks. Gold postdates the stibnite and is often replaced by aurostibite. The ore zones are hosted by hydrothermally altered dikes of lamprophyres (Krásná Hora-Milešov) or are associated with local strike-slip faults (Příčovy). Formation of Sb-Au deposits probably occurred shortly after the main gold-bearing event (348-338 Ma; Au-only deposits) in the central part of the Bohemian Massif. Fluid inclusion analyses suggest that stibnite precipitated at 250 to 130 °C and gold at 200 to 130 °C from low-salinity aqueous fluids. The main quartz gangue hosting the ore precipitated from the same type of fluid at about 300 °C. Early quartz-arsenopyrite veins are not associated with the Sb-Au deposition and formed from low-salinity, aqueous-carbonic fluid at higher pressure and temperature ( 250 MPa, 400 °C). The estimated oxygen isotope composition of the ore-bearing fluid (4 ± 1‰ SMOW; based on post-ore calcite) suggests its metamorphic or mixed magmatic-metamorphic origin and excludes the involvement of meteoric water. Rapid cooling of warm hydrothermal fluids reacting with "cold" host rock was probably the most important factor in the formation of both stibnite and gold.

Genesis of Silica-Carbonate Type Mercury Ore Deposits in Coast Range California from Mantle Derived Fluids

NASA Astrophysics Data System (ADS)

Rytuba, J. J.; Kirby, S. H.; Kellner, C. R.

2016-12-01

In the Coast Range of California 51 major mercury (Hg) deposits and numerous smaller Hg occurrences began forming when subduction transitioned to the transpressive continental-transform kinematics of the San Andreas Fault System. The Hg deposits become progressively younger to the north reflecting the change in tectonic environment as the Mendocino Triple Junction moved 400 km northward since the Miocene to its present location in northern California. The silica-carbonate mercury deposits are vein and replacement ore bodies developed within and adjacent to serpentinite that was emplaced along regional faults and altered to an assemblage of silica and carbonate minerals. The initial alteration process consists of the addition of carbonate to the serpentinite followed by introduction of silica into the central core. The peripheral zone of calcite-dolomite veining may extend for several kilometers outward from a mercury deposit. The large Hg deposits formed in structural traps, such as antiformal structures, and the ores locally extend into adjacent clastic metasedimentary rocks. The mineralogy of the primary ores is simple consisting of cinnabar, metacinnabar and elemental Hg. The deposits formed from low-temperature, <120oC, CO2-CH4-H2S-rich fluids. The hydrothermal fluids are consistent with a mantle source water derived from the former forearc during subduction and after the transition to transpressive continental-transform boundary as proposed by Kirby et al. (EPS, 2014). Some of the silica-carbonate Hg deposits are overprinted by younger hot spring type Hg mineralization associated temporally with volcanic vents. These Hg deposits have distinctly different types of alteration and geochemistry and formed in the near surface from meteoric waters.

Textural and isotopic development of marble assemblages during the Barrovian-style M2 metamorphic event, Naxos, Greece

NASA Astrophysics Data System (ADS)

Baker, Judy; Matthews, Alan

1994-03-01

A detailed petrological analysis of the marble assemblages observed within the M2 metamorphic complex on Naxos is presented. Two distinct periods of mineral growth are documented; the first is associated with prograde M2 metamorphism and the second with retrograde M2 metamorphism occurring during ductile extensional thinning of the complex. The textural and miner-alogical characteristics and the carbon and oxygen isotope compositions of each generation are described, and the P-T-X CO 2 conditions at which these two mineral generations were stable, and the compositions of the fluids present during metamorphism are characterised. Whereas the low variance and stable isotope compositions of prograde siliceous dolomite assemblages are consistent with internally buffered fluid evolution, the retrograde mineral generation is shown to have grown as a result of the infiltration of a water-rich fluid phase that transported silica, Al2O3, Na2O and FeO into the host rocks. This observation, together with the stable isotope compositions of the retrograde calcite, and the fact that occurrences of veins of this type are limited to marbles in the highest grade areas ( T>600° C) of the metamorphic complex, suggests that the fluids responsible for vein formation were generated during the crystallisation of melts as the metamorphic complex cooled from peak temperatures. The existence of this second generation of minerals has significant implications for previous studies of heat transport by fluid flow on Naxos, because many of the unusually low δ18O compositions of pelites at high grades may be ascribable to the effects of interaction with retrograde M2 fluids, rather than with prograde fluids.

Distributed deformation structures in shallow water carbonates subsiding through a simple stress field (Jandaira Formation, NE Brazil)

NASA Astrophysics Data System (ADS)

Bertotti, Giovanni; Bisdom, Kevin; Bezerra, Hilario; Reijmer, John; Cazarin, Carol

2016-04-01

Despite the scarcity of major deformation structures such as folds and faults, the flat-lying, post-rift shallow water carbonates of the Jandaira Formation (Potiguar Basin, NE Brazil) display well-organized fracture systems distributed of tens of km2. Structures observed in the outcropping carbonates are sub-vertical, generally N-S trending mode I and hybrid veins and barren fractures, sub-vertical roughly E-W trending stylolites and sub-horizontal stylolites. These features developed during subsidence in a simple and constant stress field characterized by, beside gravity, a significant horizontal stress probably of tectonic origin. The corresponding depth curves have different origin and slopes and, therefore, cross each other resulting in position of the principal stresses which change with depth. As a result, the type and amount of fractures affecting subsiding rocks change despite the fact that the far-field stresses remain constant. Following early diagenesis and porosity elimination in the first 100-200m depth, Jandaira carbonates experienced wholesale fracturing at depths of 400-800m resulting in a network of NNW-NE trending fractures partly organized in conjugate sets with a low interfault angle and a sub-vertical intersection, and sub-vertical stylolites roughly perpendicular to the fractures. Intense fluid circulation was activated as a consequence through the carbonates. With increasing subsidence, sub-horizontal stylolites formed providing calcite which precipitated in the open fractures transforming them in veins. The Jandaira formation lost thereby the permeability it had reached during the previous stage. Because of the lack of major deformation, the outcrops of the Jandaira Formation is an excellent analog for carbonate reservoirs in the Middle East, South Atlantic and elsewhere.

Geology of the Alaska-Juneau lode system, Alaska

USGS Publications Warehouse

Twenhofel, William Stephens

1952-01-01

The Alaska-Juneau lode system for many years was one of the worlds leading gold-producing areas. Total production from the years 1893 to 1946 has amounted to about 94 million dollars, with principal values in contained gold but with some silver and lead values. The principal mine is the Alaska-Juneau mine, from which the lode system takes its name. The lode system is a part of a larger gold-bearing belt, generally referred to as the Juneau gold belt, along the western border of the Coast Range batholith. The rocks of the Alaska-Juneau lode system consist of a monoclinal sequence of steeply northeasterly dipping volcanic, state, and schist rocks, all of which have been metamorphosed by dynamic and thermal processes attendant with the intrusion of the Coast Range batholith. The rocks form a series of belts that trend northwest parallel to the Coast Range. In addition to the Coast Range batholith lying a mile to the east of the lode system, there are numerous smaller intrusives, all of which are sill-like in form and are thus conformable to the regional structure. The bedded rocks are Mesozoic in age; the Coast Range batholith is Upper Jurassic and Lower Cretaceous in age. Some of the smaller intrusives pre-date the batholith, others post-date it. All of the rocks are cut by steeply dipping faults. The Alaska-Juneau lode system is confined exclusively to the footwall portion of the Perseverance slate band. The slate band is composed of black slate and black phyllite with lesser amounts of thin-bedded quartzite. Intrusive into the slate band are many sill-like bodies of rocks generally referred to as meta-gabbro. The gold deposits of the lode system are found both within the slate rocks and the meta-gabbro rocks, and particularly in those places where meta-gabbro bodies interfinger with slate. Thus the ore bodies are found in and near the terminations of meta-gabbro bodies. The ore bodies are quartz stringer-lodes composed of a great number of quartz veins from 6 inches to 3 feet wide and extending along their strike and dip for several tens to hundreds of feet. In addition to quartz, the only other vein gangue mineral is ankerite. It occurs in small amounts along the borders of the quartz veins. Metallic vein minerals, in addition to native gold, are, in order of decreasing abundance, pyrrhotite, galena, sphalerite, and arsenopyrite. In the aggregate the metallic minerals comprise only 1 to 2 percent of the total amount of vein material. The wall rock, particularly the meta-gabbro, was profoundly altered by the vein-forming processes. The principal effects on the meta-gabbro were the addition of large amounts of soda, potash, titanium, carbon dioxide, and phosphorous, and the removal of considerable quantities of iron, magnesia, lime, and combined water. Silica also may have been decreased. The mineralogical changes involved in the alteration were the development of biotite and ankerite at the expense of original hornblende and feldspar, resulting in a brown-colored biotite- and ankerite-rich rock. The slates are relatively unaffected by the vein-forming processes. Because of their small size, relatively low grade, and discontinuity, no attempt has been made to mine any individual vein. The prevailing practice has been to mine large blocks of ground by a system of modified block-caving, followed by hand sorting to remove the barren country rock from the gold-bearing quartz prior to milling.

Mineralogical, stable isotope, and fluid inclusion studies of spatially related porphyry Cu and epithermal Au-Te mineralization, Fakos Peninsula, Limnos Island, Greece

NASA Astrophysics Data System (ADS)

Fornadel, Andrew P.; Voudouris, Panagiotis Ch.; Spry, Paul G.; Melfos, Vasilios

2012-05-01

The Fakos porphyry Cu and epithermal Au-Te deposit, Limnos Island, Greece, is hosted in a ~20 Ma quartz monzonite and shoshonitic subvolcanic rocks that intruded middle Eocene to lower Miocene sedimentary basement rocks. Metallic mineralization formed in three stages in quartz and quartz-calcite veins. Early porphyry-style (Stage 1) metallic minerals consist of pyrite, chalcopyrite, galena, bornite, sphalerite, molybdenite, and iron oxides, which are surrounded by halos of potassic and propylitic alteration. Stage 2 mineralization is composed mostly of quartz-tourmaline veins associated with sericitic alteration and disseminated pyrite and molybdenite, whereas Stage 3, epithermal-style mineralization is characterized by polymetallic veins containing pyrite, chalcopyrite, sphalerite, galena, enargite, bournonite, tetrahedrite-tennantite, hessite, petzite, altaite, an unknown cervelleite-like Ag-telluride, native Au, and Au-Ag alloy. Stage 3 veins are spatially associated with sericitic and argillic alteration. Fluid inclusions in quartz from Stage 1 (porphyry-style) mineralization contain five types of inclusions. Type I, liquid-vapor inclusions, which homogenize at temperatures ranging from 189.5°C to 403.3°C have salinities of 14.8 to 19.9 wt. % NaCl equiv. Type II, liquid-vapor-NaCl, Type III liquid-vapor-NaCl-XCl2 (where XCl is an unknown chloride phase, likely CaCl2), and Type IV, liquid-vapor-hematite ± NaCl homogenize to the liquid phase by liquid-vapor homogenization or by daughter crystal dissolution at temperatures of 209.3 to 740.5 °C, 267.6 to 780.8 °C, and 357.9 to 684.2 °C, respectively, and, Type V, vapor-rich inclusions. Stage 2 veins are devoid of interpretable fluid inclusions. Quartz from Stage 3 (epithermal-style) veins contains two types of fluid inclusions, Type I, liquid-vapor inclusions that homogenize to the liquid phase (191.6 to 310.0 °C) with salinities of 1.40 to 9.73 wt. % NaCl equiv., and Type II, vapor-rich inclusions. Mixing of magmatic fluids with meteoric water in the epithermal environment is responsible for the dilution of the ore fluids that formed Stage 3 veins. Eutectic melting temperatures of -35.4 to -24.3 °C for Type I inclusions hosted in both porphyry- and epithermal-style veins suggest the presence of CaCl2, MgCl2, and/or FeCl2 in the magmatic-hydrothermal fluids. Sulfur isotope values of pyrite, galena, sphalerite, and molybdenite range from δ34S = -6.82 to -0.82 per mil and overlap for porphyry and epithermal sulfides, which suggests a common sulfur source for the two styles of mineralization. The source of sulfur in the system was likely the Fakos quartz monzonite for which the isotopically light sulfur isotope values are the result of changes in oxidation state during sulfide deposition (i.e., boiling) and/or disproportionation of sulfur-rich magmatic volatiles upon cooling. It is less likely that sulfur in the sulfides was derived from the reduction of seawater sulfate or leaching of sulfides from sedimentary rocks given the absence of primary sulfides in sedimentary rocks in the vicinity of the deposit. Late-stage barite (δ34S = 10.5 per mil) is inferred to have formed during mixing of seawater with magmatic ore fluids. Petrological, mineralogical, fluid inclusion, and sulfur isotope data indicate that the metallic mineralization at Fakos Peninsula represents an early porphyry system that is transitional to a later high- to intermediate-sulfidation epithermal gold system. This style of mineralization is similar to porphyry-epithermal metallic mineralization found elsewhere in northeastern Greece (e.g., Pagoni Rachi, St. Demetrios, St. Barbara, Perama Hill, Mavrokoryfi, and Pefka).

Calcite crystal growth rate inhibition by polycarboxylic acids

USGS Publications Warehouse

Reddy, M.M.; Hoch, A.R.

2001-01-01

Calcite crystal growth rates measured in the presence of several polycarboxyclic acids show that tetrahydrofurantetracarboxylic acid (THFTCA) and cyclopentanetetracarboxylic acid (CPTCA) are effective growth rate inhibitors at low solution concentrations (0.01 to 1 mg/L). In contrast, linear polycarbocylic acids (citric acid and tricarballylic acid) had no inhibiting effect on calcite growth rates at concentrations up to 10 mg/L. Calcite crystal growth rate inhibition by cyclic polycarboxyclic acids appears to involve blockage of crystal growth sites on the mineral surface by several carboxylate groups. Growth morphology varied for growth in the absence and in the presence of both THFTCA and CPTCA. More effective growth rate reduction by CPTCA relative to THFTCA suggests that inhibitor carboxylate stereochemical orientation controls calcite surface interaction with carboxylate inhibitors. ?? 20O1 Academic Press.

Incorporation of Metals into Calcite in a Deep Anoxic Granite Aquifer.

PubMed

Drake, Henrik; Mathurin, Frédéric A; Zack, Thomas; Schäfer, Thorsten; Roberts, Nick Mw; Whitehouse, Martin; Karlsson, Andreas; Broman, Curt; Åström, Mats E

2018-01-16

Understanding metal scavenging by calcite in deep aquifers in granite is of importance for deciphering and modeling hydrochemical fluctuations and water-rock interaction in the upper crust and for retention mechanisms associated with underground repositories for toxic wastes. Metal scavenging into calcite has generally been established in the laboratory or in natural environments that cannot be unreservedly applied to conditions in deep crystalline rocks, an environment of broad interest for nuclear waste repositories. Here, we report a microanalytical study of calcite precipitated over a period of 17 years from anoxic, low-temperature (14 °C), neutral (pH: 7.4-7.7), and brackish (Cl: 1700-7100 mg/L) groundwater flowing in fractures at >400 m depth in granite rock. This enabled assessment of the trace metal uptake by calcite under these deep-seated conditions. Aquatic speciation modeling was carried out to assess influence of metal complexation on the partitioning into calcite. The resulting environment-specific partition coefficients were for several divalent ions in line with values obtained in controlled laboratory experiments, whereas for several other ions they differed substantially. High absolute uptake of rare earth elements and U(IV) suggests that coprecipitation into calcite can be an important sink for these metals and analogousactinides in the vicinity of geological repositories.

Fabrication of porous low crystalline calcite block by carbonation of calcium hydroxide compact.

PubMed

Matsuya, Shigeki; Lin, Xin; Udoh, Koh-ichi; Nakagawa, Masaharu; Shimogoryo, Ryoji; Terada, Yoshihiro; Ishikawa, Kunio

2007-07-01

Calcium carbonate (CaCO(3)) has been widely used as a bone substitute material because of its excellent tissue response and good resorbability. In this experimental study, we propose a new method obtaining porous CaCO(3) monolith for an artificial bone substitute. In the method, calcium hydroxide compacts were exposed to carbon dioxide saturated with water vapor at room temperature. Carbonation completed within 3 days and calcite was the only product. The mechanical strength of CaCO(3) monolith increased with carbonation period and molding pressure. Development of mechanical strength proceeded through two steps; the first rapid increase by bonding with calcite layer formed at the surface of calcium hydroxide particles and the latter increase by the full conversion of calcium hydroxide to calcite. The latter process was thought to be controlled by the diffusion of CO(2) through micropores in the surface calcite layer. Porosity of calcite blocks thus prepared had 36.8-48.1% depending on molding pressure between 1 MPa and 5 MPa. We concluded that the present method may be useful for the preparation of bone substitutes or the preparation of source material for bone substitutes since this method succeeded in fabricating a low-crystalline, and thus a highly reactive, porous calcite block.

Ikaite precipitation in a lacustrine environment - implications for palaeoclimatic studies using carbonates from Laguna Potrok Aike (Patagonia, Argentina)

NASA Astrophysics Data System (ADS)

Oehlerich, Markus; Mayr, Christoph; Griesshaber, Erika; Lücke, Andreas; Oeckler, Oliver M.; Ohlendorf, Christian; Schmahl, Wolfgang W.; Zolitschka, Bernd

2013-07-01

The monoclinic mineral ikaite (CaCO3 · 6H2O) and its pseudomorphs are potentially important archives for palaeoenvironmental reconstructions. Natural ikaite occurs in a small temperature range near freezing point and is reported mainly from marine and only rarely from continental aquatic environments. Ikaite transforms to more stable anhydrous forms of CaCO3 after an increase in temperature or when exposed to atmospheric conditions. The knowledge about conditions for natural ikaite formation, its stable isotope fractionation factors and isotopic changes during transformation to calcite is very restricted. Here, for the first time, primary precipitation of idiomorphic ikaite and its calcite pseudomorphs are reported from a subsaline lake, Laguna Potrok Aike, in southern Argentina. The calculated stable oxygen isotope fractionation factor between lake water and ikaite-derived calcite (αPAI = 1.0324 at a temperature of 4.1 °C) is close to but differs from that of primarily inorganically precipitated calcite. Pseudomorphs after ikaite rapidly disintegrate into calcite powder that is indistinguishable from μm-sized calcite crystals in the sediment record of Laguna Potrok Aike suggesting an ikaite origin of sedimentary calcites. Therefore, the Holocene carbonates of Laguna Potrok Aike have the potential to serve as a recorder of past hydrological variation.

A novel determination of calcite dissolution kinetics in seawater

NASA Astrophysics Data System (ADS)

Subhas, Adam V.; Rollins, Nick E.; Berelson, William M.; Dong, Sijia; Erez, Jonathan; Adkins, Jess F.

2015-12-01

We present a novel determination of the dissolution kinetics of inorganic calcite in seawater. We dissolved 13 C -labeled calcite in unlabeled seawater, and traced the evolving δ13 C composition of the fluid over time to establish dissolution rates. This method provides sensitive determinations of dissolution rate, which we couple with tight constraints on both seawater saturation state and surface area of the dissolving minerals. We have determined dissolution rates for two different abiotic calcite materials and three different grain sizes. Near-equilibrium dissolution rates are highly nonlinear, and are well normalized by geometric surface area, giving an empirical dissolution rate dependence on saturation state (Ω) of: This result substantiates the non-linear response of calcite dissolution to undersaturation. The bulk dissolution rate constant calculated here is in excellent agreement with those determined in far from equilibrium and dilute solution experiments. Plots of dissolution versus undersaturation indicates the presence of at least two dissolution mechanisms, implying a criticality in the calcite-seawater system. Finally, our new rate determination has implications for modeling of pelagic and seafloor dissolution. Nonlinear dissolution kinetics in a simple 1-D lysocline model indicate a possible transition from kinetic to diffusive control with increasing water depth, and also confirm the importance of respiration-driven dissolution in setting the shape of the calcite lysocline.

Templating Growth of a Pseudomorphic Lepidocrocite Microshell at the Calcite–Water Interface

DOE PAGES

Yuan, Ke; Lee, Sang Soo; Wang, Jun; ...

2018-01-05

The growth of lepidocrocite (gamma-FeOOH) has been observed through oxidation of Fe(II) on calcite (CaCO 3). Here, we seek to understand the structural relation between lepidocrocite and the calcite substrate and its growth mechanism. The formation of iron oxyhydroxide layers having distinct morphologies was observed during the dissolution of calcite in acidic Fe(II)-rich solutions. A pseudomorphic lepidocrocite shell together with multiple iron oxyhydroxide layers encapsulated within the shell was imaged by optical and transmission X-ray microscopies. The presence of a several-nanometer-thick ordered lepidocrocite film was observed by X-ray reflectivity, with the lepidocrocite (100) plane oriented parallel to the calcite (104)more » surface. Lath-shaped lepidocrocite aggregates formed during the initial precipitation, which eventually grew into clusters of parallel platy crystals. The formation of a nanometer-thick well-ordered lepidocrocite film on a pristine calcite surface appears critical for the subsequent pseudomorphic overgrowth. Detachment of the lepidocrocite film from the dissolving calcite surface yielded a free-standing pseudomorphic iron oxyhydroxide shell, suggesting weak interactions between the shell and the calcite substrate. This growth mechanism yields the potential of using carbonate minerals as templates for pseudomorphic synthesis of iron oxyhydroxides having well-defined size and morphology.« less

Mineralogical Evidence for the Palaeohydrogeological Stability of a Deep Groundwater System in Fractured Rock, in West Cumbria, Northwest England

NASA Astrophysics Data System (ADS)

Milodowski, A. E.; Gillespie, M. R.; Chenery, S. R. N.; Naden, J.; Shaw, R. P.

2014-12-01

An important requirement of the safety assessment for a geological disposal facility (GDF) for radioactive waste is to be able to demonstrate the long-term chemical stability of the groundwater system at repository depth over the long period of time during which the waste will be a hazard, typically up to one million years. Of particular concern in the UK is the potential for oxidising groundwater to penetrate to repository depth during periods of glaciation, thereby increasing the mobility of some transuranic radionuclides.Between 1990 and 1998, United Kingdom Nirex Limited carried out geological investigations into the suitability of a potential site in the Sellafield area of NW England, for a GDF for L/ILW. As part of these investigations, detailed petrological analysis of fracture mineralisation in 23 deep boreholes identified a complex sequence of mineralisation events referred to as ME1-ME9. The distribution of the ME9 calcite mineralisation correlates closely with present-day groundwater flows. The ME9 calcite has been studied in more detail to understand the evolution of the deep groundwater system. The morphology and growth zoning characteristics of the calcites reflects the groundwater chemistry. Freshwater calcites display c-axis flattened to equant crystals, and are non-ferroan and strongly zoned with Mn-rich and Mn-free bands. Deeper saline-zone calcites display c-axis elongated crystals, with high Mn:Fe and low Mn:Fe growth zones. Calcite in the transition zone between the saline and fresh groundwater display saline-type cores overgrown by freshwater-type calcite, indicating a small depression of the position of the transition zone during the growth of the calcites. Sr isotope ratios and fluid inclusion chemistry confirm a link between ME9 calcite and the present regional groundwater system. Modelling of the oxygen isotope data indicates that some growth zones in the ME9 calcite precipitated from groundwater potentially containing a significant proportion of glacially-recharged water, and that this may have reached depths of up to 1000 m. However, the chemical (REE,Fe and Mn) compositions of the ME9 calcite show that despite the potential contribution of glacially-recharged water to the deep groundwater system, conditions at repository depth (< 500 m) have continually remained reducing.

Influence of deformation on dolomite rim growth kinetics

NASA Astrophysics Data System (ADS)

Helpa, Vanessa; Rybacki, Erik; Grafulha Morales, Luiz Fernando; Dresen, Georg

2015-04-01

Using a gas-deformation apparatus stacks of oriented calcite (CaCO3) and magnesite (MgCO3) single crystals were deformed at T = 750° C and P = 400 MPa to examine the influence of stress and strain on magnesio-calcite and dolomite (CaMg[CO3]2) growth kinetics. Triaxial compression and torsion tests performed at constant stresses between 7 and 38 MPa and test durations between 4 and 171 hours resulted in bulk strains of 0.03-0.2 and maximum shear strains of 0.8-5.6, respectively. The reaction rims consist of fine-grained (2-7 μm) dolomite with palisade-shaped grains growing into magnesite reactants and equiaxed granular dolomite grains next to calcite. In between dolomite and pure calcite, magnesio-calcite grains evolved with an average grain size of 20-40 μm. Grain boundaries tend to be straighter at high bulk strains and equilibrium angles at grain triple junctions are common within the magnesio-calcite layer. Transmission electron microscopy shows almost dislocation free palisades and increasing dislocation density within granular dolomite towards the magnesio-calcite boundary. Within magnesio-calcite grains, dislocations are concentrated at grain boundaries. Variation of time at fixed stress (˜17 MPa) yields a parabolic time dependence of dolomite rim width, indicating diffusion-controlled growth, similar to isostatic rim growth behavior. In contrast, the magnesio-calcite layer growth is enhanced compared to isostatic conditions. Triaxial compression at given time shows no significant change of dolomite rim thickness (11±2 μm) and width of magnesio-calcite layers (33±5 μm) with increasing stress. In torsion experiments, reaction layer thickness and grain size decrease from the center (low stress/strain) to the edge (high strain/stress) of samples. Chemical analysis shows nearly stoichiometric composition of dolomite palisades, but enhanced Ca content within granular grains, indicating local disequilibrium with magnesio-calcite, in particular for twisted samples. The shift from local equilibrium is ˜3 mol% in triaxial compression and ˜7 mol% in torsion. Electron backscatter diffraction analysis reveals a crystallographic preferred orientation (CPO) within the reaction layers with [0001] axes parallel to the compression/rotation axis and poles of {2-1-10} and {10-10} prismatic planes parallel to the reaction interface. Compared to isostatic annealing, the CPO is more pronounced and the amount of low-angle grain boundaries is increased. At the imposed experimental conditions, most of the bulk deformation is accommodated by calcite single, which is stronger than magnesite. Application of flow laws for magnesio-calcite and dolomite suggest that the fine-grained reaction products should deform by grain boundary diffusion creep, resulting in lower flow strength than the single crystal reactants. However, microstructural observations indicate that deformation of granular dolomite and magnesio-calcite is at least partially assisted by dislocation creep, which would result in an almost similar strength to calcite. Therefore, flattening of the reaction layers during triaxial compression may be counterbalanced by enhanced reaction rates, resulting in almost constant layer thickness, independent of the applied stress. For simple shear, the reduced reaction kinetics in the high stress/strain region of twisted samples may be related to increased nucleation rates, resulting in a lower grain size and rim thickness.

Fluid inclusions and preliminary studies of hydrothermal alteration in core hole PLTG-1, Platanares geothermal area, Honduras

USGS Publications Warehouse

Bargar, K.E.

1991-01-01

The Platanares geothermal area in western Honduras consists of more than 100 hot springs that issue from numerous hot-spring groups along the banks or within the streambed of the Quebrada de Agua Caliente (brook of hot water). Evaluation of this geothermal area included drilling a 650-m deep PLTG-1 drill hole which penetrated a surface mantling of stream terrace deposits, about 550 m of Tertiary andesitic lava flows, and Cretaceous to lower Tertiary sedimentary rocks in the lower 90 m of the drill core. Fractures and cavities in the drill core are partly to completely filled by hydrothermal minerals that include quartz, kaolinite, mixed-layer illite-smectite, barite, fluorite, chlorite, calcite, laumontite, biotite, hematite, marcasite, pyrite, arsenopyrite, stibnite, and sphalerite; the most common open-space fillings are calcite and quartz. Biotite from 138.9-m depth, dated at 37.41 Ma by replicate 40Ar/39 Ar analyses using a continuous laser system, is the earliest hydrothermal mineral deposited in the PLTG-1 drill core. This mid-Tertiary age indicates that at least some of the hydrothermal alteration encountered in the PLTG-1 drill core occured in the distant past and is unrelated to the present geothermal system. Furthermore, homogenization temperatures (Th) and melting-point temperatures (Tm) for fluid inclusions in two of the later-formed hydrothermal minerals, calcite and barite, suggest that the temperatures and concentration of dissolved solids of the fluids present at the time these fluid inclusions formed were very different from the present temperatures and fluid chemistry measured in the drill hole. Liquid-rich secondary fluid inclusions in barite and caicite from drill hole PLTG-1 have Th values that range from about 20??C less than the present measured temperature curve at 590.1-m depth to as much as 90??C higher than the temperature curve at 46.75-m depth. Many of the barite Th measurements (ranging between 114?? and 265??C) plot above the reference surface boiling-point curve for pure water assuming hydrostatic conditions; however, the absence of evidence for boiling in the fluid inclusions indicates that at the time the minerals formed, the ground surface must have been at least 80 m higher than at present and underwent stream erosion to the current elevation. Near-surface mixed-layer illite-smectite is closely associated with barite and appears to have formed at about the same temperature range (about 120?? to 200??C) as the fluid-inclusion Th values for barite. Fluid-inclusion Th values for calcite range between about 136?? and 213??C. Several of the calcite Th values are significantly lower than the present measured temperature curve. The melting-point temperatures (Tm) of fluid-inclusion ice yield calculated salinities, ranging from near zero to as much as 5.4 wt. % NaCl equivalent, which suggest that much of the barite and calcite precipitated from fluids of significantly greater salinity than the present low salinity Platanares hot-spring water or water produced from the drill hole. ?? 1991.

The Formation of Boundary Clinopyroxenes and Associated Glass Veins in Type B1 CAIs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paque, J M; Beckett, J R; Ishii, H A

2008-05-18

We used focused ion beam thin section preparation and scanning transmission electron microscopy (FIB/STEM) to examine the interfacial region between spinel and host melilite for three spinel grains, two from the mantle and one from the core of an Allende type B1 inclusion, and a second pair of spinel grains from a type B1 inclusion from the Leoville carbonaceous chondrite. The compositions of boundary clinopyroxenes decorating spinel surfaces are generally consistent with those of coarser clinopyroxenes from the same region of the inclusion, suggesting little movement of spinels between mantle and core regions after the formation of boundary clinopyroxenes. Themore » host melilite displays no anomalous compositions near the interface, and anorthite or other late-stage minerals are not observed, suggesting that crystallization of residual liquid was not responsible for the formation of boundary clinopyroxenes. Allende spinels display either direct spinel-melilite contact or an intervening boundary clinopyroxene between the two phases. In the core, boundary clinopyroxene is mantled by a thin (1-2 {micro}m thick) layer of normally zoned (X{sub Ak} increasing away from the melilite-clinopyroxene contact) melilite with X{sub Ak} matching that of the host melilite at the melilite-melilite contact. In the mantle, X{sub Ak} near boundary spinels is constant. Spinels in a Leoville type B1 inclusion are more complex with boundary clinopyroxene, as observed in Allende, but also variable amounts of glass ({approx}1 {micro}m width), secondary calcite, perovskite, and an unknown Mg-, Al-, OH-rich and Ca-, Si-poor crystalline phase that may be a layered double hydrate. Glass compositions are consistent to first order with a precursor consisting mostly of Mg-carpholite or sudoite with some aluminous diopside. One possible scenario of formation for the glass veins is that open system alteration of melilite produced a porous, hydrated aggregate of Mg-carpholite or sudoite + aluminous diopside that was shock melted and quenched to a glass. The unknown crystalline phase may be a shocked remnant of the precursor phase assemblage but is more likely to have formed later by alteration of the glass. Calcite appears to be an opportunistic fracture filling that postdated all major shock events. Boundary clinopyroxenes probably share a common origin with coarser-grained pyroxenes from the same region of the inclusion. In the mantle, these crystals may represent clinopyroxene crystallized in Ti-rich liquids caused by the direct dissolution of perovskite and an associated Sc-Zr-rich phase or as a reaction product between dissolving perovskite and liquid (i.e., indirect dissolution of perovskite). In the core, any perovskite and associated Ti-enriched liquids that may have originally been present disappeared before the growth of boundary clinopyroxene.« less

The effect of hydrocarbons on the microstructural evolution in rock salt: a case study on hydrocarbon bearing Ara salt from the South Oman Salt Basin

NASA Astrophysics Data System (ADS)

Schmatz, Joyce; Urai, Janos L.; Wübbeler, Franziska M. M.; Sadler, Marc

2014-05-01

It has been shown that dilatant deformation promotes the incorporation of hydrocarbons into typically low permeable rock salt (Schoenherr et al., 2007). However, there is not much knowledge on subsequent mechanisms related to recrystallization processes, which cause morphological and chemical changes of the carbonic inclusions. This work aims to contribute to an increased understanding of fluid inclusion dynamics related to grain boundary migration recrystallization and hence to facilitate the interpretation of complex microstructures in recrystallized, multiphase salt rocks. In this case study we investigate hydrocarbon-impregnated salt from the Cambrian Ara Group in the South Oman Salt Basin. The samples were cored from cm-m thick anhydrite-salt sequences overlying hydrocarbon bearing carbonate stringers in 3300 m depth. The anhydrite layers consist mainly of fine-grained anhydrite, which contains calcite, dolomite, and olivine inclusions. Solid bitumen and lighter hydrocarbon phases are observed in between the anhydrite grains and along cracks. Anhydrite layers host salt veins, which contain fragments of anhydrite. These fragments do not differ in composition or structure from the host material and the related vein microstructures indicate crack-seal mechanisms. Halite in the salt layers is almost entirely recrystallized with solid inclusions consisting of anhydrite, calcite, dolomite and olivine with hydrocarbon-coatings present inside grains and along grain boundaries. Solid inclusions cause pinning indicated by a decreased recrystallized grain size and by the presence of grains with preserved substructures representing earlier deformation phases. We observe two types of carbonic inclusions: I) solid bitumen coatings along grain boundaries and microcracks, interpreted to be incorporated into the salt in an overpressure state that allowed dilatancy of the salt, and II) less degraded, liquid hydrocarbons along grain boundaries in the vicinity of the anhydrite, interpreted to be incorporated into the salt in a subsequent deformation phase. Type II inclusions usually form arrays of isolated inclusions (liquid hydrocarbons, vapor, and aqueous phases in minor proportions) along grain boundaries of the recrystallized grains, presumably formed in a surface-energy controlled shrinking process from thin fluid films. Here, the contact with mobile grain boundaries promoted necking down and decomposition of multiphase inclusions. We present a model, which describes the dynamic behavior of liquid hydrocarbons in mobile grain boundaries after their enclosure into the salt layers. The model is based on numerous microanalytical methods, such as optical microscopy, fluorescence microscopy, cryo-SEM, and EDX. Schoenherr, J., et al. (2007), Limits to the sealing capacity of rock salt: A case study of the infra-Cambrian Ara Salt from the South Oman salt basin, AAPG Bulletin, 91(11), 1541-1557

Portal Vein Embolization as an Oncosurgical Strategy Prior to Major Hepatic Resection: Anatomic, Surgical, and Technical Considerations

PubMed Central

Orcutt, Sonia T.; Kobayashi, Katsuhiro; Sultenfuss, Mark; Hailey, Brian S.; Sparks, Anthony; Satpathy, Bighnesh; Anaya, Daniel A.

2016-01-01

Preoperative portal vein embolization (PVE) is used to extend the indications for major hepatic resection, and it has become the standard of care for selected patients with hepatic malignancies treated at major hepatobiliary centers. To date, various techniques with different embolic materials have been used with similar results in the degree of liver hypertrophy. Regardless of the specific strategy used, both surgeons and interventional radiologists must be familiar with each other’s techniques to be able to create the optimal plan for each individual patient. Knowledge of the segmental anatomy of the liver is paramount to fully understand the liver segments that need to be embolized and resected. Understanding the portal vein anatomy and the branching variations, along with the techniques used to transect the portal vein during hepatic resection, is important because these variables can affect the PVE procedure and the eventual surgical resection. Comprehension of the advantages and disadvantages of approaches to the portal venous system and the various embolic materials used for PVE is essential to best tailor the procedures for each patient and to avoid complications. Before PVE, meticulous assessment of the portal vein branching anatomy is performed with cross-sectional imaging, and embolization strategies are developed based on the patient’s anatomy. The PVE procedure consists of several technical steps, and knowledge of these technical tips, potential complications, and how to avoid the complications in each step is of great importance for safe and successful PVE and ultimately successful hepatectomy. Because PVE is used as an adjunct to planned hepatic resection, priority must always be placed on safety, without compromising the integrity of the future liver remnant, and close collaboration between interventional radiologists and hepatobiliary surgeons is essential to achieve successful outcomes. PMID:27014696

Total individual ion activity coefficients of calcium and carbonate in seawater at 25°C and 35%. salinity, and implications to the agreement between apparent and thermodynamic constants of calcite and aragonite

USGS Publications Warehouse

Plummer, Niel; Sundquist, Eric T.

1982-01-01

We have calculated the total individual ion activity coefficients of carbonate and calcium,  and , in seawater. Using the ratios of stoichiometric and thermodynamic constants of carbonic acid dissociation and total mean activity coefficient data measured in seawater, we have obtained values which differ significantly from those widely accepted in the literature. In seawater at 25°C and 35%. salinity the (molal) values of  and  are 0.038 ± 0.002 and 0.173 ± 0.010, respectively. These values of  and  are independent of liquid junction errors and internally consistent with the value . By defining  and  on a common scale (), the product  is independent of the assigned value of  and may be determined directly from thermodynamic measurements in seawater. Using the value  and new thermodynamic equilibrium constants for calcite and aragonite, we show that the apparent constants of calcite and aragonite are consistent with the thermodynamic equilibrium constants at 25°C and 35%. salinity. The demonstrated consistency between thermodynamic and apparent constants of calcite and aragonite does not support a hypothesis of stable Mg-calcite coatings on calcite or aragonite surfaces in seawater, and suggests that the calcite critical carbonate ion curve of Broecker and Takahashi (1978,Deep-Sea Research25, 65–95) defines the calcite equilibrium boundary in the oceans, within the uncertainty of the data.

Optical properties of selected components of mineral dust aerosol processed with organic acids and humic material

NASA Astrophysics Data System (ADS)

Alexander, Jennifer M.; Grassian, V. H.; Young, M. A.; Kleiber, P. D.

2015-03-01

Visible light scattering phase function and linear polarization profiles of mineral dust components processed with organic acids and humic material are measured, and results are compared to T-matrix simulations of the scattering properties. Processed samples include quartz mixed with humic material, and calcite reacted with acetic and oxalic acids. Clear differences in light scattering properties are observed for all three processed samples when compared to the unprocessed dust or organic salt products. Results for quartz processed with humic acid sodium salt (NaHA) indicate the presence of both internally mixed quartz-NaHA particles and externally mixed NaHA aerosol. Simulations of light scattering suggest that the processed quartz particles become more moderate in shape due to the formation of a coating of humic material over the mineral core. Experimental results for calcite reacted with acetic acid are consistent with an external mixture of calcite and the reaction product, calcium acetate. Modeling of the light scattering properties does not require any significant change to the calcite particle shape distribution although morphology changes cannot be ruled out by our data. It is expected that calcite reacted with oxalic acid will produce internally mixed particles of calcite and calcium oxalate due to the low solubility of the product salt. However, simulations of the scattering for the calcite-oxalic acid system result in rather poor fits to the data when compared to the other samples. The poor fit provides a less accurate picture of the impact of processing in the calcite-oxalic acid system.

ENVIRONMENTAL MANAGEMENT SCIENCE PROGRAM PROJECT NUMBER 87016 CO-PRECIPITATION OF TRACE METALS IN GROUNDWATER AND VADOSE ZONE CALCITE: IN SITU CONTAINMENT AND STABILIZATION OF STRONTIUM-90 AND OTHER DIVALENT METALS AND RADIONUCLIDES AT ARID WESTERN DOE SITES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferris, F. Grant; Fujita, Yoshiko; Smith, Robert W.

2004-06-15

Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) weapons complex. In situ containment and stabilization of these contaminants in vadose zones or groundwater is a cost-effective treatment strategy. Our facilitated approach relies upon the hydrolysis of introduced urea to cause the acceleration of calcium carbonate precipitation (and trace metal coprecipitation) by increasing groundwater pH and alkalinity (Fujita et al., 2000; Warren et al., 2001). Subsurface urea hydrolysis is catalyzed by the urease enzyme, which may be either introduced with the urea or produced in situ by ubiquitous subsurface ureamore » hydrolyzing microorganisms. Because the precipitation processes are irreversible and many western aquifers are saturated with respect to calcite, the co-precipitated metals and radionuclides will be effectively removed from groundwater. The rate at which trace metals are incorporated into calcite is a function of calcite precipitation kinetics, adsorption interactions between the calcite surface and the trace metal in solution (Zachara et al., 1991), solid solution properties of the trace metal in calcite (Tesoriero and Pankow, 1996), and also the surfaces upon which the calcite is precipitating. A fundamental understanding of the coupling of calcite precipitation and trace metal partitioning, and how this occurs in aquifers and vadose environments is lacking. This report summarizes work undertaken during the second year of this project.« less

Nuclear anomalies in the buccal cells of calcite factory workers

PubMed Central

2010-01-01

The micronucleus (MN) assay on exfoliated buccal cells is a useful and minimally invasive method for monitoring genetic damage in humans. To determine the genotoxic effects of calcite dust that forms during processing, MN assay was carried out in exfoliated buccal cells of 50 (25 smokers and 25 non-smokers) calcite factory workers and 50 (25 smokers and 25 non-smokers) age- and sex-matched control subjects. Frequencies of nuclear abnormalities (NA) other than micronuclei, such as binucleates, karyorrhexis, karyolysis and ‘broken eggs', were also evaluated. Micronuclei and the other aforementioned anomalies were analysed by two way analysis of covariance. The linear correlations between the types of micronucleus and nuclear abnormalities were determined by Spearman's Rho. There was a positive correlation between micronuclei and other types of nuclear abnormalities in accordance with the Spearman's Rho test. Results showed statistically significant difference between calcite fabric workers and control groups. MN and NA frequencies in calcite fabric workers were significantly higher than those in control groups (p < 0.05). The results of this study indicate that calcite fabric workers are under risk of significant cytogenetic damage. PMID:21637497

Direct ink writing of silica-bonded calcite scaffolds from preceramic polymers and fillers.

PubMed

Fiocco, L; Elsayed, H; Badocco, D; Pastore, P; Bellucci, D; Cannillo, V; Detsch, R; Boccaccini, A R; Bernardo, E

2017-05-11

Silica-bonded calcite scaffolds have been successfully 3D-printed by direct ink writing, starting from a paste comprising a silicone polymer and calcite powders, calibrated in order to match a SiO 2 /CaCO 3 weight balance of 35/65. The scaffolds, fabricated with two slightly different geometries, were first cross-linked at 350 °C, then fired at 600 °C, in air. The low temperature adopted for the conversion of the polymer into amorphous silica, by thermo-oxidative decomposition, prevented the decomposition of calcite. The obtained silica-bonded calcite scaffolds featured open porosity of about 56%-64% and compressive strength of about 2.9-5.5 MPa, depending on the geometry. Dissolution studies in SBF and preliminary cell culture tests, with bone marrow stromal cells, confirmed the in vitro bioactivity of the scaffolds and their biocompatibility. The seeded cells were found to be alive, well anchored and spread on the samples surface. The new silica-calcite composites are expected to be suitable candidates as tissue-engineering 3D scaffolds for regeneration of cancellous bone defects.

Three-dimensional hydration layer mapping on the (10.4) surface of calcite using amplitude modulation atomic force microscopy.

PubMed

Marutschke, Christoph; Walters, Deron; Walters, Deron; Hermes, Ilka; Bechstein, Ralf; Kühnle, Angelika

2014-08-22

Calcite, the most stable modification of calcium carbonate, is a major mineral in nature. It is, therefore, highly relevant in a broad range of fields such as biomineralization, sea water desalination and oil production. Knowledge of the surface structure and reactivity of the most stable cleavage plane, calcite (10.4), is pivotal for understanding the role of calcite in these diverse areas. Given the fact that most biological processes and technical applications take place in an aqueous environment, perhaps the most basic - yet decisive - question addresses the interaction of water molecules with the calcite (10.4) surface. In this work, amplitude modulation atomic force microscopy is used for three-dimensional (3D) mapping of the surface structure and the hydration layers above the surface. An easy-to-use scanning protocol is implemented for collecting reliable 3D data. We carefully discuss a comprehensible criterion for identifying the solid-liquid interface within our data. In our data three hydration layers form a characteristic pattern that is commensurate with the underlying calcite surface.

A Raman spectroscopic comparison of calcite and dolomite.

PubMed

Sun, Junmin; Wu, Zeguang; Cheng, Hongfei; Zhang, Zhanjun; Frost, Ray L

2014-01-03

Raman spectroscopy was used to characterize and differentiate the two minerals calcite and dolomite and the bands related to the mineral structure. The (CO3)(2-) group is characterized by four prominent Raman vibrational modes: (a) the symmetric stretching, (b) the asymmetric deformation, (c) asymmetric stretching and (d) symmetric deformation. These vibrational modes of the calcite and dolomite were observed at 1440, 1088, 715 and 278 cm(-1). The significant differences between the minerals calcite and dolomite are observed by Raman spectroscopy. Calcite shows the typical bands observed at 1361, 1047, 715 and 157 cm(-1), and the special bands at 1393, 1098, 1069, 1019, 299, 258 and 176 cm(-1) for dolomite are observed. The difference is explained on the basis of the structure variation of the two minerals. Calcite has a trigonal structure with two molecules per unit cell, and dolomite has a hexagonal structure. This is more likely to cause the splitting and distorting of the carbonate groups. Another cause for the difference is the cation substituting for Mg in the dolomite mineral. Copyright © 2013 Elsevier B.V. All rights reserved.

A Raman spectroscopic comparison of calcite and dolomite

NASA Astrophysics Data System (ADS)

Sun, Junmin; Wu, Zeguang; Cheng, Hongfei; Zhang, Zhanjun; Frost, Ray L.

2014-01-01

Raman spectroscopy was used to characterize and differentiate the two minerals calcite and dolomite and the bands related to the mineral structure. The (CO3)2- group is characterized by four prominent Raman vibrational modes: (a) the symmetric stretching, (b) the asymmetric deformation, (c) asymmetric stretching and (d) symmetric deformation. These vibrational modes of the calcite and dolomite were observed at 1440, 1088, 715 and 278 cm-1. The significant differences between the minerals calcite and dolomite are observed by Raman spectroscopy. Calcite shows the typical bands observed at 1361, 1047, 715 and 157 cm-1, and the special bands at 1393, 1098, 1069, 1019, 299, 258 and 176 cm-1 for dolomite are observed. The difference is explained on the basis of the structure variation of the two minerals. Calcite has a trigonal structure with two molecules per unit cell, and dolomite has a hexagonal structure. This is more likely to cause the splitting and distorting of the carbonate groups. Another cause for the difference is the cation substituting for Mg in the dolomite mineral.

Modeling Remineralization of Desalinated Water by Micronized Calcite Dissolution.

PubMed

Hasson, David; Fine, Larissa; Sagiv, Abraham; Semiat, Raphael; Shemer, Hilla

2017-11-07

A widely used process for remineralization of desalinated water consists of dissolution of calcite particles by flow of acidified desalinated water through a bed packed with millimeter-size calcite particles. An alternative process consists of calcite dissolution by slurry flow of micron-size calcite particles with acidified desalinated water. The objective of this investigation is to provide theoretical models enabling design of remineralization by calcite slurry dissolution with carbonic and sulfuric acids. Extensive experimental results are presented displaying the effects of acid concentration, slurry feed concentration, and dissolution contact time. The experimental data are shown to be in agreement within less than 10% with theoretical predictions based on the simplifying assumption that the slurry consists of uniform particles represented by the surface mean diameter of the powder. Agreement between theory and experiment is improved by 1-8% by taking into account the powder size distribution. Apart from the practical value of this work in providing a hitherto lacking design tool for a novel technology. The paper has the merit of being among the very few publications providing experimental confirmation to the theory describing reaction kinetics in a segregated flow system.

A comparison of amorphous calcium carbonate crystallization in aqueous solutions of MgCl2 and MgSO4: implications for paleo-ocean chemistry

NASA Astrophysics Data System (ADS)

Han, Mei; Zhao, Yanyang; Zhao, Hui; Han, Zuozhen; Yan, Huaxiao; Sun, Bin; Meng, Ruirui; Zhuang, Dingxiang; Li, Dan; Liu, Binwei

2018-04-01

Based on the terminology of "aragonite seas" and "calcite seas", whether different Mg sources could affect the mineralogy of carbonate sediments at the same Mg/Ca ratio was explored, which was expected to provide a qualitative assessment of the chemistry of the paleo-ocean. In this work, amorphous calcium carbonate (ACC) was prepared by direct precipitation in anhydrous ethanol and used as a precursor to study crystallization processes in MgSO4 and MgCl2 solutions having different concentrations at 60 °C (reaction times 240 and 2880 min). Based on the morphology of the aragonite crystals, as well as mineral saturation indices and kinetic analysis of geochemical processes, it was found that these crystals formed with a spherulitic texture in 4 steps. First, ACC crystallized into columnar Mg calcite by nearly oriented attachment. Second, the Mg calcite changed from columnar shapes into smooth dumbbell forms. Third, the Mg calcite transformed into rough dumbbell or cauliflower-shaped aragonite forms by local dissolution and precipitation. Finally, the aragonite transformed further into spherulitic radial and irregular aggregate forms. The increase in Ca2+ in the MgSO4 solutions compared with the MgCl2 solutions indicates the fast dissolution and slow precipitation of ACC in the former solutions. The phase transition was more complete in the 0.005 M MgCl2 solution, whereas Mg calcite crystallized from the 0.005 M MgSO4 solution, indicating that Mg calcite could be formed more easily in an MgSO4 solution. Based on these findings, aragonite and Mg calcite relative to ACC could be used to provide a qualitative assessment of the chemistry of the paleo-ocean. Therefore, calcite seas relative to high-Mg calcite could reflect a low concentration MgSO4 paleo-ocean, while aragonite seas could be related to an MgCl2 or high concentration of MgSO4 paleo-ocean.

Unravelling the enigmatic origin of calcitic nanofibres in soils and caves: purely physicochemical or biogenic processes?

NASA Astrophysics Data System (ADS)

Bindschedler, S.; Cailleau, G.; Braissant, O.; Millière, L.; Job, D.; Verrecchia, E. P.

2014-05-01

Calcitic nanofibres are ubiquitous habits of secondary calcium carbonate (CaCO3) accumulations observed in calcareous vadose environments. Despite their widespread occurrence, the origin of these nanofeatures remains enigmatic. Three possible mechanisms fuel the debate: (i) purely physicochemical processes, (ii) mineralization of rod-shaped bacteria, and (iii) crystal precipitation on organic templates. Nanofibres can be either mineral (calcitic) or organic in nature. They are very often observed in association with needle fibre calcite (NFC), another typical secondary CaCO3 habit in terrestrial environments. This association has contributed to some confusion between both habits, however they are truly two distinct calcitic features and their recurrent association is likely to be an important fact to help understanding the origin of nanofibres. In this paper the different hypotheses that currently exist to explain the origin of calcitic nanofibres are critically reviewed. In addition to this, a new hypothesis for the origin of nanofibres is proposed based on the fact that current knowledge attributes a fungal origin to NFC. As this feature and nanofibres are recurrently observed together, a possible fungal origin for nanofibres which are associated with NFC is investigated. Sequential enzymatic digestion of the fungal cell wall of selected fungal species demonstrates that the fungal cell wall can be a source of organic nanofibres. The obtained organic nanofibres show a striking morphological resemblance when compared to their natural counterparts, emphasizing a fungal origin for part of the organic nanofibres observed in association with NFC. It is further hypothesized that these organic nanofibres may act as templates for calcite nucleation in a biologically influenced mineralization process, generating calcitic nanofibres. This highlights the possible involvement of fungi in CaCO3 biomineralization processes, a role still poorly documented. Moreover, on a global scale, the organomineralization of organic nanofibres into calcitic nanofibres might be an overlooked process deserving more attention to specify its impact on the biogeochemical cycles of both Ca and C.

Indications for the past redox environments in deep groundwaters from the isotopic composition of carbon and oxygen in fracture calcite, Olkiluoto, SW Finland.

PubMed

Sahlstedt, Elina; Karhu, Juha A; Pitkanen, Petteri

2010-09-01

In paleohydrogeological studies, the geochemical and isotope geochemical composition of fracture calcites can be utilised to gain information about the evolution of the composition of deep groundwaters in crystalline bedrock. The aim of our study was to investigate the latest hydrogeochemical evolution of groundwaters in the crystalline bedrock at Olkiluoto, which is the planned site for deep geological disposal of spent nuclear fuel. Samples were collected from drill cores intercepting water-conducting fractures at the upper ~500 m of the bedrock. The latest fracture calcite generations were identified using optical microscopy and electron microprobe. They occur as thin ~10-200 μm crusts or small euhedral crystals on open fracture surfaces. These latest calcite fillings were carefully sampled and analysed for the isotopic composition on carbon and oxygen. In addition, fluid inclusion homogenisation temperatures were determined on selected calcite samples. Fluid inclusion data indicated a low temperature of formation for the latest fracture calcite fillings. The δ(18)O values of calcite in these fracture fillings vary only slightly, from-7.3 to-11.5 ‰ (Vienna Pee Dee Belemnite, VPDB), whereas the δ(13)C values fluctuate widely, from-30 to+31 ‰ (VPDB). The δ(13)C values of latest calcite fillings show a systematic pattern with depth, with high and variable δ(13)C values below 50 m. The high δ(13)C values indicate active methanogenesis during the formation of the latest calcite fillings. In contrast, the present-day methanic redox environment is restricted to depths below 200-300 m. It is possible that the shift in the redox environment at Olkiluoto has occurred during infiltration of SO2-(4)-rich marine waters, the latest of such events being the infiltration of brackish waters of the Littorina Sea stage of the Baltic Sea at ~8000-3000 BP.

Mineralogical, crystallographic, and isotopic constraints on the precipitation of aragonite and calcite at Shiqiang and other hot springs in Yunnan Province, China

NASA Astrophysics Data System (ADS)

Jones, Brian; Peng, Xiaotong

2016-11-01

Two active spring vent pools at Shiqiang (Yunnan Province, China) are characterized by a complex array of precipitates that coat the wall around the pool and the narrow ledges that surround the vent pool. These precipitates include arrays of aragonite crystals, calcite cone-dendrites, red spar calcite, unattached dodecahedral and rhombohedral calcite crystals, and late stage calcite that commonly coats and disguises the earlier formed precipitates. Some of the microbial mats that grow on the ledges around the pools have been partly mineralized by microspheres that are formed of Si and minor amounts of Fe. The calcite and aragonite that are interspersed with each other at all scales are both primary precipitates. Some laminae, for example, change laterally from aragonite to calcite over distances of only a few millimetres. The precipitates at Shiqiang are similar to precipitates found in and around the vent pools of other springs found in Yunnan Province, including those at Gongxiaoshe, Zhuyuan, Eryuan, and Jifei. In all cases, the δDwater and δ18Owater indicate that the spring water is of meteoric origin. These are thermogene springs with the carrier CO2 being derived largely from the mantle and reaction of the waters with bedrock. Variations in the δ13Ctravertine values indicate that the waters in these springs were mixed, to varying degrees, with cold groundwater and its soil-derived CO2. Calcite and aragonite precipitation took place once the spring waters had become supersaturated with respect to CaCO3, probably as a result of rapid CO2 degassing. These precipitates, which were not in isotopic equilibrium with the spring water, are characterized by their unusual crystal morphologies. The precipitation of calcite and aragonite, seemingly together, can probably be attributed to microscale variations in the saturation levels that are, in turn, attributable to microscale variations in the rate of CO2 degassing.

The coordination of sulfur in synthetic and biogenic Mg calcites: The red coral case

NASA Astrophysics Data System (ADS)

Perrin, J.; Rivard, C.; Vielzeuf, D.; Laporte, D.; Fonquernie, C.; Ricolleau, A.; Cotte, M.; Floquet, N.

2017-01-01

Sulfur has been recognized in biogenic calcites for a long time. However, its structural position is matter of debate. For some authors, sulfur is a marker of the organic matrix while it is part of the calcite structure itself for others. To better understand the place of sulfur in calcite, sulfated magnesian calcites (S-MgCalcite) have been synthetized at high pressure and temperature and studied by μ-XANES spectroscopy. S-MgCalcite XANES spectra show two different types of sulfur: sulfate (SO42-) as a predominant species and a small contribution of sulfite (SO32-), both substituting for carbonate ions in the calcite structure. To address the question of the position of sulfur in biogenic calcites, the oxidation states of sulfur in the skeleton and organic tissues of Corallium rubrum have been investigated by micro X-ray fluorescence (μ-XRF) and sulfur K-edge micro X-ray absorption near edge structure (μ-XANES) spectroscopy at the European Synchrotron Radiation Facility (ESRF, Grenoble, France) on beamline ID21. In the skeleton, sulfur is mainly present as oxidized sulfur SO42- (+VI), plus a weak sulfite contribution. XANES spectra indicate that sulfur is inorganically incorporated as sulfur structurally substituted to carbonate ions (SSS). Although an organic matrix is present in the red coral skeleton, reduced organic sulfur could not be detected by μ-XANES spectroscopy in the skeleton probably due to low organic/inorganic sulfur ratio. In the organic tissues surrounding the skeleton, several sulfur oxidation states have been detected including disulfide (S-S), thioether (R-S-CH3), sulfoxide (SO2), sulfonate (SO2O-) and sulfate (SO42-). The unexpected occurrence of inorganic sulfate within the organic tissues suggests the presence of pre-organized organic/inorganic complexes in the circulatory system of the red coral, precursors to biomineralization ahead of the growth front.

Unravelling the enigmatic origin of calcitic nanofibres in soils and caves: purely physicochemical or biogenic processes?

NASA Astrophysics Data System (ADS)

Bindschedler, S.; Cailleau, G.; Braissant, O.; Millière, L.; Job, D.; Verrecchia, E. P.

2014-01-01

Calcitic nanofibres are ubiquitous habits of secondary calcium carbonate (CaCO3) accumulations observed in calcareous vadose environments. Despite their widespread occurrence, the origin of these nanofeatures remains enigmatic. Three possible mechanisms fuel the debate: (i) purely physicochemical processes, (ii) mineralization of rod-shaped bacteria, and (iii) crystal precipitation on organic templates. Nanofibres can be either mineral (calcitic) or organic in nature. They are very often observed in association with Needle Fibre Calcite (NFC), another typical secondary CaCO3 habit in terrestrial environments. This association has contributed to some confusion between both habits, however they are truly two distinct calcitic features and their recurrent association is likely to be an important fact to help understanding the origin of nanofibres. In this manuscript the different hypotheses that currently exist to explain the origin of calcitic nanofibres are critically reviewed. In addition to this, a new hypothesis for the origin of nanofibres is proposed based on the fact that current knowledge attributes a fungal origin to NFC. As this feature and nanofibres are recurrently observed together, a possible fungal origin for nanofibres which are associated with NFC is investigated. Sequential enzymatic digestion of the fungal cell wall of selected fungal species demonstrates that the fungal cell wall can be a source of organic nanofibres. The obtained organic nanofibres show a striking morphological resemblance when compared to their natural counterparts, emphasizing a fungal origin for part of the organic nanofibres observed in association with NFC. It is further hypothesized that these organic nanofibres may act as templates for calcite nucleation in a biologically-influenced mineralization process, generating calcitic nanofibres. This highlights the possible involvement of Fungi in CaCO3 biomineralization processes, a role still poorly documented at present-day. Moreover, on a global scale, the organomineralization of organic nanofibres into calcitic nanofibres might have a great, however overlooked, impact on the biogeochemical cycles of both Ca and C.

Manganese-calcium intermixing facilitates heteroepitaxial growth at the 10 1 ¯ 4 calcite-water interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Man; Riechers, Shawn L.; Ilton, Eugene S.

2017-10-01

In situ atomic force microscopy (AFM) measurements were performed to probe surface precipitates that formed on the (10-14) surface of calcite (CaCO3) single crystals following reaction with Mn2+-bearing aqueous solutions with a range of initial concentrations. Three-dimensional epitaxial islands were observed to precipitate and grow on the surfaces and in situ time-sequenced measurements demonstrated that their growth rates were commensurate with those obtained for epitaxial islands formed on calcite crystals reacted with Cd2+-bearing aqueous solutions of the same range in supersaturation with respect to the pure metal carbonate phase. This finding was unexpected as rhodochrosite (MnCO3) and calcite display amore » 10% lattice mismatch, based on the area of their (10-14) surface unit cells, whereas the lattice mismatch is only 4% for otavite (CdCO3) and calcite. Coatings of varying thicknesses were therefore synthesized by reacting calcite single crystals with calcite-equilibrated aqueous solutions with concentrations of up to 250 µM MnCl2 and analyzed to determine the composition of the surface precipitates. Ex situ X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray reflectivity (XRR), and AFM measurements of the reacted crystals demonstrated the formation of an epitaxial (Mn,Ca)CO3 solid solution with a spatially complex composition atop the calcite surface, whereby the first few nanometers were rich in Ca and the Mn content increased with distance from the original calcite surface, culminating in a topmost region of almost pure MnCO3 for the thickest coatings. These findings explain the measured growth rates (the effective lattice mismatch was much smaller than nominal mismatch) and highlight the strong influence played by the substrate on the composition of surface precipitates in aqueous conditions.« less

Strontium Incorporation Into Calcite Generated by Bacterial Ureolysis

NASA Astrophysics Data System (ADS)

Fujita, Y.; Ingram, J. A.; Cortez, M. M.; Redden, G. D.; Smith, R. W.

2002-12-01

Strontium incorporation into calcite generated by bacterial ureolytic activity was investigated as part of a larger effort to evaluate the use of in situ urea hydrolysis for accelerating co-precipitation of trace metals and radionuclides in contaminated aquifers. 90Sr, a uranium fission product with a half-life of 29 years, is a significant subsurface contaminant at several Department of Energy facilities and could be immobilized using this remediation strategy. Experiments were conducted in a medium designed to simulate the groundwater of the Snake River Plain Aquifer in eastern Idaho, amended with strontium. Initially the solution was undersaturated with respect to calcite. As a model ureolytic organism, we used Bacillus pasteurii, a well-characterized bacterium known for high urease activity and previously shown to induce calcite precipitation in urea-amended medium. To gain information on the effect of the bacterial surfaces, we also looked at precipitation in the presence of a bacterial species that did not hydrolyze urea, as well as in the absence of bacteria. In the absence of bacterial ureolysis, carbonate precipitation was induced by addition of ammonium carbonate. All products were identified as calcite by X-ray diffraction. Strontium uptake was observed in all cases, but was greatest in the system including bacterial ureolysis. Sputter depth element profiling by time-of-flight secondary ion mass spectrometry (TOF-SIMS) confirmed this finding, showing highest Sr:Ca ratios in the bacterially generated calcite throughout the depth (~350 nm) investigated. Environmental Scanning Electron Microscopy (ESEM) of the solids revealed regular crystals containing the outlines of embedded or entombed bacterial cells, suggesting that calcite precipitated directly on the cell surfaces when present. Analysis by X-ray Absorption Near Edge Spectroscopy (XANES) indicated that in both the biotically and abiotically generated calcites the Sr was incorporated into the calcite lattice structure, rather than forming strontium carbonate. These findings are encouraging with respect to long term containment and stabilization of strontium by the proposed remediation strategy.

Weathering of post-impact hydrothermal deposits from the Haughton impact structure: implications for microbial colonization and biosignature preservation.

PubMed

Izawa, M R M; Banerjee, Neil R; Osinski, G R; Flemming, R L; Parnell, J; Cockell, C S

2011-01-01

Meteorite impacts are among the very few processes common to all planetary bodies with solid surfaces. Among the effects of impact on water-bearing targets is the formation of post-impact hydrothermal systems and associated mineral deposits. The Haughton impact structure (Devon Island, Nunavut, Canada, 75.2 °N, 89.5 °W) hosts a variety of hydrothermal mineral deposits that preserve assemblages of primary hydrothermal minerals commonly associated with secondary oxidative/hydrous weathering products. Hydrothermal mineral deposits at Haughton include intra-breccia calcite-marcasite vugs, small intra-breccia calcite or quartz vugs, intra-breccia gypsum megacryst vugs, hydrothermal pipe structures and associated surface "gossans," banded Fe-oxyhydroxide deposits, and calcite and quartz veins and coatings in shattered target rocks. Of particular importance are sulfide-rich deposits and their associated assemblage of weathering products. Hydrothermal mineral assemblages were characterized structurally, texturally, and geochemically with X-ray diffraction, micro X-ray diffraction, optical and electron microscopy, and inductively coupled plasma atomic emission spectroscopy. Primary sulfides (marcasite and pyrite) are commonly associated with alteration minerals, including jarosite (K,Na,H(3)O)Fe(3)(SO(4))(2)(OH)(6), rozenite FeSO(4)·4(H(2)O), copiapite (Fe,Mg)Fe(4)(SO(4))(6)(OH)(2)·20(H(2)O), fibroferrite Fe(SO(4))(OH)·5(H(2)O), melanterite FeSO(4)·7(H(2)O), szomolnokite FeSO(4)·H(2)O, goethite α-FeO(OH), lepidocrocite γ-FeO(OH) and ferrihydrite Fe(2)O(3)·0.5(H(2)O). These alteration assemblages are consistent with geochemical conditions that were locally very different from the predominantly circumneutral, carbonate-buffered environment at Haughton. Mineral assemblages associated with primary hydrothermal activity, and the weathering products of such deposits, provide constraints on possible microbial activity in the post-impact environment. The initial period of active hydrothermal circulation produced primary mineral assemblages, including Fe sulfides, and was succeeded by a period dominated by oxidation and low-temperature hydration of primary minerals by surface waters. Active hydrothermal circulation can enable the rapid delivery of nutrients to microbes. Nutrient availability following the cessation of hydrothermal circulation is likely more restricted; therefore, the biological importance of chemical energy from hydrothermal mineral deposits increases with time. Weathering of primary hydrothermal deposits and dissolution and reprecipitation of mobile weathering products also create many potential habitats for endolithic microbes. They also provide a mechanism that may preserve biological materials, potentially over geological timescales. © Mary Ann Liebert, Inc.

Ore-fluid evolution at the Getchell Carlin-type gold deposit, Nevada, USA

USGS Publications Warehouse

Cline, J.S.; Hofstra, A.A.

2000-01-01

Minerals and fluid-inclusion populations were examined using petrography, microthermometry, quadrupole mass-spectrometer gas analyses and stable-isotope studies to characterize fluids responsible for gold mineralization at the Getchell Carlin-type gold deposit. The gold-ore assemblage at Getchell is superimposed on quartz-pyrite vein mineralization associated with a Late-Cretaceous granodiorite stock that intruded Lower-Paleozoic sedimentary rocks. The ore assemblage, of mid-Tertiary age, consists of disseminated arsenian pyrite that contains submicrometer gold, jasperoid quartz, and later fluorite and orpiment that fill fractures and vugs. Late ore-stage realgar and calcite enclose ore-stage minerals. Pre-ore quartz trapped fluids with a wide range of salinities (1 to 21 wt.% NaCl equivalent), gas compositions (H2O, CO2, and CH4), and temperatures (120 to >360??C). Oxygen- and hydrogen-isotope ratios indicate that pre-ore fluids likely had a magmatic source, and were associated with intrusion of the granodiorite stock and related dikes. Ore-stage jasperoid contains moderate salinity, aqueous fluid inclusions trapped at 180 to 220??C. Ore fluids contain minor CO2 and trace H2S that allowed the fluid to react with limestone host rocks and transport gold, respectively. Aqueous inclusions in fluorite indicate that fluid temperatures declined to ~175??C by the end of ore-stage mineralization. As the hydrothermal system collapsed, fluid temperatures declined to 155 to 115??C and realgar and calcite precipitated. Inclusion fluids in ore-stage minerals have high ??D(H2O) and ??18O(H2O) values that indicate that the fluid had a deep source, and had a metamorphic or magmatic origin, or both. Late ore-stage fluids extend to lower ??D(H2O) values, and have a wider range of ??18O(H2O) values suggesting dilution by variably exchanged meteoric waters. Results show that deeply sourced ore fluids rose along the Getchell fault system, where they dissolved carbonate wall rocks and deposited gold-enriched pyrite and jasperoid quartz. Gold and pyrite precipitated together as H2S in the ore fluids reacted with iron in the host rocks. As ore fluids mixed with local aquifer fluids, ore fluids became cooler and more dilute. Cooling caused precipitation of ore-stage fluorite and orpiment, and late ore-stage realgar. Phase separation and/or neutralization of the ore fluid during the waning stages of the hydrothermal ore system led to deposition of late ore-stage calcite.

Medical Services: Medical Record Administration and Health Care Documentation

DTIC Science & Technology

1999-05-03

prepared for each patient who must have one. (5) Ensure that a blood sample for deoxyribonucleic acid ( DNA ) identification is on file with the DNA ...degenerative joint disease DM diabetes mellitus DNA deoxyribonucleic acid DNR do not resuscitate DO Doctor of Osteopathy DOA dead on arrival DOB date...vein thrombosis DWI driving while intoxicated Dx diagnosis EBL estimated blood loss EBV Epstein-Barr virus ECG; EKG electrocardiogram E. coli

The Chicxulub crater - impact metamorphism of sulfate and carbonate lithologies

NASA Astrophysics Data System (ADS)

Deutsch, A.; Langenhorst, F.; Hornemann, U.; Ivanov, B. A.

2003-04-01

It is discussed whether in the aftermath of the Chicxulub event, impact-released CO_2 and SO_x have changed the Earth's climate, acting also as lethal thread for life. Undoubtedly, vaporization of carbonates and sulfates, which are major target lithologies at the Chicxulub impact site, occurred in the footprint of the projectile. What happened to these lithologies outside this very restricted zone was so far unconstrained. Petrologic observations on PEMEX and UNAM as well as on the CSDP cores allow to set up a general classification for shock-related pro-grade effects on sulfate and carbonate sedimentary rocks. Shock effects in lithic breccias are restricted to brecciation and formation of twins in calcite. Suevites mostly lack melted carbonate clasts; annealing effects in anhydrite fragments are absent. The underlying melt breccias contain anhydrite fragments still displaying a sedimentary texture, and limestone clasts, whose texture reflect crystallization from melt. Impact melt breccias from deeper levels frequently contain partially resorbed anhydrite clasts and a melt matrix with the Ca-rich mineral assemblage quartz + plagioclase + clinopyroxene; this mineral assemblage provides evidence for partial dissociation of CaSO_4. Large clasts of anhydrite consist of equant crystals with 120^o triple junctions, a feature indicative for re-crystallization in the solid state. Tagamites (impact melt rocks) are virtually free of clasts from sedimentary lithologies. These rocks have an extremely high formation temperature, which caused total dissociation of CaSO_4 and CaCO_3. Finally, up to 100 μm wide veins of anhydrite + calcite + quartz cut the matrix of all lithologies except the tagamites. They probably represent "degassing vents". The given scheme is in qualitative accordance with data of shock recovery and annealing experiments as well as with modeling results. In addition, it substantiates that annealing plays a fundamental role in the impact metamorphism of sedimentary rocks.

Evaluation of meteorites as habitats for terrestrial microorganisms: Results from the Nullarbor Plain, Australia, a Mars analogue site

NASA Astrophysics Data System (ADS)

Tait, Alastair W.; Wilson, Siobhan A.; Tomkins, Andrew G.; Gagen, Emma J.; Fallon, Stewart J.; Southam, Gordon

2017-10-01

Unambiguous identification of biosignatures on Mars requires access to well-characterized, long-lasting geochemical standards at the planet's surface that can be modified by theoretical martian life. Ordinary chondrites, which are ancient meteorites that commonly fall to the surface of Mars and Earth, have well-characterized, narrow ranges in trace element and isotope geochemistry compared to martian rocks. Given that their mineralogy is more attractive to known chemolithotrophic life than the basaltic rocks that dominate the martian surface, exogenic rocks (e.g., chondritic meteorites) may be good places to look for signs of prior life endemic to Mars. In this study, we show that ordinary chondrites, collected from the arid Australian Nullarbor Plain, are commonly colonized and inhabited by terrestrial microorganisms that are endemic to this Mars analogue site. These terrestrial endolithic and chasmolithic microbial contaminants are commonly found in close association with hygroscopic veins of gypsum and Mg-calcite, which have formed within cracks penetrating deep into the meteorites. Terrestrial bacteria are observed within corrosion cavities, where troilite (FeS) oxidation has produced jarosite [KFe3(SO4)2(OH)6]. Where terrestrial microorganisms have colonized primary silicate minerals and secondary calcite, these mineral surfaces are heavily etched. Our results show that inhabitation of meteorites by terrestrial microorganisms in arid environments relies upon humidity and pH regulation by minerals. Furthermore, microbial colonization affects the weathering of meteorites and production of sulfate, carbonate, Fe-oxide and smectite minerals that can preserve chemical and isotopic biosignatures for thousands to millions of years on Earth. Meteorites are thus habitable by terrestrial microorganisms, even under highly desiccating environmental conditions of relevance to Mars. They may therefore be useful as chemical and isotopic ;standards; that preserve evidence of life, thereby providing the possibility of universal context for recognition of microbial biosignatures on Earth, Mars and throughout the solar system.

Constraints of C-O-S isotope compositions and the origin of the Ünlüpınar volcanic-hosted epithermal Pb-Zn ± Au deposit, Gümüşhane, NE Turkey

NASA Astrophysics Data System (ADS)

Akaryali, Enver; Akbulut, Kübra

2016-03-01

The Eastern Pontide Orogenic Belt (EPOB) constitutes one of the best examples of the metallogenic provinces in on the Alpine-Himalayan belt. This study focuses on the genesis of the Ünlüpınar Pb-Zn ± Au deposit in the southern part of the Eastern Pontide Orogenic Belt. The main lithological units in the study area are the Early Carboniferous Kurtoğlu Metamorphic Complex the Late Carboniferous Köse Granitoid and the Early-Middle Jurassic Şenköy Formation. The studied deposit is hosted by the Şenköy Formation, which consists predominantly of basaltic-andesitic rocks and associated pyroclastic rocks that are calc-alkaline in composition. Silicic, sulfidic, argillic, chloritic, hematitic, carbonate and limonite are the most obvious alteration types observed in the deposit site. Ore microscopy studies exhibit that the mineral paragenesis in deposits includes pyrite, chalcopyrite, sphalerite, galena, gold, quartz and calcite. Electron microprobe analyses conducted on sphalerite indicate that the Zn/Cd ratio varies between 84 and 204, and these ratios point at a hydrothermal deposit related to granitic magmas. Fluid inclusion studies in calcite and quartz show that the homogenization temperature of the studied deposit ranges between 90-160 °C and 120-330 °C respectively. The values of sulfur isotope analysis of pyrite, sphalerite and galena minerals vary between 1.6‰ and 5.7‰, and the results of oxygen and carbon isotope analysis range between 8.4‰ and 18‰ and -5‰ and -3.6‰, respectively. The average formation temperature of the ore was calculated as 264 °C with a sulfur isotope geothermometer. All of the data indicate that the Ünlüpınar deposit is an epithermal vein-type mineralization that was formed depending on the granitic magmatism.

Subseafloor fluid mixing and fossilized microbial life in a Cretaceous 'Lost City'-type hydrothermal system at the Iberian Margin

NASA Astrophysics Data System (ADS)

Klein, F.; Humphris, S. E.; Guo, W.; Schubotz, F.; Schwarzenbach, E. M.; Orsi, W.

2015-12-01

Subseafloor mixing of reduced hydrothermal fluids with seawater is believed to provide the energy and substrates needed to support autotrophic microorganisms in the hydrated oceanic mantle (serpentinite). Despite the potentially significant implications for the distribution of microbial life on Earth and other water-bearing planetary bodies, our understanding of such environments remains elusive. In the present study we examined fossilized microbial communities and fluid mixing processes in the subseafloor of a Cretaceous 'Lost City'-type hydrothermal system at the passive Iberia Margin (ODP Leg 149, Hole 897D). Brucite and calcite co-precipitated from mixed fluids ca. 65m below the Cretaceous palaeo-seafloor at temperatures of 32±4°C within steep chemical gradients (fO2, pH, CH4, SO4, ΣCO2, etc) between weathered, carbonate-rich serpentinite breccia and serpentinite. Mixing of oxidized seawater and strongly reducing hydrothermal fluid at moderate temperatures created conditions capable of supporting microbial activity within the oceanic basement. Dense microbial colonies are fossilized in brucite-calcite veins that are strongly enriched in organic carbon but depleted in 13C. We detected a combination of bacterial diether lipid biomarkers, archaeol and archaeal tetraethers analogous to those found in brucite-carbonate chimneys at the active Lost City hydrothermal field. The exposure of mantle rocks to seawater during the breakup of Pangaea fueled chemolithoautotrophic microbial communities at the Iberia Margin during the Cretaceous, possibly before the onset of seafloor spreading in the Atlantic. 'Lost City'-type serpentinization systems have been discovered at mid-ocean ridges, in forearc settings of subduction zones and at continental margins. It appears that, wherever they occur, they can support microbial life, even in deep subseafloor environments as demonstrated in the present study. Because equivalent systems have likely existed throughout most of Earth's history, fluid mixing may have provided the substrates and energy to support a unique subseafloor community of microorganisms over geological timescales.

Subseafloor fluid mixing and fossilized microbial life in a Cretaceous 'Lost City'-type hydrothermal system at the Iberian Margin

NASA Astrophysics Data System (ADS)

Klein, F.; Humphris, S. E.; Guo, W.; Schubotz, F.; Schwarzenbach, E. M.; Orsi, W.

2014-12-01

Subseafloor mixing of reduced hydrothermal fluids with seawater is believed to provide the energy and substrates needed to support autotrophic microorganisms in the hydrated oceanic mantle (serpentinite). Despite the potentially significant implications for the distribution of microbial life on Earth and other water-bearing planetary bodies, our understanding of such environments remains elusive. In the present study we examined fossilized microbial communities and fluid mixing processes in the subseafloor of a Cretaceous 'Lost City'-type hydrothermal system at the passive Iberia Margin (ODP Leg 149, Hole 897D). Brucite and calcite co-precipitated from mixed fluids ca. 65m below the Cretaceous palaeo-seafloor at temperatures of 32±4°C within steep chemical gradients (fO2, pH, CH4, SO4, ΣCO2, etc) between weathered, carbonate-rich serpentinite breccia and serpentinite. Mixing of oxidized seawater and strongly reducing hydrothermal fluid at moderate temperatures created conditions capable of supporting microbial activity within the oceanic basement. Dense microbial colonies are fossilized in brucite-calcite veins that are strongly enriched in organic carbon but depleted in 13C. We detected a combination of bacterial diether lipid biomarkers, archaeol and archaeal tetraethers analogous to those found in brucite-carbonate chimneys at the active Lost City hydrothermal field. The exposure of mantle rocks to seawater during the breakup of Pangaea fueled chemolithoautotrophic microbial communities at the Iberia Margin during the Cretaceous, possibly before the onset of seafloor spreading in the Atlantic. 'Lost City'-type serpentinization systems have been discovered at mid-ocean ridges, in forearc settings of subduction zones and at continental margins. It appears that, wherever they occur, they can support microbial life, even in deep subseafloor environments as demonstrated in the present study. Because equivalent systems have likely existed throughout most of Earth's history, fluid mixing may have provided the substrates and energy to support a unique subseafloor community of microorganisms over geological timescales.

Stable isotope and 14C study of biogenic calcrete in a termite mound, Western Cape, South Africa, and its palaeoenvironmental significance

NASA Astrophysics Data System (ADS)

Potts, Alastair J.; Midgley, Jeremy J.; Harris, Chris

2009-09-01

Late Quaternary terrestrial climate records from the semi-arid zone of the Western Cape of South Africa are rare. However, palaeoenvironmental information may be inferred from ancient termite mounds of the region. Calcrete lenses in these mounds have δ 13C and δ 18O values that show systematic changes with radiocarbon dates, which range from 33,629-36,709 to 21,676-23,256 cal yr BP. These dates confirm that these heuweltjies had been present in the landscape since the last glacial period. The decrease in δ 13C and δ 18O from 33,629-36,709 to 21,676-23,256 cal yr BP indicates that climate information is recorded by the calcretes. It is suggested that a progressive decline in air temperature and an increase in moisture availability, and a decline in abundance of C 4 or CAM plants, occurred in the region during the time heuweltjie calcite precipitated.

The chronology of hand stencils in European Palaeolithic rock art: implications of new U-series results from El Castillo Cave (Cantabria, Spain).

PubMed

García-Diez, Marcos; Garrido, Daniel; Hoffmann, Dirk; Pettitt, Paul; Pike, Alistair; Zilhão, Joao

2015-07-20

The hand stencils of European Paleolithic art tend to be considered of pre-Magdalenian age and scholars have generally assigned them to the Gravettian period. At El Castillo Cave, application of U-series dating to calcite accretions has established a minimum age of 37,290 years for underlying red hand stencils, implying execution in the earlier part of the Aurignacian if not beforehand. Together with the series of red disks, one of which has a minimum age of 40,800 years, these motifs lie at the base of the El Castillo parietal stratigraphy. The similarity in technique and colour support the notion that both kinds of artistic manifestations are synchronic and define an initial, non-figurative phase of European cave art. However, available data indicate that hand stencils continued to be painted subsequently. Currently, the youngest, reliably dated examples fall in the Late Gravettian, approximately 27,000 years ago.

In-situ growth of calcite at Devils Hole, Nevada: Comparison of field and laboratory rates to a 500,000 year record of near-equilibrium calcite growth

USGS Publications Warehouse

Plummer, Niel; Busenberg, E.; Riggs, A.C.

2000-01-01

Calcite grew continuously for 500,000 years on the submerged walls of an open fault plane (Devils Hole) in southern Nevada, U.S.A. at rates of 0.3 to 1.3 mm/ka, but ceased growing approximately 60,000 years ago, even though the fault plane remained open and was continuously submerged. The maximum initial in-situ growth rate on pre-weighed crystals of Iceland spar placed in Devils Hole (calcite saturation index, SI, is 0.16 to 0.21 at 33.7??C) for growth periods of 0.75 to 4.5 years was 0.22 mm/ka. Calcite growth on seed crystals slowed or ceased following initial contact with Devils Hole groundwater. Growth rates measured in synthetic Ca-HCO3 solutions at 34??C, CO2 partial pressures of 0.101, 0.0156 (similar to Devils Hole groundwater) and 0.00102 atm, and SI values of 0.2 to 1.9 were nearly independent of P(CO)(2), decreased with decreasing saturation state, and extrapolated through the historical Devils Hole rate. The results show that calcite growth rate is highly sensitive to saturation state near equilibrium. A calcite crystal retrieved from Devils Hole, and used without further treatment of its surface, grew in synthetic Devils Hole groundwater when the saturation index was raised nearly 10-fold that of Devils Hole water, but the rate was only 1/4 that of fresh laboratory crystals that had not contacted Devils Hole water. Apparently, inhibiting processes that halted calcite growth in Devils Hole 60,000 years ago continue today.

In-situ growth of calcite at Devils Hole, Nevada--Comparison of field and laboratory rates to a 500,000 year record of near-equilibrium calcite growth

USGS Publications Warehouse

Plummer, Niel; Busenberg, Eurybiades; Riggs, Alan C.

2000-01-01

Calcite grew continuously for 500,000 years on the submerged walls of an open fault plane (Devils Hole) in southern Nevada, U.S.A. at rates of 0.3 to 1.3 mm/ka, but ceased growing approximately 60,000 years ago, even though the fault plane remained open and was continuously submerged. The maximum initial in-situ growth rate on pre-weighed crystals of Iceland spar placed in Devils Hole (calcite saturation index, SI, is 0.16 to 0.21 at 33.7 °C) for growth periods of 0.75 to 4.5 years was 0.22 mm/ka. Calcite growth on seed crystals slowed or ceased following initial contact with Devils Hole groundwater. Growth rates measured in synthetic Ca-HCO3 solutions at 34 °C, CO2 partial pressures of 0.101, 0.0156 (similar to Devils Hole groundwater) and 0.00102 atm, and SI values of 0.2 to 1.9 were nearly independent of PCO2, decreased with decreasing saturation state, and extrapolated through the historical Devils Hole rate. The results show that calcite growth rate is highly sensitive to saturation state near equilibrium. A calcite crystal retrieved from Devils Hole, and used without further treatment of its surface, grew in synthetic Devils Hole groundwater when the saturation index was raised nearly 10-fold that of Devils Hole water, but the rate was only 1/4 that of fresh laboratory crystals that had not contacted Devils Hole water. Apparently, inhibiting processes that halted calcite growth in Devils Hole 60,000 years ago continue today.

Mg/Ca, Sr/Ca and Ca isotope ratios in benthonic foraminifers related to test structure, mineralogy and environmental controls

NASA Astrophysics Data System (ADS)

Gussone, Nikolaus; Filipsson, Helena L.; Kuhnert, Henning

2016-01-01

We analysed Mg/Ca, Sr/Ca and Ca isotope ratios of benthonic foraminifers from sediment core tops retrieved during several research cruises in the Atlantic Ocean, in order to improve the understanding of isotope fractionation and element partitioning resulting from biomineralisation processes and changes in ambient conditions. Species include foraminifers secreting tests composed of hyaline low magnesium calcite, porcelaneous high magnesium calcite as well as aragonite. Our results demonstrate systematic isotope fractionation and element partitioning patterns specific for these foraminiferal groups. Calcium isotope fractionation is similar in porcelaneous and hyaline calcite tests and both groups demonstrate the previously described anomaly with enrichment of heavy isotopes around 3-4 °C (Gussone and Filipsson, 2010). Calcium isotope ratios of the aragonitic species Hoeglundina elegans, on the other hand, are about 0.4‰ lighter compared to the calcitic species, which is in general agreement with stronger fractionation in inorganic aragonite compared to calcite. However, the low and strongly variable Sr content suggests additional processes during test formation, and we propose that transmembrane ion transport or a precursor phase to aragonite may be involved. Porcelaneous tests, composed of high Mg calcite, incorporate higher amounts of Sr compared to hyaline low Mg calcite, in agreement with inorganic calcite systematics, but also porcelaneous tests with reduced Mg/Ca show high Sr/Ca. While calcium isotopes, Sr/Ca and Mg/Ca in benthonic foraminifers primarily appear to fractionate and partition with a dominant inorganic control, δ44/40Ca temperature and growth rate dependencies of benthonic foraminifer tests favour a dominant contribution of light Ca by transmembrane transport relative to unfractionated seawater Ca to the calcifying fluid, thus controlling the formation of foraminiferal δ44/40Ca and Sr/Ca proxy signals.

Manganese-calcium intermixing facilitates heteroepitaxial growth at the (1014) calcite-water interface

DOE PAGES

Xu, Man; Riechers, Shawn L.; Ilton, Eugene S.; ...

2017-09-05

For this research, in situ atomic force microscopy (AFM) measurements were performed to probe surface precipitates that formed on the (10more » $$\\bar{1}$$4) surface of calcite (CaCO 3) single crystals following reaction with Mn2 +-bearing aqueous solutions. Three-dimensional epitaxial islands were observed to precipitate and grow on the surfaces. In situ time-sequenced measurements demonstrated that the growth rates were commensurate with those obtained for epitaxial islands formed on calcite crystals reacted with Cd2 +-bearing aqueous solutions of the same range in supersaturation with respect to the pure metal carbonate phase. This finding was unexpected as rhodochrosite (MnCO 3) and calcite display a 10% lattice mismatch, based on the area of their (10$$\\bar{1}$$4) surface unit cells, whereas the lattice mismatch is only 4% for otavite (CdCO 3) and calcite. Coatings of varying thicknesses were therefore synthesized by reacting calcite single crystals in calcite-equilibrated aqueous solutions with up to 250 μM MnCl 2. Ex situ X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray reflectivity (XRR), and AFM measurements of the reacted crystals demonstrated the formation of an epitaxial (Mn,Ca)CO 3 solid solution. The epitaxial solid solution had a spatially complex composition, whereby the first few nanometers were rich in Ca and the Mn content increased with distance from the original calcite surface, culminating in a topmost region of almost pure MnCO 3 for the thickest coatings. The effective lattice mismatch was therefore much smaller than the nominal mismatch thus explaining the measured growth rates. Lastly, these findings highlight the strong influence played by the substrate on the composition of surface precipitates in aqueous conditions.« less

Thermal and Evolved Gas Behavior of Calcite Under Mars Phoenix TEGA Operating Conditions

NASA Technical Reports Server (NTRS)

Ming, D.W.; Niles, P.B.; Morris, R.V.; Boynton, W.V.; Golden, D.C.; Lauer, H.V.; Sutter, B.

2009-01-01

The Mars Phoenix Scout Mission with its diverse instrument suite successfully examined several soils on the Northern plains of Mars. The Thermal and Evolved Gas Analyzer (TEGA) was employed to detect organic and inorganic materials by coupling a differential scanning calorimeter (DSC) with a magnetic-sector mass spectrometer (MS). Martian soil was heated up to 1000 C in the DSC ovens and evolved gases from mineral decomposition products were examined with the MS. TEGA s DSC has the capability to detect endothermic and exothermic reactions during heating that are characteristic of minerals present in the Martian soil. Initial TEGA results indicated the presence of endothermic peaks with onset temperatures that ranged from 675 C to 750 C with corresponding CO2 release. This result suggests the presence of calcite (CaCO3. CaO + CO2). Organic combustion to CO2 is not likely since this mostly occurs at temperatures below 550 C. Fe-carbonate and Mg-carbonate are not likely because their decomposition temperatures are less than 600 C. TEGA enthalpy determinations suggest that calcite, may occur in the Martian soil in concentrations of approx.1 to 5 wt. %. The detection of calcite could be questioned based on previous results that suggest Mars soils are mostly acidic. However, the Phoenix landing site soil pH was measured at pH 8.3 0.5, which is typical of terrestrial soils where pH is controlled by calcite solubility. The range of onset temperatures and calcite concentration as calculated by TEGA is poorly con-strained in part because of limited thermal data of cal-cite at reduced pressures. TEGA operates at <30 mbar while most calcite literature thermal data was obtained at 1000 mbar or higher pressures.

The chemical evolution of a travertine-depositing stream: Geochemical processes and mass transfer reactions

USGS Publications Warehouse

Lorah, Michelle M.; Herman, Janet S.

1988-01-01

This field study focuses on quantitatively defining the chemical changes occurring in Falling Spring Creek, a travertine-depositing stream located in Alleghany County, Virginia. The processes of CO2outgassing and calcite precipitation or dissolution control the chemical evolution of the stream. The observed chemical composition of the water was used with the computerized geochemical model WATEQF to calculate aqueous speciation, saturation indices, and CO2 partial pressure values. Mass balance calculations were performed to obtain mass transfers of CO2 and calcite. Reaction times, estimated from stream discharge, were used with the mass transfer results to calculate rates of CO2, outgassing and calcite precipitation between consecutive sampling points. The stream, which is fed by a carbonate spring, is supersaturated with respect to CO2 along the entire 5.2-km flow path. Outgassing of CO2 drives the solution to high degrees of supersaturation with respect to calcite. Metabolic uptake of CO2 by photosynthetic plants is insignificant, because the high supply rate of dissolved carbon dioxide and the extreme agitation of the stream at waterfalls and rapids causes a much greater amount of inorganic CO2 outgassing to occur. Calcite precipitation is kinetically inhibited until near the crest of a 20-m vertical waterfall. Calcite precipitation rates then reach a maximum at the waterfall where greater water turbulence allows the most rapid escape of CO2. Physical evidence for calcite precipitation exists in the travertine deposits which are first observed immediately above the waterfall and extend for at least 1.0 km below the falls. Net calcite precipitation occurs at all times of the year but is greatest during low-flow conditions in the summer and early fall.

Occurrence and genesis of Quaternary microbialitic tufa at Hammam Al Ali, Oman

NASA Astrophysics Data System (ADS)

Khalaf, Fikry I.

2017-05-01

Remnants of late Quaternary microbialitic tufa occurs within a shallow depression in the Hammam Al Ali hot spring area, which is located approximately 14.5 km to the southwest of Muscat, Oman. The tufa precipitated from hot spring water supersaturated with respect to calcium carbonate and is mostly of a porous phytogenic type, with occasional detrital and stromatolitic types. Microscopic and nanoscopic examination revealed that the tufa deposits developed through two successive processes of calcite precipitation, biotic and abiotic, preceded by limited precipitation of unstable aragonite. It is suggested that biologically mediated precipitation results in the construction of incomplete skeletal calcite crystals. The latter provide a base for classical physiochemical precipitation and, eventually, the development of complete sparry calcite crystals. The initiation of dendritic calcite crystals in the stromatolitic tufa as incomplete biogenic skeletal crystals and their characteristic growth pattern indicates that the tufa represents a clear example of hot spring calcitic microbialite.

Experimental diagenesis: insights into aragonite to calcite transformation of Arctica islandica shells by hydrothermal treatment

NASA Astrophysics Data System (ADS)

Casella, Laura A.; Griesshaber, Erika; Yin, Xiaofei; Ziegler, Andreas; Mavromatis, Vasileios; Müller, Dirk; Ritter, Ann-Christine; Hippler, Dorothee; Harper, Elizabeth M.; Dietzel, Martin; Immenhauser, Adrian; Schöne, Bernd R.; Angiolini, Lucia; Schmahl, Wolfgang W.

2017-03-01

Biomineralised hard parts form the most important physical fossil record of past environmental conditions. However, living organisms are not in thermodynamic equilibrium with their environment and create local chemical compartments within their bodies where physiologic processes such as biomineralisation take place. In generating their mineralised hard parts, most marine invertebrates produce metastable aragonite rather than the stable polymorph of CaCO3, calcite. After death of the organism the physiological conditions, which were present during biomineralisation, are not sustained any further and the system moves toward inorganic equilibrium with the surrounding inorganic geological system. Thus, during diagenesis the original biogenic structure of aragonitic tissue disappears and is replaced by inorganic structural features. In order to understand the diagenetic replacement of biogenic aragonite to non-biogenic calcite, we subjected Arctica islandica mollusc shells to hydrothermal alteration experiments. Experimental conditions were between 100 and 175 °C, with the main focus on 100 and 175 °C, reaction durations between 1 and 84 days, and alteration fluids simulating meteoric and burial waters, respectively. Detailed microstructural and geochemical data were collected for samples altered at 100 °C (and at 0.1 MPa pressure) for 28 days and for samples altered at 175 °C (and at 0.9 MPa pressure) for 7 and 84 days. During hydrothermal alteration at 100 °C for 28 days most but not the entire biopolymer matrix was destroyed, while shell aragonite and its characteristic microstructure was largely preserved. In all experiments up to 174 °C, there are no signs of a replacement reaction of shell aragonite to calcite in X-ray diffraction bulk analysis. At 175 °C the replacement reaction started after a dormant time of 4 days, and the original shell microstructure was almost completely overprinted by the aragonite to calcite replacement reaction after 10 days. Newly formed calcite nucleated at locations which were in contact with the fluid, at the shell surface, in the open pore system, and along growth lines. In the experiments with fluids simulating meteoric water, calcite crystals reached sizes up to 200 µm, while in the experiments with Mg-containing fluids the calcite crystals reached sizes up to 1 mm after 7 days of alteration. Aragonite is metastable at all applied conditions. Only a small bulk thermodynamic driving force exists for the transition to calcite. We attribute the sluggish replacement reaction to the inhibition of calcite nucleation in the temperature window from ca. 50 to ca. 170 °C or, additionally, to the presence of magnesium. Correspondingly, in Mg2+-bearing solutions the newly formed calcite crystals are larger than in Mg2+-free solutions. Overall, the aragonite-calcite transition occurs via an interface-coupled dissolution-reprecipitation mechanism, which preserves morphologies down to the sub-micrometre scale and induces porosity in the newly formed phase. The absence of aragonite replacement by calcite at temperatures lower than 175 °C contributes to explaining why aragonitic or bimineralic shells and skeletons have a good potential of preservation and a complete fossil record.

Age and significance of the Quaternary cemented deposits of the Duje Valley (Picos de Europa, Northern Spain)

NASA Astrophysics Data System (ADS)

Villa, Elisa; Stoll, Heather; Farias, Pedro; Adrados, Luna; Edwards, R. Lawrence; Cheng, Hai

2013-01-01

Cemented calcareous breccias appear in the Picos de Europa (Cantabrian Mountains, Spain) resting on glacially abraded surfaces and covered by moraines. U/Th dating of the calcite coating the clasts was successful in two samples, the oldest one indicating that the breccias accumulated during or prior to Marine Isotope Stage (MIS) 11, and the youngest indicating later cementation during MIS 8. The former introduces a limit for the age of the glaciation preceding the breccias, which cannot correspond to an event younger than MIS 12. This is the oldest absolute age so far obtained for intercalated glacial/interglacial deposits of the Iberian Peninsula.

Constraints on the thermal history of Taylorsville Basin, Virginia, U.S.A., from fluid-inclusion and fission-track analyses: Implications for subsurface geomicrobiology experiments

USGS Publications Warehouse

Tseng, H.-Y.; Onstott, T.C.; Burruss, R.C.; Miller, D.S.

1996-01-01

Microbial populations have been found at the depth of 2621-2804 m in a borehole near the center of Triassic Taylorsville Basin, Virginia. To constrain possible scenarios for long-term survival in or introduction of these microbial populations to the deep subsurface, we attempted to refine models of thermal and burial history of the basin by analyzing aqueous and gaseous fluid inclusions in calcite/quartz veins or cements in cuttings from the same borehole. These results are complemented by fission-track data from the adjacent boreholes. Homogenization temperatures of secondary aqueous fluid inclusions range from 120?? to 210??C between 2027- and 3069-m depth, with highest temperatures in the deepest samples. The salinities of these aqueous inclusions range from 0 to ??? 4.3 eq wt% NaCl. Four samples from the depth between 2413 and 2931 m contain both two-phase aqueous and one-phase methane-rich inclusions in healed microcracks. The relative CH4 and CO2 contents of these gaseous inclusions was estimated by microthermometry and laser Raman spectroscopy. If both types of inclusions in sample 2931 m were trapped simultaneously, the density of the methane-rich inclusions calculated from the Peng - Robinson equation of state implies an entrapment pressure of 360 ?? 20 bar at the homogenization temperature (162.5 ?? 12.5??C) of the aqueous inclusions. This pressure falls between the hydrostatic and lithostatic pressures at the present depth 2931 m of burial. If we assume that the pressure regime was hydrostatic at the time of trapping, then the inclusions were trapped at 3.6 km in a thermal gradient of ??? 40??C/km. The high temperatures recorded by the secondary aqueous inclusions are consistent with the pervasive resetting of zircon and apatite fission-track dates. In order to fit the fission-track length distributions of the apatite data, however, a cooling rate of 1-2??C/Ma following the thermal maximum is required. To match the integrated dates, the thermal maximum would have occurred at ??? 200 Ma. The timing of the maximum temperature is consistent with rapid burial of the Taylorsville Basin to twice its present-day depth and thermal re-equilibration with a 40??C/km geothermal gradient, followed by slow exhumation. The results may imply that the microorganisms did not survive in situ, but were transported from the cooler portions of the basin sometime after maximum burial and heating.

Computer-Controlled Microwave Drying of Potentially Difficult Organic and Inorganic Soils

DTIC Science & Technology

1990-12-01

materials, fly ash, gypsum rich soils, calcite rich soils, organic clay,, peat, and halloysite rich soils. Because specimen sizes too large to be...measurement Field monitoring equipment User’s manual 19. A3STRACT (Continued). materials, organic clay, fly ash, and calcite rich soils are demonstrated...39 Factors Influencing Dehydration ..................................... 42 PART X: STUDIES OF CALCITE

Metamorphism and gold mineralization in the Blue Ridge, Southernmost Appalachians

USGS Publications Warehouse

Stowell, H.H.; Lesher, C.M.; Green, N.L.; Sha, P.; Guthrie, G.M.; Sinha, A.K.

1996-01-01

Lode gold mineralization in the Blue Ridge of the southernmost Appalachians is hosted by metavolcanic rocks (e.g., Anna Howe mine, AL; Royal Vindicator mine, GA), metaplutonic rocks (e.g., Hog Mountain mine, AL), and metasedimentary rocks (e.g., Lowe, Tallapoosa, and Jones Vein mines, AL). Most gold occurs in synkinematic quartz ?? plagioclase ?? pyrite ?? pyrrhotite ?? chlorite veins localized along polydeformational faults that juxtapose rocks with significantly different peak metamorphic mineral assemblages. Mineralogy, chemistry, and O and H isotope studies suggest that the three types of host rocks have undergone differing amounts and types of alteration during mineralization. Limited wall-rock alteration in metavolcanic- and metasediment-hosted deposits, and relatively extensive wall-rock alteration in granitoid-hosted deposits, suggests that most deposits formed from fluids that were close to equilibrium with metavolcanic and metasedimentary rocks. Stable isotope compositions of the fluids calculated from vein minerals and vein selvages are consistent with a predominantly metasedimentary fluid source, but vary from deposit to deposit (-22 to -47??? ??D, 4-5??? ??18O, and 5-7??? ??34S at Anna Howe and Royal Vindicator; -48 to -50??? ??D, 9-13??? ??18O, and ca. 19??? ??34S at Lowe and Jones Vein; and -22 to -23??? ??D, 8-11??? ??18O, 9-10??? ??34S, and -6 ??13C at Hog Mountain). Silicate mineral thermobarometry of vein, vein selvage, and wall-rock mineral assemblages indicate that mineralization and regional metamorphism occured at greenschist to amphibolite facies (480?? ?? 75??C at Anna Howe, 535?? ?? 50??C at 6.4 ?? 1 kbars at Lowe, 530?? ?? 50??C at 6.9 ?? 1 kbars at Tallapoosa, and 460?? ?? 50??C at 5.5 ?? 1 kbars at Hog Mountain). Oxygen isotope fractionation between vein minerals and selvage minerals consistently records equilibration temperatures that are similar to or slightly lower than those estimated from silicate thermometry. Auriferous veins contain numerous fluid inclusions that were emplaced in several stages and can be subdivided into five compositional types based on salt and CO2 concentrations. Fluid inclusion isochores for early formed inclusions from these veins intercept the pressure and temperature conditions estimated from silicate mineral thermobarometry and stable isotope thermometry, and are compatible with entrapment at those conditions. These fluids exhibit significant variation in salinity (XNaClequiv = 0.0-0.2) and CO2 (XCO2 = 0.0-0.2), suggesting variation in fluid-wall-rock interaction that accompanied gold deposition during declining temperatures. Less abundant and later fluids within the veins are dominantly CO2. The association of gold mineralization with structurally controlled concordant and discordant quartz sulfide veins, and the temperatures and pressures of wall-rock alteration and regional metamorphism indicate that the present distribution of gold is a result of metamorphism during progressive D2-D3 deformation. Isotopic data for alteration envelopes date this event as Alleghanian: 279 ?? 14 Ma (K-Ar whole rock) and 343 ?? 18 Ma (K-Ar biotite) at Lowe; and 315 ?? 18 Ma (Rb-Sr whole-rock isochron; 87Sr/86Sr, = 0.7061 ?? 0.0008) and 294 ?? 16 Ma (K-Ar whole-rock) at Hog Mountain. Available data are compatible with development of the lodes during early Alleghanian overthrusting of allochthons over sedimentary rocks of the autochthonous North American margin. The implication is that the fluids were derived from metasedimentary and/or metavolcanic formations in the lower parts of the crystalline thrust stack (or possibly from underlying autochthonous sedimentary formations), ascended along permeable fault zones, and were emplaced as veins into dilatent areas in and adjacent to the fault zones.

Quantifying Rock Weakening Due to Decreasing Calcite Mineral Content by Numerical Simulations

PubMed Central

2018-01-01

The quantification of changes in geomechanical properties due to chemical reactions is of paramount importance for geological subsurface utilisation, since mineral dissolution generally reduces rock stiffness. In the present study, the effective elastic moduli of two digital rock samples, the Fontainebleau and Bentheim sandstones, are numerically determined based on micro-CT images. Reduction in rock stiffness due to the dissolution of 10% calcite cement by volume out of the pore network is quantified for three synthetic spatial calcite distributions (coating, partial filling and random) using representative sub-cubes derived from the digital rock samples. Due to the reduced calcite content, bulk and shear moduli decrease by 34% and 38% in maximum, respectively. Total porosity is clearly the dominant parameter, while spatial calcite distribution has a minor impact, except for a randomly chosen cement distribution within the pore network. Moreover, applying an initial stiffness reduced by 47% for the calcite cement results only in a slightly weaker mechanical behaviour. Using the quantitative approach introduced here substantially improves the accuracy of predictions in elastic rock properties compared to general analytical methods, and further enables quantification of uncertainties related to spatial variations in porosity and mineral distribution. PMID:29614776

Iodine Incorporation in Calcite: Insights from Computational and Experimental Study

NASA Astrophysics Data System (ADS)

Feng, X.; Redfern, S. A. T.

2016-12-01

The incorporation of iodine into calcite is important both in the context of radioactive waste disposal (carbonates seem to be the principal host for iodine at the Hnaford site) as well as in paleoproxy methods applied in paleo-oceanography, where iodine content has been proposed as a proxy for fO2. Here, we report on studies of iodine incorporation into calcite carried out by a combination of earlier X-Ray absorption spectroscopy, Raman spectroscopy, X-Ray diffraction and new ab initio DFT calculations (using VASP). Our results show that iodine is principally incorporated into the calcite lattice as IO3, replacing carbon in the carbonate group. The much larger size of iodine, and different outer shell electronic configuration, leads to a distortion of the calcite structure locally. Our DFT results show that the adjacent layers of CO3 groups are significantly distorted, over a length scale of around 0.5 nm, and that this distortion leads to a slight increase in enthalpy associated with the iodine point defect. The relationship to the distorted structure of calcite II is considered, and the role of iodine as an agent of "internal pressure" will be discussed.

Quantifying Rock Weakening Due to Decreasing Calcite Mineral Content by Numerical Simulations.

PubMed

Wetzel, Maria; Kempka, Thomas; Kühn, Michael

2018-04-01

The quantification of changes in geomechanical properties due to chemical reactions is of paramount importance for geological subsurface utilisation, since mineral dissolution generally reduces rock stiffness. In the present study, the effective elastic moduli of two digital rock samples, the Fontainebleau and Bentheim sandstones, are numerically determined based on micro-CT images. Reduction in rock stiffness due to the dissolution of 10% calcite cement by volume out of the pore network is quantified for three synthetic spatial calcite distributions (coating, partial filling and random) using representative sub-cubes derived from the digital rock samples. Due to the reduced calcite content, bulk and shear moduli decrease by 34% and 38% in maximum, respectively. Total porosity is clearly the dominant parameter, while spatial calcite distribution has a minor impact, except for a randomly chosen cement distribution within the pore network. Moreover, applying an initial stiffness reduced by 47% for the calcite cement results only in a slightly weaker mechanical behaviour. Using the quantitative approach introduced here substantially improves the accuracy of predictions in elastic rock properties compared to general analytical methods, and further enables quantification of uncertainties related to spatial variations in porosity and mineral distribution.

Selective adsorption of benzhydroxamic acid on fluorite rendering selective separation of fluorite/calcite

NASA Astrophysics Data System (ADS)

Jiang, Wei; Gao, Zhiyong; Khoso, Sultan Ahmed; Gao, Jiande; Sun, Wei; Pu, Wei; Hu, Yuehua

2018-03-01

Fluorite, a chief source of fluorine in the nature, usually coexists with calcite mineral in ore deposits. Worldwide, flotation techniques with a selective collector and/or a selective depressant are commonly preferred for the separation of fluorite from calcite. In the present study, an attempt was made to use benzhydroxamic acid (BHA) as a collector for the selective separation of fluorite from calcite without using any depressant. Results obtained from the flotation experiments for single mineral and mixed binary minerals revealed that the BHA has a good selective collecting ability for the fluorite when 50 mg/L of BHA was used at pH of 9. The results from the zeta potential and X-ray photoelectron spectroscopy (XPS) indicated that the BHA easily chemisorbs onto the fluorite as compared to calcite. Crystal chemistry calculations showed the larger Ca density and the higher Ca activity on fluorite surface mainly account for the selective adsorption of BHA on fluorite, leading to the selective separation of fluorite from calcite. Moreover, a stronger hydrogen bonding with BHA and the weaker electrostatic repulsion with BHA- also contribute to the stronger interaction of BHA species with fluorite surface.

Site-specific incorporation of uranyl carbonate species at the calcite surface

NASA Astrophysics Data System (ADS)

Reeder, Richard J.; Elzinga, Evert J.; Tait, C. Drew; Rector, K. D.; Donohoe, Robert J.; Morris, David E.

2004-12-01

Spatially resolved luminescence spectra from U(VI) co-precipitated at the (101¯4) growth surface of synthetic calcite single crystals confirm heterogeneous incorporation corresponding to the distribution of structurally non-equivalent steps composing the vicinal surfaces of spiral growth hillocks. Spectral structure from U(VI) luminescence at the "-" vicinal regions and featureless, weak luminescence at the "+" vicinal regions are consistent with previously reported observations of enrichment at the former sites during calcite growth. Luminescence spectra differ between the non-equivalent regions of the crystal, with the spectral features from the "-" vicinal region corresponding to those observed in bulk calcite samples. Subtle spectral shifts are observed from U(VI) co-precipitated with microcrystalline calcite synthesized by a different method, and all of the U(VI)-calcite sample spectra differ significantly from that of U(VI) co-precipitated with aragonite. The step-selective incorporation of U(VI) can be explained by a proposed model in which the allowed orientation for adsorption of the dominant calcium uranyl triscarbonate species is controlled by the atomic arrangement at step edges. Differences in the tilt angles of carbonate groups between non-equivalent growth steps favor adsorption of the calcium uranyl triscarbonate species at "-" steps, as observed in experiments.

Physical and stable-isotope evidence for formation of secondary calcite and silica in the unsaturated zone, Yucca Mountain, Nevada

USGS Publications Warehouse

Whelan, J.F.; Paces, J.B.; Peterman, Z.E.

2002-01-01

Calcite and silica form coatings on fracture footwalls and cavity floors in the welded tuffs at Yucca Mountain, the potential site of a high-level radioactive waste repository. These secondary mineral deposits are heterogeneously distributed in the unsaturated zone (UZ) with fewer than 10% of possible depositional sites mineralized. The paragenetic sequence, compiled from deposits throughout the UZ, consists of an early-stage assemblage of calcite??fluorite??zeolites that is frequently capped by chalcedony??quartz. Intermediate- and late-stage deposits consist largely of calcite, commonly with opal on buried growth layers or outermost crystal faces of the calcite. Coatings on steep-dipping fractures usually are thin (??? 3 mm) with low-relief outer surfaces whereas shallow-dipping fractures and lithophysal cavities typically contain thicker, more coarsely crystalline deposits characterized by unusual thin, tabular calcite blades up to several cms in length. These blades may be capped with knobby or corniced overgrowths of late-stage calcite intergrown with opal. The observed textures in the fracture and cavity deposits are consistent with deposition from films of water fingering down fracture footwalls or drawn up faces of growing crystals by surface tension and evaporated at the crystal tips. Fluid inclusion studies have shown that most early-stage and some intermediate-stage calcite formed at temperatures of 35 to 85??C. Calcite deposition during the past several million years appears to have been at temperatures < 30??C. The elevated temperatures indicated by the fluid inclusions are consistent with temperatures estimated from calcite ??18O values. Although others have interpreted the elevated temperatures as evidence of hydrothermal activity and flooding of the tuffs of the potential repository, the authors conclude that the temperatures and fluid-inclusion assemblages are consistent with deposition in a UZ environment that experienced prolonged heat input from gradual cooling of nearby plutons. The physical restriction of the deposits (and, therefore, fluid flow) to fracture footwalls and cavity floors and the heterogeneous and limited distribution of the deposits provides compelling evidence that they do not reflect flooding of the thick UZ at Yucca Mountain. The textures and isotopic and chemical compositions of these mineral deposits are consistent with deposition in a UZ setting from meteoric waters percolating downward along fracture flow paths.

Ages and Origins of Calcite and Opal in the Exploratory Studies Facility Tunnel, Yucca Mountain, Nevada

USGS Publications Warehouse

Paces, James B.; Neymark, Leonid A.; Marshall, Brian D.; Whelan, Joseph F.; Peterman, Zell E.

2001-01-01

Deposits of calcite and opal are present as coatings on open fractures and lithophysal cavities in unsaturated-zone tuffs at Yucca Mountain, Nevada, site of a potential high-level radioactive waste repository. Outermost layers of calcite and opal have radiocarbon ages of 16,000 to 44,000 years before present and thorium-230/uranium ages of 28,000 to more than 500,000 years before present. These ages are young relative to the 13-million-year age of the host rocks. Multiple subsamples from the same outer layer typically show a range of ages with youngest ages from the thinnest subsamples. Initial uranium-234/uranium-238 activity ratios between 1 and 9.5 show a distinct negative correlation with thorium-230/uranium age and are greater than 4 for all but one sample younger than 100,000 years before present. These data, along with micrometer-scale layering and distinctive crystal morphologies, are interpreted to indicate that deposits formed very slowly from water films migrating through open cavities. Exchanges of carbon dioxide and water vapor probably took place between downward-migrating liquids and upward-migrating gases at low rates, resulting in oversaturation of mineral constituents at crystal extremities and more or less continuous deposition of very thin layers. Therefore, subsamples represent mixtures of older and younger layers on a scale finer than sampling techniques can resolve. Slow, long-term rates of deposition (less than about 5 millimeters of mineral per million years) are inferred from subsamples of outermost calcite and opal. These growth rates are similar to those calculated assuming that total coating thicknesses of 10 to 40 millimeters accumulated over 12 million years. Calcite has a wide range of delta carbon-13 values from about -8.2 to 8.5 per mil and delta oxygen-18 values from about 10 to 21 per mil. Systematic microsampling across individual mineral coatings indicates basal (older) calcite tends to have the largest delta carbon-13 values and smallest delta oxygen-18 values compared to calcite from intermediate and outer positions. Basal calcite has relatively small strontium-87/strontium-86 ratios, between 0.7105 and 0.7120, that are similar to the initial isotopic compositions of the strontium-rich tuff units, whereas outer calcite has more radiogenic strontium-87/strontium-86 ratios between 0.7115 and 0.7127. Isotopic compositions of strontium, oxygen, and carbon in the outer (youngest) unsaturated-zone calcite are coincident with those measured in Yucca Mountain calcrete, which formed by pedogenic processes. The physical and isotopic data from calcite and opal indicate that they formed from solutions of meteoric origin percolating through a limited network of connected fracture pathways in the unsaturated zone rather than by inundation from ascending ground water originating in the saturated zone. Mineral assemblages, textures, and distributions within the unsaturated zone are distinctly different from those deposited below the water table at Yucca Mountain. The calcite and opal typically are present only on footwall surfaces of a small fraction of fractures and only on floors of a small fraction of lithophysal cavities. The similarities in the carbon, oxygen, and strontium isotopic compositions between fracture calcite and soil-zone calcite, as well as the gradation of textures from detritus-rich micrite in the soil to detritus-free spar 10 to 30 meters below the surface, also support a genetic link between the two depositional environments. Older deposits contain oxygen isotope compositions that indicate elevated temperatures of mineral formation during the early stages of deposition; however, in the youngest deposits these values are consistent with deposition under geothermal gradients similar to modern conditions. Correlations between mineral ages and varying Pleistocene climate conditions are not apparent from the current data. Cumulative evidence from calcite and opal deposits indicate

New Comprehensive System to Construct Speleothem Fabrics Time Series

NASA Astrophysics Data System (ADS)

Frisia, S.; Borsato, A.

2014-12-01

Speleothem fabrics record processes that influence the way geochemical proxy data are encoded in speleothems, yet, there has been little advance in the use of fabrics as a complement to palaeo-proxy datasets since the fabric classification proposed by us in 2010. The systematic use of fabrics documentation in speleothem science has been limited by the absence of a comprehensive, numerical system that would allow constructing fabric time series comparable with the widely used geochemical time series. Documentation of speleothem fabrics is fundamental for a robust interpretation of speleothem time series where stable isotopes and trace elements are used as proxy, because fabrics highlight depositional as well as post-depositional processes whose understanding complements reconstructions based on geochemistry. Here we propose a logic system allowing transformation of microscope observations into numbers tied to acronyms that specify each fabric type and subtype. The rationale for ascribing progressive numbers to fabrics is based on the most up-to-date growth models. In this conceptual framework, the progression reflects hydrological conditions, bio-mediation and diagenesis. The lowest numbers are given to calcite fabrics formed at relatively constant drip rates: the columnar types (compact and open). Higher numbers are ascribed to columnar fabrics characterized by presence of impurities that cause elongation or lattice distortion (Elongated, Fascicular Optic and Radiaxial calcites). The sequence progresses with the dendritic fabrics, followed by micrite (M), which has been observed in association with microbial films. Microsparite (Ms) and mosaic calcite (Mc) have the highest numbers, being considered as diagenetic. Acronyms and subfixes are intended to become universally acknowledged. Thus, fabrics can be plotted vs. age to yield time series, where numbers are replaced by the acronyms. This will result in a visual representation of climate- or environmental-related parameters underpinning speleothem crystal growth. The Fabric log thus becomes a useful tool providing robustness to the geochemical data or test the overall utility of the speleothem record.

Multi-proxy evidence of millennial climate variability from multiple Bahamian speleothems

NASA Astrophysics Data System (ADS)

Arienzo, Monica M.; Swart, Peter K.; Broad, Kenneth; Clement, Amy C.; Pourmand, Ali; Kakuk, Brian

2017-04-01

Northern Hemisphere tropical paleoclimate records support significant changes associated with Dansgaard Oeschger (D/O) events and Heinrich stadials 1 to 6 during the last 64,000 years. However, few absolutely dated terrestrial records from the western Atlantic span the last six Heinrich stadials. Here we present geochemical results from three new stalagmites collected from a cave in the Bahamas which encompass Heinrich stadials 1 to 6. We build on a previous study of the δ13C and δ18O values of the calcite and δ18O value of fluid inclusions from a single stalagmite from the same cave spanning the last three Heinrich stadials. Absolute geochronometry using U-Th equilibrium series demonstrates that the stalagmites formed between 63.8 and 13.8 kyr BP. The δ13C and δ18O values of the calcite show higher values associated with Heinrich stadials 1-6, and lower values during the D/O interstadial events. The Sr/Ca ratios of the calcite are shown to be relatively invariant, while in two of the samples the Mg/Ca ratios track the δ13C values. Increases in the δ18O values across Heinrich stadials 1-6 are interpreted as being driven by lower temperatures. The two deeper occurring stalagmites demonstrate increased Mg/Ca ratios and δ13C values during Heinrich stadials 1 and 2 which are interpreted as a signal of reduced flow rates in the epikarst and increased water/rock interactions as a result of increased aridity which potentially occurred across all six Heinrich stadials. The observed reductions in mean annual temperature and amount of precipitation across Heinrich stadials are proposed to be driven by a reduction in sea surface temperatures in the North Atlantic and an expanded Bermuda High. During D/O interstadials, the Bahamas cave records likely indicate warmer and/or wetter climate; however the isotopic shifts are not as significant as the isotopic excursions associated with Heinrich stadials.

The influence of kinetics on the oxygen isotope composition of calcium carbonate

NASA Astrophysics Data System (ADS)

Watkins, James M.; Nielsen, Laura C.; Ryerson, Frederick J.; DePaolo, Donald J.

2013-08-01

Paleotemperature reconstructions rely on knowledge of the equilibrium separation of oxygen isotopes between aqueous solution and calcium carbonate. Although oxygen isotope separation is expected on theoretical grounds, the temperature-dependence remains uncertain because other factors, such as slow exchange of isotopes between dissolved CO2-species and water, can obscure the temperature signal. This is problematic for crystal growth experiments on laboratory timescales and for interpreting the oxygen isotope composition of crystals formed in natural settings. We present results from experiments in which inorganic calcite is precipitated in the presence of 0.25 μM dissolved bovine carbonic anhydrase (CA). The presence of dissolved CA accelerates oxygen isotope equilibration between the dissolved carbon species CO2, H2CO3, HCO3-, CO32- and water, thereby eliminating this source of isotopic disequilibrium during calcite growth. The experimental results allow us to isolate, for the first time, kinetic oxygen isotope effects occurring at the calcite-water interface. We present a framework of ion-by-ion growth of calcite that reconciles our new measurements with measurements of natural cave calcites that are the best candidate for having precipitated under near-equilibrium conditions. Our findings suggest that isotopic equilibrium between calcite and water is unlikely to have been established in laboratory experiments or in many natural settings. The use of CA in carbonate precipitation experiments offers new opportunities to refine oxygen isotope-based geothermometers and to interrogate environmental variables other than temperature that influence calcite growth rates.

Control and distribution of uranium in coral reefs during diagenesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gvirtzman, G.; Friedman, G.M.; Miller, D.S.

1973-12-01

The concentration of about 2 ppM of uranium in the aragonitic skeletons of modern scleractinian corals which we studied is a constant value, regardless of occurrence, anatomy, or taxonomy. The presence of cement of aragonite or high- magnesian calcite usually raises the concentration of bulk samples to about 3 ppM. Modern corals may contain up to 50% of cementing minerals. Organisms, such as corals and coralline algae, while secreting their skeleton, discriminate against the uptake of uranium, whereas the uptake of uranium by mineral cements is less restrained. Aragonite cement contains about 3.6 ppM and highmagnesian calcite cement 2.6 ppMmore » uranium. During leaching by freshwater, the aragonite of the skeletons of corals dissolves out. This creates hollow molds which fill with drusy low-magnesian calcite. In emergent reefs from the shores of the Red Sea which display the ellects of progressive diagenesis this calcite is enriched in uranium (3.9 ppM) beyond that found in marine cements. Second-generation calcite, which fills original voids in the corals from the emergent reefs, contains a lower level of uranium concent ration (1.3 ppM). The level of concentration of uranium in low-magnesian calcite of diagenetically altered corals is a function of the availability of uranium in meteoric waters. In aragonite as well as in high- and low-magnesian calcite uranium replaces calcium or occupies lattice vacancies in the crystal lattice. (auth)« less

Surface Complexation Modeling of Calcite Zeta Potential Measurement in Mixed Brines for Carbonate Wettability Characterization

NASA Astrophysics Data System (ADS)

Song, J.; Zeng, Y.; Biswal, S. L.; Hirasaki, G. J.

2017-12-01

We presents zeta potential measurements and surface complexation modeling (SCM) of synthetic calcite in various conditions. The systematic zeta potential measurement and the proposed SCM provide insight into the role of four potential determining cations (Mg2+, SO42- , Ca2+ and CO32-) and CO2 partial pressure in calcite surface charge formation and facilitate the revealing of calcite wettability alteration induced by brines with designed ionic composition ("smart water"). Brines with varying potential determining ions (PDI) concentration in two different CO2 partial pressure (PCO2) are investigated in experiments. Then, a double layer SCM is developed to model the zeta potential measurements. Moreover, we propose a definition for contribution of charged surface species and quantitatively analyze the variation of charged species contribution when changing brine composition. After showing our model can accurately predict calcite zeta potential in brines containing mixed PDIs, we apply it to predict zeta potential in ultra-low and pressurized CO2 environments for potential applications in carbonate enhanced oil recovery including miscible CO2 flooding and CO2 sequestration in carbonate reservoirs. Model prediction reveals that pure calcite surface will be positively charged in all investigated brines in pressurized CO2 environment (>1atm). Moreover, the sensitivity of calcite zeta potential to CO2 partial pressure in the various brine is found to be in the sequence of Na2CO3 > Na2SO4 > NaCl > MgCl2 > CaCl2 (Ionic strength=0.1M).

Initial formation of calcite crystals in the thin prismatic layer with the periostracum of Pinctada fucata.

PubMed

Suzuki, Michio; Nakayama, Seiji; Nagasawa, Hiromichi; Kogure, Toshihiro

2013-02-01

Although the formation mechanism of calcite crystals in the prismatic layer has been studied well in many previous works, the initial state of calcite formation has not been observed in detail using electron microscopes. In this study, we report that the soft prismatic layer with transparent color (the thin prismatic layer) in the tip of the fresh shell of Pinctada fucata was picked up to observe the early calcification phase. A scanning electron microscope (SEM) image showed that the growth tip of the thin prismatic layer was covered by the periostracum, which was also where the initial formation of calcite crystals began. A cross-section containing the thin calcite crystals in the thin prismatic layer with the periostracum was made using a focused ion beam (FIB) system. In a transmission electron microscope (TEM) observation, the thin calcite crystal (thickness is about 1μm) on the periostracum was found to be a single crystal with the c-axis oriented perpendicular to the shell surface. On the other hand, many aggregated small particles consisting of bassanite crystals were observed in the periostracum suggesting the possibility that not only organic sulfate but also inorganic sulfates exist in the prismatic layer. These discoveries in the early calcification phase of the thin prismatic layer may help to clarify the mechanism of regulating the nucleation and orientation of the calcite crystal in the shell. Copyright © 2012 Elsevier Ltd. All rights reserved.

Sea urchin tooth mineralization: calcite present early in the aboral plumula.

PubMed

Stock, Stuart R; Veis, Arthur; Xiao, Xianghui; Almer, Jonathan D; Dorvee, Jason R

2012-11-01

In both vertebrate bone, containing carbonated hydroxyapatite as the mineral phase, and in invertebrate hard tissue comprised of calcium carbonate, a popular view is that the mineral phase develops from a long-lived amorphous precursor which later transforms into crystal form. Important questions linked to this popular view are: when and where is the crystallized material formed, and is amorphous solid added subsequently to the crystalline substrate? Sea urchin teeth, in which the earliest mineral forms within isolated compartments, in a time and position dependent manner, allow direct investigation of the timing of crystallization of the calcite primary plates. Living teeth of the sea urchin Lytechinus variegatus, in their native coelomic fluid, were examined by high-energy synchrotron X-ray diffraction. The diffraction data show that calcite is present in the most aboral portions of the plumula, representing the very earliest stages of mineralization, and that this calcite has the same crystal orientation as in the more mature adoral portions of the same tooth. Raman spectroscopy of the aboral plumula confirms the initial primary plate mineral material is calcite and does not detect amorphous calcium carbonate; in the more mature adoral incisal flange, it does detect a broader calcite peak, consistent with two or more magnesium compositions. We hypothesize that some portion of each syncytial membrane in the plumula provides the information for nucleation of identically oriented calcite crystals that subsequently develop to form the complex geometry of the single crystal sea urchin tooth. Copyright © 2012 Elsevier Inc. All rights reserved.

Sea urchin tooth mineralization: Calcite present early in the aboral plumula

PubMed Central

Stock, Stuart R.; Veis, Arthur; Xiao, Xianghui; Almer, Jonathan D.; Dorvee, Jason R.

2012-01-01

In both vertebrate bone, containing carbonated hydroxyapatite as the mineral phase, and in invertebrate hard tissue comprised of calcium carbonate, a popular view is that the mineral phase develops from a long-lived amorphous precursor which later transforms into crystal form. Important questions linked to this popular view are: When and where is the crystallized material formed, and is amorphous solid added subsequently to the crystalline substrate? Sea urchin teeth, in which the earliest mineral forms within isolated compartments, in a time and position dependent manner, allow direct investigation of the timing of crystallization of the calcite primary plates. Living teeth of the sea urchin Lytechinus variegatus, in their native coelomic fluid, were examined by high-energy synchrotron x-ray diffraction. The diffraction data show that calcite is present in the most aboral portions of the plumula, representing the very earliest stages of mineralization, and that this calcite has the same crystal orientation as in the more mature adoral portions of the same tooth. Raman spectroscopy of the aboral plumula confirms the initial primary plate mineral material is calcite and does not detect amorphous calcium carbonate; in the more mature adoral incisal flange, it does detect a broader calcite peak, consistent with two or more magnesium compositions. We hypothesize that some portion of each syncytial membrane in the plumula provides the information for nucleation of identically oriented calcite crystals that subsequently develop to form the complex geometry of the single crystal sea urchin tooth. PMID:22940703

Dolomitic marbles from the ultrahigh-pressure metamorphic Kimi complex in Rhodope, N.E. Greece

NASA Astrophysics Data System (ADS)

Mposkos, E.; Baziotis, I.; Proyer, A.; Hoinkes, G.

2006-09-01

Dolomitic marbles from the Organi and Pandrosos areas of the ultrahigh-pressure (UHP) metamorphic Kimi complex in East Rhodope, N.E. Greece have the mineral assemblage: Cal + Dol + Ol + Phl ± Di ± Hbl ± Spl ± Ti Chu + retrograde Srp and Chl. Several generations of calcite and dolomite with variable composition and texture represent different stages of the P T evolution: The first stage is represented by matrix dolomite (X_MgCO_3 = 0.48) and relic domains of homogenous composition in matrix calcite (X_MgCO_3 = 0.11 0.13); the second stage is evident from precipitation of lath-shaped and vermicular dolomite in matrix calcite. The third stage is represented by veinlets of almost pure CaCO3 and domainal replacement of prior calcite by nearly pure CaCO3 + Ca-rich dolomite (X_MgCO_3 = 0.34 0.43). Matrix dolomite adjacent to CaCO3 veinlets also becomes Ca-rich (X_MgCO_3 = 0.42). In fact, Ca-rich dolomites with X_MgCO_3 in the range of 0.40 0.34 are reported for the first time from metamorphic marbles. Coexisting Ca-rich dolomite and Mg-poor calcite cannot be explained by the calcite-dolomite miscibility gap. This assemblage rather suggests that Mg-poor calcite was aragonite originally, which formed together with Ca-rich dolomite according to the reaction Mg Cal → Arg + Dol (1) at ultrahigh pressures and temperatures above at least 850 °C, when dolomite becomes disordered and incorporates more Ca than coexisting aragonite does in terms of Mg. The simplest explanation of these observations probably is to suggest two metamorphic events: The first one represented by relic matrix carbonates at relatively low to moderate pressures and temperatures of ca. 750 °C, and the second one limited by the minimum temperatures for dolomite disorder (ca. 850 °C) and in the aragonite + dolomite stability field, i.e. at a minimum pressure of 3 GPa and, if the presence of diamond-bearing metapelites nearby is considered, at conditions of at least 850 °C and 4.3 GPa in the diamond stability field. As there is hardly any back-reaction of Ca-rich dolomite + Mg-poor calcite to Mg-rich calcite, peak temperatures remained below the reaction (1) and the exhumation path probably crossed the aragonite-calcite transition at much lower than peak temperature. Cooling and decompression must have both occurred extremely fast in order for the µm-sized Ca-rich dolomite textures to be preserved. An alternative explanation of the formation of “UHP”-textures and compositions is by a fluid influx that not only caused serpentinisation and chloritisation of silicates but also Mg-leaching from carbonates, particularly from Mg-rich calcite and its fine grained dolomite-precipitates, thus transforming them into Mg-poor calcite + Ca-rich dolomite.

Occurrences of ikaite and pseudomorphs after ikaite in Patagonian lakes - crystal morphologies and stable isotope composition

NASA Astrophysics Data System (ADS)

Oehlerich, Markus; Mayr, Christoph; Griesshaber, Erika; Ohlendorf, Christian; Zolitschka, Bernd; Sánchez-Pastor, Nuria; Kremer, Barbara; Lücke, Andreas; Oeckler, Oliver; Schmahl, Wolfgang

2010-05-01

Ikaite (CaCO3•6H2O), a hydrated calcium carbonate mineral occasionally found in marine sediments, has so far rarely been reported from non-marine sites. Modern ikaite and calcitic pseudomorphs after ikaite were recently discovered in Patagonian Argentina at the polymictic lakes of Laguna Potrok Aike (51°57´S, 70°23´W) and Laguna Cháltel (49°57´S, 71°07´W), respectively. Both lakes are of volcanic origin and have phosphorous-rich, alkaline waters, but differ in altitude (790 m asl and 110 m asl for Laguna Cháltel and Laguna Potrok Aike, respectively) and water temperature. The aim of this study is (1) to investigate conditions for the formation of ikaite and its transformation to more stable, water-free carbonate pseudomorphs after ikaite and (2) to assess the potential of ikaite and calcite pseudomorphs after ikaite as a paleoenvironmental tool in freshwater lakes. Crystallographic, morphological and isotopic characteristics of the pseudomorphs were investigated. Ikaite crystals were found (in September 2008) primarily on aquatic macrophytes and cyanobacteria colonies at Laguna Potrok Aike. Ikaite crystals transformed quickly to calcite pseudomorphs after ikaite after recovery from the cool lake water (4°C). The crystal structure of ikaite was investigated with single crystal X-ray diffraction on samples that were permanently kept cold (in the lake water). At Laguna Cháltel calcite pseudomorphs after ikaite were discovered in littoral sediment cores from 25 m water depth. The mm-sized, porous, polycrystalline calcium carbonate aggregates from the 104 cm long sediment core of Laguna Cháltel are morphologically pseudomorphs after ikaite. SEM and XRD analyses highlight that these pseudomorphs consist of several µm-small calcite crystals in a calcitic matrix. The shape of these micro-crystals changes from rounded to fibrous with increasing sediment depth. Some specimens show casts of cyanobacteria trichomes. The oxygen isotopic composition of calcite pseudomorphs after ikaite from both lakes was analyzed. Calculating water temperatures during the ikaite precipitation assuming isotopic equilibrium for calcite and including modern water isotope ranges do not result in realistic estimates. Thus, either the calcite isotope fractionation factors are not applicable to these pseudomorphs, because e.g. the transformation to calcite pseudomorphs after ikaite caused isotope exchange or the carbonate precipitation occurred in disequilibrium. Nevertheless, the offset between oxygen isotope values of the sedimentary calcitic pseudomorphs from Laguna Cháltel and the modern ones from Laguna Potrok Aike corresponds to the differences present in lake water isotopic composition. Thus, calcite pseudomorphs after ikaite may serve as a proxy for paleo-lake water isotope variations. The crystallisation of ikaite in these lacustrine environments is presently simulated by different methods: (1) Evaporation from the lake water and (2) with modified diffusion silica gel experiments using the lake water and synthetic solutions.

Silicate versus carbonate weathering in Iceland: New insights from Ca isotopes

NASA Astrophysics Data System (ADS)

Jacobson, Andrew D.; Grace Andrews, M.; Lehn, Gregory O.; Holmden, Chris

2015-04-01

Several studies have measured riverine fluxes of Ca and carbonate alkalinity in Iceland with the aim of quantifying the role of basalt weathering in the long-term carbon cycle. A major assumption is that all of the Ca and alkalinity originates from the dissolution of Ca-bearing silicate minerals, such as plagioclase and clinopyroxene. However, hydrothermal calcite occurs throughout Iceland, and even trace levels are expected to impact river geochemistry owing to the mineral's high solubility and fast dissolution rate. To test this hypothesis, we used a new, high-precision Ca isotope MC-TIMS method (δ44/40Ca; 2σSD = ± 0.04 ‰) to trace sources of Ca in Icelandic rivers. We report elemental and Ca isotope data for rivers, high- and low-temperature groundwater, basalt, hydrothermal calcite (including Iceland Spar), and stilbite and heulandite, which are two types of zeolites commonly formed during low-grade metamorphism of basalt. In agreement with previous research, we find that rivers have higher δ44/40Ca values than basalt, with a maximum difference of ∼0.40‰. This difference may reflect isotope fractionation in the weathering zone, i.e., preferential uptake of 40Ca during clay mineral formation, adsorption, and other geochemical processes that cycle Ca. However, calcite δ44/40Ca values are also up to ∼0.40‰ higher than bedrock values, and on a diagram of δ44/40Ca versus Sr/Ca, nearly all waters plot within a plausible mixing domain bounded by the measured compositions of basalt and calcite, with glacial rivers plotting closer to calcite than non-glacial rivers. Calcite and heulandite form during hydrothermal alteration of basalt in the deep lava pile and often occur together in metabasalts now exposed at the surface. Because heulandite δ44/40Ca values are ∼1-2‰ lower than basalt, we suggest that 40Ca uptake by heudlandite explains the relatively high δ44/40Ca values of calcite and that calcite weathering in turn elevates riverine δ44/40Ca values. High mechanical erosion rates are known to facilitate the exposure and weathering of calcite, which explains the isotopic contrast between glacial and non-glacial watersheds. Using a mixing model, we find that calcite weathering provides ∼0-65% of the Ca in non-glacial rivers and ∼25-90% of the Ca in glacial rivers, with silicate weathering providing the remainder. Icelandic hydrothermal calcite contains mantle carbon. Noting that zeolite facies metamorphism and hydrothermal fluid circulation are ubiquitous characteristics of basaltic eruptions and assuming that hydrothermal calcite in other basaltic settings also contains mantle carbon, we suggest that the contribution of basalt weathering to long-term CO2 drawdown and climate regulation may be less significant than previously realized.

Retinal vein occlusion in Saudi Arabia: possible role of dehydration.

PubMed

Alghadyan, A A

1993-10-01

The medical records of 90 patients with a clinical diagnosis of retinal vein occlusion (RVO) who were seen at two referral hospitals in Saudi Arabia were reviewed. Sixty-eight (75.6%) were men. Central RVO was present in 50 patients (55.6%); branch RVO, in 35 patients (38.9%); and hemiretinal occlusion, in five patients (5.6%). Arterial hypertension was present in 43 patients (47.8%); diabetes mellitus, in 28 patients (31%); and preexisting glaucoma, in 26 patients (28.9%). The date of onset of RVO was available in 61 patients. Eighteen attacks (29.5%) had occurred during the month of Ramadan. The Student's t test of paired samples indicated that the incidence of RVO during the month of Ramadan was significantly higher than that of the other months of the Gregorian year. These findings suggest that dehydration may play a role in the pathogenesis of RVO.

Catalytic Biomineralization of Fluorescent Calcite by the Thermophilic Bacterium Geobacillus thermoglucosidasius▿

PubMed Central

Yoshida, Naoto; Higashimura, Eiji; Saeki, Yuichi

2010-01-01

The thermophilic Geobacillus bacterium catalyzed the formation of 100-μm hexagonal crystals at 60°C in a hydrogel containing sodium acetate, calcium chloride, and magnesium sulfate. Under fluorescence microscopy, crystals fluoresced upon excitation at 365 ± 5, 480 ± 20, or 545 ± 15 nm. X-ray diffraction indicated that the crystals were magnesium-calcite in calcite-type calcium carbonate. PMID:20851984

Sand-calcite crystals from Garfield County, Utah

USGS Publications Warehouse

Sargent, Kenneth A.; Zeller, H.D.

1984-01-01

Sand-calcite crystals are found in the Morrison Formation of Jurassic age in south-central Garfield County, Utah. The outcrop area is less than 1 acre, yet the locality contains many fine specimens of single, double, and complex crystals in good hexagonal form. This is the first known occurrence of sand-calcite crystals in rocks of Jurassic age and is the first reported occurrence in Utah.

Coupled phase and aqueous species equilibrium of the H 2O-CO 2-NaCl-CaCO 3 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite

NASA Astrophysics Data System (ADS)

Duan, Zhenhao; Li, Dedong

2008-10-01

A model is developed for the calculation of coupled phase and aqueous species equilibrium in the H 2O-CO 2-NaCl-CaCO 3 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite. The vapor-liquid-solid (calcite, halite) equilibrium together with the chemical equilibrium of H +, Na +, Ca 2+, CaHCO3+, Ca(OH) +, OH -, Cl -, HCO3-, CO32-, CO 2(aq) and CaCO 3(aq) in the aqueous liquid phase as a function of temperature, pressure, NaCl concentrations, CO 2(aq) concentrations can be calculated, with accuracy close to those of experiments in the stated T- P- m range, hence calcite solubility, CO 2 gas solubility, alkalinity and pH values can be accurately calculated. The merit and advantage of this model is its predictability, the model was generally not constructed by fitting experimental data. One of the focuses of this study is to predict calcite solubility, with accuracy consistent with the works in previous experimental studies. The resulted model reproduces the following: (1) as temperature increases, the calcite solubility decreases. For example, when temperature increases from 273 to 373 K, calcite solubility decreases by about 50%; (2) with the increase of pressure, calcite solubility increases. For example, at 373 K changing pressure from 10 to 500 bar may increase calcite solubility by as much as 30%; (3) dissolved CO 2 can increase calcite solubility substantially; (4) increasing concentration of NaCl up to 2 m will increase calcite solubility, but further increasing NaCl solubility beyond 2 m will decrease its solubility. The functionality of pH value, alkalinity, CO 2 gas solubility, and the concentrations of many aqueous species with temperature, pressure and NaCl (aq) concentrations can be found from the application of this model. Online calculation is made available on www.geochem-model.org/models/h2o_co2_nacl_caco3/calc.php.

Geological setting and timing of the cassiterite vein type mineralization of the Kalima area (Maniema, Democratic Republic of Congo)

NASA Astrophysics Data System (ADS)

Dewaele, S.; Muchez, Ph; Burgess, R.; Boyce, A.

2015-12-01

The Central African Mesoproterozoic Karagwe-Ankole belt in the Great Lakes area (DRCongo, Rwanda, Burundi, Uganda and Tanzania) forms a metallogenic province that hosts a variety of granite-related mineralization, which contains cassiterite, columbite-tantalite, wolframite/ferberite, spodumene and beryl. The Kalima area in the Maniema province of the DRCongo forms one of the most important areas for cassiterite mineralization in the eastern part of the DRCongo, even after many decades of exploitation. The mineralization dominantly consists of quartz veins that are hosted in Mesoproterozoic metasediments at the contact with granitic rocks of the Kalima granite (Avuanga and Yubuli) or directly crosscutting these granitic rocks (Atondo). Only limited - and mainly unmineralized pegmatites - have been described in the Lutshurukuru area. Mineralized quartz veins - and some granite bodies - intruded following the regional tectonic foliation or existing fracture zones, confirming the late-to post-tectonic origin of the fertile granite system. The emplacement of the quartz veins resulted in an alteration of the metasedimentary and granitic host-rocks, mainly resulting in muscovitization, tourmalinization and silicification. Cassiterite itself formed relatively late during vein formation and is associated with muscovite in fractures in or along the margins of the quartz veins. 40Ar-39Ar age dating of muscovite of an unmineralized pegmatite from the Lutshurukuru area gave an excellent plateau age of 1024 ± 5.5 Ma, while the muscovite associated with mineralization gave plateau ages of 986 ± 5.3 Ma for the Atondo deposit and 992.4 ± 5.4 Ma for the Yubuli deposit. The rather large spread in ages between the supposed parental granite/pegmatite and quartz veins is interpreted to reflect different magmatic events in the evolution of a composite granite system, starting at ∼1020 Ma and ending with mineralized quartz vein formation at ∼990 Ma. The latter age corresponds with the U-Pb age reported for columbite-tantalite in the area (993 ± 1 Ma at Kamisuku), which could be interpreted as the primary formation age of a new generation of mineralized pegmatites in the Kalima area, or as the resetting age of the U-Pb system during the ∼990 Ma mineralizing event. Muscovite of a mineralized greisen sample of Avuanga gave a plateau age with relaxed constraints of 1010.3 ± 5.9 Ma, which has been interpreted as a partially resetting of muscovite formed at ∼1020 Ma age, during the ∼990 Ma event.

Monoclinic deformation of calcite crystals at ambient conditions

NASA Astrophysics Data System (ADS)

Przeniosło, R.; Fabrykiewicz, P.; Sosnowska, I.

2016-09-01

High resolution synchrotron radiation powder diffraction shows that the average crystal structure of calcite at ambient conditions is described with the trigonal space group R 3 bar c but there is a systematic hkl-dependent Bragg peak broadening. A modelling of this anisotropic peak broadening with the microstrain model from Stephens (1999) [15] is presented. The observed lattice parameters' correlations can be described by assuming a monoclinic-type deformation of calcite crystallites. A quantitative model of this monoclinic deformation observed at ambient conditions is described with the space group C 2 / c . The monoclinic unit cell suggested at ambient conditions is related with the monoclinic unit cell reported in calcite at high pressure (Merrill and Bassett (1975) [10]).

Transcutaneous laser treatment of leg veins.

PubMed

Meesters, Arne A; Pitassi, Luiza H U; Campos, Valeria; Wolkerstorfer, Albert; Dierickx, Christine C

2014-03-01

Leg telangiectasias and reticular veins are a common complaint affecting more than 80% of the population to some extent. To date, the gold standard remains sclerotherapy for most patients. However, there may be some specific situations, where sclerotherapy is contraindicated such as needle phobia, allergy to certain sclerosing agents, and the presence of vessels smaller than the diameter of a 30-gauge needle (including telangiectatic matting). In these cases, transcutaneous laser therapy is a valuable alternative. Currently, different laser modalities have been proposed for the management of leg veins. The aim of this article is to present an overview of the basic principles of transcutaneous laser therapy of leg veins and to review the existing literature on this subject, including the most recent developments. The 532-nm potassium titanyl phosphate (KTP) laser, the 585-600-nm pulsed dye laser, the 755-nm alexandrite laser, various 800-983-nm diode lasers, and the 1,064-nm neodymium yttrium-aluminum-garnet (Nd:YAG) laser and various intense pulsed light sources have been investigated for this indication. The KTP and pulsed dye laser are an effective treatment option for small vessels (<1 mm). The side effect profile is usually favorable to that of longer wavelength modalities. For larger veins, the use of a longer wavelength is required. According to the scarce evidence available, the Nd:YAG laser produces better clinical results than the alexandrite and diode laser. Penetration depth is high, whereas absorption by melanin is low, making the Nd:YAG laser suitable for the treatment of larger and deeply located veins and for the treatment of patients with dark skin types. Clinical outcome of Nd:YAG laser therapy approximates that of sclerotherapy, although the latter is associated with less pain. New developments include (1) the use of a nonuniform pulse sequence or a dual-wavelength modality, inducing methemoglobin formation and enhancing the optical absorption properties of the target structure, (2) pulse stacking and multiple pass laser treatment, (3) combination of laser therapy with sclerotherapy or radiofrequency, and (4) indocyanin green enhanced laser therapy. Future studies will have to confirm the role of these developments in the treatment of leg veins. The literature still lacks double-blind controlled clinical trials comparing the different laser modalities with each other and with sclerotherapy. Such trials should be the focus of future research.

Rb-Sr, K-Ar, and stable isotope evidence for the ages and sources of fluid components of gold-bearing quartz veins in the northern Sierra Nevada foothills metamorphic belt, California

USGS Publications Warehouse

Böhlke, John Karl; Kistler, R. W.

1986-01-01

Gold-bearing quartz veins occur in and near major fault zones in deformed oceanic and island-arc rocks west of the main outcrop of the Sierra Nevada composite batholith. Veins typically occupy minor reverse faults that crosscut blueschist to amphibolite-grade metamorphic rocks whose metamorphic ages range from early Paleozoic to Jurassic. Vein micas and carbonate-quartz-mica assemblages that formed by hydrothermal metasomatism of ultramafic wall rocks in the Alleghany, Grass Valley, Washington, and Mother Lode districts yield concordant K-Ar and Rb-Sr ages. The dated veins are significantly younger than prograde metamorphism, penetrative deformation, and accretion of their host rocks to the continental margin. New and previously published mineralization ages from 13 localities in the Sierra foothills range from about 140 to 110 m.y. ago, with mean and median between 120 and 115 m.y. The age relations suggest that mineralizing fluids were set in motion by deep magmatic activity related to the resumption of east-dipping subduction along the western margin of North America following the Late Jurassic Nevadan collision event.CO 2 -bearing fluids responsible for metasomatism and much of the vein mica, carbonate, albite, and quartz deposition in several northern mines were isotopically heavy (delta 18 O [asymp] 8-14ppm; delta D between about -10 and -50ppm) and do not resemble seawater, magmatic, or meteoric waters. Metasomatic and vein-filling mica, dolomite, magnesite, and quartz in altered ultramafic rocks generally formed from fluids with similar Sr and O isotope ratios at a given locality. Consistent quartz-mica delta 18 O fractionations (delta 18 O (sub Q-M) = 4.5-4.9ppm) from various localities imply uniform equilibration temperatures, probably between 300 degrees and 350 degrees C. On a local (mine) scale, fluids responsible for both carbonate alteration of mafic and ultramafic wall rocks and albitic alteration of felsic and pelitic rocks had similar Sr isotope ratios.Samples from three veins in the central Alleghany district fit a 115.7 + or - 3-m.y. Rb-Sr isochron with a ( 87 Sr/ 86 Sr) i value of approximately 0.7119. Inferred 87 Sr/ 86 Sr ratios of metasomatic fluids from mines in different parts of the foothills region vary considerably (0.704-0.718), suggesting that Sr was derived from sources ranging from "western assemblage" Mesozoic ophiolitic or arc volcanic rocks to early Paleozoic continent-derived clastic rocks of the Shoo Fly Complex. Systematic geographic variations in both Sr and O isotopes can be rationalized by assuming extensive fluid interaction with rocks similar to the ones that are exposed within a few kilometers of the veins, but the ultimate sources of the fluids, and of Au and other constituents, may be independent of these. Isotopically lighter (meteoric?) fluids deposited some late quartz overgrowths and occupied secondary fluid inclusions in earlier vein quartz.

Geochemical and geochronological constraints on the genesis of Au-Te deposits at Cripple Creek, Colorado

USGS Publications Warehouse

Kelley, K.D.; Romberger, S.B.; Beaty, D.W.; Pontius, J.A.; Snee, L.W.; Stein, H.J.; Thompson, T.B.

1998-01-01

The Cripple Creek district (653 metric tons (t) of Au) consists of Au-Te veins and disseminated gold deposits that are spatially related to alkaline igneous rocks in an Oligocene intrusive complex. Vein paragenesis includes quartz-biotite-K feldspar-fluorite-pyrite followed by base metal sulfides and telluride minerals. Disseminated deposits consist of microcrystalline native gold with pyrite that are associated with zones of pervasive adularia. New 40Ar/39Ar dates indicate that there was a complex magmatic and hydrothermal history. Relatively felsic rocks (tephriphonolite, trachyandesite, and phonolite) were emplaced into the complex over about 1 m.y., from 32.5 ?? 0.1 (1??) to 31.5 ?? 0.1 Ma. A younger episode of phonolite emplacement outside of the complex is indicated by an age of 30.9 ?? 0.1 Ma. Field relationships suggest that at least one episode of mafic and ultramafic dike emplacement occurred after relatively more felsic rocks and prior to the main gold mineralizing event. Only a single whole-rock date for mafic phonolite (which indicated a maximum age of 28.7 Ma) was obtained. However, constraints on the timing of mineralization are provided by paragenetically early vein minerals and K feldspar from the disseminated gold pyrite deposits. Early vein minerals (31.3 ?? 0.1-29.6 ?? 0.1 Ma) and K feldspar (29.8 ?? 0.1 Ma) from the Cresson disseminated deposit, together with potassically altered phonolite adjacent to the Pharmacist vein (28.8 and 28.2 ?? 0.1 Ma), suggest there was a protracted history of hydrothermal activity that began during the waning stages of phonolite and early mafic-ultramafic activity and continued, perhaps intermittently, for at least 2 m.y. Estimated whole-rock ??18O values of the alkaline igneous rocks range from 6.4 to 8.2 per mil. K feldspar and albite separates from igneous rocks have lead isotope compositions of 206Pb/204Pb = 17.90 to 18.10, 207Pb/204Pb = 15.51 to 15.53, and 208Pb/204Pb = 38.35 to 38.56. These isotopic compositions, together with major and trace element data, indicate that the phonolitic magmas probably evolved by fractional crystallization of an alkali basalt that assimilated lower crustal material. Upper crustal contamination of the magmas was not significant. The 206Pb/204Pb compositions of vein galenas almost entirely overlap those of phonolites, suggesting a genetic relationship between alkaline magmatism and mineralization. However, a trend toward higher 207Pb/204Pb (15.57-15.60) and 208Pb/204Pb ratios (38.94-39.48) of some galenas suggests a contribution to the ore fluid from surrounding Early Proterozoic rocks, probably through leaching by mineralizing fluids. Limited stable isotope compositions of quartz, K feldspar, and biotite from this and previous studies support a largely magmatic origin for the early vein fluids. It is suggested that three features were collectively responsible for generating alkaline magmas and associated mineral deposits: (1) the timing of magmatism and mineralization, which coincided with the transition between subduction-related compression and extension related to continental rifting; (2) the location of Cripple Creek at the junction of four major Precambrian units and at the intersection of major northeast-trending regional structures with northwest-trending faults, which served as conduits for magmas and subsequent hydrothermal fluids; and (3) the complex magmatic history which included emplacement of relatively felsic magmas followed by successively more mafic magmas with time.

A High-Resolution Lipid Biomarker Perspective on North Iceland Shelf Marine Climate over the Last Millennium

NASA Astrophysics Data System (ADS)

Harning, D.; Sepúlveda, J.; Andrews, J. T.; Cabedo-Sanz, P.; Belt, S. T.; Marchitto, T. M.; Stoner, J. S.; Geirsdóttir, Á.; Miller, G. H.

2017-12-01

Icelandic climate is vulnerable to variations in the dominance of competing Arctic and Atlantic ocean currents. The boundary between these water masses delineates the Polar Front, which today occupies the North Iceland Shelf (NIS). To date, Holocene oceanographic reconstructions along the NIS have employed a variety of proxies including Mg/Ca and δ18O of benthic and planktonic foraminifera, quartz and calcite wt%, the alkenone unsaturation index (Uk'37) and biotic species assemblages. Sea surface temperature (SST) proxies are primarily derived from phytoplankton resulting in a seasonal bias toward spring/summer SST. Furthermore, SST proxies can be influenced by additional confounding variables (e.g. salinity, nutrients, depth habitat of biota) resulting in markedly different Holocene temperature reconstructions between proxy datasets. To evaluate the similarities and discrepancies between various marine proxies, we investigate a high-resolution sediment core collected from the central North Iceland Shelf (B997-316GGC, 658 m depth). Sedimentation covers the last millennium, which captures the transition from the Medieval Warm Period to the Little Ice Age. Age control is constrained by 14C dates and paleomagnetic secular variation. To assess marine surface productivity and sea ice conditions, we analyze quartz and calcite wt% via XRD and a series of highly branched isoprenoid biomarkers. Quantitative paleotemperature estimates are derived from a novel combination of Mg/Ca of foraminifera and two lipid biomarker indices, Uk'37 from Prymnesiophyte alkenones and TEX86 from Thaumarchaeota glycerol dialkyl glycerol tetraethers (GDGTs). The latter TEX86 record is the first paleo application in Icelandic waters, which a recent local calibration study suggests may reflect annual or winter sub-surface (0-200 m) temperatures. Our paleotemperature records are bolstered by the analysis of additional sediment core tops, which expand the established Icelandic calibrations. Finally, we perform statistical analyses in an effort to extract a robust record of paleoceanographic change and to test the applicability of various proxies in high-latitude paleoclimate studies.

The crystal structure of calcite III

NASA Astrophysics Data System (ADS)

Smyth, Joseph R.; Ahrens, Thomas J.

The crystal structure of calcite III has been deduced from existing high pressure powder X-ray diffraction patterns, based on the assumption that it is a displacive modification of the calcite I structure. The structure is monoclinic with space group C2 and a Z of 6. There are two Ca and two C positions, and five O positions, and atom coordinates have been refined by distance-least-squares methods to give reasonable octahedral coordination for Ca and parallel, planar CO3 groups. Unit cell parameters refined from a published powder diffraction pattern at 4.1 GPa are: a = 8.746(8)Å b = 4.685(5)Å c = 8.275(8)Å and β= 94.4°. The structure has a calculated density of 2.949 Mg/m³ at 4.1 GPa which is less than that of aragonite at this pressure and consistent with early piston cylinder studies. This implies that calcite III is indeed a metastable intermediary between calcite I and aragonite.

Tracing high-pressure metamorphism in marbles: Phase relations in high-grade aluminous calcite-dolomite marbles from the Greek Rhodope massif in the system CaO-MgO-Al 2O 3-SiO 2-CO 2 and indications of prior aragonite

NASA Astrophysics Data System (ADS)

Proyer, A.; Mposkos, E.; Baziotis, I.; Hoinkes, G.

2008-08-01

Four different types of parageneses of the minerals calcite, dolomite, diopside, forsterite, spinel, amphibole (pargasite), (Ti-)clinohumite and phlogopite were observed in calcite-dolomite marbles collected in the Kimi-Complex of the Rhodope Metamorphic Province (RMP). The presence of former aragonite can be inferred from carbonate inclusions, which, in combination with an analysis of phase relations in the simplified system CaO-MgO-Al 2O 3-SiO 2-CO 2 (CMAS-CO 2) show that the mineral assemblages preserved in these marbles most likely equilibrated at the aragonite-calcite transition, slightly below the coesite stability field, at ca. 720 °C, 25 kbar and aCO 2 ~ 0.01. The thermodynamic model predicts that no matter what activity of CO 2, garnet has to be present in aluminous calcite-dolomite-marble at UHP conditions.

Calcium sulfoaluminate (Ye'elimite) hydration in the presence of gypsum, calcite, and vaterite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hargis, Craig W.; Telesca, Antonio; Monteiro, Paulo J.M., E-mail: monteiro@ce.berkeley.edu

Six calcium sulfoaluminate-based cementitious systems composed of calcium sulfoaluminate, calcite, vaterite, and gypsum were cured as pastes and mortars for 1, 7, 28 and 84 days. Pastes were analyzed with X-ray diffraction, thermogravimetric and differential thermal analyses. Mortars were tested for compressive strength, dimensional stability and setting time. Furthermore, pastes with a water/cementitious material mass ratio of 0.80 were tested for heat evolution during the first 48 h by means of isothermal conduction calorimetry. It has been found that: (1) both calcite and vaterite reacted with monosulfoaluminate to give monocarboaluminate and ettringite, with vaterite being more reactive; (2) gypsum loweredmore » the reactivity of both carbonates; (3) expansion was reduced by calcite and vaterite, irrespective of the presence of gypsum; and (4) both carbonates increased compressive strength in the absence of gypsum and decreased compressive strength less in the presence of gypsum, with vaterite's action more effective than that of calcite.« less

Chemistry of the calcite/water interface: Influence of sulfate ions and consequences in terms of cohesion forces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pourchet, Sylvie, E-mail: sylvie.pourchet@u-bourgogne.fr; Pochard, Isabelle; Brunel, Fabrice

2013-10-15

Calcite suspensions are used to mimic the behavior of more complex cementitious systems. Therefore the characterization of calcite–water interface in strong alkaline conditions, through ionic adsorption, electrokinetic measurements, static rheology and atomic force microscopy is a prerequisite. Calcium, a potential determining ion for calcite, adsorbs specifically onto the weakly positively charged calcite surface in water. This leads to an increase of the repulsive electric double layer force and thus weakens the particle cohesion. Sulfate adsorption, made at constant calcium concentration and ionic strength, significantly increases the attractive interactions between the calcite particles despite its very low adsorption. This is attributedmore » to a lowering of the electrostatic repulsion in connection with the evolution of the zeta potential. The linear relationship found between the yield stress and ζ{sup 2} proves that the classical DLVO theory applies for these systems, contrary to what was previously observed with C–S–H particles under the same conditions.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ukita, Masaya, E-mail: uktia.masaya@f.mbox.nagoya-u.ac.jp; Toyoura, Kazuaki; Nakamura, Atsutomo

The thermodynamic phase stabilities of calcite and aragonite have been investigated from lattice vibrational analyses based on first-principles calculations. Different pressure dependences in phonon feature were found between the two polymorphs, suggesting different physical origins of the pressure-induced phase transitions. In the most stable phase in calcite (calcite I), an imaginary phonon mode consisting of rotation of CO{sub 3} ions with slight displacement of Ca ions appears at the F point in the Brillouin zone above 0.8 GPa. Such a soft mode means that external pressure induces the lattice-dynamical instability of calcite I leading to the phase transition to calcite II.more » On the other hand, the origin of the phase transition in aragonite is not due to such a lattice-dynamical instability. The estimated thermodynamical properties indicate that a first-order phase transition occurs between aragonite and post-aragonite at 34.7 GPa, coinciding with the reported experimental value at room temperature (35 GPa).« less

Geology of the epithermal Ag-Au Huevos Verdes vein system and San José district, Deseado massif, Patagonia, Argentina

NASA Astrophysics Data System (ADS)

Dietrich, Andreas; Gutierrez, Ronald; Nelson, Eric P.; Layer, Paul W.

2012-03-01

The San José district is located in the northwest part of the Deseado massif and hosts a number of epithermal Ag-Au quartz veins of intermediate sulfidation style, including the Huevos Verdes vein system. Veins are hosted by andesitic rocks of the Bajo Pobre Formation and locally by rhyodacitic pyroclastic rocks of the Chon Aike Formation. New 40Ar/39Ar constraints on the age of host rocks and mineralization define Late Jurassic ages of 151.3 ± 0.7 Ma to 144.7 ± 0.1 Ma for volcanic rocks of the Bajo Pobre Formation and of 147.6 ± 1.1 Ma for the Chon Aike Formation. Illite ages of the Huevos Verdes vein system of 140.8 ± 0.2 and 140.5 ± 0.3 Ma are 4 m.y. younger than the volcanic host rock unit. These age dates are among the youngest reported for Jurassic volcanism in the Deseado massif and correlate well with the regional context of magmatic and hydrothermal activity. The Huevos Verdes vein system has a strike length of 2,000 m, with several ore shoots along strike. The vein consists of a pre-ore stage and three main ore stages. Early barren quartz and chalcedony are followed by a mottled quartz stage of coarse saccharoidal quartz with irregular streaks and discontinuous bands of sulfide-rich material. The banded quartz-sulfide stage consists of sulfide-rich bands alternating with bands of quartz and bands of chlorite ± illite. Late-stage sulfide-rich veinlets are associated with kaolinite gangue. Ore minerals are argentite and electrum, together with pyrite, sphalerite, galena, chalcopyrite, minor bornite, covellite, and ruby silver. Wall rock alteration is characterized by narrow (< 3 m) halos of illite and illite/smectite next to veins, grading outward into propylitic alteration. Gangue minerals are dominantly massive quartz intergrown with minor to accessory adularia. Epidote, illite, illite/smectite, and, preferentially at deeper levels, Fe-chlorite gangue indicate near-neutral pH hydrothermal fluids at temperatures of >220°C. Kaolinite occurring with the late sulfide-rich veinlet stage indicates pH < 4 and a temperature of <200°C. The Huevos Verdes system has an overall strike of 325°, dipping on average 65° NE. The orientations of individual ore shoots are controlled by vein strike and intersecting north-northwest-striking faults. We propose a structural model for the time of mineralization of the San José district, consisting of a conjugate shear pair of sinistral north-northwest- and dextral west-northwest-striking faults that correspond to R and R' in the Riedel shear model and that are related to master faults (M) of north-northeast-strike. Veins of 315° strike can be interpreted as nearly pure extensional fractures (T). Variations in vein strike predict an induced sinistral shear component for strike directions of >315°, whereas strike directions of <315° are predicted with an induced dextral strike-slip movement. The components of the structural model appear to be present on a regional scale and are not restricted to the San José district.

The long-term impact of magnesium in seawater on foraminiferal mineralogy: Mechanism and consequences

NASA Astrophysics Data System (ADS)

Dijk, I.; Nooijer, L. J.; Hart, M. B.; Reichart, G.-J.

2016-03-01

Foraminifera are unicellular protists, primarily known for their calcium carbonate shells that provide an extensive fossil record. This record, ranging from Cambrian to present shows both major shifts and gradual changes in the relative occurrence of taxa producing different polymorphs of carbonate. Here we present evidence for coupling between shifts in calcite- versus aragonite-producing species and periods with, respectively, low and high seawater Mg/Ca throughout the Phanerozoic. During periods when seawater Mg/Ca is <2 mol/mol, low-Mg calcite-producing species dominate the foraminiferal community. Vice versa, high-Mg calcite- and aragonite-producing species are more abundant during periods with relatively high seawater Mg/Ca. This alteration in dominance of the phase precipitated is due to selective recovery of groups producing the favorable polymorph after shifts from calcite to aragonite seas. In addition, relatively high extinction rates of species producing the mineral phase not favored by the seawater Mg/Ca of that time may be responsible for this alteration. These results imply that the current high seawater Mg/Ca will, in the long term, favor prevalence of high-Mg and aragonite-producing foraminifera over calcite-producing taxa, possibly shifting the balance toward a community in which calcite production is less dominant.

Monitoring bacterially induced calcite precipitation in porous media using magnetic resonance imaging and flow measurements

NASA Astrophysics Data System (ADS)

Sham, E.; Mantle, M. D.; Mitchell, J.; Tobler, D. J.; Phoenix, V. R.; Johns, M. L.

2013-09-01

A range of nuclear magnetic resonance (NMR) techniques are employed to provide novel, non-invasive measurements of both the structure and transport properties of porous media following a biologically mediated calcite precipitation reaction. Both a model glass bead pack and a sandstone rock core were considered. Structure was probed using magnetic resonance imaging (MRI) via a combination of quantitative one-dimensional profiles and three-dimensional images, applied before and after the formation of calcite in order to characterise the spatial distribution of the precipitate. It was shown through modification and variations of the calcite precipitation treatment that differences in the calcite fill would occur but all methods were successful in partially blocking the different porous media. Precipitation was seen to occur predominantly at the inlet of the bead pack, whereas precipitation occurred almost uniformly along the sandstone core. Transport properties are quantified using pulse field gradient (PFG) NMR measurements which provide probability distributions of molecular displacement over a set observation time (propagators), supplementing conventional permeability measurements. Propagators quantify the local effect of calcite formation on system hydrodynamics and the extent of stagnant region formation. Collectively, the combination of NMR measurements utilised here provides a toolkit for determining the efficacy of a biological-precipitation reaction for partially blocking porous materials.

Carbonate Minerals with Magnesium in Triassic Terebratula Limestone in the Term of Limestone with Magnesium Application as a Sorbent in Desulfurization of Flue Gases

NASA Astrophysics Data System (ADS)

Stanienda-Pilecki, Katarzyna

2017-09-01

This article presents the results of studies of Triassic (Muschelkalk) carbonate rock samples of the Terebratula Beds taken from the area of the Polish part of the Germanic Basin. It is the area of Opole Silesia. The rocks were studied in the term of possibility of limestone with magnesium application in desulfurization of flue gases executed in power plants. Characteristic features of especially carbonate phases including magnesium-low-Mg calcite, high-Mg calcite, dolomite and huntite were presented in the article. They were studied to show that the presence of carbonate phases with magnesium, especially high-Mg calcite makes the desulfurization process more effective. Selected rock samples were examined using a microscope with polarized, transmitted light, X-ray diffraction, microprobe measurements and FTIR spectroscopy. The results of studies show a domination of low magnesium calcite in the limestones of the Terebratula Beds. In some samples dolomite and lower amounts of high-Mg calcite occurred. Moreover, huntite was identified. The studies were very important, because carbonate phases like high-Mg calcite and huntite which occurred in rocks of the Triassic Terebratula Beds were not investigated in details by other scientists but they presence in limestone sorbent could influence the effectiveness of desulfurization process.

Analytical electron microscopy of biogenic and inorganic carbonates

NASA Technical Reports Server (NTRS)

Blake, David F.

1989-01-01

In the terrestrial sedimentary environment, the mineralogically predominant carbonates are calcite-type minerals (rhombohedral carbonates) and aragonite-type minerals (orthorhombic carbonates). Most common minerals precipitating either inorganically or biogenically are high magnesium calcite and aragonite. High magnesium calcite (with magnesium carbonate substituting for more than 7 mole percent of the calcium carbonate) is stable only at temperatures greater than 700 C or thereabouts, and aragonite is stable only at pressures exceeding several kilobars of confining pressure. Therefore, these carbonates are expected to undergo chemical stabilization in the diagenetic environment to ultimately form stable calcite and dolomite. Because of the strong organic control of carbonate deposition in organisms during biomineralization, the microchemistry and microstructure of invertebrate skeletal material is much different than that present in inorganic carbonate cements. The style of preservation of microstructural features in skeletal material is therefore often quite distinctive when compared to that of inorganic carbonate even though wholesale recrystallization of the sediment has taken place. Microstructural and microchemical comparisons are made between high magnesium calcite echinoderm skeletal material and modern inorganic high magnesium calcite inorganic cements, using analytical electron microscopy and related techniques. Similar comparisons are made between analogous materials which have undergone stabilization in the diagenetic environment. Similar analysis schemes may prove useful in distinguishing between biogenic and inorganic carbonates in returned Martian carbonate samples.

Mechanism of calcite co-orientation in the sea urchin tooth.

PubMed

Killian, Christopher E; Metzler, Rebecca A; Gong, Y U T; Olson, Ian C; Aizenberg, Joanna; Politi, Yael; Wilt, Fred H; Scholl, Andreas; Young, Anthony; Doran, Andrew; Kunz, Martin; Tamura, Nobumichi; Coppersmith, Susan N; Gilbert, P U P A

2009-12-30

Sea urchin teeth are remarkable and complex calcite structures, continuously growing at the forming end and self-sharpening at the mature grinding tip. The calcite (CaCO(3)) crystals of tooth components, plates, fibers, and a high-Mg polycrystalline matrix, have highly co-oriented crystallographic axes. This ability to co-orient calcite in a mineralized structure is shared by all echinoderms. However, the physico-chemical mechanism by which calcite crystals become co-oriented in echinoderms remains enigmatic. Here, we show differences in calcite c-axis orientations in the tooth of the purple sea urchin ( Strongylocentrotus purpuratus ), using high-resolution X-ray photoelectron emission spectromicroscopy (X-PEEM) and microbeam X-ray diffraction (muXRD). All plates share one crystal orientation, propagated through pillar bridges, while fibers and polycrystalline matrix share another orientation. Furthermore, in the forming end of the tooth, we observe that CaCO(3) is present as amorphous calcium carbonate (ACC). We demonstrate that co-orientation of the nanoparticles in the polycrystalline matrix occurs via solid-state secondary nucleation, propagating out from the previously formed fibers and plates, into the amorphous precursor nanoparticles. Because amorphous precursors were observed in diverse biominerals, solid-state secondary nucleation is likely to be a general mechanism for the co-orientation of biomineral components in organisms from different phyla.

Cockade-textured cataclasite and silica gel from damage zone in carbonated ultramafics: markers of cycles of seismic activity?

NASA Astrophysics Data System (ADS)

Scarsi, Marco; Crispini, Laura; Garofalo, Paolo; Capponi, Giovanni

2016-04-01

Shallow crustal processes occurring during seismic slips and generating fracture networks are of great interest due to their complex interplay with a spectrum of other geological processes . Our study focuses on faults with peculiar core textures, similar to those of "cockade breccia" (Genna et al., 1996) and "clast cortex grains" (Rempe et al., 2014), and on their relation with syntectonic hydrothermal alteration linked with Au bearing-quartz and chalcedony veins. Our work aims to study the enviromental conditions for the formation of such peculiar texture, their relation with the hydrothermal vein system and their potential as shallow seismic indicators. We present field, microstructural and petrochemical data of a peculiar damage zone of fault rocks located in carbonated peridotites and serpentinites of the Ligurian Alps (Voltri Massif, Italy). These are mainly reverse faults, which are coeval with syntectonic Au-bearing quartz veins and chalcedony veins (Giorza et al., 2010), in which lherzolites occupy the hangingwall of the faults and serpentinites the footwall. The fault rocks show evidence for carbonation, as olivine and serpentine are clearly transformed into an assemblage made of magnesite, dolomite and minor ankerite. The damage zones of the faults are serpentinite-rich and about 10 m in thickness, while the cataclasite cores are carbonate-rich and ca. 1 m thick. The top of the fault core shows the occurrence of a chalcedony shear veins with chatter marks and slikenlines on the surface. The "cockade breccia" is made of spherical aggregates of Fe-Mg carbonates and are 1 mm to 3 cm in size. These aggregates show cores of microcrystalline Fe-Mg carbonates, and concentric outer layers of relatively coarser Fe-Mg carbonates with radial or laminated texture. In some cases, these aggregates show evidence for rotation along secondary slip zones. We interpret all these features as the products of chemical interaction between the olivine and serpentine initially present within the fault rocks and the hydrothermal fluid that flowed within these faults. These interactions were probably similar to those occurring within the coeval Au- and chalcedony veins. Field evidence and theoretical considerations indicate that the reverse faults could have experienced stages of fault-valve behaviour (Sibson et al., 1998), which consisted in cycles of fluid pressure build-ups, fault opening, fluid flushing, and mineral precipitation during the seismic failure of the faults. These cycles varied transiently fault permeabilities. During the fluid pressure build up stage the radial coarse grains developed, while during the fluid flushing stage the clast cortex grains developed their laminated texture. The Au-quartz and chalcedony veins could have formed during the stages of fluid pressure drops following fault slip (Sibson et al., 1998, 2004). References Capponi G. & Crispini L., 1997, Progressive shear deformation in the metasediments of the Voltri Group (Ligurian Alps, Italy): occurence of structure recording extension parallel to the regional foliation, Boll. Soc. Geol. It., 116, 267-277. Genna A., Jébrack M., Marcoux E., Milési J.P., 1996, Genesis of cockade breccias in the tectonic evolution of the Cirotan epithermal gold system, West Java, Can. Journ. of Earth Sci., 33, 93-102. Giorza A., 2010, Late to post-metamorphic hydrotermalism in the Voltri Unit (Lavagnina Lakes Area, NW Alps). Structural-Petrological-Geochemical approach, PhD Thesis, University of Turin. Rempe M., Smith S. A. F., Ferri F., Mitchell T. M., 2014, Clast-cortex aggregates in experimental and natural calcite-bearing fault zones, Journ. Of Struct. Geol., 68, 142-157. Sibson R. H., 2004, Controls of maximum fluid overpressure defining conditions for mesozonal mineralization, Journ. of Struct. Geol., 26, 6-7, 1127-1136. Sibson R. H., Robert F., Poulsen H., 1998, High-angle reverse faults, fluid-pressure cycling, and mesothermal gold-quartz deposits, Geology, 16, 551-555. Spagnolo C., 2006, Late orogenic tectonics in the eastern sector of the Ligurian Alps, PhD Thesis, Univesity of Genoa.

Catalysis and chemical mechanisms of calcite dissolution in seawater.

PubMed

Subhas, Adam V; Adkins, Jess F; Rollins, Nick E; Naviaux, John; Erez, Jonathan; Berelson, William M

2017-07-18

Near-equilibrium calcite dissolution in seawater contributes significantly to the regulation of atmospheric [Formula: see text] on 1,000-y timescales. Despite many studies on far-from-equilibrium dissolution, little is known about the detailed mechanisms responsible for calcite dissolution in seawater. In this paper, we dissolve 13 C-labeled calcites in natural seawater. We show that the time-evolving enrichment of [Formula: see text] in solution is a direct measure of both dissolution and precipitation reactions across a large range of saturation states. Secondary Ion Mass Spectrometer profiles into the 13 C-labeled solids confirm the presence of precipitated material even in undersaturated conditions. The close balance of precipitation and dissolution near equilibrium can alter the chemical composition of calcite deeper than one monolayer into the crystal. This balance of dissolution-precipitation shifts significantly toward a dissolution-dominated mechanism below about [Formula: see text] Finally, we show that the enzyme carbonic anhydrase (CA) increases the dissolution rate across all saturation states, and the effect is most pronounced close to equilibrium. This finding suggests that the rate of hydration of [Formula: see text] is a rate-limiting step for calcite dissolution in seawater. We then interpret our dissolution data in a framework that incorporates both solution chemistry and geometric constraints on the calcite solid. Near equilibrium, this framework demonstrates a lowered free energy barrier at the solid-solution interface in the presence of CA. This framework also indicates a significant change in dissolution mechanism at [Formula: see text], which we interpret as the onset of homogeneous etch pit nucleation.

Catalysis and chemical mechanisms of calcite dissolution in seawater

PubMed Central

Adkins, Jess F.; Rollins, Nick E.; Naviaux, John; Erez, Jonathan; Berelson, William M.

2017-01-01

Near-equilibrium calcite dissolution in seawater contributes significantly to the regulation of atmospheric CO2 on 1,000-y timescales. Despite many studies on far-from-equilibrium dissolution, little is known about the detailed mechanisms responsible for calcite dissolution in seawater. In this paper, we dissolve 13C-labeled calcites in natural seawater. We show that the time-evolving enrichment of 𝜹13C in solution is a direct measure of both dissolution and precipitation reactions across a large range of saturation states. Secondary Ion Mass Spectrometer profiles into the 13C-labeled solids confirm the presence of precipitated material even in undersaturated conditions. The close balance of precipitation and dissolution near equilibrium can alter the chemical composition of calcite deeper than one monolayer into the crystal. This balance of dissolution–precipitation shifts significantly toward a dissolution-dominated mechanism below about Ω= 0.7. Finally, we show that the enzyme carbonic anhydrase (CA) increases the dissolution rate across all saturation states, and the effect is most pronounced close to equilibrium. This finding suggests that the rate of hydration of CO2 is a rate-limiting step for calcite dissolution in seawater. We then interpret our dissolution data in a framework that incorporates both solution chemistry and geometric constraints on the calcite solid. Near equilibrium, this framework demonstrates a lowered free energy barrier at the solid–solution interface in the presence of CA. This framework also indicates a significant change in dissolution mechanism at Ω= 0.7, which we interpret as the onset of homogeneous etch pit nucleation. PMID:28720698

Common Ion Effects In Zeoponic Substrates: Dissolution And Cation Exchange Variations Due to Additions of Calcite, Dolomite and Wollastonite

NASA Technical Reports Server (NTRS)

Beiersdorfer, R. E.; Ming, D. W.; Galindo, C., Jr.

2003-01-01

c1inoptilolite-rich tuff-hydroxyapatite mixture (zeoponic substrate) has the potential to serve as a synthetic soil-additive for plant growth. Essential plant macro-nutrients such as calcium, phosphorous, magnesium, ammonium and potassium are released into solution via dissolution of the hydroxyapatite and cation exchange on zeolite charged sites. Plant growth experiments resulting in low yield for wheat have been attributed to a Ca deficiency caused by a high degree of cation exchange by the zeolite. Batch-equilibration experiments were performed in order to determine if the Ca deficiency can be remedied by the addition of a second Ca-bearing, soluble, mineral such as calcite, dolomite or wollastonite. Variations in the amount of calcite, dolomite or wollastonite resulted in systematic changes in the concentrations of Ca and P. The addition of calcite, dolomite or wollastonite to the zeoponic substrate resulted in an exponential decrease in the phosphorous concentration in solution. The exponential rate of decay was greatest for calcite (5.60 wt. % -I), intermediate for wollastonite (2.85 wt.% -I) and least for dolomite (1.58 wt.% -I). Additions of the three minerals resulted in linear increases in the calcium concentration in solution. The rate of increase was greatest for calcite (3.64), intermediate for wollastonite (2.41) and least for dolomite (0.61). The observed changes in P and Ca concentration are consistent with the solubilities of calcite, dolomite and wollastonite and with changes expected from a common ion effect with Ca. Keywords: zeolite, zeoponics, common-ion effect, clinoptilolite, hydroxyapatite