Biostratigraphy and structure of paleozoic host rocks and their relationship to Carlin-type gold deposits in the Jerritt Canyon mining district, Nevada

USGS Publications Warehouse

Peters, S.G.; Armstrong, A.K.; Harris, A.G.; Oscarson, R.L.; Noble, P.J.

2003-01-01

The Jerritt Canyon mining district in the northern Independence Range, northern Nevada, contains multiple, nearly horizontal, thrust masses of platform carbonate rocks that are exposed in a series of north- to northeast-elongated, tectonic windows through rocks of the Roberts Mountains allochthon. The Roberts Mountains allochthon was emplaced during the Late Devonian to Early Mississippian Antler orogeny. These thrust masses contain structurally and stratigraphically controlled Carlin-type gold deposits. The gold deposits are hosted in tectonically truncated units of the Silurian to Devonian Hanson Creek and Roberts Mountains Formations that lie within structural slices of an Eastern assemblage of Cambrian to Devonian carbonate rocks. In addition, these multiply thrust-faulted and folded host rocks are structurally interleaved with Mississippian siliciclastic rocks and are overlain structurally by Cambrian to Devonian siliciclastic units of the Roberts Mountains allochthon. All sedimentary rocks were involved in thrusting, high-angle faulting, and folding, and some of these events indicate substantial late Paleozoic and/or Mesozoic regional shortening. Early Pennsylvanian and late Eocene dikes also intrude the sedimentary rocks. These rocks all were uplifted into a northeast-trending range by subsequent late Cenozoic Basin and Range faulting. Eocene sedimentary and volcanic rocks flank part of the range. Pathways of hydrothermal fluid flow and locations of Carlin-type gold orebodies in the Jerritt Canyon mining district were controlled by structural and host-rock geometries within specific lithologies of the stacked thrust masses of Eastern assemblage rocks. The gold deposits are most common proximal to intersections of northeast-striking faults, northwest-striking dikes, and thrust planes that lie adjacent to permeable stratigraphic horizons. The host stratigraphic units include carbonate sequences that contained primary intercrystalline permeability, which provided initial pathways for fluid flow and later served as precipitation sites for ore minerals. Alteration, during, and perhaps prior to mineralization, enhanced primary permeability by dissolution, by removal of calcite, and by formation of dolomite. Ore-stage sulfide minerals and alteration minerals commonly precipitated in pore spaces among dolomite grains. Microveinlets and microbrecciation in zones of intense alteration also provided networks of secondary permeability that further enhanced fluid flux and produced additional sites for ore deposition.

Diagenesis and clay mineral formation at Gale Crater, Mars

PubMed Central

Bridges, J C; Schwenzer, S P; Leveille, R; Westall, F; Wiens, R C; Mangold, N; Bristow, T; Edwards, P; Berger, G

2015-01-01

The Mars Science Laboratory rover Curiosity found host rocks of basaltic composition and alteration assemblages containing clay minerals at Yellowknife Bay, Gale Crater. On the basis of the observed host rock and alteration minerals, we present results of equilibrium thermochemical modeling of the Sheepbed mudstones of Yellowknife Bay in order to constrain the formation conditions of its secondary mineral assemblage. Building on conclusions from sedimentary observations by the Mars Science Laboratory team, we assume diagenetic, in situ alteration. The modeling shows that the mineral assemblage formed by the reaction of a CO2-poor and oxidizing, dilute aqueous solution (Gale Portage Water) in an open system with the Fe-rich basaltic-composition sedimentary rocks at 10–50°C and water/rock ratio (mass of rock reacted with the starting fluid) of 100–1000, pH of ∽7.5–12. Model alteration assemblages predominantly contain phyllosilicates (Fe-smectite, chlorite), the bulk composition of a mixture of which is close to that of saponite inferred from Chemistry and Mineralogy data and to that of saponite observed in the nakhlite Martian meteorites and terrestrial analogues. To match the observed clay mineral chemistry, inhomogeneous dissolution dominated by the amorphous phase and olivine is required. We therefore deduce a dissolving composition of approximately 70% amorphous material, with 20% olivine, and 10% whole rock component. PMID:26213668

Diagenesis and clay mineral formation at Gale Crater, Mars

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

Bridges, J. C.; Schwenzer, S. P.; Leveille, R.

The Mars Science Laboratory rover Curiosity found host rocks of basaltic composition and alteration assemblages containing clay minerals at Yellowknife Bay, Gale Crater. On the basis of the observed host rock and alteration minerals, we present results of equilibrium thermochemical modeling of the Sheepbed mudstones of Yellowknife Bay in order to constrain the formation conditions of its secondary mineral assemblage. Building on conclusions from sedimentary observations by the Mars Science Laboratory team, we assume diagenetic, in situ alteration. The modeling shows that the mineral assemblage formed by the reaction of a CO₂-poor and oxidizing, dilute aqueous solution (Gale Portage Water)more » in an open system with the Fe-rich basaltic-composition sedimentary rocks at 10–50°C and water/rock ratio (mass of rock reacted with the starting fluid) of 100–1000, pH of ~7.5–12. Model alteration assemblages predominantly contain phyllosilicates (Fe-smectite, chlorite), the bulk composition of a mixture of which is close to that of saponite inferred from Chemistry and Mineralogy data and to that of saponite observed in the nakhlite Martian meteorites and terrestrial analogues. To match the observed clay mineral chemistry, inhomogeneous dissolution dominated by the amorphous phase and olivine is required. We therefore deduce a dissolving composition of approximately 70% amorphous material, with 20% olivine, and 10% whole rock component.« less

Diagenesis and clay mineral formation at Gale Crater, Mars

DOE PAGES

Bridges, J. C.; Schwenzer, S. P.; Leveille, R.; ...

2015-01-18

The Mars Science Laboratory rover Curiosity found host rocks of basaltic composition and alteration assemblages containing clay minerals at Yellowknife Bay, Gale Crater. On the basis of the observed host rock and alteration minerals, we present results of equilibrium thermochemical modeling of the Sheepbed mudstones of Yellowknife Bay in order to constrain the formation conditions of its secondary mineral assemblage. Building on conclusions from sedimentary observations by the Mars Science Laboratory team, we assume diagenetic, in situ alteration. The modeling shows that the mineral assemblage formed by the reaction of a CO₂-poor and oxidizing, dilute aqueous solution (Gale Portage Water)more » in an open system with the Fe-rich basaltic-composition sedimentary rocks at 10–50°C and water/rock ratio (mass of rock reacted with the starting fluid) of 100–1000, pH of ~7.5–12. Model alteration assemblages predominantly contain phyllosilicates (Fe-smectite, chlorite), the bulk composition of a mixture of which is close to that of saponite inferred from Chemistry and Mineralogy data and to that of saponite observed in the nakhlite Martian meteorites and terrestrial analogues. To match the observed clay mineral chemistry, inhomogeneous dissolution dominated by the amorphous phase and olivine is required. We therefore deduce a dissolving composition of approximately 70% amorphous material, with 20% olivine, and 10% whole rock component.« less

Mineralogy and fluid inclusions study of carbonate-hosted Mississippi valley-type Ain Allega Pb-Zn-Sr-Ba ore deposit, Northern Tunisia

NASA Astrophysics Data System (ADS)

Abidi, R.; Slim-Shimi, N.; Somarin, A.; Henchiri, M.

2010-05-01

The Ain Allega Pb-Zn-Sr-Ba ore deposit is located in the flysch zone on the Eastern edge of the Triassic diapir of Jebel Hamra. It is part of the extrusive Triassic evaporate formation along the Ghardimaou-Cape Serrat faults. The ore body consists of argilic-dolomite breccias surrounded by argilo-gypsum Triassic formation, which forms the hanging wall of the deposit, and rimmed by the Paleocene marls. The ore minerals show a cap-rock type mineralization with different styles particularly impregnation in dolomite, cement of breccias, replacement ore and open space filling in the dissolution cavities and fractures. Ore minerals include sphalerite, galena, marcasite and pyrite. Principal gangue minerals are composed of barite, celestite, calcite, dolomite and quartz. The ore minerals are hosted by the Triassic carbonate rocks which show hydrothermal alteration, dissolution and brecciation. X-ray - crystallographic study of barite-celestite mineral series shows that pure barite and celestite are the abundant species, whereas strontianiferous barite (85-96.5% BaSO 4) and barian-celestite (95% SrSO 4) are minor. Primary and secondary mono-phase (liquid only) fluid inclusions are common in celestite. Microthermometric analyses in two-phases (liquid and vapour) fluid inclusions suggest that gangue and ore minerals were precipitated by a low-temperature (180 °C) saline (16.37 wt.% NaCl equivalent) solution originated possibly from a basinal brine with some input from magmatic or metamorphic fluid. Based on geology, mineralogy, texture and fluid characteristics, the Ain Allega deposit is classified as a carbonate-hosted Mississippi valley-type deposit.

Modeling coupled thermal-hydrological-chemical processes in theunsaturated fractured rock of Yucca Mountain, Nevada: Heterogeneity andseepage

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

Mukhopadhyay, Sumit; Sonnenthal, Eric L.; Spycher, Nicolas

An understanding of processes affecting seepage intoemplacement tunnels is needed for correctly predicting the performance ofunderground radioactive waste repositories. It has been previouslyestimated that the capillary and vaporization barriers in the unsaturatedfractured rock of Yucca Mountain are enough to prevent seepage underpresent day infiltration conditions. It has also been thought that asubstantially elevated infiltration flux will be required to causeseepage after the thermal period is over. While coupledthermal-hydrological-chemical (THC) changes in Yucca Mountain host rockdue to repository heating has been previously investigated, those THCmodels did not incorporate elements of the seepage model. In this paper,we combine the THC processes inmore » unsaturated fractured rock with theprocesses affecting seepage. We observe that the THC processes alter thehydrological properties of the fractured rock through mineralprecipitation and dissolution. We show that such alteration in thehydrological properties of the rock often leads to local flow channeling.We conclude that such local flow channeling may result in seepage undercertain conditions, even with nonelevated infiltrationfluxes.« less

The role of fluids in rock layering development: a pressure solution self-organized process revealed by laboratory experiments

NASA Astrophysics Data System (ADS)

Gratier, Jean-Pierre; Noiriel, Catherine; Renard, Francois

2015-04-01

Natural deformation of rocks is often associated with stress-driven differentiation processes leading to irreversible transformations of their microstructures. The development mechanisms of such processes during diagenesis, tectonic, metamorphism or fault differentiation are poorly known as they are difficult to reproduce experimentally due to the very slow kinetics of stress-driven chemical processes. Here, we show that experimental compaction with development of differentiated layering, similar to what happens in natural deformation, can be obtained by indenter techniques in laboratory conditions. Samples of plaster mixed with clay and of diatomite loosely interbedded with volcanic dust were loaded in presence of their saturated aqueous solutions during several months at 40°C and 150°C, respectively. High-resolution X-ray microtomography and scanning electron microscopy observations show that the layering development is a pressure solution self-organized process. Stress-driven dissolution of the soluble minerals (either gypsum or silica) is initiated in the areas initially richer in insoluble minerals (clays or volcanic dust) because the kinetics of diffusive mass transfer along the soluble/insoluble mineral interfaces is much faster than along the healed boundaries of the soluble minerals. The passive concentration of insoluble minerals amplifies the localization of dissolution along some layers oriented perpendicular to the maximum compressive stress. Conversely, in the areas with initial low content in insoluble minerals and clustered soluble minerals, dissolution is slower. Consequently, these areas are less deformed, they host the re-deposition of the soluble species and they act as rigid objects that concentrate the dissolution near their boundaries thus amplifying the differentiation. A crucial parameter required for self-organized process of pressure solution is the presence of a fluid that is a good solvent of at least some of the rock-forming minerals. Another general requirement for the development of such differentiated layering is the heterogeneous mixing of variously soluble and insoluble species. From a general point of view, the development of diagenetic or tectonic layering has crucial consequences in geological processes. The main one is to modify the composition and microstructure of rocks by dissolution of the most soluble species, passive concentration of the insoluble species and re-deposition of the dissolved species at a distance that depends on the transport efficiency (diffusion or advection). Consequently, layering development modifies both the rheological and the transfer properties of rocks. It is the most common strain localization process in the upper crust when a reactive fluid phase is present, complementary to other strain localization processes in the lithosphere. A specific effect is the development of anisotropic properties that may favor local sliding on weak surfaces. This is particularly important in fault zones where pressure solution processes are at work. Modeling of differentiated layering during natural deformation must be rooted in the stress-driven dissolution and transport properties of the various minerals forming the rocks, and on the evolution of their rheological properties. The strength evolution can be taken into account through a weakening factor in the zone of dissolution and a strengthening factor in the zone of deposition. The kinetics evolution is controlled by the critical parameters of pressure solution.

Impact of silica diagenesis on the porosity of fine-grained strata: An analysis of Cenozoic mudstones from the North Sea

NASA Astrophysics Data System (ADS)

Wrona, Thilo; Taylor, Kevin G.; Jackson, Christopher A.-L.; Huuse, Mads; Najorka, Jens; Pan, Indranil

2017-04-01

Silica diagenesis has the potential to drastically change the physical and fluid flow properties of its host strata and therefore plays a key role in the development of sedimentary basins. The specific processes involved in silica diagenesis are, however, still poorly explained by existing models. This knowledge gap is addressed by investigating the effect of silica diagenesis on the porosity of Cenozoic mudstones of the North Viking Graben, northern North Sea through a multiple linear regression analysis. First, we identify and quantify the mineralogy of these rocks by scanning electron microscopy and X-ray diffraction, respectively. Mineral contents and host rock porosity data inferred from wireline data of two exploration wells are then analyzed by multiple linear regressions. This robust statistical analysis reveals that biogenic opal-A is a significant control and authigenic opal-CT is a minor influence on the porosity of these rocks. These results suggest that the initial porosity of siliceous mudstones increases with biogenic opal-A production during deposition and that the porosity reduction during opal-A/CT transformation results from opal-A dissolution. These findings advance our understanding of compaction, dewatering, and lithification of siliceous sediments and rocks. Moreover, this study provides a recipe for the derivation of the key controls (e.g., composition) on a rock property (e.g., porosity) that can be applied to a variety of problems in rock physics.

Theoretical and Numerical Investigation of the Cavity Evolution in Gypsum Rock

NASA Astrophysics Data System (ADS)

Li, Wei; Einstein, Herbert H.

2017-11-01

When water flows through a preexisting cylindrical tube in gypsum rock, the nonuniform dissolution alters the tube into an enlarged tapered tube. A 2-D analytical model is developed to study the transport-controlled dissolution in an enlarged tapered tube, with explicit consideration of the tapered geometry and induced radial flow. The analytical model shows that the Graetz solution can be extended to model dissolution in the tapered tube. An alternative form of the governing equations is proposed to take advantage of the invariant quantities in the Graetz solution to facilitate modeling cavity evolution in gypsum rock. A 2-D finite volume model was developed to validate the extended Graetz solution. The time evolution of the transport-controlled and the reaction-controlled dissolution models for a single tube with time-invariant flow rate are compared. This comparison shows that for time-invariant flow rate, the reaction-controlled dissolution model produces a positive feedback between the tube enlargement and dissolution, while the transport-controlled dissolution does not.

Thermohydrological conditions and silica redistribution near high-level nuclear wastes emplaced in saturated geological formations

NASA Astrophysics Data System (ADS)

Verma, A.; Pruess, K.

1988-02-01

Evaluation of the thermohydrological conditions near high-level nuclear waste packages is needed for the design of the waste canister and for overall repository design and performance assessment. Most available studies in this area have assumed that the hydrologic properties of the host rock are not changed in response to the thermal, mechanical, or chemical effects caused by waste emplacement. However, the ramifications of this simplifying assumption have not been substantiated. We have studied dissolution and precipitation of silica in liquid-saturated hydrothermal flow systems, including changes in formation porosity and permeability. Using numerical simulation, we compare predictions of thermohydrological conditions with and without inclusion of silica redistribution effects. Two cases were studied, namely, a canister-scale problem, and a repository-wide thermal convection problem and different pore models were employed for the permeable medium (fractures with uniform or nonuniform cross sections). We find that silica redistribution in water-saturated conditions does not have a sizeable effect on host rock and canister temperatures, pore pressures, or flow velocities.

Fayalite Dissolution and Siderite Formation in Water-Saturated Supercritical CO2

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

Qafoku, Odeta; Kovarik, Libor; Kukkadapu, Ravi K.

2012-11-25

Olivines, a significant constituent of basaltic rocks, have the potential to immobilize permanently CO2 after it is injected in the deep subsurface, due to carbonation reactions occurring between CO2 and the host rock. To investigate the reactions of fayalitic olivine with supercritical CO2 (scCO2) and formation of mineral carbonates, experiments were conducted at temperatures of 35 °C to 80 °C, 90 atm pressure and anoxic conditions. For every temperature, the dissolution of fayalite was examined both in the presence of liquid water and H2O-saturated scCO2. The experiments were conducted in a high pressure batch reactor at reaction time extending upmore » to 85 days. The newly formed products were characterized using a comprehensive suite of bulk and surface characterization techniques X-ray diffraction, Transmission/Emission Mössbauer Spectroscopy, Scanning Electron Microscopy coupled with Focused Ion Beam, and High Resolution Transmission Electron Microscopy. Siderite with rhombohedral morphology was formed at 35 °C, 50 °C, and 80 °C in the presence of liquid water and scCO2. In H2O-saturated scCO2, the formation of siderite was confirmed only at high temperature (80 °C). Characterization of reacted samples in H2O-saturated scCO2 with high resolution TEM indicated that siderite formation initiated inside voids created during the initial steps of fayalite dissolution. Later stages of fayalite dissolution result in the formation of siderite in layered vertical structures, columns or pyramids with a rhombus base morphology.« less

Do Hf isotopes in magmatic zircons represent those of their host rocks?

NASA Astrophysics Data System (ADS)

Wang, Di; Wang, Xiao-Lei; Cai, Yue; Goldstein, Steven L.; Yang, Tao

2018-04-01

Lu-Hf isotopic system in zircon is a powerful and widely used geochemical tracer in studying petrogenesis of magmatic rocks and crustal evolution, assuming that zircon Hf isotopes can represent initial Hf isotopes of their parental whole rock. However, this assumption may not always be valid. Disequilibrium partial melting of continental crust would preferentially melt out non-zircon minerals with high time-integrated Lu/Hf ratios and generate partial melts with Hf isotope compositions that are more radiogenic than those of its magma source. Dissolution experiments (with hotplate, bomb and sintering procedures) of zircon-bearing samples demonstrate this disequilibrium effect where partial dissolution yielded variable and more radiogenic Hf isotope compositions than fully dissolved samples. A case study from the Neoproterozoic Jiuling batholith in southern China shows that about half of the investigated samples show decoupled Hf isotopes between zircons and the bulk rocks. This decoupling could reflect complex and prolonged magmatic processes, such as crustal assimilation, magma mixing, and disequilibrium melting, which are consistent with the wide temperature spectrum from ∼630 °C to ∼900 °C by Ti-in-zircon thermometer. We suggest that magmatic zircons may only record the Hf isotopic composition of their surrounding melt during crystallization and it is uncertain whether their Hf isotopic compositions can represent the primary Hf isotopic compositions of the bulk magmas. In this regard, using zircon Hf isotopic compositions to trace crustal evolution may be biased since most of these could be originally from disequilibrium partial melts.

Mineralogy maketh mountains: Granitic landscapes shaped by dissolution

NASA Astrophysics Data System (ADS)

Eggleton, Richard A.

2017-05-01

In tectonically quiet regions, the shape of the landscape is controlled by the erosion resistance of the rocks. Erosion largely depends on the release of particles from the weathering rock, which in turn requires a degree of dissolution of the more soluble grains. The rate of dissolution of the common rock forming minerals allows the construction of a numerical Rock Weatherability Scale (RWS) based on the rock's modal mineralogical analysis. Applied regionally to three granitic landscape regions of the Bega Valley of southern New South Wales, the Tate Batholith and Featherbed Volcanics of north Queensland, and granitoids in the Beaufort region of Victoria, the mean elevation of the larger plutons in each region correlates highly (r = 0.83-0.93) with their RWS. Variation in composition within a pluton also shows there is a clear connection between changes in RWS and relief within the pluton. From these results it is apparent that the landscape of such granitic terrains is determined very largely by mineral dissolution rates, with plagioclase composition and content being a major factor.

Instability of an infiltration-driven dissolution-precipitation front with a nonmonotonic porosity profile

NASA Astrophysics Data System (ADS)

Kondratiuk, Paweł; Dutka, Filip; Szymczak, Piotr

2016-04-01

Infiltration of a rock by an external fluid very often drives it out of chemical equilibrium. As a result, alteration of the rock mineral composition occurs. It does not however proceed uniformly in the entire rock volume. Instead, one or more reaction fronts are formed, which are zones of increased chemical activity, separating the altered (product) rock from the yet unaltered (primary) one. The reaction fronts propagate with velocities which are usually much smaller than those of the infiltrating fluid. One of the simplest examples of such alteration is the dissolution of some of the minerals building the primary rock. For instance, calcium carbonate minerals in the rock matrix can be dissolved by infiltrating acidic fluids. In such a case the product rock has higher porosity and permeability than the primary one. Due to positive feedbacks between the reactant transport, fluid flow, and porosity generation, the reaction fronts in porosity-generating replacement systems are inherently unstable. An arbitrarily small protrusion of the front gets magnified and develops into a highly porous finger-like or funnel-like structure. This feature of dissolution fronts, dubbed the "reactive-infiltration instability" [1], is responsible for the formation of a number of geological patterns, such as solution pipes or various karst forms. It is also of practical importance, since spontaneous front breakup and development of localized highly porous flow paths (a.k.a. "wormholes") is favourable by petroleum engineers, who apply acidization to oil-bearing reservoirs in order to increase their permeability. However, more complex chemical reactions might occur during infiltration of a rock by a fluid. In principle, the products of dissolution might react with other species present either in the fluid or in the rock and reprecipitate [2]. The dissolution and precipitation fronts develop and and begin to propagate with equal velocities, forming a single dissolution-precipitation front. The porosity profile is not monotonic as in the case of pure dissolution, but it typically has a minimum in the vicinity of the front. Additionally, the porosity difference between the initial rock far-downstream and the well-developed secondary rock far-upstream can be either negative or positive, which either destabilizes of stabilized the front. We propose a theoretical model of a simple infiltration-driven dissolution-precipitation system and find the morphology of the resulting planar reaction front. By performing linear stability analysis of the stationary planar solutions we show that the front can be unstable for a wide range of control parameters, even if the porosity of the secondary rock is lower than the porosity of the primary rock. Next, by numerical simulations of the full nonlinear model we present the long-term evolution of the system. [1] D. Chadam et al., IMA J. Appl. Math. 36, 207-221, 1986. [2] A. Putnis, Rev. Mineral. Geochemistry, 70(1), 87-124, 2009.

Dissolution of glass wool, rock wool and alkaline earth silicate wool: morphological and chemical changes in fibers.

PubMed

Campopiano, Antonella; Cannizzaro, Annapaola; Angelosanto, Federica; Astolfi, Maria Luisa; Ramires, Deborah; Olori, Angelo; Canepari, Silvia; Iavicoli, Sergio

2014-10-01

The behavior of alkaline earth silicate (AES) wool and of other biosoluble wools in saline solution simulating physiological fluids was compared with that of a traditional wool belonging to synthetic vitreous fibers. Morphological and size changes of fibers were studied by scanning electron microscopy (SEM). The elements extracted from fibers were analyzed by inductively coupled plasma atomic emission spectrometry. SEM analysis showed a larger reduction of length-weighted geometric mean fiber diameter at 4.5 pH than at 7.4 pH. At the 7.4 pH, AES wool showed a higher dissolution rate and a dissolution time less than a few days. Their dissolution was highly non-congruent with rapid leaching of calcium. Unlike rock wool, glass wool dissolved more rapidly at physiological pH than at acid pH. Dissolution of AES and biosoluble rock wool is accompanied by a noticeable change in morphology while by no change for glass wool. Biosoluble rock wool developed a leached surface with porous honeycomb structure. SEM analysis showed the dissolution for glass wool is mainly due to breakage transverse of fiber at pH 7.4. AES dissolution constant (Kdis) was the highest at pH 7.4, while at pH 4.5 only biosoluble rockwool 1 showed a higher Kdis. Copyright © 2014 Elsevier Inc. All rights reserved.

The Yatela gold deposit in Mali, West Africa: The final product of a long-lived history of hydrothermal alteration and weathering

NASA Astrophysics Data System (ADS)

Masurel, Quentin; Miller, John; Hein, Kim A. A.; Hanssen, Eric; Thébaud, Nicolas; Ulrich, Stanislav; Kaisin, Jean; Tessougue, Samuel

2016-01-01

The Yatela gold deposit is located in the Kédougou-Kénieba inlier (KKI), a window of ca. 2200-2050 Ma rocks that are exposed in eastern Senegal and western Mali. The geology of the KKI differs from other Paleoproterozoic granite-greenstone belts and sedimentary basins by the abundance of carbonate rocks. The Yatela deposit occurs within 8 km of the regional-scale Senegal-Mali Shear Zone. Country rocks in the Yatela region have been subjected to polycyclic deformation and regional greenschist-facies metamorphism. A syn-kinematic diorite stock has intruded the metasedimentary sequences in the open pit and is associated with a hornblende-hornfels contact aureole. Field relationships and micro-textural data indicate that the primary gold mineralisation is shear-hosted. The similar relative timing and structural setting between the Yatela primary gold mineralisation and other world-class deposits in the region (e.g., Loulo, Lawrence et al., 2013a; Massawa, Treloar et al., 2014; Sadiola Hill, Masurel et al., in press) suggest that regional orogenic gold mineralisation occurred during a period of transcurrent tectonics, after the cessation of regional compressional deformation. The primary gold mineralisation at Yatela, however, is low-grade and sub-economic. It is hosted by marbles and, to a lesser extent, diorite. The primary ore is pyrite-rich, with abundant chalcopyrite, minor arsenopyrite and accessory Zn-Pb-Sb-Fe-Ag-Co-Ni-bearing mineral species. Post-Birimian surficial dissolution of hydrothermally altered and mineralised host marbles resulted in the creation of troughs, which were draped and infilled with a ferruginous dissolution residue enriched in gold. This auriferous residuum formed the economic resource mined at Yatela until decommissioning in 2013. The Yatela gold deposit is unique with respect to mineralisation types encountered in West Africa because an auriferous residuum of economic interest (>1 Moz) derives from an underlying sub-economic Birimian occurrence. This study provides a new appreciation for the economic interest of Yatela-style orebodies and their prospectivity in other gold provinces of the West African Craton where carbonates are present, such as in the Siguiri basin in Guinea and the Ity region in western Côte d'Ivoire.

A salt diapir-related Mississippi Valley-type deposit: the Bou Jaber Pb-Zn-Ba-F deposit, Tunisia: fluid inclusion and isotope study

NASA Astrophysics Data System (ADS)

Bouhlel, Salah; Leach, David L.; Johnson, Craig A.; Marsh, Erin; Salmi-Laouar, Sihem; Banks, David A.

2016-08-01

The Bou Jaber Ba-F-Pb-Zn deposit is located at the edge of the Bou Jaber Triassic salt diapir in the Tunisia Salt Diapir Province. The ores are unconformity and fault-controlled and occur as subvertical column-shaped bodies developed in dissolution-collapse breccias and in cavities within the Late Aptian platform carbonate rocks, which are covered unconformably by impermeable shales and marls of the Fahdene Formation (Late Albian-Cenomanian age). The host rock is hydrothermally altered to ankerite proximal to and within the ore bodies. Quartz, as fine-grained bipyramidal crystals, formed during hydrothermal alteration of the host rocks. The ore mineral assemblage is composed of barite, fluorite, sphalerite, and galena in decreasing abundance. The ore zones outline distinct depositional events: sphalerite-galena, barite-ankerite, and fluorite. Fluid inclusions, commonly oil-rich, have distinct fluid salinities and homogenization temperatures for each of these events: sphalerite-galena (17 to 24 wt% NaCl eq., and Th from 112 to 136 °C); ankerite-barite (11 to 17 wt% NaCl eq., and Th from 100 to 130 °C); fluorite (19 to 21 wt% NaCl eq., Th from 140 to 165 °C). The mean temperature of the ore fluids decreased from sphalerite (125 °C) to barite (115 °C) and increased during fluorite deposition (152 °C); then decreased to ˜110 °C during late calcite precipitation. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses of fluid inclusions in fluorite are metal rich (hundreds to thousands ppm Pb, Zn, Cu, Fe) but the inclusions in barite are deficient in Pb, Zn, Cu, Fe. Inclusions in fluorite have Cl/Br and Na/Br ratios of several thousand, consistent with dissolution of halite while the inclusions analysed in barite have values lower than seawater which are indicative of a Br-enriched brine derived from evaporation plus a component of halite dissolution. The salinity of the barite-hosted fluid inclusions is less than obtained simply by the evaporation of seawater to halite saturation and requires a dilution of more than two times by meteoric water. The higher K/Na values in fluid inclusions from barite suggest that the brines interacted with K-rich rocks in the basement or siliciclastic sediments in the basin. Carbonate gangue minerals (ankerite and calcite) have δ13C and δ18O values that are close to the carbonate host rock and indicate fluid equilibrium between carbonate host rocks and hydrothermal brines. The δ34S values for sphalerite and galena fall within a narrow range (1 to 10 ‰) with a bulk value of 7.5 ‰, indicating a homogeneous source of sulfur. The δ34S values of barite are also relatively homogeneous (22 ‰), with 6 ‰ higher than the δ34S of local and regional Triassic evaporites (15 ‰). The latter are believed to be the source of sulfate. Temperature of deposition together with sulfur isotope data indicate that the reduced sulfur in sulfides was derived through thermochemical sulfate reduction of Triassic sulfate via hydrocarbons produced probably from Late Cretaceous source rocks. The 87Sr/86Sr ratio in the Bou Jaber barite (0.709821 to 0.711408) together with the lead isotope values of Bou Jaber galena (206Pb/204Pb = 18.699 to 18.737; 207Pb/204Pb = 15.635 to 15.708 and 208Pb/204Pb = 38.321 to 38.947) show that metals were extracted from homogeneous crustal source(s). The tectonic setting of the Bou Jaber ore deposit, the carbonate nature of the host rocks, the epigenetic style of the mineralization and the mineral associations, together with sulfur and oxygen isotope data and fluid inclusion data show that the Bou Jaber lead-zinc mineralization has the major characteristics of a salt diapir-related Mississippi Valley-type (MVT) deposit with superimposed events of fluorite and of barite deposition. Field relations are consistent with mineral deposition during the Eocene-Miocene Alpine orogeny from multiple hydrothermal events: (1) Zn-Pb sulfides formed by mixing of two fluids: one fluid metal-rich but reduced sulfur-poor and a second fluid reduced sulfur-rich; (2) barite precipitation involved the influx of a meteoric water component that mixed with a barium-rich fluid; and (3) fluorite precipitated from a highly saline fluid with higher temperatures.

Modeling Coupled Thermal-Hydrological-Chemical Processes in the Unsaturated Fractured Rock of Yucca Mountain, Nevada: Heterogeneity and Seepage

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

S. Mukhopadhyay; E.L. Donnenthal; N. Spycher

An understanding of processes affecting seepage into emplacement tunnels is needed for correctly predicting the performance of underground radioactive waste repositories. It has been previously estimated that the capillary and vaporization barriers in the unsaturated fractured rock of Yucca Mountain are enough to prevent seepage under present day infiltration conditions. It has also been thought that a substantially elevated infiltration flux will be required to cause seepage after the thermal period is over. While coupled thermal-hydrological-chemical (THC) changes in Yucca Mountain host rock due to repository heating has been previously investigated, those THC models did not incorporate elements of themore » seepage model. In this paper, we combine the THC processes in unsaturated fractured rock with the processes affecting seepage. We observe that the THC processes alter the hydrological properties of the fractured rock through mineral precipitation and dissolution. We show that such alteration in the hydrological properties of the rock often leads to local flow channeling. We conclude that such local flow channeling may result in seepage under certain conditions, even with nonelevated infiltration fluxes.« less

Dissolution of salt on the east flank of the Permian Basin in the southwestern U.S.A.

USGS Publications Warehouse

Johnson, K.S.

1981-01-01

Hydrogeologic studies prove that natural dissolution of bedded salt occurs at shallow depths in many parts of the Permian Basin of the southwestern U.S.A. This is especially well-documented on the east side of the basin in study areas on the Cimarron River and Elm Fork in western Oklahoma, and on the Red River in the southeastern part of the Texas Panhandle. Four requirements for salt dissolution are: (1) a deposit of salt; (2) a supply of water unsaturated with respect to NaCl; (3) an outlet for removal of brine; and (4) energy to cause water to flow through the system. The supply of fresh groundwater in the region is recharged through permeable rocks, alluvium, terrace deposits, karstic features and fractures. Groundwater dissolves salt at depths of 10-250 m, and the resulting brine moves laterally and upward under hydrostatic pressure through caverns, fractures in disrupted rock, and clastic or carbonate aquifers until it reaches the land surface, where it forms salt plains and salt springs. In many areas, salt dissolution produces a self-perpetuating cycle: dissolution causes cavern development, followed by collapse and subsidence of overlying rock; then the resulting disrupted rock has a greater vertical permeability that allows increased water percolation and additional salt dissolution. ?? 1981.

Alpha Recoil Flux of Radon in Groundwater and its Experimental Measurement

NASA Astrophysics Data System (ADS)

Mehta, N.; Harvey, C. F.; Kocar, B. D.

2016-12-01

Groundwater Radon (Rn222) activity is primarily controlled by alpha recoil process (radioactive decay), however, evaluating the rate and extent of this process, and its impact on porewater radioactivity, remains uncertain. Numerous factors contribute to this uncertainty, including the spatial distribution of parent radionuclides (e.g. U238, Th232 , Ra226 and Ra228) within native materials, differences in nuclide recoil length in host matrix and the physical structure of the rock strata (pore size distribution and porosity). Here, we experimentally measure Radon activities within porewater contributed through alpha recoil, and analyze its variations as a function of pore structure and parent nuclide distribution within host matrices, including Marcellus shale rock and Serrie-Copper Pegmatite. The shale cores originate from the Marcellus formation in Mckean, Pennsylvania collected at depths ranging from 1000-7000 feet, and the U-Th-rich Pegmatite is obtained from South Platte District, Colorado. Columns are packed with granulated rock of varying surface area (30,000-60,000 cm2/g) and subjected to low salinity sodium chloride solution in a close loop configuration. The activity of Radon (Rn222) and radium (Ra226) in the saline fluid is measured over time to determine recoil supply rates. Mineralogical and trace element data for rock specimens are characterized using XRD and XRF, and detailed geochemical profiles are constructed through total dissolution and analysis using ICP-MS and ICP-OES. Naturally occurring Radium nuclides and its daughters are quantified using a low-energy Germanium detector. The parent nuclide (U238 and Th232) distribution in the host rock is studied using X-Ray Absorption Spectroscopy (XAS). Our study elucidates the contribution of alpha recoil on the appearance and distribution of Radon (Rn222) within porewater of representative rock matrices. Further, we illustrate the effects of chemical and physical heterogeneity on the rate of this process, which may inform models predicting the fate and transport of radionuclides in subsurface environments.

Hydrothermal element fluxes from Copahue, Argentina: A “beehive” volcano in turmoil

NASA Astrophysics Data System (ADS)

Varekamp, Johan C.; Ouimette, Andrew P.; Herman, Scott W.; Bermúdez, Adriana; Delpino, Daniel

2001-11-01

Copahue volcano erupted altered rock debris, siliceous dust, pyroclastic sulfur, and rare juvenile fragments between 1992 and 1995, and magmatic eruptions occurred in July October 2000. Prior to 2000, the Copahue crater lake, acid hot springs, and rivers carried acid brines with compositions that reflected close to congruent rock dissolution. The ratio between rock-forming elements and chloride in the central zone of the volcano-hydrothermal system has diminished over the past few years, reflecting increased water/rock ratios as a result of progressive rock dissolution. Magmatic activity in 2000 provided fresh rocks for the acid fluids, resulting in higher ratios between rock-forming elements and chloride in the fluids and enhanced Mg fluxes. The higher Mg fluxes started several weeks prior to the eruption. Model data on the crater lake and river element flux determinations indicate that Copahue volcano was hollowed out at a rate of about 20000 25000 m3/yr, but that void space was filled with about equal amounts of silica and liquid elemental sulfur. The extensive rock dissolution has weakened the internal volcanic structure, making flank collapse a volcanic hazard at Copahue.

Replication in plastic of three-dimensional fossils preserved in indurated clastic sedimentary rocks

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

Zapasink, H.T.; Johnston, P.A.

A new technique for replicating in plastic the fossils preserved in clastic rocks should now make available reliable morphologic and frequency data, comparable in quality to those derived from acid-prepared silicified faunas, for a major segment of the fossil record. The technique involves 3 steps: the dissolution of carbonate in fossiliferous rocks with hydrochloric acid, impregnation of resulting voids with liquid plastic, and dissolution of the rock matrix with hydrofluoric acid, leaving a concentrate of plastic-replaced fossils.

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.

Initiation of and distributed deformation at and around stylolite interfaces: Insights from detailed microstructural analysis

NASA Astrophysics Data System (ADS)

Ebner, M.; Piazolo, S.; Koehn, D.

2009-04-01

In the present contribution we investigate the microstructure of bedding parallel and bedding normal stylolites in carbonate rocks. We focused our study on micro-stylolites which represent an initial stage of this localised pressure solution process as stylolite roughness amplitude is a function of strain. We use electron backscatter diffraction analysis (EBSD) and orientation contrast imaging to address the following issues: (i) What causes the initiation of stylolite interfaces at a submicroscopic scale, (ii) is there distributed deformation around the stylolite interface and (iii) what is the role of the interface (residuum)? Our findings demonstrate that the characteristic stylolite teeth are initiated at a pre-existing heterogeneity in the host-rock. This quenched noise in carbonate rocks is typically composed of clay particles in the submicron scale. In addition, qtz-grains are present along especially pronounced stylolite peaks. The stylolite interface evolves with increasing strain from individual clay particles separated by grain-grain contacts of calcite along the interface to a continuous layer of clay and oxides. Thickness variation of the residuum along the interface is inferred to be strongly influenced by the pre-existing distribution of pinning particles that are more resistant to dissolution. Another important observation is that a shaped preferred orientation (SPO) exists in a halo around the stylolite. This SPO increases with proximity to the stylolite interface. Within this halo, crystal plastic deformation is expressed by subgrain formation with subgrain boundaries usually aligned parallel to shortening direction. Bedding normal (tectonic) stylolites which overprint already compacted beds i.e. with a pre-existing sedimentary SPO parallel to the bedding plane exhibit a SPO at a high angle to the sedimentary SPO. We conclude that stylolite roughness is primarily caused by pre-existing heterogeneities in the host-rock which are more resistant to dissolution e.g. clay particles and/or qtz grains. Secondly, we demonstrate that stylolite formation is not a process that is restricted to the stylolite interface itself but a process that is active in a broader zone around the actual interface.

Subsidence and collapse sinkholes in soluble rock: a numerical perspective

NASA Astrophysics Data System (ADS)

Kaufmann, Georg; Romanov, Douchko; Hiller, Thomas

2016-04-01

Soluble rocks such as limestone, gypsum, anhydrite, and salt are prone to subsidence and the sudden creation of collapse sinkholes. The reason for this behaviour stems from the solubility of the rock: Water percolating through fissures and bedding partings can remove material from the rock walls and thus increase the permeability of the host rock by orders of magnitudes. This process occurs on time scales of 1,000-100,000 years, resulting in enlarged fractures, voids and cavities, which then carry flow efficiently through the rock. The enlargement of sub-surface voids to the meter-size within such short times creates mechanical conditions prone to collapse. The collapse initiates at depth, but then propagates to the surface. By means of numerical modelling, we discuss the long-term evolution of secondary porosity in gypsum rocks, resulting in zones of sub-surface voids, which then become mechanically unstable and collapse. We study two real-world case scenarios, in which we can relate field observations to our numerical model: (i) A dam-site scenario, where flow around the dam caused widespread dissolution of gypsum and subsequent subsidence of the dam and a nearby highway. (ii) A natural collapse sinkhole forming as a result of freshwater inflow into a shallow anhydrite formation with rapid evolution of voids in the sub-surface.

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.

Driving forces for metamorphic vein filling during bauxite dehydration: insights from Li and Al transfer illustrated by LIBS compositional profiles (Western Alps)

NASA Astrophysics Data System (ADS)

Verlaguet, Anne; Brunet, Fabrice; Goffé, Bruno; Menut, Denis; Findling, Nathaniel; Poinssot, Christophe

2015-04-01

In subduction zones, the significant amounts of aqueous fluid released in the course of the successive dehydration reactions occurring during prograde metamorphism are expected to strongly influence the rock rheology, as well as kinetics of metamorphic reactions and mass transfer efficiency. Mineralized veins, ubiquitous in metamorphic rocks, can be seen as preserved witnesses of fluid and mass redistribution that partly accommodate the rock deformation (lateral segregation). However, the driving forces and mechanisms of mass transfer towards fluid-filled open spaces remain somewhat unclear. The aim of this study is to investigate the vein-forming processes and the modalities of mass transfer during local fluid-rock interactions, and their links with fluid production and rock deformation, with new insights from Laser Induced Breakdown Spectroscopy (LIBS) profiles. This study focuses on karstic pockets (metre scale) of Triassic metabauxites embedded in thick carbonate units, that have been isolated from large-scale fluid flow during HP-LT Alpine metamorphism (W. Vanoise, French Alps). These rocks display several generations of metamorphic veins containing various Al-bearing minerals, which give particular insights into mass transfer processes. It is proposed that the internally-derived fluid (~13 vol% produced by successive dehydration reactions) has promoted the opening of fluid-filled open spaces (euhedral habits of vein minerals) and served as medium for diffusive mass transfer from rock to vein. Based on mineralogical and textural features, two vein types can be distinguished: (1) some veins are filled with newly formed products of either prograde (chloritoid) or retrograde (chlorite) metamorphic reactions; in this case, fluid-filled open spaces seem to offer energetically favourable nucleation/growth sites; (2) the second vein type is filled with cookeite (Li-Al-rich chlorite) or pyrophyllite, which were present in the host-rock prior to the vein formation. In this closed chemical system, mass transfer from rock to vein was achieved through the fluid, in a dissolution-transport-precipitation process. To investigate the modalities of mass transfer towards this second vein type, LIBS profiles were performed in the host-rock, taking Li concentration as a proxy for cookeite distribution. Cookeite is highly concentrated (45-65 vol%) in regularly spaced veins, and the LIBS profiles show that cookeite is evenly distributed in the host-rock comprised between two veins. The absence of diffusion profiles suggests that the characteristic diffusion distance for Li, Al and Si is greater than or equal to the distance separating two cookeite veins (2-4 cm). This is in agreement with characteristic diffusion lengths calculated from both grain boundary and pore fluid diffusion coefficients, for the estimated duration of the peak of metamorphism. Which driving forces are responsible for cookeite selective transfer towards veins? Chemical potential gradients between host-rock pores and veins may have developed in response to either (1) a stress difference: thermochemical calculations show that pressure-solution processes may affect preferentially cookeite and pyrophyllite; (2) a difference in interfacial energy, phyllosilicates showing very different morphologies in host-rocks (fibers) compared to veins (euhedral crystals); fluid-mineral interfacial energy may be maximal in the small host-rock pores, which can maintain higher cookeite solubility than large fluid-filled open spaces (i.e., veins).

Hydrothermal element fluxes from Copahue, Argentina: A "beehive" volcano in turmoil

USGS Publications Warehouse

Varekamp, J.C.; Ouimette, A.P.; Herman, S.W.; Bermudez, A.; Delpino, D.

2001-01-01

Copahue volcano erupted altered rock debris, siliceous dust, pyroclastic sulfur, and rare juvenile fragments between 1992 and 1995, and magmatic eruptions occurred in July-October 2000. Prior to 2000, the Copahue crater lake, acid hot springs, and rivers carried acid brines with compositions that reflected close to congruent rock dissolution. The ratio between rock-forming elements and chloride in the central zone of the volcano-hydrothermal system has diminished over the past few years, reflecting increased water/rock ratios as a result of progressive rock dissolution. Magmatic activity in 2000 provided fresh rocks for the acid fluids, resulting in higher ratios between rock-forming elements and chloride in the fluids and enhanced Mg fluxes. The higher Mg fluxes started several weeks prior to the eruption. Model data on the crater lake and river element flux determinations indicate that Copahue volcano was hollowed out at a rate of about 20 000-25 000 m3/yr, but that void space was filled with about equal amounts of silica and liquid elemental sulfur. The extensive rock dissolution has weakened the internal volcanic structure, making flank collapse a volcanic hazard at Copahue.

Hypogenic speleogenesis in quartzite: The case of Corona 'e Sa Craba Cave (SW Sardinia, Italy)

NASA Astrophysics Data System (ADS)

Sauro, Francesco; De Waele, Jo; Onac, Bogdan P.; Galli, Ermanno; Dublyansky, Yuri; Baldoni, Eleonora; Sanna, Laura

2014-04-01

The paper presents a detailed study demonstrating the hypogenic origin of the Corona 'e Sa Craba quartzite cave in SW Sardinia (Italy). Although the quartzite host-rock of this cave derived from silicification of Cambrian dolostones and dissolution of carbonate remnants could have had a role in the speleogenesis, detailed morphologic and petrographic investigation revealed clear evidence of quartz dissolution without signs of mechanical erosion by running waters. Thin section microscopy and scanning electron microscope (SEM) images show pervasive dissolution morphologies, such as pits and notches on quartz crystals causing the deep arenization of the cave walls, suggesting that the dissolution of quartz had a primary role in the formation of the void. The study of secondary cave minerals and the sulfur isotopic composition of sulfates and sulfides, coupled with data on fluid inclusions, allowed reconstruction of the peculiar speleogenetic history of this hypogenic hydrothermal quartzite cave. The cave formed by reduced hydrothermal fluids, probably under basic-neutral pH in phreatic conditions. The presence of abundant cations of Ba2 + in reduced Cl-rich fluids enhanced the quartz dissolution rate, allowing the formation of the voids in deep settings. During the Late Oligocene uplift of the area, the hydrothermal fluids in the cave reached oxygen-rich conditions, thus a minerogenetic phase started with the deposition of barite when the temperature of the fluid was ≤ 50 °C. The presence of cinnabar crusts in the lower part of the cave walls and on the boulders suggests a later volcanic phase with Hg-rich vapors ascending from below. Other minerals such as alunite, basaluminite, gypsum and halloysite (typical of an acid sulfate alteration environment), and phosphates were formed in a final, much more recent stage. The δ34S values of the cave sulfate minerals indicate that S is derived from the remobilization of original Precambrian Pb-Zn Mississippi Valley Type ores. These last two stages did not significantly affect the morphology of the cave. The Corona 'e Sa Craba appears to be the world's first example of a hypogenic cave in quartzite where the speleogenetic mechanisms have been studied and reconstructed in detail, using a variety of modern methods. This study confirms that dissolution of quartz by thermal alkaline fluids at depth can produce large dissolutional voids in the apparently poorly soluble quartzite rocks.

Effects of bioleaching on the mechanical and chemical properties of waste rocks

NASA Astrophysics Data System (ADS)

Yin, Sheng-Hua; Wu, Ai-Xiang; Wang, Shao-Yong; Ai, Chun-Ming

2012-01-01

Bioleaching processes cause dramatic changes in the mechanical and chemical properties of waste rocks, and play an important role in metal recovery and dump stability. This study focused on the characteristics of waste rocks subjected to bioleaching. A series of experiments were conducted to investigate the evolution of rock properties during the bioleaching process. Mechanical behaviors of the leached waste rocks, such as failure patterns, normal stress, shear strength, and cohesion were determined through mechanical tests. The results of SEM imaging show considerable differences in the surface morphology of leached rocks located at different parts of the dump. The mineralogical content of the leached rocks reflects the extent of dissolution and precipitation during bioleaching. The dump porosity and rock size change under the effect of dissolution, precipitation, and clay transportation. The particle size of the leached rocks decreased due to the loss of rock integrity and the conversion of dry precipitation into fine particles.

Rock-fluid chemical interactions at reservoir conditions: The influence of brine chemistry and extent of reaction

NASA Astrophysics Data System (ADS)

Anabaraonye, B. U.; Crawshaw, J.; Trusler, J. P. M.

2016-12-01

Following carbon dioxide injection in deep saline aquifers, CO2 dissolves in the formation brines forming acidic solutions that can subsequently react with host reservoir minerals, altering both porosity and permeability. The direction and rates of these reactions are influenced by several factors including properties that are associated with the brine system. Consequently, understanding and quantifying the impacts of the chemical and physical properties of the reacting fluids on overall reaction kinetics is fundamental to predicting the fate of the injected CO2. In this work, we present a comprehensive experimental study of the kinetics of carbonate-mineral dissolution in different brine systems including sodium chloride, sodium sulphate and sodium bicarbonate of varying ionic strengths. The impacts of the brine chemistry on rock-fluid chemical reactions at different extent of reactions are also investigated. Using a rotating disk technique, we have investigated the chemical interactions between the CO2-saturated brines and carbonate minerals at conditions of pressure (up to 10 MPa) and temperature (up to 373 K) pertinent to carbon storage. The changes in surface textures due to dissolution reaction were studied by means of optical microscopy and vertical scanning interferometry. Experimental results are compared to previously derived models.

Fracture Dissolution of Carbonate Rock: An Innovative Process for Gas Storage

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

James W. Castle; Ronald W. Falta; David Bruce

2006-10-31

The goal of the project is to develop and assess the feasibility and economic viability of an innovative concept that may lead to commercialization of new gas-storage capacity near major markets. The investigation involves a new approach to developing underground gas storage in carbonate rock, which is present near major markets in many areas of the United States. Because of the lack of conventional gas storage and the projected growth in demand for storage capacity, many of these areas are likely to experience shortfalls in gas deliverability. Since depleted gas reservoirs and salt formations are nearly non-existent in many areas,more » alternatives to conventional methods of gas storage are required. The need for improved methods of gas storage, particularly for ways to meet peak demand, is increasing. Gas-market conditions are driving the need for higher deliverability and more flexibility in injection/withdrawal cycling. In order to meet these needs, the project involves an innovative approach to developing underground storage capacity by creating caverns in carbonate rock formations by acid dissolution. The basic concept of the acid-dissolution method is to drill to depth, fracture the carbonate rock layer as needed, and then create a cavern using an aqueous acid to dissolve the carbonate rock. Assessing feasibility of the acid-dissolution method included a regional geologic investigation. Data were compiled and analyzed from carbonate formations in six states: Indiana, Ohio, Kentucky, West Virginia, Pennsylvania, and New York. To analyze the requirements for creating storage volume, the following aspects of the dissolution process were examined: weight and volume of rock to be dissolved; gas storage pressure, temperature, and volume at depth; rock solubility; and acid costs. Hydrochloric acid was determined to be the best acid to use because of low cost, high acid solubility, fast reaction rates with carbonate rock, and highly soluble products (calcium chloride) that allow for the easy removal of calcium waste from the well. Physical and chemical analysis of core samples taken from prospective geologic formations for the acid dissolution process confirmed that many of the limestone samples readily dissolved in concentrated hydrochloric acid. Further, some samples contained oily residues that may help to seal the walls of the final cavern structure. These results suggest that there exist carbonate rock formations well suited for the dissolution technology and that the presence of inert impurities had no noticeable effect on the dissolution rate for the carbonate rock. A sensitivity analysis was performed for characteristics of hydraulic fractures induced in carbonate formations to enhance the dissolution process. Multiple fracture simulations were conducted using modeling software that has a fully 3-D fracture geometry package. The simulations, which predict the distribution of fracture geometry and fracture conductivity, show that the stress difference between adjacent beds is the physical property of the formations that has the greatest influence on fracture characteristics by restricting vertical growth. The results indicate that by modifying the fracturing fluid, proppant type, or pumping rate, a fracture can be created with characteristics within a predictable range, which contributes to predicting the geometry of storage caverns created by acid dissolution of carbonate formations. A series of three-dimensional simulations of cavern formation were used to investigate three different configurations of the acid-dissolution process: (a) injection into an open borehole with production from that same borehole and no fracture; (b) injection into an open borehole with production from that same borehole, with an open fracture; and (c) injection into an open borehole connected by a fracture to an adjacent borehole from which the fluids are produced. The two-well configuration maximizes the overall mass transfer from the rock to the fluid, but it results in a complex cavern shape. Numerical simulations were performed to evaluate the ability of storage caverns produced by the acid-dissolution method to store natural gas. In addition, analyses were conducted to evaluate cavern stability during gas injection and withdrawal from storage caverns created in carbonate formations by the acid-dissolution method. The stability analyses were conducted using FLAC2D, a commercially available geotechnical analysis and design software. The analyses indicate that a tall cylindrical cavern with a domed roof and floor will be stable under the expected range of in situ and operational conditions. This result suggests that it should be feasible to avoid mechanical instabilities that could potentially diminish the effectiveness of the storage facility. The feasibility of using pressure transients measured at the ground surface was investigated as a means to evaluate (Abstract truncated)« less

Monitoring carbonate dissolution using spatially resolved under-sampled NMR propagators and MRI

NASA Astrophysics Data System (ADS)

Sederman, A. J.; Colbourne, A.; Mantle, M. D.; Gladden, L. F.; Oliveira, R.; Bijeljic, B.; Blunt, M. J.

2017-12-01

The dissolution of a porous rock matrix by an acidic flow causes a change in the pore structure and consequently the pattern of fluid flow and rock permeability. This process is relevant to many areas of practical relevance such as enhanced oil recovery, water contaminant migration and sequestration of supercritical CO2. The most important governing factors for the type of change in the pore space are related by the Péclet (Pe) and Damköhler (Da) dimensionless numbers; these compare the transport properties of the fluid in the porous medium with the reactive properties of the solid matrix and the incident fluid respectively. Variation in Pe and Da can cause very different evolution regimes of the pore space and flow can occur, ranging from a uniform dissolution through different "wormholing" regimes (shown on the left hand side of figure 1) to face dissolution. NMR has a unique capability of measuring both the flow and structural changes during such dissolution whilst the characteristics of flow in the highly heterogeneous matrix that is formed can be predicted by the CTRW modelling approach. Here, NMR measurements of displacement probability distributions, or propagators, have been used to monitor the evolution of fluid flow during a reactive dissolution rock core floods. Developments in the NMR method by undersampling the acquisition data enable spatially resolved measurements of the propagators to be done at sufficient displacement resolution and in a timescale that is short enough to capture the changes in structure and flow. The highly under-sampled (4%) data, which typically reduces the acquisition time from 2 hours to 6 minutes, has been shown to produce equivalent propagator results to the fully sampled experiment. Combining these propagator measurements with quantitative and fast imaging techniques a full time-resolved picture of the dissolution reaction is built up. Experiments have been done for both Ketton and Estaillades carbonate rock cores, which exhibit very different dissolution behaviours, and for which experiments and model comparisons will be shown.

Mineral growth in rocks: kinetic-rheological models of replacement, vein formation, and syntectonic crystallization

NASA Astrophysics Data System (ADS)

Fletcher, Raymond C.; Merino, Enrique

2001-11-01

We model three cases of coupling between mineral growth kinetics and mechanical response of the rock: (i) dispersed spherical crystals growing by replacement in a hydrostatically stressed elastic rock; (ii) growth of veins or vein networks accommodated by viscous relaxation of surrounding rock; and (iii) syntectonic crystallization in a rock undergoing bulk pure shear. Such models for the microscopic environment of mineral growth, together with additional assumptions or knowledge about rheological behavior and aggregate geometry, provide refined estimates of the behavior of a macroscopic volume element, which could be combined with geochemical reaction-transport models. Crucial in the models are the various consequences-pressure solution, creep, fracturing-of the local stress that is necessarily generated by mineral growth in rocks (other than in pores). In the first model, the dispersed spherical crystals of mineral A are assumed to grow within a spherical volume of rock consisting of mineral B, the ;mineralized zone; (MZ), itself embedded in elastic rock. The macroscopic stress in the MZ and the far-field stress in the surrounding rock are uniform and hydrostatic. Mineral growth of the A crystals is driven by supersaturation with respect to mineral A, is accommodated by replacement of B grains, and leads to an expansion of the MZ described by an infinitesimal strain. The radial growth rate of a spherical crystal of mineral A, with replacement of mineral B, is da/dt=kARTln(ΩA)[kBV0B/(kBV0B+kAV0A)], where kA and kB are kinetic constants, R is the gas constant, T the temperature in kelvin, and V0A and V0B are specific volumes. Reference saturation states of mineral A, ΩA > 1, and host mineral B, ΩB = 1, are specified at the far-field hydrostatic stress, σ0. The microscopic environment of each crystal of A is modeled by a representative volume element (RVE) consisting of a sphere of mineral A embedded in a spherical shell of mineral B. In each RVE, stress is neither uniform nor hydrostatic. The model links the local microscopic stress with the macroscopic stress in the MZ and surrounding rock. The second model refers to veins that make room for themselves by growing, not to veins that form by cementation of previously opened, or opening, cracks. If the growth of mineral A as propagating veins or as an interconnected vein network takes place by deformation and expansion of the MZ-with the deformation itself driven by the stress arising from the supersaturation-driven growth-the surrounding rock undergoes deformation and is treated as viscous. The rate of growth in vein width, w, is dw/dt=2kA[RTln(ΩA)-SV0A]/(1+M), where M = 16ηkAV0Ac2/(3b3), η is the medium viscosity, c is the vein radius, and each vein is treated as centered in a spherical RVE of radius b. S is an effective tensile stress required for vein propagation. For a vein network, in which veins surround equant polyhedra of rock of radius b, we set c = b and drop the term in S for simplicity. Veins may also widen by replacement. The ratio of vein widening by expansion to that by replacement is (dw/dt)expansion/(dw/dt)replacement={(3b/16η)/[(3b/16η)+kAV0A]}/[kBV0B/(KBV0B+kAV0A)]. Both mechanisms of accommodation contribute equally when η = 3b/(16kBV0B); at higher viscosity, replacement is dominant. The incipient growth of a cylindrical crystal with circular cross section in a medium deforming in pure shear simulates syntectonic crystallization. Both dissolution and deformation of the host accommodate growth. In the model, the crystal tends to grow faster in the direction of maximum rate of extension. In this direction, the host mineral may either dissolve to accommodate growth, or precipitate to form a pressure shadow. Accommodation by host dissolution is greatest in the direction of maximum rate of shortening.

Dynamic Pore-Scale Imaging of Reactive Transport in Heterogeneous Carbonates at Reservoir Conditions Across Multiple Dissolution Regimes

NASA Astrophysics Data System (ADS)

Menke, H. P.; Bijeljic, B.; Andrew, M. G.; Blunt, M. J.

2014-12-01

Sequestering carbon in deep geologic formations is one way of reducing anthropogenic CO2 emissions. When supercritical CO2 mixes with brine in a reservoir, the acid generated has the potential to dissolve the surrounding pore structure. However, the magnitude and type of dissolution are condition dependent. Understanding how small changes in the pore structure, chemistry, and flow properties affect dissolution is paramount for successful predictive modelling. Both 'Pink Beam' synchrotron radiation and a Micro-CT lab source are used in dynamic X-ray microtomography to investigate the pore structure changes during supercritical CO2 injection in carbonate rocks of varying heterogeneity at high temperatures and pressures and various flow-rates. Three carbonate rock types were studied, one with a homogeneous pore structure and two heterogeneous carbonates. All samples are practically pure calcium carbonate, but have widely varying rock structures. Flow-rate was varied in three successive experiments by over an order of magnitude whlie keeping all other experimental conditions constant. A 4-mm carbonate core was injected with CO2-saturated brine at 10 MPa and 50oC. Tomographic images were taken at 30-second to 20-minute time-resolutions during a 2 to 4-hour injection period. A pore network was extracted using a topological analysis of the pore space and pore-scale flow modelling was performed directly on the binarized images with connected pathways and used to track the altering velocity distributions. Significant differences in dissolution type and magnitude were found for each rock type and flowrate. At the highest flow-rates, the homogeneous carbonate was seen to have predominately uniform dissolution with minor dissolution rate differences between the pores and pore throats. Alternatively, the heterogeneous carbonates which formed wormholes at high flow rates. At low flow rates the homogeneous rock developed wormholes, while the heterogeneous samples showed evidence of compact dissolution. This study serves as a unique benchmark for pore-scale reactive transport modelling directly on the binarized Micro-CT images. Dynamic pore-scale imaging methods offer advantages in helping explain the dominant processes at the pore scale so that they may be up-scaled for accurate model prediction.

The Effect of Micrite on Velocity, Its Sensitivity to Pressure, and Dissolution of Carbonates

NASA Astrophysics Data System (ADS)

El Husseiny, A.; Vanorio, T.

2014-12-01

This study investigates the effect of micrite on the acoustic properties of well-controlled microstructures created in the laboratory to closely mimic carbonate rocks. In particular, we examine the effect of micrite content on the elastic stiffness rock, its sensitivity to pressure, and induced dissolution upon saturation with a reactive fluid. We followed Dunham's classification and fabricated the samples by mixing coarse (sand size) and very fine (micrite size) calcite grains in different ratios, with the addition of cement and then cold-compressing the mixture. The acoustic velocities were measured under bench-top conditions and as functions of confining pressure before and after the injection of a CO2aqueous solution. Our bench-top measurements indicated that micrite makes the frame of the carbonate samples stiffer. Since the sensitivity of the elastic stiffness to pressure decreases as the content of micrite increases (see figure 1), we hypothesize a stiffer pore structure (i.e., rounder pores) in micrite-richer fabrics. Furthermore, the presence of micrite makes the carbonate sample more reactive upon dissolution. The concentration of Ca+2 cations in the fluid measured at the outlet after the injection of the CO2 aqueous solution shows larger dissolution in the micrite-rich samples likely due to the higher surface area of the micrite aggregates. The content of micrite also seems to affect the evolution of stiffness as dissolution proceeds. As the content of micrite increases, the enhanced dissolution translates into a marked softening of the rock frame. We conclude that the content of micrite can play an important role in the complex rock-fluid interaction of carbonates as well as when comparing Gassmann's predictions to velocity measurements of saturated carbonates.

Factors controlling groundwater quality in the Yeonjegu District of Busan City, Korea, using the hydrogeochemical processes and fuzzy GIS.

PubMed

Venkatramanan, Senapathi; Chung, Sang Yong; Selvam, Sekar; Lee, Seung Yeop; Elzain, Hussam Eldin

2017-10-01

The hydrogeochemical processes and fuzzy GIS techniques were used to evaluate the groundwater quality in the Yeonjegu district of Busan Metropolitan City, Korea. The highest concentrations of major ions were mainly related to the local geology. The seawater intrusion into the river water and municipal contaminants were secondary contamination sources of groundwater in the study area. Factor analysis represented the contamination sources of the mineral dissolution of the host rocks and domestic influences. The Gibbs plot exhibited that the major ions were derived from the rock weathering condition. Piper's trilinear diagram showed that the groundwater quality was classified into five types of CaHCO 3 , NaHCO 3 , NaCl, CaCl 2 , and CaSO 4 types in that order. The ionic relationship and the saturation mineral index of the ions indicated that the evaporation, dissolution, and precipitation processes controlled the groundwater chemistry. The fuzzy GIS map showed that highly contaminated groundwater occurred in the northeastern and the central parts and that the groundwater of medium quality appeared in most parts of the study area. It suggested that the groundwater quality of the study area was influenced by local geology, seawater intrusion, and municipal contaminants. This research clearly demonstrated that the geochemical analyses and fuzzy GIS method were very useful to identify the contaminant sources and the location of good groundwater quality.

Numerical modelling of fluid-rock interactions: Lessons learnt from carbonate rocks diagenesis studies

NASA Astrophysics Data System (ADS)

Nader, Fadi; Bachaud, Pierre; Michel, Anthony

2015-04-01

Quantitative assessment of fluid-rock interactions and their impact on carbonate host-rocks has recently become a very attractive research topic within academic and industrial realms. Today, a common operational workflow that aims at predicting the relevant diagenetic processes on the host rocks (i.e. fluid-rock interactions) consists of three main stages: i) constructing a conceptual diagenesis model including inferred preferential fluids pathways; ii) quantifying the resulted diagenetic phases (e.g. depositing cements, dissolved and recrystallized minerals); and iii) numerical modelling of diagenetic processes. Most of the concepts of diagenetic processes operate at the larger, basin-scale, however, the description of the diagenetic phases (products of such processes) and their association with the overall petrophysical evolution of sedimentary rocks remain at reservoir (and even outcrop/ well core) scale. Conceptual models of diagenetic processes are thereafter constructed based on studying surface-exposed rocks and well cores (e.g. petrography, geochemistry, fluid inclusions). We are able to quantify the diagenetic products with various evolving techniques and on varying scales (e.g. point-counting, 2D and 3D image analysis, XRD, micro-CT and pore network models). Geochemical modelling makes use of thermodynamic and kinetic rules as well as data-bases to simulate chemical reactions and fluid-rock interactions. This can be through a 0D model, whereby a certain process is tested (e.g. the likelihood of a certain chemical reaction to operate under specific conditions). Results relate to the fluids and mineral phases involved in the chemical reactions. They could be used as arguments to support or refute proposed outcomes of fluid-rock interactions. Coupling geochemical modelling with transport (reactive transport model; 1D, 2D and 3D) is another possibility, attractive as it provides forward simulations of diagenetic processes and resulting phases. This contribution is based on several studies that were undertaken on carbonate rocks diagenesis in some of the major reservoir rocks in the Middle East and outcrop analogues in Europe. Here, the main processes at hand are related to fracture-related dolomitization and carbonate dissolution. We would like to present the workflows we have followed and the questioning that resulted for a series of case studies. The way forward, seems evident as the integration of workflows and numerical modelling tools at different scales, bringing better constrains on the boundary data and less uncertainty.

Karst Lands: The dissolution of carbonate rock produces unique landscapes and poses significant hydrological and environmental concerns

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

White, W.B.; Culver, D.C.; Herman, J.S.

1995-09-01

Karst lands are produced by the action of water on soluble rocks, a process among the most dynamic of all erosive forces that counterbalance the uplifting forces of tectonics. The dissolution of carbonate rock, primarily limestone and dolomite, produces unique landscapes and poses significant hydrological and environmental concerns. The major topic areas discussed in this article include the following: processes that form karst; karst drainage basins; discharge from karst aquifers; caves as paleoclimatic recorders; caves as ecosystems; water issues in karst regions; and sinkholes, soil piping and subsidence. 20 refs., 9 figs.

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.

Ultramafic-derived arsenic in a fractured bedrock aquifer

USGS Publications Warehouse

Ryan, P.C.; Kim, J.; Wall, A.J.; Moen, J.C.; Corenthal, L.G.; Chow, D.R.; Sullivan, C.M.; Bright, K.S.

2011-01-01

In the fractured bedrock aquifer of northern Vermont, USA, As concentrations in groundwater range from <1 to 327??g/L (<13-4360nm/L) and these elevated occurrences have a general spatial association with ultramafic rock bodies. The ultramafic rocks in this region are comprised mainly of serpentinites and talc-magnesite rocks with average As concentration of 93ppm and a range from 1 to 1105ppm. By comparison, the other main lithologies in the study area are depleted in As relative to the ultramafics: the average As concentration in metabasaltic rocks is 4.1ppm with a range of <1-69ppm, and mean As concentration in meta-sedimentary phyllites and schists is 22ppm with a range of <1-190ppm. In the ultramafic rocks, As is correlated with Sb and light rare earth elements, indicating that As was introduced to the ultramafic rocks during metasomatism by fluids derived from the subducting slab. Evidence from sequential chemical extraction, X-ray diffraction (XRD) and stoichiometric analysis indicates that the majority of the As is located in antigorite and magnesite (MgCO3) with lesser amounts in magnetite (Fe3O4). Hydrochemistry of monitoring wells drilled into fractured ultramafic rock in a groundwater recharge area with no anthropogenic As source reveals above background As (2-9??g/L) and an Mg-HCO3 hydrochemical signature that reflects dissolution of antigorite and magnesite, confirming that As in groundwater can be derived from ultramafic rock dissolution. Arsenic mobility in groundwater affected by ultramafic rock dissolution may be enhanced by alkaline pH values and relatively high HCO3- concentrations. ?? 2011 Elsevier Ltd.

Metal transports and enrichments in iron depositions hosted in basaltic rocks. II: Metal rich fluids and Fe origin

NASA Astrophysics Data System (ADS)

Zhang, Ronghua; Zhang, Xuetong; Hu, Shumin

2015-12-01

This study focuses on revealing the mechanism of metal transport, enrichment and Fe origin of iron deposition during water basalt interactions occurred in basaltic rocks. Observations of the iron deposits (anhydrite-magnetite-pyroxene type deposits) hosted in K-rich basaltic rocks in the Mesozoic volcanic area of the Middle-Lower Yangtze River valley, China, indicate that the mechanism of metal transport and enrichment for those deposits are significant objective to scientists, and the Fe origin problem is not well resolved. Here the metal transport, enrichment and iron origin have been investigated in high temperature experiments of water basaltic interactions. These deposits were accompanying a wide zone with metal alteration. The effects of hydrothermal alteration on major rock-forming element concentrations in basaltic rock were investigated by systematically comparing the chemical compositions of altered rocks with those of fresh rocks. In the deposits, these metals are distributed throughout altered rocks that exhibit vertical zoning from the deeper to the shallow. Then, combined with the investigations of the metal-alterations, we performed kinetic experiments of water-basaltic rock interactions using flow-through reactors in open systems at temperatures from 20 °C to 550 °C, 23-34 MPa. Release rates for the rock-forming elements from the rocks have been measured. Experiments provide the release rates for various elements at a large temperature range, and indicate that the dissolution rates (release rates) for various elements vary with temperature. Si, Al, and K have high release rates at temperatures from 300 °C to 500 °C; the maximum release rates (RMX) for Si are reached at temperatures from 300 °C to 400 °C. The RMXs for Ca, Mg, and Fe are at low temperatures from 20 °C to 300 °C. Results demonstrate that Fe is not released from 400 °C to 550 °C, and indicate that when deep circling fluids passed through basaltic rocks, Fe was not mobile, and fixed in the rocks at temperatures from 400 °C to 550 °C. Significance of the results is to provide evidence that the Fe of ores originated from basalt, and Fe-oxides precipitated across the critical state of water. Simultaneously, Ca, Mg and Fe are fixed in the deeper altered rocks (mafic minerals). But, Fe was dissolved at relatively low temperatures (100-300 °C). Si, Al, and K were easily mobile from basalt by upward flowing fluids from 300 °C to 400 °C and transported to the upper part (silicified and argillized rock).

Stable isotope reactive transport modeling in water-rock interactions during CO2 injection

NASA Astrophysics Data System (ADS)

Hidalgo, Juan J.; Lagneau, Vincent; Agrinier, Pierre

2010-05-01

Stable isotopes can be of great usefulness in the characterization and monitoring of CO2 sequestration sites. Stable isotopes can be used to track the migration of the CO2 plume and identify leakage sources. Moreover, they provide unique information about the chemical reactions that take place on the CO2-water-rock system. However, there is a lack of appropriate tools that help modelers to incorporate stable isotope information into the flow and transport models used in CO2 sequestration problems. In this work, we present a numerical tool for modeling the transport of stable isotopes in groundwater reactive systems. The code is an extension of the groundwater single-phase flow and reactive transport code HYTEC [2]. HYTEC's transport module was modified to include element isotopes as separate species. This way, it is able to track isotope composition of the system by computing the mixing between the background water and the injected solution accounting for the dependency of diffusion on the isotope mass. The chemical module and database have been expanded to included isotopic exchange with minerals and the isotope fractionation associated with chemical reactions and mineral dissolution or precipitation. The performance of the code is illustrated through a series of column synthetic models. The code is also used to model the aqueous phase CO2 injection test carried out at the Lamont-Doherty Earth Observatory site (Palisades, New York, USA) [1]. References [1] N. Assayag, J. Matter, M. Ader, D. Goldberg, and P. Agrinier. Water-rock interactions during a CO2 injection field-test: Implications on host rock dissolution and alteration effects. Chemical Geology, 265(1-2):227-235, July 2009. [2] Jan van der Lee, Laurent De Windt, Vincent Lagneau, and Patrick Goblet. Module-oriented modeling of reactive transport with HYTEC. Computers & Geosciences, 29(3):265-275, April 2003.

Geochemical signatures of copper redistribution in IOCG-type mineralisation, Gawler Craton, South Australia

NASA Astrophysics Data System (ADS)

Uvarova, Yulia A.; Pearce, Mark A.; Liu, Weihua; Cleverley, James S.; Hough, Robert M.

2018-04-01

The Emmie Bluff iron oxide, copper, gold (IOCG) prospect is located in the Olympic Dam district, South Australia, and hosts sub-economic 150-m-thick Cu-Au mineralisation associated with the hematite-chlorite-sericite alteration with chalcopyrite commonly replacing pre-existing pyrite at a depth of 800 m. With the use of cutting-edge synchrotron X-ray fluorescence microscopy and field emission gun-scanning electron microscopy, it is shown for the first time that sub-economic IOCG mineralisation in the Olympic Dam district was affected by a late fluid event, which resulted in partial dissolution of Cu mineralisation and transport of Cu in the form of chloride complexes. The porous chlorite-sericite matrix associated with the late alteration of chalcopyrite hosts a Cu-Cl-OH phase previously undescribed in IOCG rocks, which was identified as one of the polymorphs of the atacamite group of minerals, Cu2Cl(OH)3. Thermodynamic modelling shows that "atacamite" is produced during dissolution of chalcopyrite by an oxidised, Cl-bearing fluid. An acidic environment is produced within millimetres of the chalcopyrite grains during oxidation. This process drives chlorite recrystallisation that is recorded by compositional variation of chlorite proximal to chalcopyrite. The existence of the atacamite is discussed in the context of fluid evolution and interaction with IOCG-type mineralisation and its implications to ore preservation versus destruction and remobilisation.

The onset of an eruption: selective assimilation of hydrothermal minerals during pre-eruptive magma ascent of the 2010 summit eruption of Eyjafjallajökull volcano, Iceland

NASA Astrophysics Data System (ADS)

Pistolesi, M.; Cioni, R.; Francalanci, L.; Bertagnini, A.; D'Oriano, C.; Braschi, E.; Höskuldsson, A.

2016-11-01

The complex processes occurring in the initial phases of an eruption are often recorded in the products of its opening stage, which are usually characterized by small volume and limited dispersal, and thus generally poorly studied. The 2010 eruption of Eyjafjallajökull (Iceland) represents a unique opportunity for these investigations thanks to the good preservation of tephra deposits within the ice/snow pack. A detailed geochemical investigation on the glassy groundmass of single ash clasts disclosed a population of fragments with unusual high 87Sr/86Sr (up to 0.70668) for Icelandic magmatism, and anomalous elemental composition with respect to most of the juvenile material of the eruption. This suggests that during its rise, before intruding into the ice cover, magma at a dyke tip selectively assimilated hydrothermal minerals with seawater-related, high-Sr isotopic ratios (zeolites, silica phases, anhydrite) hosted in altered volcanic/epiclastic rocks. According to the observed precursory seismicity, only restricted to few hours before the onset of the eruption, this process could have accompanied subcritical aseismic fracture opening during the days before the eruption, possibly related to stress corrosion-cracking processes, which enhanced the partial dissolution/melting and subsequent selective assimilation of the host rocks.

Planetary Differentiation by Aerial Metasomatism

NASA Astrophysics Data System (ADS)

Baker, D. R.

2018-05-01

Dissolution of surficial rocks will occur on planetary bodies with steam atmospheres. Although the amount of dissolved material is small, metasomatism of chondritic compositions produces siliceous crustal materials and enriches residual rocks.

Kinetics of carbonate dissolution in CO2-saturated aqueous system at reservoir conditions

NASA Astrophysics Data System (ADS)

Peng, Cheng; Crawshaw, John P.; Maitland, Geoffrey; Trusler, J. P. Martin

2014-05-01

In recent years, carbon capture and storage (CCS) has emerged as a key technology for limiting anthropogenic CO2 emissions while allowing the continued utilisation of fossil fuels. The most promising geological storage sites are deep saline aquifers because the capacity, integrity and injection economics are most favourable, and the environmental impact can be minimal. Many rock-fluid chemical reactions are known to occur both during and after CO2 injection in saline aquifers. The importance of rock-fluid reactions in the (CO2 + H2O) system can be understood in terms of their impact on the integrity and stability of both the formation rocks and cap rocks. The chemical interactions between CO2-acidified brines and the reservoir minerals can influence the porosity and permeability of the formations, resulting in changes in the transport processes occurring during CO2 storage. Since carbonate minerals are abundant in sedimentary rocks, one of the requirements to safely implement CO2 storage in saline aquifers is to characterise the reactivity of carbonate minerals in aqueous solutions at reservoir conditions. In this work, we reported measurements of the intrinsic rate of carbonate dissolution in CO2-saturated water under high-temperature high-pressure reservoir conditions extending up to 373 K and 14 MPa. The rate of carbonate dissolution in CO2-free HCl(aq) was also measured at ambient pressure at temperatures up to 353 K. Various pure minerals and reservoir rocks were investigated in this study, including single-crystals of calcite and magnesite, and samples of dolomite, chalks and sandstones. A specially-designed batch reactor system, implementing the rotating disc technique, was used to obtain the intrinsic reaction rate at the solid/liquid interface, free of mass transfer effects. The effective area and mineralogy of the exposed surface was determined by a combination of surface characterisation techniques including XRD, SEM, EDX and optical microscopy. The results of the study indicate that the rotating disc technique can allow accurate measurement of the carbonate dissolution rate under surface-reaction-controlled conditions, and that the carbonate dissolution rate typically increases with the increase of temperature, CO2 partial pressure and solution acidity. The study shows that the dissolution of carbonate in CO2-free acidic solutions can be described as a first order heterogeneous reaction; however, this model is not sufficient to describe the reaction kinetics of carbonate minerals in the (CO2 + H2O) system, particularly for high reactivity carbonates, such as calcite, at reservoir conditions. For these systems, both pH and the activity of CO2(aq) influence the dissolution rate. Based on the experimental results, kinetic models have been developed and parameterised to describe the dissolution of different carbonate minerals. The results of this study should facilitate more rigorous modelling of mineral dissolution in deep saline aquifers used for CO2 storage. We gratefully acknowledge the funding of QCCSRC provided jointly by Qatar Petroleum, Shell, and the Qatar Science & Technology Park. Keywords: Carbon Dioxide, Carbonate, High Pressure, High Temperature, Reaction Kinetics.

Estimation of Carbon Sink in Surface Carbonate Rocks of Guangxi Province by Using Remote Sensing Images

NASA Astrophysics Data System (ADS)

Jia, B.; Zhou, G.; Wang, H.; Yue, T.; Huang, W.

2018-04-01

Studies of the imbalance of source sinks in the carbon cycle show that CO2 absorbed during rock weathering is part of the "miss carbon" of the global carbon cycle. The carbon sink contribution of carbonate rocks obviously plays a very important role in the absorption of atmospheric CO2. Estimation of carbon sinks in karst dynamic system of Guangxi province has great significance for further understanding of global karst carbon cycle and global climate research. This paper quotes the rock data from Tao Xiaodong's paper, which is obtained using RS and GIS techniques. At the same time, the dissolution rate model studied by Zhou Guoqing and others was used to estimate the dissolution rate of carbonate rocks in Guangxi Province. Finally, the CO2 content consumed by carbonate karstification in Guangxi Province was 1342910.447 t a-1. The results obtained are in the same order of magnitude as the CO2 content consumed by carbonate rock karstification in Guangxi Province calculated by Tao Xiaodong.

Estimating rock and slag wool fiber dissolution rate from composition.

PubMed

Eastes, W; Potter, R M; Hadley, J G

2000-12-01

A method was tested for calculating the dissolution rate constant in the lung for a wide variety of synthetic vitreous silicate fibers from the oxide composition in weight percent. It is based upon expressing the logarithm of the dissolution rate as a linear function of the composition and using a different set of coefficients for different types of fibers. The method was applied to 29 fiber compositions including rock and slag fibers as well as refractory ceramic and special-purpose, thin E-glass fibers and borosilicate glass fibers for which in vivo measurements have been carried out. These fibers had dissolution rates that ranged over a factor of about 400, and the calculated dissolution rates agreed with the in vivo values typically within a factor of 4. The method presented here is similar to one developed previously for borosilicate glass fibers that was accurate to a factor of 1.25. The present coefficients work over a much broader range of composition than the borosilicate ones but with less accuracy. The dissolution rate constant of a fiber may be used to estimate whether disease would occur in animal inhalation or intraperitoneal injection studies of that fiber.

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

Detwiler, Russell

Fractures provide flow paths that can potentially lead to fast migration of fluids or contaminants. A number of energy-­related applications involve fluid injections that significantly perturb both the pressures and chemical composition of subsurface fluids. These perturbations can cause both mechanical deformation and chemical alteration of host rocks with potential for significant changes in permeability. In fractured rock subjected to coupled chemical and mechanical stresses, it can be difficult to predict the sign of permeability changes, let alone the magnitude. This project integrated experimental and computational studies to improve mechanistic understanding of these coupled processes and develop and test predictivemore » models and monitoring techniques. The project involved three major components: (1) study of two-­phase flow processes involving mass transfer between phases and dissolution of minerals along fracture surfaces (Detwiler et al., 2009; Detwiler, 2010); (2) study of fracture dissolution in fractures subjected to normal stresses using experimental techniques (Ameli, et al., 2013; Elkhoury et al., 2013; Elkhoury et al., 2014) and newly developed computational models (Ameli, et al., 2014); (3) evaluation of electrical resistivity tomography (ERT) as a method to detect and quantify gas leakage through a fractured caprock (Breen et al., 2012; Lochbuhler et al., 2014). The project provided support for one PhD student (Dr. Pasha Ameli; 2009-­2013) and partially supported a post-­doctoral scholar (Dr. Jean Elkhoury; 2010-­2013). In addition, the project provided supplemental funding to support collaboration with Dr. Charles Carrigan at Lawrence Livermore National Laboratory in connection with (3) and supported one MS student (Stephen Breen; 2011-­2013). Major results from each component of the project include the following: (1) Mineral dissolution in fractures occupied by two fluid phases (e.g., oil-­water or water-­CO{sub 2}) causes changes in local capillary forces and redistribution of fluids. These coupled processes enhance channel formation and the potential for development of fast flow paths through fractures. (2) Dissolution in fractures subjected to normal stress can result in behaviors ranging from development of dissolution channels and rapid permeability increases to fracture healing and significant permeability decreases. The timescales associated with advective transport of dissolved ions in the fracture, mineral dissolution rates, and diffusion within the adjacent porous matrix dictate the sign and magnitude of the resulting permeability changes. Furthermore, a high--resolution mechanistic model that couples elastic deformation of contacts and aperture-­dependent dissolution rates predicts the range of observed behaviors reasonably well. (3) ERT has potential as a tool for monitoring gas leakage in deep formations. Using probabilistic inversion methods further enhances the results by providing uncertainty estimates of inverted parameters.« less

CO 2-induced chemo-mechanical alteration in reservoir rocks assessed via batch reaction experiments and scratch testing

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

Aman, Michael; Espinoza, D. Nicolas; Ilgen, Anastasia G.

Here, the injection of carbon dioxide (CO 2) into geological formations results in a chemical re-equilibration between the mineral assemblage and the pore fluid, with ensuing mineral dissolution and re-precipitation. Hence, target rock formations may exhibit changes of mechanical and petrophysical properties due to CO 2 exposure. We conducted batch reaction experiments with Entrada Sandstone and Summerville Siltstone exposed to de-ionized water and synthetic brine under reservoir pressure (9–10 MPa) and temperature (80°C) for up to four weeks. Samples originate from the Crystal Geyser field site, where a naturally occurring CO 2 seepage alters portions of these geologic formations. Wemore » conducted micro-scratch tests on rock samples without alteration, altered under laboratory conditions, and naturally altered over geologic time. Scratch toughness and hardness decrease as a function of exposure time and water salinity up to 52% in the case of Entrada and 87% in the case of Summerville after CO 2-induced alteration in the laboratory. Imaging of altered cores with SEM-EDS and X-ray microCT methods show dissolution of carbonate and silica cements and matrix accompanied by minor dissolution of Fe-oxides, clays, and other silicates. Parallel experiments using powdered samples confirm that dissolution of carbonate and silica are the primary reactions. The batch reaction experiments in the autoclave utilize a high fluid to rock volume ratio and represent an end member of possible alteration associated with CO 2 storage systems. These types of tests serve as a pre-screening tool to identify the susceptibility of rock facies to CO 2-related chemical-mechanical alteration during long-term CO 2 storage.« less

CO 2-induced chemo-mechanical alteration in reservoir rocks assessed via batch reaction experiments and scratch testing

DOE PAGES

Aman, Michael; Espinoza, D. Nicolas; Ilgen, Anastasia G.; ...

2017-09-22

Here, the injection of carbon dioxide (CO 2) into geological formations results in a chemical re-equilibration between the mineral assemblage and the pore fluid, with ensuing mineral dissolution and re-precipitation. Hence, target rock formations may exhibit changes of mechanical and petrophysical properties due to CO 2 exposure. We conducted batch reaction experiments with Entrada Sandstone and Summerville Siltstone exposed to de-ionized water and synthetic brine under reservoir pressure (9–10 MPa) and temperature (80°C) for up to four weeks. Samples originate from the Crystal Geyser field site, where a naturally occurring CO 2 seepage alters portions of these geologic formations. Wemore » conducted micro-scratch tests on rock samples without alteration, altered under laboratory conditions, and naturally altered over geologic time. Scratch toughness and hardness decrease as a function of exposure time and water salinity up to 52% in the case of Entrada and 87% in the case of Summerville after CO 2-induced alteration in the laboratory. Imaging of altered cores with SEM-EDS and X-ray microCT methods show dissolution of carbonate and silica cements and matrix accompanied by minor dissolution of Fe-oxides, clays, and other silicates. Parallel experiments using powdered samples confirm that dissolution of carbonate and silica are the primary reactions. The batch reaction experiments in the autoclave utilize a high fluid to rock volume ratio and represent an end member of possible alteration associated with CO 2 storage systems. These types of tests serve as a pre-screening tool to identify the susceptibility of rock facies to CO 2-related chemical-mechanical alteration during long-term CO 2 storage.« less

Dissolution Rates and Reaction Products of Olivine Interaction with Ammonia-Rich Fluid

NASA Astrophysics Data System (ADS)

Zandanel, A. E.; Truche, L.; Hellmann, R.; Tobie, G.; Marrocchi, Y.

2018-05-01

Olivine dissolution rates and reaction products in NH3-rich fluids are determined from experiments simulating H2O-rock interaction on Enceladus. Kinetic rates are calculated from flow through experiments and reaction products from static experiments.

Making a black shale shine: the interaction of hydrothermal fluids and diagenetic processes

NASA Astrophysics Data System (ADS)

Gleeson, Sarah; Magnall, Joe; Reynolds, Merilie

2016-04-01

Hydrothermal fluids are important agents of mass and thermal transfer in the upper crust. This is exemplified by shale-hosted massive sulphide deposits (SHMS), which are anomalous accumulations of Zn and Pb sulphides (± barite) in sedimentary basins created by hydrothermal fluids. These deposits occur in passive margin settings and, typically, there is no direct evidence of magmatic input. Recent studies of Paleozoic deposits in the North American Cordillera (MacMillan Pass and Red Dog Districts) have shown that the deposits are formed in a sub-seafloor setting, where the potential for thermal and chemical gradients is high. Mineralization is characterized by the replacement and displacement of unconsolidated, partially lithified and lithified biosiliceous mudstones (± carbonates), and commonly the sulphide mineralization post-dates, and replaces, bedded barite units in the sediments. The Red Dog District (Alaska, USA) contain some of the largest Zn-Pb deposits ever discovered. The host-rocks are dominantly carbonaceous mudstones, with carbonate units and some radiolarites. The ore forms massive sulphide bodies that replace pyritized mudstones, barite and carbonate units. Lithological and textural relationships provide evidence that much of the ore formed in bioturbated, biosiliceous zones that may have had high primary porosity and/or permeability. Sediment permeability may have been further modified by aging of the silica rich sediments and the dissolution/replacement of carbonate and barite beds. At the Tom and Jason deposits (MacMillan Pass, Yukon) the fault-controlled hydrothermal upflow zone is uniquely preserved as an unequivocal vent complex. Here, the metal bearing fluids are hot (300°C), low salinity (6 wt% NaCl equiv.) and acidic (pH < 4.5). These fluids were initially in thermal and chemical disequilibrium with a partially lithified organic rich host-rock but cooled rapidly during fluid rock interaction and the input of diagenetic pore fluids. Paragenetically-constrained sulphur isotope analyses provide evidence that at MacMillan Pass and in the Red Dog deposits, reduced sulphur was generated during open system diagenesis and euxinic conditions were not present at the time of mineralization. Furthermore, the formation of diagenetic barite provided an important mechanism of sulphur concentration into the host rock. Both features combined to produce an effective metal trap in the sub-surface. Ultimately, interactions between hydrothermal and diagenetic fluids within a permeable, chemically reactive medium contribute to the formation of SHMS deposits. Where these factors align, it is possible to produce world-class ore deposits (e.g. in the Red Dog district). The complex textures that are commonly encountered in these systems are the result of hydrothermal fluids interacting with their host-rocks in a heterogeneous and dynamic physical and chemical environment.

Dynamic Pore-Scale Imaging of Reactive Transport in Heterogeneous Carbonates at Reservior Conditions

NASA Astrophysics Data System (ADS)

Menke, Hannah; Bijeljic, Branko; Andrew, Matthew; Blunt, Martin

2014-05-01

Sequestering carbon in deep geologic formations is one way of reducing anthropogenic CO2 emissions. Carbon capture, Utilization, and Storage (CCUS) in carbonate reservoirs has the added benefit of mobilizing more oil for extraction, increasing oil reservoir yield, and generating revenue while also mitigating climate change. The magnitude, speed, and type of dissolution are dependent the intrinsic properties of the rock. Understanding how small changes in the pore structure affect dissolution is paramount for successful predictive modelling both on the pore-scale and for up-scaled reservoir simulations. We propose an experimental method whereby both 'Pink Beam' synchrotron radiation and a Micro-CT lab source are used in dynamic X-ray microtomography to investigate the pore structure changes in carbonate rocks of varying heterogeneity at high temperatures and pressures. Four carbonate rock types were studied, two relatively homogeneous carbonates, Ketton and Mt. Gambier, and two very heterogeneous carbonates, Estalliades and Portland Basebed. Each rock type was imaged under the same reservoir and flow conditions to gain insight into the impact of heterogeneity. A 4-mm carbonate core was injected with CO2-saturated brine at 10 MPa and 50oC for 2 hours. Depending on sample heterogeneity and X-ray source, tomographic images were taken at between 30-second and 20-minute time-resolutions and a 4-micron spatial resolution during injection. Changes in porosity, permeability, and structure were obtained by first binning and filtering the images, then binarizing them with watershed segmentation, and finally extracting a pore/throat network. Furthermore, pore-scale flow modelling was performed directly on the binarized image and used to track velocity distributions as the pore network evolved. Significant differences in dissolution type and magnitude were found for each rock type. The most homogeneous carbonate, Ketton, was seen to have predominately uniform dissolution with minor dissolution rate differences between the pores and pore throats. This was not true for the heterogeneous carbonates, Estalliades and Portland Basebed, which formed wormholes. Pore-scale modelling of flow directly on the voxels showed the differences in the evolution of complex flow fields with changes in dissolution regime. The PDFs of normalized velocity for uniform dissolution showed that the maximum pore velocity within the system decreased as dissolution occurred. This is due to dissolution enlarging pores and pore throats. However, in the wormholing regime, there was a large increase in maximum velocity once the wormhole broke through the length of the core and a preferential flow path was created. Additionally, this study serves as a unique benchmark for pore-scale reactive transport modelling directly on the binarized Micro-CT images. This dynamic pore-scale imaging method offers advantages in helping fully explain the dominant physical and chemical processes at the pore scale so that they may be up-scaled to the reservoir scale for increased accuracy in model prediction.

Experimental study on effects of geologic heterogeneity in enhancing dissolution trapping of supercritical CO2

NASA Astrophysics Data System (ADS)

Agartan, Elif; Trevisan, Luca; Cihan, Abdullah; Birkholzer, Jens; Zhou, Quanlin; Illangasekare, Tissa H.

2015-03-01

Dissolution trapping is one of the primary mechanisms that enhance the storage security of supercritical carbon dioxide (scCO2) in saline geologic formations. When scCO2 dissolves in formation brine produces an aqueous solution that is denser than formation brine, which leads to convective mixing driven by gravitational instabilities. Convective mixing can enhance the dissolution of CO2 and thus it can contribute to stable trapping of dissolved CO2. However, in the presence of geologic heterogeneities, diffusive mixing may also contribute to dissolution trapping. The effects of heterogeneity on mixing and its contribution to stable trapping are not well understood. The goal of this experimental study is to investigate the effects of geologic heterogeneity on mixing and stable trapping of dissolved CO2. Homogeneous and heterogeneous media experiments were conducted in a two-dimensional test tank with various packing configurations using surrogates for scCO2 (water) and brine (propylene glycol) under ambient pressure and temperature conditions. The results show that the density-driven flow in heterogeneous formations may not always cause significant convective mixing especially in layered systems containing low-permeability zones. In homogeneous formations, density-driven fingering enhances both storage in the deeper parts of the formation and contact between the host rock and dissolved CO2 for the potential mineralization. On the other hand, for layered systems, dissolved CO2 becomes immobilized in low-permeability zones with low-diffusion rates, which reduces the risk of leakage through any fault or fracture. Both cases contribute to the permanence of the dissolved plume in the formation.

New Advances in Re-Os Geochronology of Organic-rich Sedimentary Rocks.

NASA Astrophysics Data System (ADS)

Creaser, R. A.; Selby, D.; Kendall, B. S.

2003-12-01

Geochronology using 187Re-187Os is applicable to limited rock and mineral matrices, but one valuable application is the determination of depositional ages for organic-rich clastic sedimentary rocks like black shales. Clastic sedimentary rocks, in most cases, do not yield depositional ages using other radioactive isotope methods, but host much of Earth's fossil record upon which the relative geological timescale is based. As such, Re-Os dating of black shales has potentially wide application in timescale calibration studies and basin analysis, if sufficiently high precision and accuracy could be achieved. This goal requires detailed, systematic studies and evaluation of factors like standard compound stoichiometry, geologic effects, and the 187Re decay constant. Ongoing studies have resulted in an improved understanding of the abilities, limitations and systematics of the Re-Os geochronometer in black shales. First-order knowledge of the effects of processes like hydrocarbon maturation and low-grade metamorphism is now established. Hydrocarbon maturation does not impact the ability of the Re-Os geochronometer to determine depositional ages from black shales. The Re-Os age determined for the Exshaw Fm of western Canada is accurate within 2σ analytical uncertainty of the known age of the unit (U-Pb monazite from ash, conodont biostratigraphy). This suggests that the large improvement in precision attained for Re-Os dating of black shales by Cohen et al (ESPL 1999) over the pioneering work of Ravizza & Turekian (GCA 1989), relates to advances in analytical methodologies and sampling strategies, rather than a lack of disturbance by hydrocarbon maturation. We have found that a significant reduction in isochron scatter can be achieved by using an alternate dissolution medium, which preferentially attacks organic matter in which Re and Os are largely concentrated. This likely results from a more limited release of detrital Os and Re held in silicate materials during dissolution, compared with the inverse aqua regia medium used for Carius tube analysis. Using these "organic-selective" dissolution techniques, precise depositional ages have now been obtained from samples with very low TOC contents ( ˜0.5%), meaning that a greater range of clastic sedimentary rocks is amenable for Re-Os age dating. Well-fitted Re-Os isochrons of plausible geological age have also been determined from low-TOC shales subjected to chlorite-grade regional metamorphism. These results further illustrate the wide, but currently underutilized, potential of the Re-Os geochronometer in shales. The precision of age data attainable by the Re-Os system directly from black shales can be better than +/- 1% uncertainty (2σ , derived from isochron regression analysis), and the derived ages are demonstrably accurate.

Dissolution of fluorapatite by Pseudomonas fluorescens P35 resulting in fluorine release

USGS Publications Warehouse

Zhou, Jianping; Wang, Hongmei; Cravotta, Charles A.; Dong, Qiang; Xiang, Xing

2017-01-01

Chemical weathering of fluorine-bearing minerals is widely accepted as the main mechanism for the release of fluorine (F) to groundwater. Here, we propose a potential mechanism of F release via microbial dissolution of fluorapatite (Ca5(PO4)3F), which has been neglected previously. Batch culture experiments were conducted at 30°C with a phosphate-solubilizing bacteria strain, Pseudomonas fluorescens P35, and rock phosphates as the sole source of phosphate for microbial growth in parallel with abiotic controls. Rock phosphates consisted of 55–91% of fluorapatite and 5–10% of dolomite before microbial dissolution as indicated by X-ray diffraction (XRD). Mineral composition and morphology changed after microbial dissolution characterized by the disappearance of dolomite and the development of etched cavities on rock phosphate surfaces. The pH of media used was approximately 7.4 at the beginning and increased gradually to 7.7 in abiotic controls; with the inoculum, the pH decreased to acidic values of 3.7–3.8 after 27 h. Phosphate, calcium, and fluoride were released from the rock phosphate to the acidified medium. At 42 h, the concentration of F reached 8.1–10.3 mg L−1. The elevated F concentration was two times higher than the F levels in groundwater in regions diagnosed with fluorosis, and was toxic to the bacteria, as demonstrated by a precipitous decrease in live cells. Geochemical modeling demonstrated that the oxidation of glucose (the carbon source for microbial growth in the medium) to gluconic acid could decrease the pH to 3.7–3.8 and result in the dissolution of fluorapatite and dolomite. Dolomite and fluorapatite remained unsaturated, while concentrations of dissolved phosphorus (P), calcium (Ca), and F increased throughout the time course Fluorite reached saturation [saturation index (SI) 0.22–0.42] after 42 h in rock phosphate–amended biotic systems. However, fluorite was not detected in XRD patterns of the final residue from microcosms. Given that phosphate-solubilizing bacteria are ubiquitous in soil and groundwater ecosystems, they could play an important role in fluorapatite dissolution and the release of F to groundwater.

Porosity and Permeability Evolution Accompanying Hot fluid Injection into Diatomite, SUPRI TR-123

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

Diabira, I.; Castanier, L.M.; Kovscek, A.R.

2001-04-19

An experimental study of silica dissolution was performed to probe the evolution of permeability and porosity in siliceous diatomite during hot fluid injection such as water or steam flooding. Two competing mechanisms were identified. Silica solubility in water at elevated temperature causes rock dissolution thereby increasing permeability; however, the rock is mechanically weak leading to compressing of the solid matrix during injection. Permeability and porosity can decrease at the onset of fluid flow. A laboratory flow apparatus was designed and built to examine these processes in diatomite core samples.

Rock-Fluid Interactions Under Stress: How Rock Microstructure Controls The Evolution of Porosity and Permeability

NASA Astrophysics Data System (ADS)

Vanorio, T.

2016-12-01

Monitoring chemo-mechanical processes geophysically — e.g., fluid disposal or storage, thermal and chemical stimulation of reservoirs, or natural fluids simply entering a new system in the subsurface— raises numerous concerns because of the likelihood of fluid-rock chemical interactions and our limited ability to decipher the geophysical signature of coupled processes. One of the missing links is coupling the evolution of porosity, permeability, and velocity of rocks together with reactive transport, since rocks deform and their microstructure evolves, as a result of chemical reactions under stress. This study describes recent advances in rock-physics experiments to understand the effects of dissolution-induced compaction on acoustic velocity, porosity, and permeability. Data observation includes time-lapse experiments and imaging tracking transport and elastic properties, the rock microstructure, and the pH and chemical composition of the fluid permeating the rock. Results show that the removal of high surface area, mineral phases such as microcrystalline calcite and clay appears to be mostly responsible for dissolution-induced compaction. Nevertheless, it is the original rock microstructure and its response to stress that ultimately defines how solution-transfer and rock compaction feed back upon each other. This work has a dual aim: understanding the mechanisms underlying permanent modifications to the rock microstructure and providing a richer set of experimental information to inform the formulation of new simulations and rock modeling.

Column Experiments to Interpret Weathering in Columbia Hills

NASA Technical Reports Server (NTRS)

Hausrath, E. M.; Morris, R.V.; Ming, D.W.; Golden, D.C.; Galindo, C.; Sutter, B.

2009-01-01

Phosphate mobility has been postulated as an indicator of early aqueous activity on Mars. In addition, rock surfaces analyzed by the Mars Exploration Rover Spirit are consistent with the loss of a phosphate- containing mineral To interpret phosphate alteration behavior on Mars, we performed column dissolution experiments leaching the primary phases Durango fluorapatite, San Carlos olivine, and basalt glass (Stapafjell Volcano, courtesy of S. Gislason, University of Iceland) [3,4]) with acidic solutions. These phases were chosen to represent quickly dissolving phases likely present in Columbia Hills. Column dissolution experiments are closer to natural dissolution conditions than batch experiments, although they can be difficult to interpret. Acidic solutions were used because the leached layers on the surfaces of these rocks have been interpreted as resulting from acid solutions [5].

A porous silica rock ("tripoli") in the footwall of the Jurassic Úrkút manganese deposit, Hungary: composition, and origin through carbonate dissolution

USGS Publications Warehouse

Polgari, Marta; Szabo, Zoltan; Szabo-Drubina, Magda; Hein, James R.; Yeh, Hsueh-Wen

2005-01-01

The mineralogical, chemical, and isotopic compositions were determined for a white tripoli from the footwall of the Jurassic Úrkút Mn-oxide ore deposit in the Bakony Mountains, Hungary. The tripoli consists of quartz and chalcedony, with SiO2 contents up to 100 wt.%; consequently, trace-element contents are very low. Oxygen isotopes and quartz crystallinity indicate a low-temperature diagenetic origin for this deposit. The tripoli was formed by dissolution of the carbonate portion of the siliceous (sponge spicules) Isztimér Limestone. Dissolution of the carbonate was promoted by inorganic and organic acids generated during diagensis and left a framework composed of diagenetic silica that preserved the original volume of the limestone layer. The relative enrichment of silica and high porosity is the result of that carbonate dissolution. The silty texture of this highly friable rock is due to the structurally weak silica framework.

Hydrothermal alteration of deep fractured granite: Effects of dissolution and precipitation

NASA Astrophysics Data System (ADS)

Nishimoto, Shoji; Yoshida, Hidekazu

2010-03-01

This paper investigates the mineralogical effects of hydrothermal alteration at depth in fractures in granite. A fracture accompanied by an alteration halo and filled with clay was found at a depth of 200 m in a drill core through Toki granite, Gifu, central Japan. Microscopic observation, XRD, XRF, EPMA and SXAM investigations revealed that the microcrystalline clays consist of illite, quartz and pyrite and that the halo round the fracture can be subdivided into a phyllic zone adjacent to the fracture, surrounded by a propylitic zone in which Fe-phyllosilicates are present, and a distinctive outer alteration front characterized by plagioclase breakdown. The processes that result in these changes took place in three successive stages: 1) partial dissolution of plagioclase with partial chloritization of biotite; 2) biotite dissolution and precipitation of Fe-phyllosilicate in the dissolution pores; 3) dissolution of K-feldspar and Fe-phyllosilicate, and illite precipitation associated with development of microcracks. These hydrothermal alterations of the granite proceed mainly by a dissolution-precipitation process resulting from the infiltration of hydrothermal fluid along microcracks. Such infiltration causes locally high mobility of Al and increases the ratio of fluid to rock in the alteration halo. These results contribute to an understanding of how granitic rock becomes altered in orogenic fields such as the Japanese island arc.

Location-Related Differences in Weathering Behaviors and Populations of Culturable Rock-Weathering Bacteria Along a Hillside of a Rock Mountain.

PubMed

Wang, Qi; Wang, Rongrong; He, Linyan; Sheng, Xiafang

2017-05-01

Bacteria play important roles in rock weathering, elemental cycling, and soil formation. However, little is known about the weathering potential and population of bacteria inhabiting surfaces of rocks. In this study, we isolated bacteria from the top, middle, and bottom rock samples along a hillside of a rock (trachyte) mountain as well as adjacent soils and characterized rock-weathering behaviors and populations of the bacteria. Per gram of rock or surface soil, 10 6 -10 7 colony forming units were obtained and total 192 bacteria were isolated. Laboratory rock dissolution experiments indicated that the proportions of the highly effective Fe (ranging from 67 to 92 %), Al (ranging from 40 to 48 %), and Cu (ranging from 54 to 81 %) solubilizers were significantly higher in the top rock and soil samples, while the proportion of the highly effective Si (56 %) solubilizers was significantly higher in the middle rock samples. Furthermore, 78, 96, and 6 % of bacteria from the top rocks, soils, and middle rocks, respectively, significantly acidified the culture medium (pH < 4.0) in the rock dissolution process. Most rock-weathering bacteria (79 %) from the rocks were different to those from the soils and most of them (species level) have not been previously reported. Furthermore, location-specific rock-weathering bacterial populations were found and Bacillus species were the most (66 %) frequently isolated rock-weathering bacteria in the rocks based on cultivation methods. Notably, the top rocks and soils had the highest and lowest diversity of rock-weathering bacterial populations, respectively. The results suggested location-related differences in element (Si, Al, Fe, and Cu) releasing effectiveness and communities of rock-weathering bacteria along the hillside of the rock mountain.

Dolomitization of felsic volcaniclastic rocks in continental strata: A study from the Lower Cretaceous of the A'nan Sag in Er'lian Basin, China

NASA Astrophysics Data System (ADS)

Zhu, Shifa; Yue, Hui; Zhu, Xiaomin; Sun, Shuyang; Wei, Wei; Liu, Xin; Jia, Ye

2017-05-01

Dolomitization of fine-grained volcaniclastic rocks is common in the Lower Cretaceous of the A'nan Sag in the Er'lian Basin of China. Analysis of core samples shows that the organic-rich volcaniclastic rocks are mainly composed of reworked felsic volcanic materials and terrigenous clay minerals. The fine-grained volcaniclastic rocks can be divided into four types: volcaniclastic rocks without carbonatization, volcaniclastic rocks with ferroan dolomites, dolomitized and calcified volcaniclastic rocks, and calcified volcaniclastic rocks. The parent rocks of the volcaniclastic rocks have high silicon and potassium contents and low iron and magnesium contents, and are probably felsic magma of the calc-alkaline series. The average values of δ13CPDB of the carbonate minerals are about 3.13‰; the average values of δ18OPDB are about - 16.74‰. The compositions of C and O isotopes are probably influenced by bacterial methanogenesis. Iron, magnesium, and calcium are probably derived from illitization of terrigenous smectite. A model for dolomitization of felsic volcaniclastic rock is proposed, including three stages: 1) mixed sedimentation and bacterial methanogenesis (< 75 °C); 2) transformation of clay minerals (> 70 °C) and dolomitization (75 to 97 °C); and 3) dissolution. Late dissolution of authigenic carbonate minerals, creating abundant secondary pores, is significant for hydrocarbon accumulation.

Using SEM Analysis on Ion-Milled Shale Surface to Determine Shale-Fracturing Fluid Interaction

NASA Astrophysics Data System (ADS)

Lu, J.; Mickler, P. J.; Nicot, J. P.

2014-12-01

It is important to document and assess shale-fluid interaction during hydraulic fracturing (HF) in order to understand its impact on flowback water chemistry and rock property. A series of autoclave experiments were conducted to react shale samples from major oil and gas shales with synthetic HF containing various additives. To better determine mineral dissolution and precipitation at the rock-fluid interface, ion-milling technique was applied to create extremely flat rock surfaces that were examined before and after the autoclave experiments using a scanning electron microscope (SEM) coupled with energy dispersive spectroscopy (EDS) detectors. This method is able to reveal a level of detail not observable on broken surface or mechanically polished surface. It allows direct comparison of the same mineral and organic matter particles before and after the reaction experiments. Minerals undergone dissolution and newly precipitated materials are readily determined by comparing to the exact locations before reaction. The dissolution porosity and the thickness of precipitates can be quantified by tracing and measuring the geometry of the pores and precipitates. Changes in porosity and permeability were confirmed by mercury intrusion capillary tests.

Subarctic physicochemical weathering of serpentinized peridotite

NASA Astrophysics Data System (ADS)

Ulven, O. I.; Beinlich, A.; Hövelmann, J.; Austrheim, H.; Jamtveit, B.

2017-06-01

Frost weathering is effective in arctic and subarctic climate zones where chemical reactions are limited by the reduced availability of liquid water and the prevailing low temperature. However, small scale mineral dissolution reactions are nevertheless important for the generation of porosity by allowing infiltration of surface water with subsequent fracturing due to growth of ice and carbonate minerals. Here we combine textural and mineralogical observations in natural samples of partly serpentinized ultramafic rocks with a discrete element model describing the fracture mechanics of a solid when subject to pressure from the growth of ice and carbonate minerals in surface-near fractures. The mechanical model is coupled with a reaction-diffusion model that describes an initial stage of brucite dissolution as observed during weathering of serpentinized harzburgites and dunites from the Feragen Ultramafic Body (FUB), SE-Norway. Olivine and serpentine are effectively inert at relevant conditions and time scales, whereas brucite dissolution produces well-defined cm to dm thick weathering rinds with elevated porosity that allows influx of water. Brucite dissolution also increases the water saturation state with respect to hydrous Mg carbonate minerals, which are commonly found as infill in fractures in the fresh rock. This suggests that fracture propagation is at least partly driven by carbonate precipitation. Dissolution of secondary carbonate minerals during favorable climatic conditions provides open space available for ice crystallization that drives fracturing during winter. Our model reproduces the observed cm-scale meandering fractures that propagate into the fresh part of the rock, as well as dm-scale fractures that initiate the breakup of larger domains. Rock disintegration increases the reactive surface area and hence the rate of chemical weathering, enhances transport of dissolved and particulate matter in the weathering fluid, and facilitates CO2 uptake by carbonate precipitation. Our observations have implications for element cycling and CO2 sequestration in natural gravel and mine tailings.

Acid rock drainage and climate change

USGS Publications Warehouse

Nordstrom, D. Kirk

2009-01-01

Rainfall events cause both increases and decreases in acid and metals concentrations and their loadings from mine wastes, and unmined mineralized areas, into receiving streams based on data from 3 mines sites in the United States and other sites outside the US. Gradual increases in concentrations occur during long dry spells and sudden large increases are observed during the rising limb of the discharge following dry spells (first flush). By the time the discharge peak has occurred, concentrations are usually decreased, often to levels below those of pre-storm conditions and then they slowly rise again during the next dry spell. These dynamic changes in concentrations and loadings are related to the dissolution of soluble salts and the flushing out of waters that were concentrated by evaporation. The underlying processes, pyrite oxidation and host rock dissolution, do not end until the pyrite is fully weathered, which can take hundreds to thousands of years. These observations can be generalized to predict future conditions caused by droughts related to El Ni??o and climate change associated with global warming. Already, the time period for dry summers is lengthening in the western US and rainstorms are further apart and more intense when they happen. Consequently, flushing of inactive or active mine sites and mineralized but unmined sites will cause larger sudden increases in concentrations that will be an ever increasing danger to aquatic life with climate change. Higher average concentrations will be observed during longer low-flow periods. Remediation efforts will have to increase the capacity of engineered designs to deal with more extreme conditions, not average conditions of previous years.

Microfluidics experiments of dissolution in a fracture. Influence of Damköhler and Péclet numbers, and of the geometry on the dissolution pattern

NASA Astrophysics Data System (ADS)

Osselin, Florian; Budek, Agnieszka; Cybulski, Olgierd; Szymczak, Piotr

2015-04-01

Dissolution of natural rocks is an ever present phenomenon in nature. The shaping of natural landscapes by the dissolution of limestone gives for example birth to exceptional features like karsts. Currently dissolution is also at the heart of key research topics as Carbon Capture and Storage or Enhanced Oil Recovery. The basics principles of dissolution are well-known, however, the sheer amount of different patterns arising from these mechanisms and the strong dependency on parameters such as pore network, chemical composition and flow rate, make it particularly difficult to study theoretically and experimentally. In this study we present a microfluidic experiment simulating the behavior of a dissolving fluid in a fracture. The experiments consist of a chip of gyspum inserted between two polycarbonate plates and subjected to a constant flow rate of pure water. The point in using microfluidics is that it allows a complete control on the experimental parameters such as geometry and chemical composition of the porous medium, flow rate, fracture aperture, roughness of the fracture walls, and an in situ observation of the geometry evolution which is impossible with 3D natural rocks. Thanks to our experiments we have been able to cover the whole range of dissolution patterns, from wormholing or DLA fingering to homogeneous dissolution, by changing Péclet and Damköhler numbers. Moreover, we have been able to tweak the geometry of our artificial fracture, inserting finger seeds or non-dissolvable obstacles. The comparison of the experimental patterns with the numerical dissolution code dissol (Szymczak and Ladd 2011) has then shown a very good correlation of the patterns, giving confidence in both experiments and modeling.

Quantifying porosity and permeability of fractured carbonates and fault rocks in natural groundwater reservoirs

NASA Astrophysics Data System (ADS)

Pirmoradi, Reza; Wolfmayr, Mariella; Bauer, Helene; Decker, Kurt

2017-04-01

This study presents porosity and permeability data for a suite of different carbonate rocks from two major groundwater reservoirs in eastern Austria that supply more than 60% of Vienna`s drinking water. Data includes a set of lithologically different, unfractured host rocks, fractured rocks with variable fracture intensities, and fault rocks such as dilation breccias, different cataclasites and dissolution-precipitation fault rocks. Fault rock properties are of particular importance, since fault zones play an important role in the hydrogeology of the reservoirs. The reservoir rocks are exposed at two major alpine karst plateaus in the Northern Calcareous Alps. They comprise of various Triassic calcareous strata of more than 2 km total thickness that reflect facies differentiation since Anisian times. Rocks are multiply deformed resulting in a partly dense network of fractures and faults. Faults differ in scale, fault rock content, and fault rock volumes. Methods used to quantify the porosity and permeability of samples include a standard industry procedure that uses the weight of water saturated samples under hydrostatic uplift and in air to determine the total effective (matrix and fracture) porosity of rocks, measurements on plugs with a fully automated gas porosity- and permeameter using N2 gas infiltrating plugs under a defined confining pressure (Coreval Poro 700 by Vinci technologies), and percolation tests. The latter were conducted in the field along well known fault zones in order to test the differences in fractured rock permeability in situ and on a representative volume, which is not ensured with plug measurements. To calculate hydraulic conductivity by the Darcy equation the measured elapsed time for infiltrating a standard volume of water into a small borehole has been used. In general, undisturbed host rock samples are all of low porosity (average around 1%). The open porosity of the undisturbed rocks belonging to diverse formations vary from 0.18% to 2.35%. Klinkenberg permeabilities of plugs range from 0.001mD to about 0.6mD thus spreading over three orders of magnitude. Fractured rocks show significantly higher porosities (3% average) with respect to the undeformed country rocks. Plug measurements reveal quite low permeabilities (< 1mD) for this type of rock, which is owed to the measuring technique, where fractures are closed under confining pressure. A second important point is that intensely fractured rocks are underrepresented in the data as they cannot be plugged adequately. Percolation tests give better information for fractured rock permeabilities and revealed hydraulic conductivities of 10-6 m/sec for little fractured to 5x10-5 m/sec for intensely fractured rocks. Plug and rock sample data show that cataclastic fault rocks can have quite high porosities (up to 4.1%). However, plug permeabilities down to 0.03mD demonstrate that pores are too small to result in any significant permeability. Breccias show high porosities of 4% in average and very variable permeabilities between 2.2mD and 2214mD depending mainly on the degree of cementation.

Effects of salinity and the extent of water on supercritical CO2-induced phlogopite dissolution and secondary mineral formation.

PubMed

Shao, Hongbo; Ray, Jessica R; Jun, Young-Shin

2011-02-15

To ensure the viability of geologic CO2 sequestration (GCS), we need a holistic understanding of reactions at supercritical CO2 (scCO2)-saline water-rock interfaces and the environmental factors affecting these interactions. This research investigated the effects of salinity and the extent of water on the dissolution and surface morphological changes of phlogopite [KMg2.87Si3.07Al1.23O10(F,OH)2], a model clay mineral in potential GCS sites. Salinity enhanced the dissolution of phlogopite and affected the location, shape, size, and phase of secondary minerals. In low salinity solutions, nanoscale particles of secondary minerals formed much faster, and there were more nanoparticles than in high salinity solutions. The effect of water extent was investigated by comparing scCO2-H2O(g)-phlogopite and scCO2-H2O(l)-phlogopite interactions. Experimental results suggested that the presence of a thin water film adsorbed on the phlogopite surface caused the formation of dissolution pits and a surface coating of secondary mineral phases that could change the physical properties of rocks. These results provide new information for understanding reactions at scCO2-saline water-rock interfaces in deep saline aquifers and will help design secure and environmentally sustainable CO2 sequestration projects.

Multiple stable isotope fronts during non-isothermal fluid flow

NASA Astrophysics Data System (ADS)

Fekete, Szandra; Weis, Philipp; Scott, Samuel; Driesner, Thomas

2018-02-01

Stable isotope signatures of oxygen, hydrogen and other elements in minerals from hydrothermal veins and metasomatized host rocks are widely used to investigate fluid sources and paths. Previous theoretical studies mostly focused on analyzing stable isotope fronts developing during single-phase, isothermal fluid flow. In this study, numerical simulations were performed to assess how temperature changes, transport phenomena, kinetic vs. equilibrium isotope exchange, and isotopic source signals determine mineral oxygen isotopic compositions during fluid-rock interaction. The simulations focus on one-dimensional scenarios, with non-isothermal single- and two-phase fluid flow, and include the effects of quartz precipitation and dissolution. If isotope exchange between fluid and mineral is fast, a previously unrecognized, significant enrichment in heavy oxygen isotopes of fluids and minerals occurs at the thermal front. The maximum enrichment depends on the initial isotopic composition of fluid and mineral, the fluid-rock ratio and the maximum change in temperature, but is independent of the isotopic composition of the incoming fluid. This thermally induced isotope front propagates faster than the signal related to the initial isotopic composition of the incoming fluid, which forms a trailing front behind the zone of transient heavy oxygen isotope enrichment. Temperature-dependent kinetic rates of isotope exchange between fluid and rock strongly influence the degree of enrichment at the thermal front. In systems where initial isotope values of fluids and rocks are far from equilibrium and isotope fractionation is controlled by kinetics, the temperature increase accelerates the approach of the fluid to equilibrium conditions with the host rock. Consequently, the increase at the thermal front can be less dominant and can even generate fluid values below the initial isotopic composition of the input fluid. As kinetics limit the degree of isotope exchange, a third front may develop in kinetically limited systems, which propagates with the advection speed of the incoming fluid and is, therefore, traveling fastest. The results show that oxygen isotope signatures at thermal fronts recorded in rocks and veins that experienced isotope exchange with fluids can easily be misinterpreted, namely if bulk analytical techniques are applied. However, stable isotope microanalysis on precipitated minerals may - if later isotope exchange is kinetically limited - provide a valuable archive of the transient thermal and hydrological evolution of a system.

Carbon Mobility at Subduction Interfaces via Deformation-Enhanced Fluid Infiltration: Evidence from the Swiss/Italian Alps

NASA Astrophysics Data System (ADS)

Jaeckel, K. P.; Bebout, G. E.; Angiboust, S.

2016-12-01

The interplay between fluid flow and deformation along subduction interfaces, and the extent to which deformation-enhanced fluid infiltration can drive decarbonation and carbonate dissolution, remain poorly understood. Recent work on HP/UHP decarbonation in W. Alps suites has indicated that, in intact volumes of metasediment, metabasalt, and ophicarbonate away from major shear zones and with few veins, carbonate is largely retained to 80-90 km depths (Cook-Kollars et al., 2014; Collins et al., 2015; Chem. Geol.). Yet uncertain is whether forearc fluid infiltration focused in intensely sheared and fractured zones could result in greater mobilization of C from subducting sections, in quantities sufficient to impact subduction zone C cycling. Lower-plate rocks at Arosa and Dent Blanche interface exposures (Bachmann et al., 2009, JGR; Angiboust et al., 2015, G3) are primarily calc-schist intercalated with meta-ultramafic and metamafic schist and contain carbonate-bearing veins of varying abundance and texture. At some localities, these sections contain blocks of carbonate, metabasalt, and upper-plate gneiss. Strongly deformed veins concordant with the foliation parallel to the thrust interface commonly contain carbonate and quartz. In highly sheared regions in the Arosa Zone, δ18O(VSMOW) values of some host-rocks and veins are shifted from +20 ± 2‰, values observed regionally for the Schistes Lustres, to values of +11 to +13‰. These shifts can be explained by interaction with externally-derived H2O-rich fluids with δ18O of +9 to +11‰. Smaller datasets for Dent Blanche localities hint at similar δ18O shifts. Most of these rocks contain little evidence of C release by decarbonation reactions. Evidence exists for local-scale dissolution of carbonate, during pressure solution, and carbonate-bearing veins reflect C mobility in fluids. Ongoing work assesses whether volumes of carbonate removed in some regions balance with those precipitated nearby in veins and pressure shadows.

Emplacement, petrological and magnetic susceptibility characteristics of diverse magmatic epidote-bearing granitoid rocks in Brazil, Argentina and Chile

NASA Astrophysics Data System (ADS)

Sial, A. N.; Toselli, A. J.; Saavedra, J.; Parada, M. A.; Ferreira, V. P.

1999-03-01

Magmatic epidote (mEp)-bearing granitoids from five Neoproterozoic tectonostratigraphic terranes in Northeastern (NE) Brazil, Early Palaeozoic calc-alkalic granitoids in Northwestern (NW) Argentina and from three batholiths in Chile have been studied. The elongated shape of some of these plutons suggests that magmas filled fractures and that dyking was probably the major mechanism of emplacement. Textures reveal that, in many cases, epidote underwent partial dissolution by host magma and, in these cases, may have survived dissolution by relatively rapid upward transport by the host magma. In plutons where such a mechanism is not evident, unevenly distributed epidote at outcrop scale is armoured by biotite or near-solidus K-feldspar aggregates, which probably grew much faster than epidote dissolution, preventing complete resorption of epidote by the melt. Al-in-hornblende barometry indicates that, in most cases, amphibole crystallized at P≥5 kbar. Kyanite-bearing thermal aureoles surrounding plutons that intruded low-grade metamorphic rocks in NE Brazil support pluton emplacement at intermediate to high pressure. mEp show overall chemical variation from 20 to 30 mol% (mole percent) pistacite (Ps) and can be grouped into two compositional ranges: Ps 20-24 and Ps 27-30. The highest Ps contents are in epidotes of plutons in which hornblende solidified under P<5 kbar. The percentage of corrosion of individual epidote crystals included in plagioclase in high-K calc-alkalic granitoids in NE Brazil, emplaced at 5-7 kbar pressure, yielded estimates of magma transport rate from 70 to 350 m year -1. Most of these plutons lack Fe-Ti oxide minerals and Fe +3 is mostly associated with the epidote structure. Consequently, magnetic susceptibility (MS) in the Neoproterozoic granitoids in NE Brazil, as well as Early Palaeozoic plutons in Argentina and Late Palaeozoic plutons in Chile, is usually low (<0.50×10 -3 SI), which is typical behavior of plutons which crystallized under low fO 2 (ilmenite-series granitoids), although Fe/(Fe+Mg) ratios in hornblende (0.40-0.65) indicate crystallization under high fO 2. Mesozoic to Tertiary calc-alkalic plutons in Chile, however, exhibit iron oxide minerals and MS values >3.0×10 -3 SI, typical of magnetite-series granitoids crystallized under higher oxygen fugacity. In NE Brazil, Argentina and Chile, it seems that mEp is more common in Precambrian to Palaeozoic ilmenite-series granitoids, while its occurrence in magnetite-series granitoids is more restricted to Mesozoic to Tertiary granitoids.

Dissolution of bedded rock salt: A seismic profile across the active eastern margin of the Hutchinson Salt Member, central Kansas

USGS Publications Warehouse

Anderson, N.L.; Hopkins, J.; Martinez, A.; Knapp, R.W.; Macfarlane, P.A.; Watney, W.L.; Black, R.

1994-01-01

Since late Tertiary, bedded rock salt of the Permian Hutchinson Salt Member has been dissolved more-or-less continuously along its active eastern margin in central Kansas as a result of sustained contact with unconfined, undersaturated groundwater. The associated westward migration of the eastern margin has resulted in surface subsidence and the contemporaneous sedimentation of predominantly valley-filling Quarternary alluvium. In places, these alluvium deposits extend more than 25 km to the east of the present-day edge of the main body of contiguous rock salt. The margin could have receded this distance during the past several million years. From an environmental perspective, the continued leaching of the Hutchinson Salt is a major concern. This predominantly natural dissolution occurs in a broad zone across the central part of the State and adversely affects groundwater and surface-water quality as nonpoint source pollution. Significant surface subsidence occurs as well. Most of these subsidence features have formed gradually; others developed in a more catastrophic manner. The latter in particular pose real threats to roadways, railways, and buried oil and gas pipelines. In an effort to further clarify the process of natural salt dissolution in central Kansas and with the long-term goal of mitigating the adverse environmental affects of such leaching, the Kansas Geological Survey acquired a 4-km seismic profile across the eastern margin of the Hutchinson Salt in the Punkin Center area of central Kansas. The interpretation of these seismic data (and supporting surficial and borehole geologic control) is consistent with several hypotheses regarding the process and mechanisms of dissolution. More specifically these data support the theses that: 1. (1) Dissolution along the active eastern margin of the Hutchinson Salt Member was initiated during late Tertiary. Leaching has resulted in the steady westward migration of the eastern margin, surface subsidence, and the contemporaneous deposition of predominantly valley-filling Quarternary alluvium. 2. (2) Along the active eastern margin, the rock salt has been leached vertically from the top down, and horizontally along the uppermost remnant bedded soluble layer(s). As a result, the eastern margin thickens gradually (up to 90 m) and in a stepwise manner from east to west for distances on the order 5-15 km. 3. (3) In places, the Hutchinson Salt Member has been leached locally along NNE-trending paleoshear zones situated to the west of the present-day edge of the main body of contiguous rock salt. Leaching at these sites initiated when the main dissolution front impinged upon preexisting shear zones. ?? 1994.

Reactive Transport Models with Geomechanics to Mitigate Risks of CO2 Utilization and Storage

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

Deo, Milind; Huang, Hai; Kweon, Hyukmin

2016-03-28

Reactivity of carbon dioxide (CO 2), rocks and brine is important in a number of practical situations in carbon dioxide sequestration. Injectivity of CO 2 will be affected by near wellbore dissolution or precipitation. Natural fractures or faults containing specific minerals may reactivate leading to induced seismicity. In this project, we first examined if the reactions between CO 2, brine and rocks affect the nature of the porous medium and properties including petrophysical properties in the timeframe of the injection operations. This was done by carrying out experiments at sequestration conditions (2000 psi for corefloods and 2400 psi for batchmore » experiments, and 600°C) with three different types of rocks – sandstone, limestone and dolomite. Experiments were performed in batch mode and corefloods were conducted over a two-week period. Batch experiments were performed with samples of differing surface area to understand the impact of surface area on overall reaction rates. Toughreact, a reactive transport model was used to interpret and understand the experimental results. The role of iron in dissolution and precipitation reactions was observed to be significant. Iron containing minerals – siderite and ankerite dissolved resulting in changes in porosity and permeability. Corefloods and batch experiments revealed similar patterns. With the right cationic balance, there is a possibility of precipitation of iron bearing carbonates. The results indicate that during injection operations mineralogical changes may lead to injectivity enhancements near the wellbore and petrophysical changes elsewhere in the system. Limestone and dolomite cores showed consistent dissolution at the entrance of the core. The dissolution led to formation of wormholes and interconnected dissolution zones. Results indicate that near wellbore dissolution in these rock-types may lead to rock failure. Micro-CT images of the cores before and after the experiments revealed that an initial high-permeability pathway facilitated the formation of wormholes. The peak cation concentrations and general trends were matched using Toughreact. Batch reactor modeling showed that the geometric factors obtained using powder data that related effective surface area to the BET surface area had to be reduced for fractured samples and cores. This indicates that the available surface area in consolidated samples is lower than that deduced from powder experiments. Field-scale modeling of reactive transport and geomechanics was developed in parallel at Idaho National Laboratory. The model is able to take into account complex chemistry, and consider interactions of natural fractures and faults. Poroelastic geomechanical considerations are also included in the model.« less

Weathering profiles in soils and rocks on Earth and Mars

NASA Astrophysics Data System (ADS)

Hausrath, E.; Adcock, C. T.; Bamisile, T.; Baumeister, J. L.; Gainey, S.; Ralston, S. J.; Steiner, M.; Tu, V.

2017-12-01

Interactions of liquid water with rock, soil, or sediments can result in significant chemical and mineralogical changes with depth. These changes can include transformation from one phase to another as well as translocation, addition, and loss of material. The resulting chemical and mineralogical depth profiles can record characteristics of the interacting liquid water such as pH, temperature, duration, and abundance. We use a combined field, laboratory, and modeling approach to interpret the environmental conditions preserved in soils and rocks. We study depth profiles in terrestrial field environments; perform dissolution experiments of primary and secondary phases important in soil environments; and perform numerical modeling to quantitatively interpret weathering environments. In our field studies we have measured time-integrated basaltic mineral dissolution rates, and interpreted the impact of pH and temperature on weathering in basaltic and serpentine-containing rocks and soils. These results help us interpret fundamental processes occurring in soils on Earth and on Mars, and can also be used to inform numerical modeling and laboratory experiments. Our laboratory experiments provide fundamental kinetic data to interpret processes occurring in soils. We have measured dissolution rates of Mars-relevant phosphate minerals, clay minerals, and amorphous phases, as well as dissolution rates under specific Mars-relevant conditions such as in concentrated brines. Finally, reactive transport modeling allows a quantitative interpretation of the kinetic, thermodynamic, and transport processes occurring in soil environments. Such modeling allows the testing of conditions under longer time frames and under different conditions than might be possible under either terrestrial field or laboratory conditions. We have used modeling to examine the weathering of basalt, olivine, carbonate, phosphate, and clay minerals, and placed constraints on the duration, pH, and solution chemistry of past aqueous alteration occurring on Mars.

Lithologic Controls on Critical Zone Processes in a Variably Metamorphosed Shale-Hosted Watershed

NASA Astrophysics Data System (ADS)

Eldam Pommer, R.; Navarre-Sitchler, A.

2017-12-01

Local and regional shifts in thermal maturity within sedimentary shale systems impart significant variation in chemical and physical rock properties, such as pore-network morphology, mineralogy, organic carbon content, and solute release potential. Even slight variations in these properties on a watershed scale can strongly impact surface and shallow subsurface processes that drive soil formation, landscape evolution, and bioavailability of nutrients. Our ability to map and quantify the effects of this heterogeneity on critical zone processes is hindered by the complex coupling of the multi-scale nature of rock properties, geochemical signatures, and hydrological processes. This study addresses each of these complexities by synthesizing chemical and physical characteristics of variably metamorphosed shales in order to link rock heterogeneity with modern earth surface and shallow subsurface processes. More than 80 samples of variably metamorphosed Mancos Shale were collected in the East River Valley, Colorado, a headwater catchment of the Upper Colorado River Basin. Chemical and physical analyses of the samples show that metamorphism decreases overall rock porosity, pore anisotropy, and surface area, and introduces unique chemical signatures. All of these changes result in lower overall solute release from the Mancos Shale in laboratory dissolution experiments and a change in rock-derived solute chemistry with decreasing organic carbon and cation exchange capacity (Ca, Na, Mg, and K). The increase in rock competency and decrease in reactivity of the more thermally mature shales appear to subsequently control river morphology, with lower channel sinuosity associated with areas of the catchment underlain by metamorphosed Mancos Shale. This work illustrates the formative role of the geologic template on critical zone processes and landscape development within and across watersheds.

Diagenesis of the Machar Field (British North Sea) chalk: Evidence for decoupling of diagenesis in fractures and the host rock

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

Maliva, R.G.; Dickson, J.A.D.; Smalley, P.C.

1995-01-02

The Chalk Group (Cretaceous/Tertiary) in the Machar Field (British North Sea) contains both fracture-filling and microcrystalline calcite cements. Modeling of fluid-rock interaction using data on light stable isotopes obtained by whole rock analyses and laser ablation analyses of calcite cements reveal that the fracture and matrix diagenetic systems were largely decoupled. The calcium and carbonate of the fracture-filling calcite cements were derived largely from the adjacent chalk matrix. The fracture diagenetic system had a high water-rock ratio, which maintained a relatively stable water {delta}{sup 18}O ratio during calcite dissolution and precipitation. The chalk matrix, on the contrary, had a lowmore » molar water-rock ratio during recrystallization, which resulted in increases in the pore-water {delta}{sup 18}O value during recrystallization at elevated temperatures. This evolution of the pore-water {delta}{sup 18}O value is manifested by highly variable cement {delta}{sup 18}O values. The present-day formation waters of the Machar Field have {sup 87}Sr/{sup 86}Sr ratios significantly higher than the whole rock and fracture-filling cement calcite values, evidence that the chemical composition of the formation waters is not representative of that of the pore waters during chalk recrystallization. Little diagenesis is therefore now occurring in the Machar Field. The diagenetic systems of the chalk matrix and fractures both had a high degree of openness with respect to carbon, because of the introduction of organically derived bicarbonate rather than advection of water through the chalk. The bulk of calcite cementation in fractures and the recrystallization and cementation of the chalk matrix occurred at temperatures in the 80--100 C range, at or just below the present-day reservoir temperature of 97 C.« less

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

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.

Characterization of reactive flow-induced evolution of carbonate rocks using digital core analysis- part 1: Assessment of pore-scale mineral dissolution and deposition.

PubMed

Qajar, Jafar; Arns, Christoph H

2016-09-01

The application of X-ray micro-computed tomography (μ-CT) for quantitatively characterizing reactive-flow induced pore structure evolution including local particle detachment, displacement and deposition in carbonate rocks is investigated. In the studies conducted in this field of research, the experimental procedure has involved alternating steps of imaging and ex-situ core sample alteration. Practically, it is impossible to return the sample, with micron precision, to the same position and orientation. Furthermore, successive images of a sample in pre- and post-alteration states are usually taken at different conditions such as different scales, resolutions and signal-to-noise ratios. These conditions accompanying with subresolution features in the images make voxel-by-voxel comparisons of successive images problematic. In this paper, we first address the respective challenges in voxel-wise interpretation of successive images of carbonate rocks subject to reactive flow. Reactive coreflood in two carbonate cores with different rock types are considered. For the first rock, we used the experimental and imaging results published by Qajar et al. (2013) which showed a quasi-uniform dissolution regime. A similar reactive core flood was conducted in the second rock which resulted in wormhole-like dissolution regime. We particularly examine the major image processing operations such as transformation of images to the same grey-scale, noise filtering and segmentation thresholding and propose quantitative methods to evaluate the effectiveness of these operations in voxel-wise analysis of successive images of a sample. In the second part, we generalize the methodology based on the three-phase segmentation of normalized images, microporosity assignment and 2D histogram of image intensities to estimate grey-scale changes of individual image voxels for a general case where the greyscale images are segmented into arbitrary number of phases. The results show that local (voxel-based) porosity changes can be decomposed into local mineral dissolution and deposition. Moreover, it is found that the microporosity evolutions are differently distributed in the samples after the reactive coreflood experiments. In the last part of the paper, for the case of quasi-uniform dissolution, we combine the tomographic images with numerical calculations of permeability along the core to characterize the relationship between changes in permeability and the fractions of the mineral dissolved and deposited. A consistency is found between the calculated longitudinal permeability changes and the quantified distribution of mineral dissolved and deposited along the sample. Copyright © 2016 Elsevier B.V. All rights reserved.

Characterization of reactive flow-induced evolution of carbonate rocks using digital core analysis- part 1: Assessment of pore-scale mineral dissolution and deposition

NASA Astrophysics Data System (ADS)

Qajar, Jafar; Arns, Christoph H.

2016-09-01

The application of X-ray micro-computed tomography (μ-CT) for quantitatively characterizing reactive-flow induced pore structure evolution including local particle detachment, displacement and deposition in carbonate rocks is investigated. In the studies conducted in this field of research, the experimental procedure has involved alternating steps of imaging and ex-situ core sample alteration. Practically, it is impossible to return the sample, with micron precision, to the same position and orientation. Furthermore, successive images of a sample in pre- and post-alteration states are usually taken at different conditions such as different scales, resolutions and signal-to-noise ratios. These conditions accompanying with subresolution features in the images make voxel-by-voxel comparisons of successive images problematic. In this paper, we first address the respective challenges in voxel-wise interpretation of successive images of carbonate rocks subject to reactive flow. Reactive coreflood in two carbonate cores with different rock types are considered. For the first rock, we used the experimental and imaging results published by Qajar et al. (2013) which showed a quasi-uniform dissolution regime. A similar reactive core flood was conducted in the second rock which resulted in wormhole-like dissolution regime. We particularly examine the major image processing operations such as transformation of images to the same grey-scale, noise filtering and segmentation thresholding and propose quantitative methods to evaluate the effectiveness of these operations in voxel-wise analysis of successive images of a sample. In the second part, we generalize the methodology based on the three-phase segmentation of normalized images, microporosity assignment and 2D histogram of image intensities to estimate grey-scale changes of individual image voxels for a general case where the greyscale images are segmented into arbitrary number of phases. The results show that local (voxel-based) porosity changes can be decomposed into local mineral dissolution and deposition. Moreover, it is found that the microporosity evolutions are differently distributed in the samples after the reactive coreflood experiments. In the last part of the paper, for the case of quasi-uniform dissolution, we combine the tomographic images with numerical calculations of permeability along the core to characterize the relationship between changes in permeability and the fractions of the mineral dissolved and deposited. A consistency is found between the calculated longitudinal permeability changes and the quantified distribution of mineral dissolved and deposited along the sample.

Results of mineral, chemical, and sulfate isotopic analyses of water, soil, rocks, and soil extracts from the Pariette Draw Watershed, Uinta Basin, Utah

USGS Publications Warehouse

Morrison, Jean M.; Tuttle, Michele L.W.; Fahy, Juli W.

2015-08-06

The goal of this study was to establish a process-based understanding of salt, Se, and B behavior to address whether these contaminants can be better managed, or if uncontrollable natural processes will overwhelm any attempts to bring Pariette Draw into compliance with respect to recently established total maximum daily limits (TMDLs). We collected data to refine our knowledge about the role of rock weathering and soil formation in the transport and storage of salt in the watershed and to show how salt is cycled under irrigated and natural conditions. Our approach was to sample rock, soils, and sediment on irrigated and natural terrain for mineralogical analysis to determine the residence of salt and associated Se and B, classify minerals as primary (related to rock formation) or secondary weathering products, and characterize mineral dissolution kinetics. Mineral and chemical analyses and selective extractions of rocks and soils provide useful information in understanding solute movement and mineral dissolution/ formation. The resulting data are critical in determining residence of salt, Se, and B in weathered rock and soil and understanding the mobility during water-rock-soil interactions. This report summarizes our methods for sample and data collection and tabulates the mineral, chemical, and isotopic data collected.

Mineral displacement and -dissolution processes and their relevance to rock porosity and permeability in Rotliegend sandstones of the Altmark natural gas field (central Germany) - results from CO2 laboratory batch experiments

NASA Astrophysics Data System (ADS)

Pudlo, Dieter; Enzmann, Frieder; Heister, Katja; Werner, Lars; Ganzer, Leonhard; Reitenbach, Viktor; Henkel, Steven; Albrecht, Daniel; Gaupp, Reinhard

2014-05-01

The Rotliegend reservoir sandstones of the Altmark area (central Germany) comprise the second largest natural gas field of Europe. These sandstones were deposited on a playa-like continental platform with braided river systems, ephemeral lakes and aeolian dunes under semi-arid conditions. Some of the pristine, red coloured deposits suffered intensive late diagenetic alteration and are now preserved as bleached, high porous and permeable sandstones. To evaluate the relevance of distinct fluids and their fluid-rock alteration reactions on such bleaching processes we performed laboratory static batch experiments on the Altmark sandstones. These 4-6 week lasting runs were conducted with CO2 saturated synthetic brines under typical Altmark reservoir conditions (p= 20 MPa, T= 125°C). Thereby mineralogical, petrophysical and (hydro- and geo-) chemical rock features were maintained prior and after the experiments. Chemical data proved the dissolution of carbonate and sulphate minerals during the runs, whereas the variation in abundance of further elements was within the detection limit of analytical accuracy. However, FE-SEM investigations on used, evaporated brines reveal the presence of illite and chlorite minerals within a matrix of Ca-, Si-, Fe, Al-, Na- and S components (carbonate, anhydrite, albite and Fe-(hydr-) oxides ?). By porosity and relative permeability measurements an increase in both rock features was observed after the runs, indicating that mineral dissolution and/or (clay) fine migration/detachment occurred during the experiments. Mineral dissolution, especially of pore-filling cements (e.g. carbonate-, sulphate minerals) is also deduced by BET analysis, in determining the specific surface of the sandstones. The size of these reactive surfaces increased after the experiments, suggesting that after the dissolution of pore-filling cements, formerly armoured grain rimming clay cutans were exposed to potential migrating fluids. These findings are also supported by µ-CT investigations. Here, the achieved 3D modelling data indicate an increase in reactive surface areas exposed to the pore space (which is in accord to the BET observations), as well as an enhancement in rock porosity and permeability after the runs. Moreover, these simulations showed that a remarkable mass (mineral) transfer was induced by the experiments, which led to a displacement of the porosity and permeability distribution in the sandstones and therefore a change in the fluid flow characteristics within the rocks - a parameter most important for every fluid-rock process. These observations are quite astonishing because they suggest that not only fluid velocity (e.g. during fluid flow experiments) might detach and transport grain rimming (clay) minerals, but also that physico-chemical reactions may enforce the release of such solids, even during almost static p-/T-/Xfluid conditions, as used in our experiments.

GaMin’11 – an international inter-laboratory comparison for geochemical CO₂ - saline fluid - mineral interaction experiments

DOE PAGES

Ostertag-Henning, C.; Risse, A.; Thomas, B.; ...

2014-12-31

Due to the strong interest in geochemical CO₂-fluid-rock interaction in the context of geological storage of CO₂ a growing number of research groups have used a variety of different experimental ways to identify important geochemical dissolution or precipitation reactions and – if possible – quantify the rates and extent of mineral or rock alteration. In this inter-laboratory comparison the gas-fluid-mineral reactions of three samples of rock-forming minerals have been investigated by 11 experimental labs. The reported results point to robust identification of the major processes in the experiments by most groups. The dissolution rates derived from the changes in compositionmore » of the aqueous phase are consistent overall, but the variation could be reduced by using similar corrections for changing parameters in the reaction cells over time. The comparison of experimental setups and procedures as well as of data corrections identified potential improvements for future gas-fluid-rock studies.« less

Dissolution and secondary mineral precipitation in basalts due to reactions with carbonic acid

NASA Astrophysics Data System (ADS)

Kanakiya, Shreya; Adam, Ludmila; Esteban, Lionel; Rowe, Michael C.; Shane, Phil

2017-06-01

One of the leading hydrothermal alteration processes in volcanic environments is when rock-forming minerals with high concentrations of iron, magnesium, and calcium react with CO2 and water to form carbonate minerals. This is used to the advantage of geologic sequestration of anthropogenic CO2. Here we experimentally investigate how mineral carbonation processes alter the rock microstructure due to CO2-water-rock interactions. In order to characterize these changes, CO2-water-rock alteration in Auckland Volcanic Field young basalts (less than 0.3 Ma) is studied before and after a 140 day reaction period. We investigate how whole core basalts with similar geochemistry but different porosity, permeability, pore geometry, and volcanic glass content alter due to CO2-water-rock reactions. Ankerite and aluminosilicate minerals precipitate as secondary phases in the pore space. However, rock dissolution mechanisms are found to dominate this secondary mineral precipitation resulting in an increase in porosity and decrease in rigidity of all samples. The basalt with the highest initial porosity and volcanic glass volume shows the most secondary mineral precipitation. At the same time, this sample exhibits the greatest increase in porosity and permeability, and a decrease in rock rigidity post reaction. For the measured samples, we observe a correlation between volcanic glass volume and rock porosity increase due to rock-fluid reactions. We believe this study can help understand the dynamic rock-fluid interactions when monitoring field scale CO2 sequestration projects in basalts.

Estimation of dissolution rate from in vivo studies of synthetic vitreous fibers.

PubMed

Eastes, W; Potter, R M; Hadley, J G

2000-11-01

Although the dissolution rate of a fiber was originally defined by a measurement of dissolution in simulated lung fluid in vitro, it is feasible to determine it from animal studies as well. The dissolution rate constant for a fiber may be extracted from the decrease in long fiber diameter observed in certain intratracheal instillation experiments or from the observed long fiber retention in short-term biopersistence studies. These in vivo dissolution rates agree well with those measured in vitro for the same fibers. For those special types of fibers, the high-alumina rock wool fibers that could not be measured in vitro, the method provides a way of obtaining a chemical dissolution rate constant from an animal study. The inverse of the in vivo dissolution rate, the fiber dissolution time, correlates well with the weighted half life of long fibers in a biopersistence study, and the in vivo dissolution rate may be estimated accurately from this weighted half-life.

Geochemistry of vanadium in an epigenetic, sandstone-hosted vanadium- uranium deposit, Henry Basin, Utah

USGS Publications Warehouse

Wanty, R.B.; Goldhaber, M.B.; Northrop, H.R.

1990-01-01

The epigenetic Tony M vanadium-uranium orebody in south-central Utah is hosted in fluvial sandstones of the Morrison Formation (Upper Jurassic). Measurements of the relative amounts of V+3 and V +4 in ore minerals show that V+3 is more abundant. Thermodynamic calculations show that vanadium was more likely transported to the site of mineralization as V+4. The ore formed as V+4 was reduced by hydrogen sulfide, followed by hydrolysis and precipitation of V+3 in oxide minerals or chlorite. Uranium was transported as uranyl ion (U+6), or some complex thereof, and reduced by hydrogen sulfide, forming coffinite. Detrital organic matter in the rocks served as the carbon source for sulfate-reducing bacteria. Vanadium most likely was derived from the dissolution of iron-titanium oxides. Uranium probably was derived from the overlying Brushy Basin Member of the Morrison Formation. Previous studies have shown that the ore formed at the density-stratified interface between a basinal brine and dilute meteoric water. The mineralization processes described above occurred within the mixing zone between these two fluids. -from Authors

Dissolution Rates and Mineral Lifetimes of Phosphate Containing Minerals and Implications for Mars

NASA Astrophysics Data System (ADS)

Adcock, C. T.; Hausrath, E.

2011-12-01

The objectives of NASA's Mars Exploration Program include exploring the planet's habitability and the possibility of past, present, or future life. This includes investigating "possible supplies of bioessential elements" [1]. Phosphate is one such bioessential element for life as we understand it. Phosphate is also abundant on Mars [2], and the phosphate rich minerals chlorapatite, fluorapatite, and merrillite have been observed in Martian meteorites [3]. Surface rock analyses from the MER Spirit also show the loss of a phosphate rich mineral from the rocks Wishstone and Watchtower at Gusev Crater [4,5], implying mineral dissolution. Dissolution rates of phosphate containing minerals are therefore important for characterizing phosphate mobility and bioavailability on Mars. Previous studies have measured dissolution rates of fluorapatite [6-8]. However, chlorapatite and merrillite (a non-terrestrial mineral similar to whitlockite) are more common phosphate minerals found in Martian meteorites [3], and few dissolution data exist for these minerals. We have begun batch dissolution experiments on chlorapatite, synthesized using methods of [9], and whitlockite, synthesized using a method modified from [10]. Additionally, we are dissolving Durango fluorapatite to compare to dissolution rates in literature, and natural Palermo whitlockite to compare to dissolution rates of our synthesized whitlockite. Batch dissolution experiments were performed after [8], using a 0.01 molar KNO3 solution with 0.1500g-0.3000g mineral powders and starting solution volumes of 180ml in LDPE reaction vessels. HNO3 or KOH were used to adjust initial pH as required. Dissolution rates are calculated from the rate of change of elemental concentration in solution as a function of time, and normalized to the mineral surface area as measured by BET. Resulting rates will be used to calculate mineral lifetimes for the different phosphate minerals under potential Mars-like aqueous conditions, and in future reactive transport modeling.

Evaporite-karst problems and studies in the USA

USGS Publications Warehouse

Johnson, K.S.

2008-01-01

Evaporites, including rock salt (halite) and gypsum (or anhydrite), are the most soluble among common rocks; they dissolve readily to form the same types of karst features that commonly are found in limestones and dolomites. Evaporites are present in 32 of the 48 contiguous states in USA, and they underlie about 40% of the land area. Typical evaporite-karst features observed in outcrops include sinkholes, caves, disappearing streams, and springs, whereas other evidence of active evaporite karst includes surface-collapse structures and saline springs or saline plumes that result from salt dissolution. Many evaporites also contain evidence of paleokarst, such as dissolution breccias, breccia pipes, slumped beds, and collapse structures. All these natural karst phenomena can be sources of engineering or environmental problems. Dangerous sinkholes and caves can form rapidly in evaporite rocks, or pre-existing karst features can be reactivated and open up (collapse) under certain hydrologic conditions or when the land is put to new uses. Many karst features also propagate upward through overlying surficial deposits. Human activities also have caused development of evaporite karst, primarily in salt deposits. Boreholes (petroleum tests or solution-mining operations) or underground mines may enable unsaturated water to flow through or against salt deposits, either intentionally or accidentally, thus allowing development of small to large dissolution cavities. If the dissolution cavity is large enough and shallow enough, successive roof failures can cause land subsidence and/or catastrophic collapse. Evaporite karst, natural and human-induced, is far more prevalent than is commonly believed. ?? 2007 Springer-Verlag.

Dissolution-Enlarged Fractures Imaging Using Electrical Resistivity Tomography (ERT)

NASA Astrophysics Data System (ADS)

Siami-Irdemoosa, Elnaz

In recent years the electrical imaging techniques have been largely applied to geotechnical and environmental investigations. These techniques have proven to be the best geophysical methods for site investigations in karst terrain, particularly when the overburden soil is clay-dominated. Karst is terrain with a special landscape and distinctive hydrological system developed by dissolution of rocks, particularly carbonate rocks such as limestone and dolomite, made by enlarging fractures into underground conduits that can enlarge into caverns, and in some cases collapse to form sinkholes. Bedding planes, joints, and faults are the principal structural guides for underground flow and dissolution in almost all karstified rocks. Despite the important role of fractures in karst development, the geometry of dissolution-enlarged fractures remain poorly unknown. These features are characterized by an strong contrast with the surrounding formations in terms of physical properties, such as electrical resistivity. Electrical resistivity tomography (ERT) was used as the primary geophysical tool to image the subsurface in a karst terrain in Greene County, Missouri. Pattern, orientation and density of the joint sets were interpreted from ERT data in the investigation site. The Multi-channel Analysis of Surface Wave (MASW) method and coring were employed to validate the interpretation results. Two sets of orthogonal visually prominent joints have been identified in the investigation site: north-south trending joint sets and west-east trending joint sets. However, most of the visually prominent joint sets are associated with either cultural features that concentrate runoff, natural surface drainage features or natural surface drainage.

Nature of parent rocks, mineralization styles and ore genesis of regolith-hosted REE deposits in South China: An integrated genetic model

NASA Astrophysics Data System (ADS)

Li, Yan Hei Martin; Zhao, Wen Winston; Zhou, Mei-Fu

2017-10-01

Regolith-hosted rare earth element (REE) deposits, also called ion-adsorption or weathered crust elution-deposited REE deposits are distributed over Jiangxi, Guangdong, Fujian, Hunan, Guangxi and Yunnan provinces in South China. In general, these deposits can be categorized into the HREE-dominated type, for example the famous Zudong deposit in southern Jiangxi province and the LREE-dominated type, such as the Heling and Dingnan deposits in southern Jiangxi province. Most of these deposits form from weathering of biotite and muscovite granites, syenites, monzogranites, granodiorites, granite porphyries, and rhyolitic tuffs. The parent rocks are generally peraluminous, siliceous, alkaline and contain a variety of REE-bearing minerals. Mostly, REE patterns of regolith are inherited from the parent rocks, and therefore, characteristics of the parent rocks impose a significant control on the ore formation. Data compilation shows that autometasomatism during the latest stage of granite crystallization is likely essential in forming the HREE-enriched granites, whereas LREE-enriched granites could form through magmatic differentiation. These deposits are normally two- to three-fold, but could be up to ten-fold enrichment in REE compared to the parent granites, where the maximum enrichment usually occurs from the lower B to the upper C horizon. Ce shows different behavior with the other REEs. Strongly positive Ce anomalies commonly occur at the upper part of weathering profiles, likely due to oxidation of Ce3+ to Ce4+ and removal of Ce from soil solutions through precipitation of cerianite. Vertical pH and redox gradients in weathering crusts facilitate dissolution of REE-bearing minerals at shallow level and fixation of REE at depth through either adsorption on clay minerals or precipitation of secondary minerals. At the same time, mass removal of major elements plays an important role in concentrating REE in regolith. Combination of mass removal and eluviation-illuviation dynamics is the main mechanism for REE accumulation in weathering crusts. Favorable exogenetic factors facilitate the accumulation of REE in regolith and preservation of the ore bodies. These include quasi-equilibrium between denudation and exhumation at regional scales, local geomorphology dominated by low-lying gentle slopes, adequate rainfall, and favorable groundwater conditions. Continuous operation of such a dynamic weathering system is essential in the formation of regolith-hosted REE deposits.

Subcritical crack propagation due to chemical rock weakening: macroscale chemo-plasticity and chemo-elasticity modeling

NASA Astrophysics Data System (ADS)

Hueckel, T.; Hu, M.

2015-12-01

Crack propagation in a subcritically stressed rock subject to chemically aggressive environment is analyzed and numerically simulated. Chemically induced weakening is often encountered in hydraulic fracturing of low-permeability oil/gas reservoirs and heat reservoirs, during storage of CO2 and nuclear waste corroding canisters, and other circumstances when rock matrix acidizing is involved. Upon acidizing, mineral mass dissolution is substantially enhanced weakening the rock and causing crack propagation and eventually permeability changes in the medium. The crack process zone is modeled mathematically via a chemo-plastic coupling and chemo-elastic coupling model. In plasticity a two-way coupling is postulated between mineral dissolution and a yield limit of rock matrix. The rate of dissolution is described by a rate law, but the mineral mass removal per unit volume is also a function of a variable internal specific surface area, which is in turn affected by the micro-cracking (treated as a plastic strain). The behavior of the rock matrix is modeled as rigid-plastic adding a chemical softening capacity to Cam-Clay model. Adopting the Extended Johnson's approximation of processes around the crack tip, the evolution of the stress field and deformation as a function of the chemically enhanced rock damage is modeled in a simplified way. In addition, chemical reactive transport is made dependent on plastic strain representing micro-cracking. Depending on mechanical and chemical boundary conditions, the area of enhanced chemical softening is near or somewhat away from the crack tip.In elasticity, chemo-mechanical effect is postulated via a chemical volumetric shrinkage strain proportional to mass removal variable, conceived analogously to thermal expansion. Two versions are considered: of constant coefficient of shrinkage and a variable one, coupled to deviatoric strain. Airy Potential approach used for linear elasticity is extended considering an extra term, which is uncoupled or coupled to strain. The later case requires iterations with solution of reactive transport equation. A decrease of stress intensity factor with time of reaction is well reproduced.

Anomalously low strength of serpentinite sheared against granite and implications for creep on the Hayward and Calaveras Faults

USGS Publications Warehouse

Moore, Diane E.; Lockner, David A.; Ponce, David A.

2010-01-01

Serpentinized ophiolitic rocks are juxtaposed against quartzofeldspathic rocks at depth across considerable portions of the Hayward and Calaveras Faults. The marked compositional contrast between these rock types may contribute to fault creep that has been observed along these faults. To investigate this possibility, we are conducting hydrothermal shearing experiments to look for changes in frictional properties resulting from the shear of ultramafic rock juxtaposed against quartzose rock units. In this paper we report the first results in this effort: shear of bare-rock surfaces of serpentinite and granite, and shear of antigorite-serpentinite gouge between forcing blocks of granitic rock. All experiments were conducted at 250°C. Serpentinite sheared against granite at 50 MPa pore-fluid pressure is weaker than either rock type separately, and the weakening is significantly more pronounced at lower shearing rates. In contrast, serpentinite gouge sheared dry between granite blocks is as strong as the bare granite surface. We propose that the weakening is the result of a solution-transfer process involving the dissolution of serpentine minerals at grain-to-grain contacts. Dissolution of serpentine is enhanced by modifications to pore-fluid chemistry caused by interaction of the fluid with the quartz-bearing rocks. The compositional differences between serpentinized ultramafic rocks of the Coast Range Ophiolite and quartzofeldspathic rock units such as those of the Franciscan Complex may provide the mechanism for aseismic slip (creep) in the shallow crust along the Hayward, Calaveras, and other creeping faults in central and northern California.

Origin of karst conduits in calcareous sandstone and carbonate-silicate rocks: Complex role of insoluble material

NASA Astrophysics Data System (ADS)

Bruthans, Jiri; Balak, Frantisek; Schweigstillova, Jana; Vojtisek, Jan

2017-04-01

Carbonate karst is best developed in high-grade limestones and majority of the studies is focused on these rocks. Features developed by dissolution of calcite cement in quartz sandstones and dissolution of various carbonate-silicate rocks are studied far less frequently. Unlike in common karst, the insoluble residuum has to be washed out after dissolution to create high-permeability conduits in these rocks. Aquifers in a Bohemian Cretaceous Basin (BCB), the most important hydrogeological basin in the Czech Republic, consist mainly of quartz and calcareous sandstones to siltstones. These rocks are intercalated by thin layers of calcite-cemented sandstone and low-grade limestone, the latter sometimes partly impregnated by a secondary silica. Results of tracer tests show a high flow velocity in some of the aquifers. Springs with flow rate up to 500 l/s and wells with yield up to 200 l/s occur in these rocks. Dissolution features in BCB were however not yet studied in detail. For identification and characterization of rocks prone to karstification, 350 cores were sampled mostly from boreholes but also from rock outcrops in several areas of BCB. Cores were taken from intervals where: (i) high carbonate content was expected, (ii) conduits and enlarged porosity was observed in rock outcrops or wells, (iii) inflows to boreholes were determined by well logging. Calcium carbonate content was determined by calcimetry in all cores. All cores were leached in hydrochloric acid to observe the degree of disintegration after removal of calcite, which was far dominating portion of total carbonate. Polished sections were prepared from selected cores and Ca, Si, Na, K, Al content was automatically mapped by microprobe to visualize the calcium, silica, feldspar and clay mineral distribution in cores. Conduits were photo documented in the field. Two types of sediments with distinct disintegration characteristics were observed: (i) In sandstone composed of quartz grains cemented by calcite the complete disintegration occurs when calcite content exceeds 30-50%. Such calcite-rich layers are mostly few tens of cms thick and are enclosed in quartz sandstone. Groundwater flow dissolves calcite cement and turns the rock into cohesion-less sand. Sand is consequently washed out by headward erosion in drainage areas forming high capacity conduits within the sandstone. (ii) In carbonates containing secondary silica which form reinforcing structure, even 70-80% calcite content may not be sufficient for rock disintegration during leaching. Disintegration occurs only on tectonically heavily fractured zones, where secondary silica structure is fragmented. It was found that inflows into wells are often associated with zones prone to karstification. Results clearly show that form of insoluble material is critical for karstification potential. Insoluble grain size defines minimum flow velocity needed to excavate the conduits in dissolved residuum. Impregnation by secondary silica needs to be tectonically fragmented prior conduits can occur. Research was funded by the Czech Science Foundation (GA CR No. 16-19459S) and Review of groundwater resources (Ident. No. 155996).

Dissolution-Assisted Pattern Formation During Olivine Carbonation

NASA Astrophysics Data System (ADS)

Lisabeth, Harrison; Zhu, Wenlu; Xing, Tiange; De Andrade, Vincent

2017-10-01

Olivine and pyroxene-bearing rocks in the oceanic crust react with hydrothermal fluids producing changes in the physical characteristics and behaviors of the altered rocks. Notably, these reactions tend to increase solid volume, reducing pore volume, permeability, and available reactive surface area, yet entirely hydrated and/or carbonated rocks are commonly observed in the field. We investigate the evolution of porosity and permeability of fractured dunites reacted with CO2-rich solutions in laboratory experiments. The alteration of crack surfaces changes the mechanical and transport properties of the bulk samples. Analysis of three-dimensional microstructural data shows that although precipitation of secondary minerals causes the total porosity of the sample to decrease, an interconnected network of porosity is maintained through channelized dissolution and coupled carbonate precipitation. The observed microstructure appears to be the result of chemo-mechanical coupling, which may provide a mechanism of porosity maintenance without the need to invoke reaction-driven cracking.

Dissolution-Assisted Pattern Formation During Olivine Carbonation

DOE PAGES

Lisabeth, Harrison; Zhu, Wenlu; Xing, Tiange; ...

2017-08-31

Olivine and pyroxene bearing rocks in the oceanic crust react with hydrothermal fluids producing changes in the physical characteristics and behaviors of the altered rocks. Notably, these reactions tend to increase solid volume, reducing pore volume, permeability and available reactive surface area; yet, entirely hydrated and/or carbonated rocks are commonly observed in the field. We investigate the evolution of porosity and permeability of fractured dunites reacted with CO 2-rich solutions in laboratory experiments. The alteration of crack surfaces changes the mechanical and transport properties of the bulk samples. Analysis of three-dimensional microstructural data shows that although precipitation of secondary mineralsmore » causes the total porosity of the sample to decrease, an interconnected network of porosity is maintained through channelized dissolution and coupled carbonate precipitation. Lastly, the observed microstructure appears to be the result of chemo-mechanical coupling, which may provide a mechanism of porosity maintenance without the need to invoke reaction-driven cracking.« less

A Cyclic Dissolution Test for Understanding Water Quality of Effluent from Rock Muck under Rain Events

NASA Astrophysics Data System (ADS)

Urakoshi, T.; Kawagoe, T.; Ohta, T.

2017-12-01

Effluent from rock muck piles consisting of waste rock, as a by-product of construction, sometimes contains heavy metals that affects human health and environment. Rain is the key to estimate water quality of the effluent because infiltrated rain to piles reacts with minerals of rocks. Thus, we newly proposed a dissolution test, namely cyclic injection test, considering rain events, as the following steps: Firstly, we crushed rock sample to particles of size of between 2 and 20 mm, and filled them into the column with 54 mm in diameter and 300 mm in length. Secondly, we saturated void in the column with pure water. One hour after, we opened a valve of the bottom of the column, and collected effluent. Thirdly, we preserved the column for 14 days. After then, we injected 200 ml of pure water from the top of the column within about 15 minutes, and collected efflent. We repeated injection of pure water every 14 days. We conducted the cyclic injection test for altered volcanic rock sample, and observed that the effluent just after the injection showed highest concentration. This result indicated that dissolved chemicals were released from minerals to capillary water after an injection, and advected outside of the column at the next injection.

Illitization within bentonite engineered barrier system in clay repositories for nuclear waste and its effect on the swelling stress: a coupled THMC modeling study

NASA Astrophysics Data System (ADS)

Zheng, L.; Rutqvist, J.; Birkholzer, J. T.; Liu, H. H.

2014-12-01

Geological repositories for disposal of high-level nuclear waste generally rely on a multi-barrier system to isolate radioactive waste from the biosphere. An engineered barrier system (EBS), which comprises in many design concepts a bentonite backfill, is widely used. Clay formations have been considered as a host rock throughout the world. Illitization, the transformation of smectite to illite, could compromise some beneficiary features of EBS bentonite and clay host rock such as sorption and swelling capacity. It is the major determining factor to establish the maximum design temperature of the repositories because it is believed that illitization could be greatly enhanced at temperatures higher than 100 oC. However, existing experimental and modeling studies on the occurrence of illitization and related performance impacts are not conclusive, in part because the relevant couplings between the thermal, hydrological, chemical, and mechanical (THMC) processes have not been fully represented in the models. Here we present a fully coupled THMC simulation study of a generic nuclear waste repository in a clay formation with a bentonite-backfilled EBS. Two scenarios were simulated for comparison: a case in which the temperature in the bentonite near the waste canister can reach about 200 oC and a case in which the temperature in the bentonite near the waste canister peaks at about 100 oC. The model simulations demonstrate that illitization is in general more significant under higher temperature. However, the quantity of illitization is affected by many chemical factors and therefore varies a great deal. The most important chemical factors are the concentration of K in the pore water as well as the abundance and dissolution rate of K-feldspar. For the particular case and bentonite properties studied, the reduction in swelling stress as a result of chemical changes vary from 2% up to 70% depending on chemical and temperature conditions, and key mechanical parameters. The modeling work is illustrative in light of the relative importance of different processes occurring in EBS bentonite and clay host rock at higher than 100 oC conditions, and could be of greater use when site specific data are available.

Microbially mediated alteration of crystalline basalts as identified from analogical reactive percolation experiments

NASA Astrophysics Data System (ADS)

Moore, Rachael; Ménez, Bénédicte; Stéphant, Sylvian; Dupraz, Sébastien; Ranchou-Peyruse, Magali; Ranchou-Peyruse, Anthony; Gérard, Emmanuelle

2017-04-01

Alteration in the ocean crust through fluid circulation is an ongoing process affecting the first kilometers and at low temperatures some alteration may be microbially mediated. Hydrothermal activity through the hard rock basement supports diverse microbial communities within the rock by providing nutrient and energy sources. Currently, the impact of basement hosted microbial communities on alteration is poorly understood. In order to identify and quantify the nature of microbially mediated alteration two reactive percolation experiments mimicking circulation of CO2 enriched ground water were performed at 35 °C and 30 bar for 21 days each. The experiments were performed using a crystalline basalt substrate from an earlier drilled deep Icelandic aquifer. One experiment was conducted on sterile rock while the other was conducted with the addition of a microbial inoculate derived from groundwater enrichment cultures obtained from the same aquifer. µCT on the experimental basaltic substrate before and after the reactive percolation experiment along with synchrotron radiation x-ray tomographic microscopy and the mineralogical characterization of resulting material allows for the comparative volumetric quantification of dissolution and precipitation. The unique design of this experiment allows for the identification of alteration which occurs solely abiotically and of microbially mediated alteration. Experimental results are compared to natural basaltic cores from Iceland retrieved following a large field CO2 injection experiment that stimulated microbial activity at depth.

Replacement processes in crystalline rocks

NASA Astrophysics Data System (ADS)

John, Timm; Putnis, Andrew

2010-05-01

A substantial question in metamorphism is what is the mechanism that dominates the conversion of one mineral assemblage to another in response to a change in the ambient physical and/or chemical conditions. Petrological, microstructural, and isotopic data indicate that aqueous fluids must be involved even in the reequilibration of large-scale systems. Fluid-mineral reactions take place by dissolution - precipitation processes, but converting one solid rock to another requires pervasive, either dominantly advective or diffusive fluid-mediated transport through the entire rock. The generation of reaction-induced porosity and the spatial and temporal coupling of dissolution and precipitation can account for fluid and element transport through rocks and the replacement of one mineral assemblage by another. To determine the mechanism of metamorphic reactions we refer to examples of interfaces and reaction textures which contain both the "before" (precursor) and "after" mineral assemblages - case studies where the process of conversion is frozen in. We will illustrate some aspects of the role of fluids in metamorphic reactions and discuss how reactive fluids can pervasively infiltrate a rock. The examples we will use are focussed on crystalline rocks and include reactions from the lower continental crust, the subducting oceanic crust, and the continental upper crust to show that except at very high-temperature conditions, essentially the same mechanisms are responsible for converting rocks to thermodynamically more stable mineral assemblages for given Pressure-Temperature-fluid composition (P-T-X) conditions.

Kaolinite, illite and quartz dissolution in the karstification of Paleozoic sandstones of the Furnas Formation, Paraná Basin, Southern Brazil

NASA Astrophysics Data System (ADS)

Melo, Mário Sérgio de; Guimarães, Gilson Burigo; Chinelatto, Adilson Luiz; Giannini, Paulo César Fonseca; Pontes, Henrique Simão; Chinelatto, Adriana Scoton Antonio; Atencio, Daniel

2015-11-01

Karstification processes in sandstones of the Furnas Formation, Silurian to Devonian of the Paraná Basin, have been described since the mid-twentieth century. However, some geologists still doubt the idea of true karst in sandstones. Studies carried out in the Campos Gerais region, Paraná State, Southern Brazil, aimed at investigating the nature of erosion processes in Furnas Formation and the role of the dissolution in the development of their notorious erosive features and underground cavities. These studies have led to the recognition of dissolution macro to micro features ('furnas', caves, ponds, sinks, ruiniform relief on cliffs and rocky surfaces, grain corrosion, speleothems, mineral reprecipitation and incrustation). The analysis (scanning electron microscopy, energy dispersive spectrometry and x-ray diffractometry) of sandstones and their alterites has indicated significant dissolution of clay cement along with discrete quartz grain dissolution. This mesodiagenetic cement (kaolinite and illite) is dissolved and reprecipitated as clay minerals with poorly developed crystallinity along with other minerals, such as variscite and minerals of the alunite supergroup, suggesting organic participation in the processes of dissolution and incrustation. The mineral reprecipitation usually forms centimetric speleothems, found in cavities and sheltered rocky surfaces. The cement dissolution associated with other factors (fractures, wet weather, strong hydraulic gradient, antiquity of the landforms) leads to the rock arenisation, the underground erosion and the appearance of the karst features. Carbonate rocks in the basement may locally be increasing the karst forms in the overlying Furnas Formation. The recognition of the karst character of the Furnas Formation sandstones has important implications in the management of underground water resources (increasingly exploited in the region), in the use of the unique geological heritage and in the prevention of geo-environmental accidents resulting from underground erosion phenomena.

Late Cenozoic regional collapse due to evaporite flow and Dissolution in the Carbondale Collapse Center, West-Central Colorado

USGS Publications Warehouse

Kirkham, R.M.; Streufert, R.K.; Budahn, J.R.; Kunk, Michael J.; Perry, W.J.

2001-01-01

Dissolution and flow of Pennsylvanian evaporitic rocks in west-central Colorado created the Carbondale Collapse Center, a 450 mi2 structural depression with about 4,000 ft of vertical collapse during the late Cenozoic. This paper describes evidence of collapse in the lower Roaring Fork River valley. Both the lateral extent and amount of vertical collapse is constrained by deformed upper Cenozoic volcanic rocks that have been correlated using field mapping, 40Ar/39Ar geochronology, geochemistry, and paleomagnetism. The Carbondale Collapse Center is one of at least two contiguous areas that have experienced major evaporite tectonism during the late Cenozoic. Historic sinkholes, deformed Holocene deposits, and modern high-salinity loads in the rivers and thermal springs indicate the collapse process continues today. Flow of evaporitic rocks is an important element in the collapse process, and during initial stages of collapse it was probably the primary causative mechanism. Dissolution, however, is the ultimate means by which evaporite is removed from the collapse area. As the Roaring Fork River began to rapidly down-cut through a broad volcanic plateau during the late Miocene, the underlying evaporite beds were subjected to differential overburden pressures. The evaporitic rocks flowed from beneath the upland areas where overburden pressures remained high, toward the Roaring Fork River Valley where the pressures were much lower. Along the valley the evaporitic rocks rose upward, sometimes as diapirs, forming or enhancing a valley anticline in bedrock and locally upwarping Pleistocene terraces. Wherever the evaporites encountered relatively fresh ground water, they were dissolved, forming underground voids into which overlying bedrock and surficial deposits subsided. The saline ground water eventually discharged to streams and rivers through thermal springs and by seepage into alluvial aquifers.

Laboratory tools to quantify biogenic dissolution of rocks and minerals: a model rock biofilm growing in percolation columns

NASA Astrophysics Data System (ADS)

Seiffert, Franz; Bandow, Nicole; Kalbe, Ute; Milke, Ralf; Gorbushina, Anna

2016-04-01

Sub-aerial biofilms (SAB) are ubiquitous, self-sufficient microbial ecosystems found on mineral surfaces at all altitudes and latitudes. SABs, which are the principal causes of weathering on exposed terrestrial surfaces, are characterised by patchy growth dominated by associations of algae, cyanobacteria, fungi and heterotrophic bacteria. A recently developed in vitro system to study colonisation of rocks exposed to air included two key SAB participants - the rock-inhabiting ascomycete Knufia petricola (CBS 123872) and the phototrophic cyanobacterium Nostoc punctiforme ATCC29133. Both partners are genetically tractable and we used them here to study weathering of granite, K-feldspar and plagioclase. Small fragments of the various rocks or minerals (1 to 6 mm) were packed into flow-through columns and incubated with 0.1% glucose and 10 µM thiamine-hydrochloride (90 µL.min-1) to compare weathering with and without biofilms. Dissolution of the minerals was followed by: analysing (i) the degradation products in the effluent from the columns via Inductively Coupled Plasma Spectroscopy and (ii) by studying polished sections of the incubated mineral fragment/grains using scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray analyses. K. petricola/N. punctiforme stimulated release of Ca, Na, Mg and Mn. Analyses of the polished sections confirmed depletion of Ca, Na and K near the surface of the fragments. The abrupt decrease in Ca concentration observed in peripheral areas of plagioclase fragments favoured a dissolution-reprecipitation mechanism. Percolation columns in combination with a model biofilm can thus be used to study weathering in closed systems. Columns can easily be filled with different minerals and biofilms, the effluent as well as grains can be collected after long-term exposure under axenic conditions and easily analysed.

Assessment of mechanical rock alteration caused by CO 2 -water mixtures using indentation and scratch experiments

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

Sun, Yuhao; Aman, Michael; Espinoza, D. Nicolas

CO2 injection into geological formations disturbs the geochemical equilibrium between water and minerals. Thus, some mineral phases are prone to dissolution and precipitation with ensuing changes of petrophysical and geomechanical properties of the host formations. Chemically-assisted degradation of mechanical properties can endanger the structural integrity of the storage formation and must be carefully studied and considered to guarantee safe long-term trapping. Few experimental data sets involving CO2 alteration and mechanical testing of rock samples are available since these experiments are length, expensive, and require specialized equipment and personnel. Autoclave experiments are easier to perform and control but result in amore » limited 'skin depth' of chemically-altered zone near the surface of the sample. This article presents the validation of micro-indentation and micro-scratch tests as efficient tools to assess the alteration of mechanical properties of rocks geochemically altered by CO2-water mixtures. Results from tests on sandstone and siltstone from Crystal Geyser, Utah naturally altered by CO2-acidified water show that mechanical parameters measured with indentation (indentation hardness, Young's modulus and contact creep compliance rate) and scratching (scratch hardness and fracture toughness) consistently indicated weakening of the rock after CO2-induced alteration. Decreases of measured parameters vary from 14% to 87%. Experimental results and analyses show that micromechanical tests are potentially quick and reliable tools to determine the change of mechanical properties of rocks subject to exposure to CO2-acidified water, particularly in well-controlled autoclave experiments. Measured parameters are not intended to provide inputs for coupled reservoir simulation with geomechanics but rather to inform the execution of larger scale tests investigating the susceptibility of rock facies to chemical alteration by CO2-water mixtures. Recognizing this susceptibility of rock facies of CO2 geological storage target formations is critical to controlling undesired emergent behavior associated with CO2 sequestration.« less

Microdiamonds from the European Variscan Orogenic Belt

NASA Astrophysics Data System (ADS)

Kotkova, J.; Jakubova, P.; Whitehouse, M.; Fedortchouk, Y.

2014-12-01

Diamond, along with coesite, has been discovered recently in the continental crustal rocks of the European Variscan orogenic belt, namely the Bohemian Massif (BM). In addition to the garnet-phengite gneiss in Germany, western BM, microdiamond occurs in major rock forming minerals - garnet, kyanite - and in zircon in ultrahigh-pressure rocks overprinted under high-pressure granulite facies conditions (c. 16-20 kbar, c. 1000°C) in the northern and eastern BM. Well-preserved 10-30 μm-sized microdiamonds from northern BM exhibit diverse morphologies (SEM data) depending upon the host rock type. Octahedral diamond occurs in felsic garnet-kyanite-feldspar-quartz rock (metasediment), whereas intermediate garnet-clinopyroxene-feldspar-quartz rock contains a cubo-octahedral variety. Diamond morphology can be thus controlled by solid impurities available in the medium of crystallization (K- vs. Ca-bearing fluids or melts), as shown by experiments. Pointed-bottom negatively oriented trigonal etch pits on the octahedral diamond faces developed due to diamond resorption at CO2-dominated environment (less than 50 wt % of H2O, experimental data), possibly by action of a residual fluid. SIMS determined δ13C values range from -22 to -21 ‰ for the felsic rock and from - 26 to - 33 for the intermediate one, corresponding to the typical range of organic carbon δ13C and inconsistent with a significant mantle carbon (δ13C ~ - 5 ‰) input. Diamond-bearing domains in zircon, also analysed by SIMS, yielded a Variscan U-Pb age of c. 340 Ma. The present stage of knowledge allows us to conclude that (i) metamorphic diamonds in the BM occur in lithologies of metasedimentary character, and their carbon source was organic; (ii) crustal-derived CO2-rich fluids with impurities played an important role in diamond formation and dissolution; (iii) diamonds formed during the Variscan orogenic cycle and (iv) diamonds are best preserved in the external domain of the Variscan orogenic belt.

Acid-rock drainage at Skytop, Centre County, Pennsylvania, 2004

USGS Publications Warehouse

Hammarstrom, Jane M.; Brady, Keith; Cravotta, Charles A.

2005-01-01

Recent construction for Interstate Highway 99 (I?99) exposed pyrite and associated Zn-Pb sulfide minerals beneath a >10-m thick gossan to oxidative weathering along a 40-60-m deep roadcut through a 270-m long section of the Ordovician Bald Eagle Formation at Skytop, near State College, Centre County, Pennsylvania. Nearby Zn-Pb deposits hosted in associated sandstone and limestone in Blair and Centre Counties were prospected in the past; however, these deposits generally were not viable as commercial mines. The pyritic sandstone from the roadcut was crushed and used locally as road base and fill for adjoining segments of I?99. Within months, acidic (pH1,000 mg/L), seep waters at the base of the cut contain >100 mg/L dissolved Zn and >1 mg/L As, Co, Cu, and Ni. Lead is relatively immobile (<10 ?g/L in seep waters). The salts sequester metals and acidity between rainfall events. Episodic salt dissolution then contributes pulses of contamination including acid to surface runoff and ground water. The Skytop experience highlights the need to understand dynamic interactions of mineralogy and hydrology in order to avoid potentially negative environmental impacts associated with excavation in sulfidic rocks.

Hydrochemistry and stable isotopes (δ18O and δ2H) tools applied to the study of karst aquifers in southern mediterranean basin (Teboursouk area, NW Tunisia)

NASA Astrophysics Data System (ADS)

Ayadi, Yosra; Mokadem, Naziha; Besser, Houda; Khelifi, Faten; Harabi, Samia; Hamad, Amor; Boyce, Adrian; Laouar, Rabah; Hamed, Younes

2018-01-01

Karst aquifers receive increasing attention in Mediterranean countries as they provide large supplies water used for drinkable and irrigation purposes as well as for electricity production. In Teboursouk basin, Northwestern Tunisia, characterized by a typical karst landscape, the water hosted in the carbonates aquifers provides large parts of water supply for drinkable water and agriculture purposes. Groundwater circulation in karst aquifers is characterized by short residence time and low water-rock interaction caused by high karstification processes in the study area. Ion exchange process, rock dissolution and rainfall infiltration are the principal factors of water mineralization and spatial distribution of groundwater chemistry. The present work attempted to study karstic groundwater in Teboursouk region using hydrochemistry and stable isotopes (δ18O and δ2H) tools. Karst aquifers have good water quality with low salinity levels expressed by TDS values largely below 1.5 g/l with Ca-SO4-Cl water type prevailing in the study area. The aquifers have been recharged by rainfall originating from a mixture of Atlantic and Mediterranean vapor masses.

Assessment of fluoride contaminations in groundwater of hard rock aquifers in Madurai district, Tamil Nadu (India)

NASA Astrophysics Data System (ADS)

Thivya, C.; Chidambaram, S.; Rao, M. S.; Thilagavathi, R.; Prasanna, M. V.; Manikandan, S.

2017-05-01

The fluoride contamination in drinking water is already gone to the alarming level and it needs the immediate involvement and attention of all people to solve this problem. Fluoride problem is higher in hard rock terrains in worldwide and Madurai is such type of hard rock region. Totally 54 samples were collected from the Madurai district of Tamilnadu with respect to lithology. The samples collected were analysed for major cations and anions using standard procedures. The higher concentration of fluoride is noted in the Charnockite rock types of northern part of the study area. 20 % of samples are below 0.5 ppm and 6 % of samples are above 1.5 ppm exceeding the permissible limit. The affinity between the pH and fluoride ions in groundwater suggests that dissolution of fluoride bearing minerals in groundwater. The higher concentration of fluoride ions are observed in the lower EC concentration. The isotopic study suggests that fluoride is geogenic in nature. In factor scores, fluoride is noted in association with pH which indicates the dissolution process.

Importance of mechanical disaggregation in chemical weathering in a cold alpine environment, San Juan Mountains, Colorado

USGS Publications Warehouse

Hoch, A.R.; Reddy, M.M.; Drever, J.I.

1999-01-01

Weathering of welded tuff near the summit of Snowshoe Mountain (3660 m) in southwestern Colorado was studied by analyzing infiltrating waters in the soil and associated solid phases. Infiltrating waters exhibit anomalously high potassium to silica ratios resulting from dissolution of a potassium-rich glass that occurs as a trace phase in the rock. In laboratory experiments using rock from the field site, initial dissolution generated potassium-rich solutions similar to those observed in the field. The anomalous potassium release decreased over time (about 1 month), after which the dominant cation was calcium, with a much lower potassium to silica ratio. The anomalous potassium concentrations observed in the infiltrating soil solutions result from weathering of freshly exposed rock surfaces. Continual mechanical disaggregation of the rock due to segregation freezing exposes fresh glass to weathering and thus maintains the source of potassium for the infiltrating water. The ongoing process of creation of fresh surfaces by physical processes is an important influence on the composition of infiltrating waters in the vadose zone.

The giant Upper Yangtze Pb-Zn province in SW China: Reviews, new advances and a new genetic model

NASA Astrophysics Data System (ADS)

Zhou, Jia-Xi; Xiang, Zhen-Zhong; Zhou, Mei-Fu; Feng, Yue-Xing; Luo, Kai; Huang, Zhi-Long; Wu, Tao

2018-04-01

In the western margin of the Yangtze Block, SW China, the Emeishan large igneous province (ELIP) is spatially associated with >400 carbonate-hosted epigenetic Pb-Zn deposits. These deposits form the giant Upper Yangtze Pb-Zn metallogenic province with >20 Mt base metals. In the southeastern part of this province, the important Pb-Zn deposits include those of the Yinchangpo, Yunluhe, Maozhachang, Tianqiao, Banbanqiao, Mangdong, Shaojiwan, Liangyan, Qingshan, Shanshulin, Nayongzhi and Guanziyao deposits. Sulfide ore bodies in these deposits are (i) hosted in late Ediacaran to middle Permian limestone, dolomitic limestone and dolostone; (ii) structurally controlled by reverse fault-anticline tectonic systems; and (iii) spatially associated with the ELIP flood basalts and mafic dikes, and early Permian, early Carboniferous and early Cambrian organic matter-rich black shales. C-O isotopic compositions suggest that dolostone and limestone, mantle-derived rocks of the ELIP, and sedimentary organic matters supplied C-O to the hydrothermal systems through water/rock (W/R) interaction. New and existing S isotopic compositions of sulfides imply multiple sources of S and the reduction of sulfate through both abiotic thermochemical (TSR) and bacterially mediated (BSR) processes. Zn isotopes indicate that the sources of Zn were most likely related to the ELIP with various contributions from sediments and basements locally. Pb isotope signatures are suggestive of derivation of Pb from basements and sedimentary rocks with variable influences from the ELIP. Sr isotopes support that mantle-derived rocks, sediments and basements were involved in Pb-Zn mineralization, and they have various contributions in different deposits. We consider that the Pb-Zn deposits in the Upper Yangtze province are the mixed products of multiple S species-bearing solutions and metal-rich fluids, both of which were derived from, flowed through or interacted with multiple lithostratigraphic units in the western Yangtze Block. The change of tectonic regimes from extension to compression after eruption of basalts of the ELIP, and then to extension during Early Mesozoic, facilitated extraction, migration, and excretion of ore-forming metals and associated fluids. Mixing of fluids and reduction geochemical barrier activated TSR, causing cyclical carbonate dissolution, CO2 degassing and recrystallization (namely carbonate buffer). All these processes triggered continuous precipitation of huge amounts of hydrothermal minerals. Underplating and eruption of ELIP basalts provided heat flow, fluids and volatiles, whereas the basalts acted as an impermeable and protective layer, and even as ore-hosting rocks. These Pb-Zn deposits have spatial and genetic association with igneous activities of the ELIP, and are characterized by high ore grades (>10 wt% Pb + Zn), high concentrations of associated metals (e.g. Cu, Ag, Ge, and Cd), and medium-low temperatures (usually < 300 °C) and salinities (commonly < 20 wt% NaCl equiv.), all of which are significantly different from those of typical Mississippi Valley-type (MVT) deposits. Hence, the carbonate-hosted epigenetic Pb-Zn deposits in the Upper Yangtze metallogenic province representing to a new type of Pb-Zn deposits that are hosted in platform carbonate sequences and formed within compressional zones of passive margin tectonic settings.

Clinopyroxene dissolution in basaltic melt

NASA Astrophysics Data System (ADS)

Chen, Yang; Zhang, Youxue

2009-10-01

The history of magmatic systems may be inferred from reactions between mantle xenoliths and host basalt if the thermodynamics and kinetics of the reactions are quantified. To study diffusive and convective clinopyroxene dissolution in silicate melts, diffusive clinopyroxene dissolution experiments were conducted at 0.47-1.90 GPa and 1509-1790 K in a piston-cylinder apparatus. Clinopyroxene saturation is found to be roughly determined by MgO and CaO content. The effective binary diffusivities, DMgO and DCaO, and the interface melt saturation condition, C0MgO×C0CaO, are extracted from the experiments. DMgO and DCaO show Arrhenian dependence on temperature. The pressure dependence is small and not resolved within 0.47-1.90 GPa. C0MgO×C0CaO in the interface melt increases with increasing temperature, but decreases with increasing pressure. Convective clinopyroxene dissolution, where the convection is driven by the density difference between the crystal and melt, is modeled using the diffusivities and interface melt saturation condition. Previous studies showed that the convective dissolution rate depends on the thermodynamics, kinetics and fluid dynamics of the system. Comparing our results for clinopyroxene dissolution to results from a previous study on convective olivine dissolution shows that the kinetic and fluid dynamic aspects of the two minerals are quite similar. However, the thermodynamics of clinopyroxene dissolution depends more strongly on the degree of superheating and composition of the host melt than that of olivine dissolution. The models for clinopyroxene and olivine dissolution are tested against literature experiments on mineral-melt interaction. They are then applied to previously proposed reactions between Hawaii basalts and mantle minerals, mid-ocean ridge basalts and mantle minerals, and xenoliths digestion in a basalt at Kuandian, Northeast China.

Shallow magmatic degassing into the hydrothermal system of Copahue, Argentina

NASA Astrophysics Data System (ADS)

Varekamp, J.; Ouimette, A.; Kreulen, R.; Delpino, D.; Bermudez, A.

2001-05-01

Copahue volcano has a crater lake and acid hot springs that discharge into the Rio Agrio river system. These fluids are very concentrated (up to 6 percent sulfate), rich in rock-forming elements (up to 2000 ppm Mg) and small spheres of native sulfur float in the crater lake. The stable isotope composition of the waters (delta 18O =-2.1 to + 3.6 per mille; delta D = -49 to -26 per mille) indicates that the hot spring waters are at their most concentrated about 70 percent volcanic brine and 30 percent glacial meltwater. The crater lake waters have similar mixing proportions but added isotope effects from intense evaporation. Further dilution of the waters in the Rio Agrio gives values closer to local meteoric waters (delta 18O = -11 per mille; delta D = -77 per mille), whereas evaporation in closed ponds led to very heavy water (up to delta 18O = +12 per mille). The delta 34S value of dissolved sulfate is +14.2 per mille, whereas the native sulfur has values of -8.2 to -10.5 per mille. The heavy sulfate probably formed when SO2 disproportionated into bisulfate and native sulfur. We measured the sulfate fluxes in the Rio Agrio, and from these flux values and the stoichiometry of the disproportionation reaction we calculated the rate of liquid sulfur storage inside the volcano (6000 m3/year). During the eruptions of 1995/2000, large amounts of that stored liquid sulfur were ejected as pyroclastic sulfur. The calculated rate of rock dissolution (from rock- forming element fluxes in the Rio Agrio) suggests that the void space generated by rock dissolution is largely filled by native sulfur. The isotopic signature of the magmatic sulfur can be reconstituted at about +7 per mille, which is a source signature with superposed effects of shallow degassing. Lead isotope and 129Iodine data from the fluids indicate that subducted components may have played a role in the Copahue magma formation. Primary glass inclusions in plagioclase and olivine have 1110-1670 ppm Cl, 90-400 ppm S and low water contents (0.4 - 1.5 percent). Matrix glasses have similar volatile concentrations as many plagioclase-hosted glass inclusions. The S/Cl ratio in the hydrothermal fluids is about 2, whereas the glass inclusions have S/Cl = 0.2, indicating the strong preferential degassing of sulfur.

The effect of dissolution of volcanic glass on the water chemistry in a tuffaceous aquifer, Rainier Mesa, Nevada

USGS Publications Warehouse

White, Art F.; Claassen, H.C.; Benson, Larry V.

1980-01-01

Geochemistry of ground water associated with the Tertiary tuffs within Rainier Mesa, southern Nevada, was investigated to determine the relative importance of glass dissolution in controlling water chemistry. Water samples were obtained both from interstitial pores in core sections and from free-flowing fractures. Cation com- positions showed that calcium and magnesium decreased as a function of depth in the mesa, as sodium increased. The maximum effect occurs within alteration zones containing clinoptilolite and montmorillonite, suggesting these minerals effectively remove bivalent cations from the system. Comparisons are made between compositions of ground waters found within Rainier Mesa that apparently have not reacted with secondary minerals and compositions of waters produced by experimental dissolution of vitric and crystalline tufts which comprise the principal aquifers in the area. The two tuff phases have the same bulk chemistry but produce aqueous solutions of different chemistry. Rapid parabolic dissolution of sodium and silica from, and the retention of, potassium within the vitric phase verify previous predictions concerning water compositions associated with vitric volcanic rocks. Parabolic dissolution of the crystalline phase results in solutions high in calcium and magnesium and low in silica. Extrapolation of the parabolic dissolution mechanism for the vitric tuff to long times successfully reproduces, at com- parable pH, cation ratios existing in Rainier Mesa ground water. Comparison of mass- transfer rates of the vitric and crystalline tuffs indicates that the apparent higher glass-surface to aqueous-volume ratio associated with the vitric rocks may account for dominance of the glass reaction.

Leaching of boron, arsenic and selenium from sedimentary rocks: II. pH dependence, speciation and mechanisms of release.

PubMed

Tabelin, Carlito Baltazar; Hashimoto, Ayaka; Igarashi, Toshifumi; Yoneda, Tetsuro

2014-03-01

Sedimentary rocks excavated in Japan from road- and railway-tunnel projects contain relatively low concentrations of hazardous trace elements like boron (B), arsenic (As) and selenium (Se). However, these seemingly harmless waste rocks often produced leachates with concentrations of hazardous trace elements that exceeded the environmental standards. In this study, the leaching behaviors and release mechanisms of B, As and Se were evaluated using batch leaching experiments, sequential extraction and geochemical modeling calculations. The results showed that B was mostly partitioned with the residual/crystalline phase that is relatively stable under normal environmental conditions. In contrast, the majority of As and Se were associated with the exchangeable and organics/sulfides phases that are unstable under oxidizing conditions. Dissolution of water-soluble phases controlled the leaching of B, As and Se from these rocks in the short term, but pyrite oxidation, calcite dissolution and adsorption/desorption reactions became more important in the long term. The mobilities of these trace elements were also strongly influenced by the pH of the rock-water system. Although the leaching of Se only increased in the acidic region, those of B and As were enhanced under both acidic and alkaline conditions. Under strongly acidic conditions, the primarily release mechanism of B, As and Se was the dissolution of mineral phases that incorporated and/or adsorbed these elements. Lower concentrations of these trace elements in the circumneutral pH range could be attributed to their strong adsorption onto minerals like Al-/Fe-oxyhydroxides and clays, which are inherently present and/or precipitated in the rock-water system. The leaching of As and B increased under strongly alkaline conditions because of enhanced desorption and pyrite oxidation while that of Se remained minimal due to its adsorption onto Fe-oxyhydroxides and co-precipitation with calcite. Copyright © 2013 Elsevier B.V. All rights reserved.

Modeling the growth and interaction of stylolite networks, using the discrete element method for pressure solution

NASA Astrophysics Data System (ADS)

Makedonska, N.; Sparks, D. W.; Aharonov, E.

2012-12-01

Pressure solution (also termed chemical compaction) is considered the most important ductile deformation mechanism operating in the Earth's upper crust. This mechanism is a major player in a variety of geological processes, including evolution of sedimentary basins, hydrocarbon reservoirs, aquifers, earthquake recurrence cycles, and fault healing. Pressure solution in massive rocks often localizes into solution seams or stylolites. Field observations of stylolites often show elastic/brittle interactions in regions between pressure solution features, including and shear fractures, veins and pull-apart features. To understand these interactions, we use a grain-scale model based on the Discrete Element Method that allows granular dissolution at stressed contacts between grains. The new model captures both the slow chemical compaction process and the more abrupt brittle fracturing and sliding between grains. We simulate a sample of rock as a collection of particles, each representing either a grain or a unit of rock, bonded to each other with breakable cement. We apply external stresses to this sample, and calculate elastic and frictional interactions between the grains. Dissolution is modeled by an irreversible penetration of contacting grains into each other at a rate that depends on the contact stress and an adjustable rate constant. Experiments have shown that dissolution rates at grain contacts are greatly enhanced when there is a mineralogical contrast. Therefore, we dissolution rate constant can be increased to account for an amount of impurities (e.g. clay in a quartz or calcite sandstone) that can accumulate on dissolving contacts. This approach allows large compaction and shear strains within the rock, while allowing examination of local grain-scale heterogeneity. For example, we will describe the effect of pressure solution on the distribution of contact forces magnitudes and orientations. Contact forces in elastic granular packings are inherently heteregeneous, but stress-dependent dissolution tends to equalize them. We apply our model to the simulation of stylolite networks, particularly the interaction of stylolite tips. The stress concentrations from these tips are transmitted through the intervening rock, which can cause elastic strain, brittle damage and frictional sliding. Our model shows that grain rearrangement and compaction rate depend on the surface friction coefficient of grains. Simulation results show the development of shear zones between stylolites, and a high porosity process zone at the tips of stylolites. These features, which have been observed in field studies, are modeled and predicted for the first time. This modeling tool holds a promise to provide many new insights regarding the coupling between pressure solution and brittle deformation, i.e. between mechanical and chemical compaction.

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.

Exploring Nested Reaction Fronts to Understand How Oxygen Cracks Rocks, Carbonic and Sulfuric Acids Dissolve Rocks, and Water Transports Rocks during Weathering

NASA Astrophysics Data System (ADS)

Brantley, S. L.; Gu, X.; Sullivan, P. L.; Kim, H.; Stinchcomb, G. E.; Lebedeva, M.; Balashov, V. N.

2016-12-01

To first order, weathering is the reaction of rocks with oxidants (oxygen, nitrate, etc.), acids (carbonic, sulfuric, and organic acids), and water. To explore weathering we have been studying the depth intervals in soils, saprolite, and weathering rock where mineral reactions are localized - "reaction fronts". We limit the study to ridges or catchments in climates where precipitation is greater than potential evapotranspiration. For example, in the Susquehanna Shale Hills Critical Zone Observatory, we observe reaction fronts that generally define very rough surfaces in 3D that mimic the land surface topography, although with lower relief. Overall, the fronts form nested curved surfaces. In Shale Hills, the deepest reaction fronts are oxidation of pyrite, and dissolution of carbonate. The carbonate is inferred to dissolve at least partly due to the sulfuric acid produced by the pyrite. In addition to pyrite, chlorite also starts to oxidize at the water table. We hypothesize that these dissolution and oxidation reactions open pores and cause microfracturing that open the rock to infiltration of advecting meteoric waters. At much shallower depths, illite is observed to dissolve. In Shale Hills, these reaction fronts - pyrite, carbonate, illite - separate over meters beneath the ridges. Such separated reaction fronts have also been observed in other fractured lithologies where oxidation is the deepest reaction and is associated with weathering-induced fractures. In contrast, in some massive mafic rocks, reaction fronts are almost co-located. By studying the geometry of reaction fronts, it may be possible to elucidate the relative importance of how oxygen cracks rocks; carbonic, organic, and sulfuric acids dissolve rocks; and water mobilizes rock materials during weathering.

Environmental characterisation of coal mine waste rock in the field: an example from New Zealand

NASA Astrophysics Data System (ADS)

Hughes, J.; Craw, D.; Peake, B.; Lindsay, P.; Weber, P.

2007-08-01

Characterisation of mine waste rock with respect to acid generation potential is a necessary part of routine mine operations, so that environmentally benign waste rock stacks can be constructed for permanent storage. Standard static characterisation techniques, such as acid neutralisation capacity (ANC), maximum potential acidity, and associated acid-base accounting, require laboratory tests that can be difficult to obtain rapidly at remote mine sites. We show that a combination of paste pH and a simple portable carbonate dissolution test, both techniques that can be done in the field in a 15 min time-frame, is useful for distinguishing rocks that are potentially acid-forming from those that are acid-neutralising. Use of these techniques could allow characterisation of mine wastes at the metre scale during mine excavation operations. Our application of these techniques to pyrite-bearing (total S = 1-4 wt%) but variably calcareous coal mine overburden shows that there is a strong correlation between the portable carbonate dissolution technique and laboratory-determined ANC measurements (range of 0-10 wt% calcite equivalent). Paste pH measurements on the same rocks are bimodal, with high-sulphur, low-calcite rocks yielding pH near 3 after 10 min, whereas high-ANC rocks yield paste pH of 7-8. In our coal mine example, the field tests were most effective when used in conjunction with stratigraphy. However, the same field tests have potential for routine use in any mine in which distinction of acid-generating rocks from acid-neutralising rocks is required. Calibration of field-based acid-base accounting characteristics of the rocks with laboratory-based static and/or kinetic tests is still necessary.

Influence of microwaves on the leaching kinetics of uraninite from a low grade ore in dilute sulfuric acid.

PubMed

Madakkaruppan, V; Pius, Anitha; T, Sreenivas; Giri, Nitai; Sarbajna, Chanchal

2016-08-05

This paper describes a study on microwave assisted leaching of uranium from a low-grade ore of Indian origin. The host rock for uranium mineralization is chlorite-biotite-muscovite-quartzo-feldspathic schist. The dominant presence of siliceous minerals determined leaching of uranium values in sulfuric acid medium under oxidizing conditions. Process parametric studies like the effect of sulfuric acid concentration (0.12-0.50M), redox potential (400-500mV), particle size (600-300μm) and temperature (35°-95°C) indicated that microwave assisted leaching is more efficient in terms of overall uranium dissolution, kinetics and provide relatively less impurities (Si, Al, Mg and Fe) in the leach liquor compared to conventional conductive leaching. The kinetics of leaching followed shrinking core model with product layer diffusion as controlling mechanism. Copyright © 2016 Elsevier B.V. All rights reserved.

Reactive transport modeling of the enhancement of density-driven CO 2 convective mixing in carbonate aquifers and its potential implication on geological carbon sequestration

DOE PAGES

Islam, Akand; Sun, Alexander Y.; Yang, Changbing

2016-04-20

We study the convection and mixing of CO 2 in a brine aquifer, where the spread of dissolved CO 2 is enhanced because of geochemical reactions with the host formations (calcite and dolomite), in addition to the extensively studied, buoyancy-driven mixing. The nonlinear convection is investigated under the assumptions of instantaneous chemical equilibrium, and that the dissipation of carbonate rocks solely depends on flow and transport and chemical speciation depends only on the equilibrium thermodynamics of the chemical system. The extent of convection is quantified in term of the CO 2 saturation volume of the storage formation. Our results suggestmore » that the density increase of resident species causes significant enhancement in CO 2 dissolution, although no significant porosity and permeability alterations are observed. Furthermore, early saturation of the reservoir can have negative impact on CO 2 sequestration.« less

Reactive Transport Modeling of the Enhancement of Density-Driven CO2 Convective Mixing in Carbonate Aquifers and its Potential Implication on Geological Carbon Sequestration.

PubMed

Islam, Akand; Sun, Alexander Y; Yang, Changbing

2016-04-20

We study the convection and mixing of CO2 in a brine aquifer, where the spread of dissolved CO2 is enhanced because of geochemical reactions with the host formations (calcite and dolomite), in addition to the extensively studied, buoyancy-driven mixing. The nonlinear convection is investigated under the assumptions of instantaneous chemical equilibrium, and that the dissipation of carbonate rocks solely depends on flow and transport and chemical speciation depends only on the equilibrium thermodynamics of the chemical system. The extent of convection is quantified in term of the CO2 saturation volume of the storage formation. Our results suggest that the density increase of resident species causes significant enhancement in CO2 dissolution, although no significant porosity and permeability alterations are observed. Early saturation of the reservoir can have negative impact on CO2 sequestration.

Origin of the Okrouhlá Radouň episyenite-hosted uranium deposit, Bohemian Massif, Czech Republic: fluid inclusion and stable isotope constraints

NASA Astrophysics Data System (ADS)

Dolníček, Zdeněk; René, Miloš; Hermannová, Sylvie; Prochaska, Walter

2014-04-01

The Okrouhlá Radouň shear zone hosted uranium deposit is developed along the contact of Variscan granites and high-grade metasedimentary rocks of the Moldanubian Zone of the Bohemian Massif. The pre-ore pervasive alteration of wall rocks is characterized by chloritization of mafic minerals, followed by albitization of feldspars and dissolution of quartz giving rise to episyenites. The subsequent fluid circulation led to precipitation of disseminated uraninite and coffinite, and later on, post-ore quartz and carbonate mineralization containing base metal sulfides. The fluid inclusion and stable isotope data suggest low homogenization temperatures (˜50-140 °C during pre-ore albitization and post-ore carbonatization, up to 230 °C during pre-ore chloritization), variable fluid salinities (0-25 wt.% NaCl eq.), low fluid δ18O values (-10 to +2 ‰ V-SMOW), low fluid δ13C values (-9 to -15 ‰ V-PDB), and highly variable ionic composition of the aqueous fluids (especially Na/Ca, Br/Cl, I/Cl, SO4/Cl, NO3/Cl ratios). The available data suggest participation of three fluid endmembers of primarily surficial origin during alteration and mineralization at the deposit: (1) local meteoric water, (2) Na-Ca-Cl basinal brines or shield brines, (3) SO4-NO3-Cl-(H)CO3 playa-like fluids. Pre-ore albitization was caused by circulation of alkaline, oxidized, and Na-rich playa fluids, whereas basinal/shield brines and meteoric water were more important during the post-ore stage of alteration.

Paleomagnetic and oxygen isotopic evidence for long term diagenesis in radiolarian chert, Pindos Mountains, Greece

NASA Astrophysics Data System (ADS)

Baltuck, Miriam

1987-02-01

Paleomagnetics was used in an attempt to improve chronostratigraphy in the Middle and Upper Jurassic radiolarian chert and siliceous mudstone of the Pindos Zone, Greece. Remanent magnetism studies showed strong magnetic intensity but scattered orientation. Orientation of some pressure solution features in the radiolarities indicates their formation under horizontal pressure, a condition which in Pindos geologic history would only have occurred during early Cretaceous or Cenozoic tectonics, indicating very late diagenesis in these parts of the section. From time of deposition to later time at which diagenesis can be documented, the Earth's magnetic field would have reversed many times. Remagnetization during solution-precipitation steps of silica diagenesis could complicate the rock magnetics. Oxygen isotopic and major element analyses of radiolarite lithologies show a systematic variation of rate of silica diagenesis in different host lithologies, thus solution-precipitation would occur at widely differing times throughout the section lithologies. If the dissolution of the silica cement were physically to free magnetic material from an earlier orientation, the result could be a partial shift toward alignment with the ambient magnetic field. Alternatively, complete reorientation of particles could have occurred at varying times in different parts of the section as a function of host lithology. During the northward movement and clockwise rotation of the Apulian subplate (including Pindos) these different lithologies could completely reorient during different stages of silica diagenesis, locking the orientation of iron magnetic moments into alignment with the ambient magnetic field at time of precipitation to result in a strong intensity but scattered orientation of Pindos rock magnetics.

Heterogeneous redox conditions, arsenic mobility, and groundwater flow in a fractured-rock aquifer near a waste repository site in New Hampshire, USA

EPA Science Inventory

Anthropogenic sources of carbon from landfill or waste leachate can promote reductive dissolution of in situ arsenic (As) and enhance the mobility of As in groundwater. Groundwater from residential-supply wells in a fractured crystalline-rock aquifer adjacent to a Superfund site ...

INFLUENCE OF PH AND OXIDATION-REDUCTION POTENTIAL (EH) ON THE DISSOLUTION OF MERCURY-CONTAINING MINE WASTES FROM THE SULFUR BANK MERCURY MINE

EPA Science Inventory

This study was undertaken as a part of developing treatment alternatives for waste materials, primarily waste rock and roaster tailings, from sites contaminated with mercury (Hg) mining wastes. Leaching profiles of waste rock over a range of different pH and oxidation-reduction (...

Understanding physical rock properties and their relation to fluid-rock interactions under supercritical conditions

NASA Astrophysics Data System (ADS)

Kummerow, Juliane; Raab, Siegfried; Meyer, Romain

2017-04-01

The electrical conductivity of rocks is, in addition to lithological factors (mineralogy, porosity) and physical parameters (temperature, pressure) sensitive to the nature of pore fluids (phase, salinity), and thus may be an indicative measure for fluid-rock interactions. Especially near the critical point, which is at 374.21° C and 22.12 MPa for pure water, the physico-chemical properties of aqueous fluids change dramatically and mass transfer and diffusion-controlled chemical reactivity are enhanced, which in turn leads to the formation of element depletion/ enrichment patterns or cause mineral dissolution. At the same time, the reduction of the dielectric constant of water promotes ion association and consequently mineral precipitation. All this cause changes in the electrical conductivity of geothermal fluids and may have considerable effects on the porosity and hydraulic properties of the rocks with which they are in contact. In order to study the impact of fluid-rock interactions on the physical properties of fluids and rocks in near- and supercritical geological settings in more detail, in the framework of the EU-funded project "IMAGE" (Integrated Methods for Advanced Geothermal Exploration) hydraulic and electrical properties of rock cores from different active and exhumed geothermal areas on Iceland were measured up to supercritical conditions (Tmax = 380° C, pfluid = 23 MPa) during long-term (2-3 weeks) flow-through experiments in an internally heated gas pressure vessel at a maximum confining pressure of 42 MPa. In a second flow-through facility both the intrinsic T-dependent electrical fluid properties as well as the effect of mineral dissolution/ precipitation on the fluid conductivity were measured for increasing temperatures in a range of 24 - 422° C at a constant fluid pressure of 31 MPa. Petro- and fluid physical measurements were supplemented by a number of additional tests, comprising microstructural investigations as well as the chemical analysis of fluid samples, which were taken at every temperature level. Both physical and chemical data indicate only slight fluid-rock interactions at T < 250° C and the increase in bulk conductivity is most probably dominated by a T-dependence of the surface conductance. At higher temperatures, the decreasing fluid density causes the decrease of dielectric constant, which in turn leads to the precipitation of minerals due to a promoted association between oppositely charged ions. This is intensified at the critical point, indicated by a sharp decrease in conductivity, when regarding pure fluids. The opposite was observed in experiments, where fluid-solid interaction was allowed. In this case, the conductivity of the bulk system has increased within seconds nearly by factor 7. This points to a massive release of charge carriers due to an extensive and spontaneous increase in rock solubility, what counterbalances the effect of mineral precipitation. Moreover, the permanent oscillation of conductivities at supercritical conditions may indicate a dynamic interplay of ion depletion by mineral precipitation and the input of new charge carriers due to mineral dissolution. Regarding the permeability we can resolve the influence of mineral precipitation only, which is indicated by a decrease in rock permeability by about 5 % after the sample was exposed to supercritical conditions for 4 hours. Especially, for Si a continuous increase of ion concentration in the fluid samples is revealed for increasing temperatures, indicating a beginning mineral dissolution above 150° C. At near-critical conditions also Al and Pb as well as the rare earth elements (REE) are more intensively dissolved. From SEM analyses it is apparent that the alteration of the solid material is most effective where fresh fluid is continuously flowing around the solid, while stagnant fluids led to a much less pervasive alteration of the material. In this case, solid dissolution seems to slow down considerably or even comes to an end, what can be explained by the adjustment of a chemical equilibrium and the stabilisation of the reaction front.

Illite Dissolution Rates and Equation (100 to 280 dec C)

DOE Data Explorer

Carroll, Susan

2014-10-17

The objective of this suite of experiments was to develop a useful kinetic dissolution expression for illite applicable over an expanded range of solution pH and temperature conditions representative of subsurface conditions in natural and/or engineered geothermal reservoirs. Using our new data, the resulting rate equation is dependent on both pH and temperature and utilizes two specific dissolution mechanisms (a “neutral” and a “basic” mechanism). The form of this rate equation should be easily incorporated into most existing reactive transport codes for to predict rock-water interactions in EGS shear zones.

Impact of grain size and rock composition on simulated rock weathering

NASA Astrophysics Data System (ADS)

Israeli, Yoni; Emmanuel, Simon

2018-05-01

Both chemical and mechanical processes act together to control the weathering rate of rocks. In rocks with micrometer size grains, enhanced dissolution at grain boundaries has been observed to cause the mechanical detachment of particles. However, it remains unclear how important this effect is in rocks with larger grains, and how the overall weathering rate is influenced by the proportion of high- and low-reactivity mineral phases. Here, we use a numerical model to assess the effect of grain size on chemical weathering and chemo-mechanical grain detachment. Our model shows that as grain size increases, the weathering rate initially decreases; however, beyond a critical size no significant decrease in the rate is observed. This transition occurs when the density of reactive boundaries is less than ˜ 20 % of the entire domain. In addition, we examined the weathering rates of rocks containing different proportions of high- and low-reactivity minerals. We found that as the proportion of low-reactivity minerals increases, the weathering rate decreases nonlinearly. These simulations indicate that for all compositions, grain detachment contributes more than 36 % to the overall weathering rate, with a maximum of ˜ 50 % when high- and low-reactivity minerals are equally abundant in the rock. This occurs because selective dissolution of the high-reactivity minerals creates large clusters of low-reactivity minerals, which then become detached. Our results demonstrate that the balance between chemical and mechanical processes can create complex and nonlinear relationships between the weathering rate and lithology.

Geology and geochemistry of three sedimentary-rock-hosted disseminated gold deposits in Guizhou Province, People's Republic of China

USGS Publications Warehouse

Ashley, R.P.; Cunningham, C.G.; Bostick, N.H.; Dean, W.E.; Chou, I.-Ming

1991-01-01

Five sedimentary-rock-hosted disseminated gold deposits have been discovered since 1980 in southwestern Guizhou Province (PRC). Submicron-sized gold is disseminated in silty carbonate and carbonaceous shale host rocks of Permian and Triassic age. Arsenic, antimony, mercury, and thallium accompany the gold. Associated hydrothermal alteration resulted in decarbonatization of limestone, silicification, and argillization, and depletion of base metals, barium, and many other elements. Organic material occurs in most host rocks and ores. It was apparently devolatilized during a regional heating event that preceded hydrothermal activity, and thus was not mobilized during mineralization, and did not affect gold deposition. The geologic setting of the Guizhou deposits includes many features that are similar to those of sedimentary-rock-hosted deposits of the Great Basin, western United States. The heavy-element suite that accompanies gold is the same, but base metals are even scarcer in the Guizhou deposits than they are in U.S. deposits. The Guizhou deposits discovered to date are smaller than most U.S. deposits and have no known spatially associated igneous rocks. ?? 1991.

The Impact of the Flow Field Heterogeneity and of the Injection Rate on the Effective Reaction Rates in Carbonates: a Study at the Pore Scale

NASA Astrophysics Data System (ADS)

Nunes, J. P. P.; Bijeljic, B.; Blunt, M. J.

2015-12-01

Carbonate rocks are notoriously difficult to characterize. Their abrupt facies variations give rise to drastic changes in the petrophysical properties of the reservoir. Such heterogeneity, when further associated with variations in rock mineralogy due to diagenetic processes, result in a challenging scenario to model from the pore to the field scale. Micro-CT imaging is one of the most promising technologies to characterize porous rocks. The understanding at the pore scale of reactive and non-reactive transport is being pushed forward by recent developments in both imaging capability - 3D images with resolution of a few microns - and in modeling techniques - flow simulations in giga-cell models. We will present a particle-based method capable of predicting the evolution of petrophysical properties of carbonate cores subjected to CO2 injection at reservoir conditions (i.e. high pressures and temperatures). Reactive flow is simulated directly on the voxels of high resolution micro-CT images of rocks. Reactants are tracked using a semi-analytical streamline tracing algorithm and rock-fluid interaction is controlled by the diffusive flux of particles from the pores to the grains. We study the impact of the flow field heterogeneity and of the injection rate on the sample-averaged (i.e. effective) reaction rate of calcite dissolution in three rocks of increasing complexity: a beadpack, an oolitic limestone and a bioclastic limestone. We show how decreases in the overall dissolution rate depend on both the complexity of the pore space and also on the flow rate. This occurs even in chemically homogenous rocks. Our results suggest that the large differences observed between laboratory and field scale rates could, in part, be explained by the inhomogeneity in the flow field at the pore scale and the consequent transport-limited flux of reactants at the solid surface. Our results give valuable insight into the processes governing carbonate dissolution and provide a starting point to the refinement of upscaling techniques for reactive flows. Potential impacts for reservoir development and monitoring will also be discussed.

Hypogenic contribution to speleogenesis in a predominant epigenic karst system: A case study from the Venetian Alps, Italy

NASA Astrophysics Data System (ADS)

Tisato, Nicola; Sauro, Francesco; Bernasconi, Stefano M.; Bruijn, Rolf H. C.; De Waele, Jo

2012-05-01

Buso della Rana and Buso della Pisatela are two karstic caves located in north-east Italy. They are part of the same karst system and are developed in the Castelgomberto calcarenitic marine sediments, which were deposited in a shallow Caribbean-type sea during the Eocene. The Buso della Rana-Pisatela system developed mostly at the contact between the Castelgomberto calcarenite and underlying volcanic rocks. The system of caves is ~ 37 km long and has only three entrances, two of which are semi-artificial. The overlying karst plateau is not directly connected to the Buso della Rana-Pisatela system and, with the exception of one deep abyss, exhibits a rather poorly developed karst. This is unexpected considering the presence at depth of such a large and long cave. Gypsum (CaSO4·2H2O) has locally been observed on the walls of the Buso della Pisatela cave. Energy dispersive X-ray spectroscopy (EDS), performed with a scanning electron microscope (SEM), reveals the presence of sulfur-bearing minerals within the host rock. Gypsum was formed by oxidation of these minerals as indicated by negative δ34S values. The oxidation of sulfide minerals forms a sulfuric-acid solution that dissolves the Castelgomberto calcarenite and, once it is oversaturated in calcium, precipitates as gypsum. The lack of well-developed karst on top of the plateau and the analyses suggest that the formation mechanisms for the Buso della Rana-Pisatela system differ from classical epigenic speleogenesis. The "pyrite-effect" has been recognized in other caves and described in literature. In our case pyrite is responsible of two hypo-speleogenetic processes: i) the dissolution of a portion of the host rock and ii) the enlargement of the karst voids as a consequence of the haloclastic effect.

The role of volatile-saturation and adiabatic ascent of moderately hydrous melts on the formation of orbicules and comb layers in shallow subvolcanic conduits (Fisher Lake, Sierra Nevada).

NASA Astrophysics Data System (ADS)

McCarthy, A. J.; Müntener, O.

2016-12-01

Orbicules and comb layers are enigmatic features found sparsely distributed along plutonic contacts in a wide range of igneous environments. We provide new insights into the mechanisms responsible for the formation of these features by studying the spatial distribution, mineralogy and geochemistry of comb layers and orbicules from the Northern Sierra Nevada, Fisher Lake (USA). Over a range of studied comb textured layering, we show that the large majority of comb layers are cumulates formed by the initiation of plagioclase growth as a comb textured mineral. Plagioclase fractionation is followed by pyroxenes + oxides fractionation. Continuous crystal fractionation and conductive cooling from the host rock leads to amphibole saturation and the formation of late stage comb textured amphibole, leading to the formation of plagioclase- and plagioclase-amphibole comb textures. The lack of amphibole comb textures on orbicule rims as opposed to their widespread occurrence in comb layers, suggests that the presence of a thermal gradient plays an important role in diversifying comb textures. We propose that comb layers and orbicules are unique features which are controlled by the volatile content of ascending melts and ascent mechanisms. Thermodynamic calculations indicate that near-adiabatic decompression of water-undersaturated melts (ca. 4wt% H2O) through the crust will lead to superheating and dissolution of pre-existing minerals. Upon saturation of volatiles at shallow depth, degassing-induced undercooling of the decompressing melt will trigger heterogeneous nucleation of plagioclase on host rocks and remobilized xenoliths. The rarity of orbicules and comb layers in volcanic and plutonic rocks worldwide suggests that adiabatic decompression of moderately hydrous melts leading to superheating is a rare phenomena, with most arc melts ascending and cooling in small reservoirs throughout the crust, prior to emplacement at shallow depth as crystal-bearing magmas.

Interstitial Water Geochemistry and Low Temperature Alteration in Volcaniclastic Sediments from the Amami Sankaku Basin at IODP Site U1438 (Expedition 351)

NASA Astrophysics Data System (ADS)

Loudin, L. C.; Yogodzinski, G. M.; Sena, C.; van der Land, C.; Zhang, Z.; Marsaglia, K. M.; Meffre, S.

2014-12-01

Interstitial water (IW) geochemistry provides insight into the diagenetic transformation of sediment to rock by component dissolution/alteration and precipitation of new mineral phases as pore-filling cements, as well as providing insight into ion exchange reactions with secondary minerals. At Site U1438, 67 IW samples were collected within a ~950 m section of volcaniclastic sediments. These were analyzed for pH as well as major and trace elements. The corresponding host sediments were mineralogically characterized by XRD and petrographic observations. Three alteration zones are inferred: 1) the upper alteration zone (~0-300 mbsf) characterized by maximum IW concentrations of Si (790.1 μM), Sr (138.5 μM) and Mn (279.5 μM), consistent with volcanic glass and siliceous microfossil dissolution, enhanced reduction of Mn oxides, and carbonate recrystallization. Maximum concentrations in Li and B coupled with the lowest pH (6.7) imply that Li and B are released into the IW due to silicate dissolution and clay desorption. 2) At intermediate depths (~300 to ~550 mbsf) Mg, K, Sr, Si, Mn, Li, and B are at concentration minima, possibly due to growth of authigenic minerals. B and Li minimum concentrations occur at high pH (~9) suggesting that these elements are preferentially removed from high pH waters during the precipitation of clay mineral and zeolite cements in primary and secondary (dissolution) pores. The mineralogy of these phases is confirmed by XRD data, and their pore-filling nature is seen in thin sections of the coarser lithologies. 3) The deep alteration zone (>~550m) is characterized by an increase in B, Li, Sr and Ca. At ~650 mbsf, Ca becomes the dominant cation in solution consistent with either mineral interaction with the IW, or diffusive input from underlying igneous basement (~1400 mbsf).

Can a fractured caprock self-heal?

NASA Astrophysics Data System (ADS)

Elkhoury, Jean E.; Detwiler, Russell L.; Ameli, Pasha

2015-05-01

The ability of geologic seals to prevent leakage of fluids injected into the deep subsurface is critical for mitigating risks associated with greenhouse-gas sequestration and natural-gas production. Fractures caused by tectonic or injection-induced stresses create potential leakage pathways that may be further enhanced by mineral dissolution. We present results from reactive-flow experiments in fractured caprock (dolomitic anhydrite), where additional dissolution occurs in the rock matrix adjacent to the fracture surfaces. Preferential dissolution of anhydrite left a compacted layer of dolomite in the fractures. At lower flow rate, rock-fluid reactions proceeded to near equilibrium within the fracture with preferential flow paths persisting over the 6-month duration of the experiment and a negligible change in permeability. At higher flow rate, permeability decreased by a dramatic two orders of magnitude. This laboratory-scale observation of self-healing argues against the likelihood of runaway permeability growth in fractured porous caprock composed of minerals with different solubilities and reaction kinetics. However, scaling arguments suggest that at larger length scales this self-healing process may be offset by the formation of dissolution channels. Our results have relevance beyond the greenhouse-gas sequestration problem. Chemical disequilibrium at waste injection sites and in hydrothermal reservoirs will lead to reactive flows that may also significantly alter formation permeability.

Lattice Boltzmann simulation of dissolution-induced changes in permeability and porosity in 3D CO2 reactive transport

NASA Astrophysics Data System (ADS)

Tian, Zhiwei; Wang, Junye

2018-02-01

Dissolution and precipitation of rock matrix are one of the most important processes of geological CO2 sequestration in reservoirs. They change connections of pore channels and properties of matrix, such as bulk density, microporosity and hydraulic conductivity. This study builds on a recently developed multi-layer model to account for dynamic changes of microporous matrix that can accurately predict variations in hydraulic properties and reaction rates due to dynamic changes in matrix porosity and pore connectivity. We apply the model to simulate the dissolution and precipitation processes of rock matrix in heterogeneous porous media to quantify (1) the effect of the reaction rate on dissolution and matrix porosity, (2) the effect of microporous matrix diffusion on the overall effective diffusion and (3) the effect of heterogeneity on hydraulic conductivity. The results show the CO2 storage influenced by factors including the matrix porosity change, reaction front movement, velocity and initial properties. We also simulated dissolution-induced permeability enhancement as well as effects of initial porosity heterogeneity. The matrix with very low permeability, which can be unresolved on X-ray CT, do contribute to flow patterns and dispersion. The concentration of reactant H+ increases along the main fracture paths where the flow velocity increases. The product Ca++ shows the inversed distribution pattern against the H+ concentration. This demonstrates the capability of this model to investigate the complex CO2 reactive transport in real 3D heterogeneous porous media.

Carbon storage potential of Columbia River flood basalt

NASA Astrophysics Data System (ADS)

Wells, R. K.; Xiong, W.; Giammar, D.; Skemer, P. A.

2017-12-01

Basalt reservoirs are an important option for sequestering carbon through dissolution of host rock and precipitation of stable carbonate minerals. This study seeks to understand the nature of dissolution and surface roughening processes and their influence on the timing and spatial distribution of carbonation, in static experiments at 150 °C and 100 bar CO2. Intact samples and cores with milled pathways from Ca-rich and Fe-rich Columbia River flood basalt formations were reacted for up to 40 weeks. Experimental specimens were analyzed using SEM-EDS, microprobe, and μCT scanning, Raman spectroscopy, and 2D profilometer to characterize changes in composition and surface roughness. ICP-MS was used to examine bulk fluid chemistry. Initial dissolution of olivine grains results in higher Mg2+ and Fe2+ concentrations within the bulk solution in the first week of reaction. However, once available olivine grains are gone, Ca-rich pyroxene becomes the primary contributor of Ca2+, Mg2+, and Fe2+ within the bulk solution. The complete dissolution of olivine grains resulted in pits up to 200 μm deep. Dissolution of other minerals resulted in the formation of microscale textures, primarily along grain boundaries and fractures. The surface roughness increased by factors of up to 42, while surface area increased 20%. Based on these results, pyroxene is the sustaining contributor of divalent metal cations during dissolution of basalt, and the limited connectivity of olivine and pyroxene grains limits the exposure of new reactive surface areas. Within 6 weeks, aragonite precipitated in Ca-rich basalt samples, while Fe-rich samples precipitated of siderite. The highest concentration of carbonates occurs 1/3 into milled pathways, which simulate dead-end fractures, in low porosity basalts, and near the fracture tip in high porosity basalts. Even at elevated temperatures, the fractures are not blocked nor filled within 40 weeks of reaction. When vesicles are present, carbonates can precipitate within these pores even when the pores do not appear to connect to the main fracture pathway. Based on our experimental results, we estimate the carbon storage potential of the Ca-rich formations within the Columbia River flood basalt to be 47 kg CO2/m3, which could be reached in 38 years at a constant carbonation rate of 1.24 ± 0.54 kg CO2/m3yr.

Density-dependent groundwater flow and dissolution potential along a salt diapir in the Transylvanian Basin, Romania

NASA Astrophysics Data System (ADS)

Zechner, Eric; Danchiv, Alex; Dresmann, Horst; Mocuţa, Marius; Huggenberger, Peter; Scheidler, Stefan; Wiesmeier, Stefan; Popa, Iulian; Zlibut, Alexandru; Zamfirescu, Florian

2016-04-01

Salt diapirs and the surrounding sediments are often involved in a variety of human activities, such as salt mining, exploration and storage of hydrocarbons, and also storage of radioactive waste material. The presence of highly soluble evaporitic rocks, a complex tectonic setting related to salt diapirsm, and human activities can lead to significant environmental problems, e.g. land subsidence, sinkhole development, salt cavern collapse, and contamination of water resources with brines. In the Transylvanian town of Ocna Mures. rock salt of a near-surface diapir has been explored since the Roman ages in open excavations, and up to the 20th century in galleries and with solution mining. Most recently, in 2010 a sudden collapse in the adjacent Quaternary unconsolidated sediments led to the formation of a 70-90m wide salt lake with a max. depth of 23m. Over the last 3 years a Romanian-Swiss research project has led to the development of 3D geological and hydrogeological information systems in order to improve knowledge on possible hazards related to uncontrolled salt dissolution. One aspect which has been investigated is the possibility of density-driven flow along permeable subvertical zones next to the salt dome, and the potential for subsaturated groundwater to dissolve the upper sides of the diapir. Structural 3D models of the salt diapir, the adjacent basin sediments, and the mining galleries, led to the development of 2D numerical vertical density-dependent models of flow and transport along the diapir. Results show that (1) increased rock permeability due to diapirsm, regional tectonic thrusting and previous dissolution, and (2) more permeable sandstone layers within the adjacent basin sediments may lead to freshwater intrusion towards the top of the diapir, and, therefore, to increased potential for salt dissolution.

Sedimentary rock-hosted Au deposits of the Dian-Qian-Gui area, Guizhou, and Yunnan Provinces, and Guangxi District, China

USGS Publications Warehouse

Peters, S.G.; Jiazhan, H.; Zhiping, L.; Chenggui, J.

2007-01-01

Sedimentary rock-hosted Au deposits in the Dian-Qian-Gui area in southwest China are hosted in Paleozoic and early Mesozoic sedimentary rocks along the southwest margin of the Yangtze (South China) Precambrian craton. Most deposits have characteristics similar to Carlin-type Au deposits and are spatially associated, on a regional scale, with deposits of coal, Sb, barite, As, Tl, and Hg. Sedimentary rock-hosted Au deposits are disseminated stratabound and(or) structurally controlled. The deposits have many similar characteristics, particularly mineralogy, geochemistry, host rock, and structural control. Most deposits are associated with structural domes, stratabound breccia bodies, unconformity surfaces or intense brittle-ductile deformation zones, such as the Youjiang fault system. Typical characteristics include impure carbonate rock or calcareous and carbonaceous host rock that contains disseminated pyrite, marcasite, and arsenopyrite-usually with ??m-sized Au, commonly in As-rich rims of pyrite and in disseminations. Late realgar, orpiment, stibnite, and Hg minerals are spatially associated with earlier forming sulfide minerals. Minor base-metal sulfides, such as galena, sphalerite, chalcopyrite, and Pb-Sb-As-sulphosalts also are present. The rocks locally are silicified and altered to sericite-clay (illite). Rocks and(or) stream-sediment geochemical signatures typically include elevated concentrations of As, Sb, Hg, Tl, and Ba. A general lack of igneous rocks in the Dian-Qian-Gui area implies non-pluton-related, ore forming processes. Some deposits contain evidence that sources of the metal may have originated in carbonaceous parts of the sedimentary pile or other sedimentary or volcanic horizons. This genetic process may be associated with formation and mobilization of petroleum and Hg in the region and may also be related to As-, Au-, and Tl-bearing coal horizons. Many deposits also contain textures and features indicative of strong structural control by tectonic domes or shear zones and also suggest syndeformational ore deposition, possibly related to the Youjiang fault system. Several sedimentary rock-hosted Au deposits in the Dian-Qian-Gui area also are of the red earth-type and Au grades have been concentrated and enhanced during episodes of deep weathering. ?? 2006 Elsevier B.V. All rights reserved.

10 CFR 960.4-2-3 - Rock characteristics.

Code of Federal Regulations, 2010 CFR

2010-01-01

... thermal, chemical, mechanical, and radiation stresses expected to be induced by repository construction, operation, and closure and by expected interactions among the waste, host rock, ground water, and engineered... repository construction, operation, or closure or by interactions among the waste, host rock, ground water...

10 CFR 960.4-2-3 - Rock characteristics.

Code of Federal Regulations, 2011 CFR

2011-01-01

... thermal, chemical, mechanical, and radiation stresses expected to be induced by repository construction, operation, and closure and by expected interactions among the waste, host rock, ground water, and engineered... repository construction, operation, or closure or by interactions among the waste, host rock, ground water...

Geochemistry of host rocks in the Howards Pass district, Yukon-Northwest Territories, Canada: implications for sedimentary environments of Zn-Pb and phosphate mineralization

USGS Publications Warehouse

Slack, John F.; Falck, Hendrik; Kelley, Karen D.; Xue, Gabriel G.

2017-01-01

Detailed lithogeochemical data are reported here on early Paleozoic sedimentary rocks that host the large Howards Pass stratiform Zn-Pb deposits in Yukon-Northwest Territories. Redox-sensitive trace elements (Mo, Re, V, U) and Ce anomalies in members of the Duo Lake Formation record significant environmental changes. During the deposition of lower footwall units (Pyritic siliceous and Calcareous mudstone members), bottom waters were anoxic and sulphidic, respectively; these members formed in a marginal basin that may have become increasingly restricted with time. Relative to lower members, a major environmental change is proposed for deposition of the overlying Lower cherty mudstone member, which contains phosphorite beds up to ∼0.8 m thick in the upper part, near the base of the Zn-Pb deposits. The presence of these beds, together with models for modern phosphorite formation, suggests P input from an upwelling system and phosphorite deposition in an upper slope or outer shelf setting. The overlying Active mudstone member contains stratabound to stratiform Zn-Pb deposits within black mudstone and gray calcareous mudstone. Data for unmineralized black mudstone in this member indicate deposition under diverse redox conditions from suboxic to sulphidic. Especially distinctive in this member are uniformly low ratios of light to heavy rare earth elements that are unique within the Duo Lake Formation, attributed here to the dissolution of sedimentary apatite by downward-percolating acidic metalliferous brines. Strata that overlie the Active member (Upper siliceous mudstone member) consist mainly of black mudstone with thin (0.5–1.5 cm) laminae of fine-grained apatite, recording continued deposition on an upper slope or outer shelf under predominantly suboxic bottom waters. Results of this study suggest that exploration for similar stratiform sediment-hosted Zn-Pb deposits should include the outer parts of ancient continental margins, especially at and near stratigraphic transitions from marginal basin facies to overlying slope or shelf facies.

Computational and Experimental Investigation of Contaminant Plume Response to DNAPL Source Zone Architecture and Depletion in Porous and Fractured Media

DTIC Science & Technology

2013-09-01

Mass in the Rock Matrix. Table 4.8.5.1: Flow and Transport Parameters Used for TCE Dissolution Modeling in Discrete Fracture Approach. Table 4.8.5.2...represent the flow rate over time. Figure 4.8.4.5: The Profile of Estimated Diffusing TCE Front into the Rock Matrix. Figure 4.8.5.1: a) Mesh Used for TCE...fractured rocks . The work of Illman et al. (2009) motivates us to conduct a laboratory fractured rock block experiment in which a large number of pumping

Hydrogeochemical processes and geochemical modeling in a coastal aquifer: Case study of the Marathon coastal plain, Greece

NASA Astrophysics Data System (ADS)

Papazotos, Panagiotis; Koumantakis, Ioannis; Kallioras, Andreas; Vasileiou, Eleni; Perraki, Maria

2017-04-01

Determining the hydrogeochemical processes has always been a challenge for scientists. The aim of this work is the study of the principal hydrogeochemical processes controlling groundwater quality in the Marathon coastal plain, Greece, with emphasis on the origin of the solutes. Various physicochemical parameters and major ions of twenty-five groundwater samples were analyzed. The hydrogeochemical data of groundwater were studied in order to determine the major factors controlling the chemical composition and hydrogeochemical evolution. In the Marathon coastal plain, three different zones of the alluvial granular aquifer system have been detected, considering the geochemical processes and recharge, which affect its hydrochemical characteristics. The alluvial granular aquifer system is divided eastwards into three zones: a) the natural recharge zone, b) the reverse ion exchange zone and c) the diffusion sea water zone. Cl-is the dominant anion and Na+and Ca2+ are the dominant cations, as determined by plotting the analyses on the respective Piper diagram. Near the coastline high concentrations of Na+ and Cl- were observed indicating a zone of seawater intrusion. On the other hand, westward there is increasing concentration of HCO3- with simultaneous decrease of Na+is indication of a recharge zone from karstic aquifers of the study area. Between the aforementioned zones there is an intermediate one, where reverse ion exchange takes place due to high concentrations of dissolved Na+ and Ca2+ adsorption. The saturation indices (SI) were calculated using the geochemical modeling software PHREEQC. Mineral phases of halite, sylvite, gypsum and anhydrite were estimated to be undersaturated in the water samples, suggesting these phases are minor or absent in the host rock. On the other hand, calcite, aragonite and dolomite are close to equilibrium; these minerals are present in the host rocks or in the unsaturated zone, possibly increasing the Ca2+, Mg2+ and HCO3- concentrations when carbonates are dissolved. The analyses of the bivariate scatter plots, the ionic ratios, the Indices of Base Exchange (IBE), the Gibbs diagram and the dissolution/precipitation reactions show that evaporation and water-rock interaction mechanisms such as dissolution of carbonates, followed by reverse ion exchange, have affected the groundwater chemistry in the study area. The results revealed that groundwater chemistry and therefore the origin of the solutes in the coastal alluvial granular aquifer system of the Marathon coastal plain is primarily affected by a number of factors such as groundwater and mineral equilibrium, seawater intrusion, reverse ion exchange and nitrate concentration. A possible future research could focus on the interaction among hydrogeochemistry, mineral phases and chemical thermodynamic modeling.

Effect of mineral constituents in the bioleaching of uranium from uraniferous sedimentary rock samples, Southwestern Sinai, Egypt.

PubMed

Amin, Maisa M; Elaassy, Ibrahim E; El-Feky, Mohamed G; Sallam, Abdel Sattar M; Talaat, Mona S; Kawady, Nilly A

2014-08-01

Bioleaching, like Biotechnology uses microorganisms to extract metals from their ore materials, whereas microbial activity has an appreciable effect on the dissolution of toxic metals and radionuclides. Bioleaching of uranium was carried out with isolated fungi from uraniferous sedimentary rocks from Southwestern Sinai, Egypt. Eight fungal species were isolated from different grades of uraniferous samples. The bio-dissolution experiments showed that Aspergillus niger and Aspergillus terreus exhibited the highest leaching efficiencies of uranium from the studied samples. Through monitoring the bio-dissolution process, the uranium grade and mineralogic constituents of the ore material proved to play an important role in the bioleaching process. The tested samples asserted that the optimum conditions of uranium leaching are: 7 days incubation time, 3% pulp density, 30 °C incubation temperature and pH 3. Both fungi produced the organic acids, namely; oxalic, acetic, citric, formic, malonic, galic and ascorbic in the culture filtrate, indicating an important role in the bioleaching processes. Copyright © 2014 Elsevier Ltd. All rights reserved.

Limestone weathering rates accelerated by micron-scale grain detachment

NASA Astrophysics Data System (ADS)

Emmanuel, S.; Levenson, Y.

2014-12-01

The weathering rates of carbonate rocks is often thought to be controlled by chemical dissolution, although some studies have suggested that mechanical erosion could also play an important role. Quantifying the rates of the different processes has proved challenging due to the high degree of variability encountered in both field and lab settings. To determine the rates and mechanisms controlling long-term limestone weathering, we analyse a lidar scan of the Western Wall, a Roman period edifice located in Jerusalem. Weathering rates in fine-grained micritic limestone blocks are up to 2 orders of magnitude higher than the average rates estimated for coarse-grained limestone blocks at the same site. In addition, in experiments that use atomic force microscopy to image dissolving micritic limestone, we show that these higher reaction rates could be due to rapid dissolution along micron-scale grain boundaries, followed by mechanical detachment of tiny particles from the surface. Our analysis indicates that micron-scale grain detachment, rather than pure chemical dissolution, could be the dominant erosional mode for fine-grained rocks in many carbonate terrains.

Extreme limestone weathering rates due to micron-scale grain detachment

NASA Astrophysics Data System (ADS)

Emmanuel, Simon; Levenson, Yael

2014-05-01

Chemical dissolution is often assumed to control the weathering rates of carbonate rocks, although some studies have indicated that mechanical erosion could also play a significant role. Quantifying the rates of the different processes is challenging due to the high degree of variability encountered in both field and lab settings. To measure the rates and mechanisms controlling long-term limestone weathering, we analyse a lidar scan of the Western Wall, a Roman period edifice located in Jerusalem. Surface retreat rates in fine-grained micritic limestone blocks are found to be as much as 2 orders of magnitude higher than the average rates estimated for coarse-grained limestone blocks at the same site. In addition, in experiments that use atomic force microscopy to image dissolving micritic limestone, we show that these elevated reaction rates could be due to rapid dissolution along micron-scale grain boundaries, followed by mechanical detachment of tiny particles from the surface. Our analysis indicates that micron-scale grain detachment, rather than pure chemical dissolution, could be the dominant erosional mode for fine-grained carbonate rocks.

10 CFR 960.4-2-2 - Geochemistry.

Code of Federal Regulations, 2012 CFR

2012-01-01

.... Considering the likely chemical interactions among radionuclides, the host rock, and the ground water, the... the rock matrix, or sorption of radionuclides; inhibit the formation of particulates, colloids... geochemical conditions and a volumetric flow rate of water in the host rock that would allow less than 0.001...

Reactive Transport at the Pore Scale with Applications to the Dissolution of Carbonate Rocks for CO2 Sequestration Operations

NASA Astrophysics Data System (ADS)

Boek, E.; Gray, F.; Welch, N.; Shah, S.; Crawshaw, J.

2014-12-01

In CO2 sequestration operations, CO2 injected into a brine aquifer dissolves in the liquid to create an acidic solution. This may result in dissolution of the mineral grains in the porous medium. Experimentally, it is hard to investigate this process at the pore scale. Therefore we develop a new hybrid particle simulation algorithm to study the dissolution of solid objects in a laminar flow field, as encountered in porous media flow situations. First, we calculate the flow field using a multi-relaxation-time lattice Boltzmann (LB) algorithm implemented on GPUs, which demonstrates a very efficient use of the GPU device and a considerable performance increase over CPU calculations. Second, using a stochastic particle approach, we solve the advection-diffusion equation for a single reactive species and dissolve solid voxels according to our reaction model. To validate our simulation, we first calculate the dissolution of a solid sphere as a function of time under quiescent conditions. We compare with the analytical solution for this problem [1] and find good agreement. Then we consider the dissolution of a solid sphere in a laminar flow field and observe a significant change in the sphericity with time due to the coupled dissolution - flow process. Second, we calculate the dissolution of a cylinder in channel flow in direct comparison with corresponding dissolution experiments. We discuss the evolution of the shape and dissolution rate. Finally, we calculate the dissolution of carbonate rock samples at the pore scale in direct comparison with micro-CT experiments. This work builds on our recent research on calculation of multi-phase flow [2], [3] and hydrodynamic dispersion and molecular propagator distributions for solute transport in homogeneous and heterogeneous porous media using LB simulations [4]. It turns out that the hybrid simulation model is a suitable tool to study reactive flow processes at the pore scale. This is of great importance for CO2 storage and Enhanced Oil Recovery applications. References[1] Rice, R. G. and Do, D.D., Chem. Eng. Sci., 61, 775-778 (2006)[2] Boek, E.S. and Venturoli, M., Comp. and Maths with Appl. 59, 2305-2314 (2010)[3] Yang, J. and Boek, E.S., Comp. and Maths with Appl. 65, 882-890 (2013)[4] Yang, J. Crawshaw, J. and Boek, E.S., Water Resources Research 49, 8531-8538 (2013)

Track of fluid paleocirculation in dolomite host rock at regional scale by the Anisotropy of Magnetic Susceptibility (AMS): An example from Aptian carbonates of La Florida, Northern Spain

NASA Astrophysics Data System (ADS)

Essalhi, Mourad; Sizaret, Stanislas; Barbanson, Luc; Chen, Yan; Branquet, Yannick; Panis, Dominique; Camps, Pierre; Rochette, Pierre; Canals, Angels

2009-01-01

The present study aims to apply the AMS method (Anisotropy of Magnetic Susceptibility) at a regional scale to track the fluid circulation direction that has produced an iron metasomatism within pre-existing dolomite host rock. The Urgonian formations hosting the Zn-Pb mineralizations in La Florida (Cantabria, northern Spain) have been taken as target for this purpose. Sampling was carried out, in addition to ferroan dolomite host rock enclosing the Zn-Pb mineralizations, in dolomite host rock and limestone to make the comparison possible between magnetic signals from mineralized rocks, where fluid circulation occurred, and their surrounding formations. AMS study was coupled with petrofabric analysis carried out by texture goniometry, Scanning Electron Microscopy (SEM) observations and also Shape Preferred Orientation (SPO) statistics. SEM observations of ferroan dolomite host rock illustrate both bright and dark grey ribbons corresponding respectively to Fe enriched and pure dolomites. SPO statistics applied on four images from ferroan dolomite host rock give a well-defined orientation of ribbons related to the intermediate axis of magnetic susceptibility K2. For AMS data, two magnetic fabrics are observed. The first one is observed in ferroan dolomite host rock and characterized by a prolate ellipsoid of magnetic susceptibility with a vertical magnetic lineation. The magnetic susceptibility carrier is Fe-rich dolomite. These features are probably acquired during metasomatic fluid circulations. In Fe-rich dolomite host rock, ‹ c› axes are vertical. As a rule, (0001) planes (i.e. planes perpendicular to ‹ c› axes) are isotropic with respect to crystallographic properties. So, the magnetic anisotropy measured in this plane should reflect crystallographic modification due to fluid circulation. This is confirmed by the texture observed using the SEM. Consequently, AMS results show a dominant NE-SW elongation interpreted as the global circulation direction and a NW-SE secondary elongation that we have considered as sinuosities of the fluid trajectory. The second type of magnetic fabric is essentially observed in the limestone and characterized by an oblate form of the ellipsoid of magnetic susceptibility, a horizontal magnetic foliation and mixed magnetic susceptibility carriers. It is interpreted as a sedimentary fabric.

Hydrogeochemical processes controlling changes in fluoride ion concentration within alluvial and hard rock aquifers in a part of a semi-arid region of Northern India

NASA Astrophysics Data System (ADS)

Singh, Priyadarshini; Ashthana, Harshita; Rena, Vikas; Kumar, Pardeep; Mukherjee, Saumitra

2017-04-01

Geochemical signatures from alluvial and hard rock aquifers in a part of Northern India elucidate the chemical processes controlling fluctuations in fluoride ion concentration linked to changes in major ion groundwater chemistry. Majority of samples from the hard rock and the alluvial aquifers for pre-monsoon show both carbonate and silicate weathering, ion exchange, evaporation and rock water interaction as the processes controlling major ion chemistry whereas for post monsoon samples, contribution of silicate weathering and ion exchange process were observed. Evaporative processes causing the increase in Na+ ion concentration in premonsoon enhance the reverse ion exchange processes causing increase in Ca2+ ions which impedes fluorite mineral dissolution in the premonsoon groundwater samples within the study area. Alternately, it is observed that the removal of Ca2+ ion from solution plays a key role in increase in fluorite mineral dissolution despite its saturation in groundwater in the postmonsoon samples. Also, ion exchange process on clay surfaces is more pronounced in the postmonsoon samples leading to the uptake of Ca2+ ion upon release of Na+ and K+ ion in solution. Ca2+ ion concentration is inversely correlated with F- ion concentration in both the aquifers in the postmonsoon season validating the role of calcite precipitation as a major reason for the fluoride ion increase. Moreover, increase in silicate weathering in the postmonsoon samples leads to increase in clay particles acting as suitable sites for ion exchange enhancing Ca2+ removal from groundwater. Cationic dominance of Na+ ion in the post monsoon samples also validates the occurrence of this process. Collectively, these processes set the ideal conditions for increase in the fluoride ion concentration particularly in the alluvium aquifer waters in the postmonsoon season Keywords: geochemistry, ion-exchange, rock-water interaction, mineral dissolution, weathering.

Comparative Analysis of Fluoride Concentrations in Groundwaters in Northern and Southern Ghana: Implications for the Contaminant Sources

NASA Astrophysics Data System (ADS)

Sunkari, Emmanuel Daanoba; Zango, Musah Saeed; Korboe, Harriet Mateko

2018-04-01

Bongo and Sekyere South districts, both in the northern and southern parts of Ghana, respectively, have high populations living in rural areas and most of them use groundwater for drinking purposes. The groundwater in these areas is prone to contamination from natural and/or artificial sources. Therefore this study aims; (1) to present a comparative analysis of the fluoride concentration in groundwater samples from Bongo and Sekyere South districts and the associated groundwater-rock interaction that may be the cause for the varied fluoride concentrations, (2) to determine the leaching potential of fluoride from the host rocks as the possible mechanism for groundwater contamination. Sixty (60) groundwater samples from active pumping wells and twelve (12) rock samples from outcrops were collected from various communities in the two districts for fluoride concentration and mineralogical analysis. Based on the variations in fluoride concentration, fluoride spatial distribution maps were prepared using empirical Bayesian kriging interpolation method and analysed by means of hierarchical cluster analysis. The fluoride concentration in Bongo district varies between 1.71 and 4.0 mg/L, whereas that in Sekyere South district changes from 0.3 to 0.8 mg/L. From the mineralogical studies, biotite has the highest percentage in the Bongo district and has positive correlation with fluoride concentration in the analysed water samples than in the Sekyere South district. The elevated fluoride concentration in the Bongo district relative to the Sekyere South district is due to the dissolution of biotite in the groundwater and the sufficient groundwater-rock interaction since the water samples are mainly sourced from deeper boreholes. This high fluoride concentration has resulted in a plethora of reported cases of dental fluorosis and other health-related issues in Bongo.

Comparative Analysis of Fluoride Concentrations in Groundwaters in Northern and Southern Ghana: Implications for the Contaminant Sources

NASA Astrophysics Data System (ADS)

Sunkari, Emmanuel Daanoba; Zango, Musah Saeed; Korboe, Harriet Mateko

2018-05-01

Bongo and Sekyere South districts, both in the northern and southern parts of Ghana, respectively, have high populations living in rural areas and most of them use groundwater for drinking purposes. The groundwater in these areas is prone to contamination from natural and/or artificial sources. Therefore this study aims; (1) to present a comparative analysis of the fluoride concentration in groundwater samples from Bongo and Sekyere South districts and the associated groundwater-rock interaction that may be the cause for the varied fluoride concentrations, (2) to determine the leaching potential of fluoride from the host rocks as the possible mechanism for groundwater contamination. Sixty (60) groundwater samples from active pumping wells and twelve (12) rock samples from outcrops were collected from various communities in the two districts for fluoride concentration and mineralogical analysis. Based on the variations in fluoride concentration, fluoride spatial distribution maps were prepared using empirical Bayesian kriging interpolation method and analysed by means of hierarchical cluster analysis. The fluoride concentration in Bongo district varies between 1.71 and 4.0 mg/L, whereas that in Sekyere South district changes from 0.3 to 0.8 mg/L. From the mineralogical studies, biotite has the highest percentage in the Bongo district and has positive correlation with fluoride concentration in the analysed water samples than in the Sekyere South district. The elevated fluoride concentration in the Bongo district relative to the Sekyere South district is due to the dissolution of biotite in the groundwater and the sufficient groundwater-rock interaction since the water samples are mainly sourced from deeper boreholes. This high fluoride concentration has resulted in a plethora of reported cases of dental fluorosis and other health-related issues in Bongo.

Modeling of carbonate reservoir variable secondary pore space based on CT images

NASA Astrophysics Data System (ADS)

Nie, X.; Nie, S.; Zhang, J.; Zhang, C.; Zhang, Z.

2017-12-01

Digital core technology has brought convenience to us, and X-ray CT scanning is one of the most common way to obtain 3D digital cores. However, it can only provide the original information of the only samples being scanned, and we can't modify the porosity of the scanned cores. For numerical rock physical simulations, a series of cores with variable porosities are needed to determine the relationship between the physical properties and porosity. In carbonate rocks, the secondary pore space including dissolution pores, caves and natural fractures is the key reservoir space, which makes the study of carbonate secondary porosity very important. To achieve the variation of porosities in one rock sample, based on CT scanned digital cores, according to the physical and chemical properties of carbonate rocks, several mathematical methods are chosen to simulate the variation of secondary pore space. We use the erosion and dilation operations of mathematical morphology method to simulate the pore space changes of dissolution pores and caves. We also use the Fractional Brownian Motion model to generate natural fractures with different widths and angles in digital cores to simulate fractured carbonate rocks. The morphological opening-and-closing operations in mathematical morphology method are used to simulate distribution of fluid in the pore space. The established 3D digital core models with different secondary porosities and water saturation status can be used in the study of the physical property numerical simulations of carbonate reservoir rocks.

Evaluation of CO 2 -Fluid-Rock Interaction in Enhanced Geothermal Systems: Field-Scale Geochemical Simulations

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

Pan, Feng; McPherson, Brian J.; Kaszuba, John

Recent studies suggest that using supercritical CO 2 (scCO 2 ) instead of water as a heat transmission fluid in Enhanced Geothermal Systems (EGS) may improve energy extraction. While CO 2 -fluid-rock interactions at “typical” temperatures and pressures of subsurface reservoirs are fairly well known, such understanding for the elevated conditions of EGS is relatively unresolved. Geochemical impacts of CO 2 as a working fluid (“CO 2 -EGS”) compared to those for water as a working fluid (H 2 O-EGS) are needed. The primary objectives of this study are (1) constraining geochemical processes associated with CO 2 -fluid-rock interactions undermore » the high pressures and temperatures of a typical CO 2 -EGS site and (2) comparing geochemical impacts of CO 2 -EGS to geochemical impacts of H 2 O-EGS. The St. John’s Dome CO 2 -EGS research site in Arizona was adopted as a case study. A 3D model of the site was developed. Net heat extraction and mass flow production rates for CO 2 -EGS were larger compared to H 2 O-EGS, suggesting that using scCO 2 as a working fluid may enhance EGS heat extraction. More aqueous CO 2 accumulates within upper- and lower-lying layers than in the injection/production layers, reducing pH values and leading to increased dissolution and precipitation of minerals in those upper and lower layers. Dissolution of oligoclase for water as a working fluid shows smaller magnitude in rates and different distributions in profile than those for scCO 2 as a working fluid. It indicates that geochemical processes of scCO 2 -rock interaction have significant effects on mineral dissolution and precipitation in magnitudes and distributions.« less

Bats and bell holes: The microclimatic impact of bat roosting, using a case study from Runaway Bay Caves, Jamaica

NASA Astrophysics Data System (ADS)

Lundberg, Joyce; McFarlane, Donald A.

2009-05-01

The microclimatic effect of bats roosting in bell holes (blind vertical cylindrical cavities in cave roofs) in Runaway Bay Caves, Jamaica, was measured and the potential impact of their metabolism on dissolution modelled. Rock temperature measurements showed that bell holes with bats get significantly hotter than those without bats during bat roosting periods (by an average of 1.1 °C). The relationship is clearest for bell holes with more than about 300 g aggregate bat body mass and for bell holes that are moderately wide and deep, of W:D ratio between 0.8 and 1.6. Measurement of temperature decay after abandonment showed that rock temperature returns to normal each day during bat foraging periods. Metabolic activity from a typical population of 400 g bat (10 individuals) yields 41 g of CO 2, 417.6 kJ of heat, and 35.6 g of H 2O in each 18 hour roost period, and could produce a water film of ~ 0.44 mm, that is saturated with CO 2 at ~ 5%. The resultant rock dissolution is estimated at ~ 0.005 cm 3 CaCO 3 per day. The metabolic heat ensures that the focus of dissolution remains vertical regardless of geological controls. A typical bell hole 1 m deep may be formed in some 50,000 years by this mechanism alone. Addition of other erosional mechanisms, such as direct bacterial bio-erosion, or the formation of exfoliative organo-rock complexes, would accelerate the rate of formation. The hypothesis is developed that bell holes are initiated and formed by bat-mediated condensation corrosion and are governed by geographic distribution of clustering bats and their roosting behaviour.

Evaluation of CO 2 -Fluid-Rock Interaction in Enhanced Geothermal Systems: Field-Scale Geochemical Simulations

DOE PAGES

Pan, Feng; McPherson, Brian J.; Kaszuba, John

2017-01-01

Recent studies suggest that using supercritical CO 2 (scCO 2 ) instead of water as a heat transmission fluid in Enhanced Geothermal Systems (EGS) may improve energy extraction. While CO 2 -fluid-rock interactions at “typical” temperatures and pressures of subsurface reservoirs are fairly well known, such understanding for the elevated conditions of EGS is relatively unresolved. Geochemical impacts of CO 2 as a working fluid (“CO 2 -EGS”) compared to those for water as a working fluid (H 2 O-EGS) are needed. The primary objectives of this study are (1) constraining geochemical processes associated with CO 2 -fluid-rock interactions undermore » the high pressures and temperatures of a typical CO 2 -EGS site and (2) comparing geochemical impacts of CO 2 -EGS to geochemical impacts of H 2 O-EGS. The St. John’s Dome CO 2 -EGS research site in Arizona was adopted as a case study. A 3D model of the site was developed. Net heat extraction and mass flow production rates for CO 2 -EGS were larger compared to H 2 O-EGS, suggesting that using scCO 2 as a working fluid may enhance EGS heat extraction. More aqueous CO 2 accumulates within upper- and lower-lying layers than in the injection/production layers, reducing pH values and leading to increased dissolution and precipitation of minerals in those upper and lower layers. Dissolution of oligoclase for water as a working fluid shows smaller magnitude in rates and different distributions in profile than those for scCO 2 as a working fluid. It indicates that geochemical processes of scCO 2 -rock interaction have significant effects on mineral dissolution and precipitation in magnitudes and distributions.« less

The permeaiblity of fault-zones:the role of stylolites as incipit of dissolution

NASA Astrophysics Data System (ADS)

Magni, Silvana

2017-04-01

Fault zones and fractures play an important role in fluid circulation and then in dissolution, acting as barriers or conductors depending on the distribution of other features associated with them and on the specific conditions (lithological and structural, as well). The fault zone have a high permeability only in the early stages of the movement but shortly after recrystallization and reprecipitation processes greatly reduce the permeability within them. Indeed the dissolution is a complex phenomenon which involves both several factors that lead to the formation of caves and karst systems often complex. Traditionally, in the field of karst , the dissolution is associated with extensional structures such as faults and joints believing that they are more favorable to the water circulation. In this context compressional tectonic structures, as like the stylolites, are never considered. In fact the stylolites play an important role in the fluid circulation (Rawling, 2001) and in particular in the incipit of dissolution and then of the karst. We have so focused our research on the study of permeability of four fault zones in a karst area of Alte Murge (South Italy). Through a detailed structural analysis in the field and using the method of Caine (Caine, 1996), we reconstructed the permeability of the four previous fault zones. Our attention was focused on faults, joints and on stylolites. Contrary to the literature the dissolution and therefore the karst was mainly found along the stylolites and only secondarily along faults. No sign of dissolution was found along the joints. In the context of karst studies, the stylolites, which are structures due to pressure solution has never been taken into account, thinking that in compressional structures is not possible any circulation of water and that therefore there is no fluid-rock interaction. No consideration has been given to the enormous role that the pressure and the microfluidic that are created have in this context. The styololites, the focus of our research open important questions about their exact role as incipit of the dissolution. Through petrophysical analysis and microstructural we are characterizing the porosity and permeability near the stylolites. Recently, fluid-rock interactions and their impact on carbonate rocks is becoming very important because of an increasing interest it the carbonate reservoirs as a consequence of a progressive deterioration of the quantity and quality of the groundwater due to increasing pollution phenomena. In fact the aquifers represent about 40% of the drinking water resources and their importance will increase in coming years. REFERENCESE Caine, J.S.,Evans, J.P., Forster,C.B. (1996). Fault zone architecture and permeability structure. Geology 24, 1025-1032 Rawling,G.C., Goodwin,L.B., Wilson,J.L. (2001). Internal architecture permeability structure and hydrogeologic significance of contrasting fault-zone types. Geology 29, 43-46

Reactive silica transport in fractured porous media: Analytical solutions for a system of parallel fractures

NASA Astrophysics Data System (ADS)

Yang, Jianwen

2012-04-01

A general analytical solution is derived by using the Laplace transformation to describe transient reactive silica transport in a conceptualized 2-D system involving a set of parallel fractures embedded in an impermeable host rock matrix, taking into account of hydrodynamic dispersion and advection of silica transport along the fractures, molecular diffusion from each fracture to the intervening rock matrix, and dissolution of quartz. A special analytical solution is also developed by ignoring the longitudinal hydrodynamic dispersion term but remaining other conditions the same. The general and special solutions are in the form of a double infinite integral and a single infinite integral, respectively, and can be evaluated using Gauss-Legendre quadrature technique. A simple criterion is developed to determine under what conditions the general analytical solution can be approximated by the special analytical solution. It is proved analytically that the general solution always lags behind the special solution, unless a dimensionless parameter is less than a critical value. Several illustrative calculations are undertaken to demonstrate the effect of fracture spacing, fracture aperture and fluid flow rate on silica transport. The analytical solutions developed here can serve as a benchmark to validate numerical models that simulate reactive mass transport in fractured porous media.

Karst Landscape, China

NASA Image and Video Library

2014-04-28

Karst topography is a geological formation shaped by the dissolution of layers of soluble rock such as limestone. A good example is found in Guangxi Province in southeast China, as seen by NASA Terra spacecraft.

Crystalline gold in soil and the problem of supergene nugget formation: Freezing and exclusion as genetic mechanisms

USGS Publications Warehouse

Watterson, J.R.

1985-01-01

Many of the world's richest gold placer deposits now occur in cold regions despite differences in their climatic history. It therefore seems possible that there may be some fundamental connection between freezing climates and the local chemical behavior of gold in the weathering cycle. This hypothesis, along with the problematical occurrence of gold as euhedral crystals in arctic gravel and soil placers, has led me to review low temperature phenomena that may bear on the geochemistry of gold. Several effects which may influence the weathering of natural gold-bearing rocks, the chemical complexation of gold, and its subsequent mobility and deposition appear to be strongly connected with freeze action. The exclusion of dissolved solutes, solute gases, and particles from ice, subjects rock and soil minerals to increased corrosion from thin, unfrozen, adsorbed water films which remain at particle surfaces throughout the freezing of rocks and soils. The preferential exclusion of cations (over anions) from growing ice crystals creates charge separations and measurable current flow across waterice phase boundaries in freezing soil - a phenomenon which leads to troublesome seasonal electrolytic corrosion of pipelines buried in soil; this phenomenon may also favor the dissolution of normally insoluble metals such as gold during geologic time periods. The ice-induced accumulation of clays, organic acids, bacteria, and other organic matter at mineral surfaces may also speed chemical attack by providing a nearby sink of alternate cation-binding sites and hence rapid removal of liberated cations from solution. The latter mechanism may be operative in both the dissolution and redeposition of gold. These physical, chemical, and electrical effects are favorable to the dissolution of rocks (in addition to frost shattering) and to the dissolution, mobilization, and redeposition of gold and other noble metals and must therefore contribute significantly to the behavior of gold at low temperatures. The occurrence of large numbers of gold placer deposits in northern Canada, Alaska, and Siberia may thus be due in part to the low temperatures common to these regions. ?? 1985.

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.

Carbonation by fluid-rock interactions at high-pressure conditions: Implications for carbon cycling in subduction zones

NASA Astrophysics Data System (ADS)

Piccoli, Francesca; Vitale Brovarone, Alberto; Beyssac, Olivier; Martinez, Isabelle; Ague, Jay J.; Chaduteau, Carine

2016-07-01

Carbonate-bearing lithologies are the main carbon carrier into subduction zones. Their evolution during metamorphism largely controls the fate of carbon, regulating its fluxes between shallow and deep reservoirs. Recent estimates predict that almost all subducted carbon is transferred into the crust and lithospheric mantle during subduction metamorphism via decarbonation and dissolution reactions at high-pressure conditions. Here we report the occurrence of eclogite-facies marbles associated with metasomatic systems in Alpine Corsica (France). The occurrence of these marbles along major fluid-conduits as well as textural, geochemical and isotopic data indicating fluid-mineral reactions are compelling evidence for the precipitation of these carbonate-rich assemblages from carbonic fluids during metamorphism. The discovery of metasomatic marbles brings new insights into the fate of carbonic fluids formed in subducting slabs. We infer that rock carbonation can occur at high-pressure conditions by either vein-injection or chemical replacement mechanisms. This indicates that carbonic fluids produced by decarbonation reactions and carbonate dissolution may not be directly transferred to the mantle wedge, but can interact with slab and mantle-forming rocks. Rock-carbonation by fluid-rock interactions may have an important impact on the residence time of carbon and oxygen in subduction zones and lithospheric mantle reservoirs as well as carbonate isotopic signatures in subduction zones. Furthermore, carbonation may modulate the emission of CO2 at volcanic arcs over geological time scales.

Karst in evaporite rocks of the United States

USGS Publications Warehouse

Johnson, Kenneth S.

2002-01-01

Evaporites are the most soluble of common rocks; they are dissolved readily to form the same range of karst features that typically are found in limestones and dolomites. Evaporites, including gypsum (or anhydrite) and salt, are present in 32 of the 48 contiguous United States, and they underlie about 35-40% of the land area. Evaporite outcrops typically contain sinkholes, caves, disappearing streams, and springs. Other evidence of active karst in evaporites includes surface-collapse features and saline springs or saline plumes that result from dissolution of salt. Many evaporites, including some in the deeper subsurface, also contain evidence of paleokarst that is no longer active; this evidence includes dissolution breccias, breccia pipes, slumped beds, and collapse structures. Evaporites occur in 24 separate structural basins or geographic districts in the United States, and either local or extensive evaporite karst is known in almost all of these basins or districts. Human activities also have caused development of evaporite karst, primarily in salt deposits. Boreholes or underground mines may enable (either intentionally or inadvertently) unsaturated water to flow through or against salt deposits, thus allowing development of small to large dissolution cavities. If the dissolution cavity is large enough and shallow enough, successive roof failures can cause land subsidence or catastrophic collapse. Evaporite karst, both natural and human-induced, is far more prevalent than commonly believed.

Evidence for Differential Comminution/Aeolian Sorting and Chemical Weathering of Martian Soils Preserved in Mars Meteorite EET79001

NASA Technical Reports Server (NTRS)

Rao, M. N.; McKay, David S.

2004-01-01

Impact-melt glasses containing Martian atmospheric gases in Mars meteorite EET79001 are formed from Martian soil fines that had undergone meteoroid-comminution and aeolian sorting accompanied by chemical weathering near Mars surface. Using SiO2 and SO3 as proxy for silicates and salts respectively in Mars soils, we find that SiO2 and SO3 correlate negatively with FeO and MgO and positively with Al2O3 and CaO in these glasses, indicating that the mafic and felsic components are depleted and enriched relative to the bulk host (Lith A/B) respectively as in the case of Moon soils. Though the overall pattern of mineral fractionation is similar between the soil fines on Mars and Moon, the magnitudes of the enrichments/depletions differ between these sample-suites because of pervasive aeolian activity on Mars. In addition to this mechanical processing, the Martian soil fines, prior to impact-melting, have undergone acid-sulfate dissolution under oxidizing/reducing conditions. The S03 content in EET79001,507 (Lith B) glass is approx.18% compared to < 2% in EET79001, 506 (Lith A). SiO2 and SO3 negatively correlate with each other in ,507 glasses similar to Pathfinder soils. The positive correlation found between FeO and SO3 in ,507 glasses as well as Pathfinder rocks and soils is consistent with the deposition of ferric-hydroxysulfate on regolith grains in an oxidizing environment. As in the case of Pathfinder soils, the Al 2O3 vs SiO2 positive correlation and FeO VS S102 negative correlation observed in ,507 glasses indicate that SiO2 from the regolith is mobilized as soluble silicic acid at low pH. The large off-set in the end-member FeO abundance ( SO3=0) between Pathfinder soil-free rock and sulfur-free rock in ,507 glass precursors suggests that the soils comprising the ,507 glasses contain much larger proportion of fine-grained Martian soil fraction that registers strong mafic depletion relative to Lith B. This inference is strongly supported by the Al2O3 - SO3 negative correlation observed in both ,507 glasses and pathfinder soils. Furthermore, the flat MgO-SO3 correlation observed in the case of ,507 glasses shows that the solubilized MgSO4 is mobilized by the aqueous solutions leaving behind the rock-residue with approx.2-3% MgO. This value is similar to the approx.2% MgO found for the soil-free rock at the Pathfinder site. The EET79001 ,506 glasses, in contrast, show that Al2O3 and CaO positively correlate with SO3 indicating that Al is precipitated as amorphous hydroxysulfate at relatively high pH. The FeO - SO3 negative correlation observed in ,506 glasses yields an end-member FeO abundance of approx.21% for the sulfur-free rock, which is consistent with the 22% FeO deduced for the Viking soil-free rock. Further, the FeO and MgO negative correlation with S03 observed in ,506 glasses indicates that the divalent Fe and Mg released from ferromagnesian minerals by acid sulfate dissolution are mobilized away from the reaction sites as soluble sulfates under reducing environment. A similar negative correlation between FeO and SO3 and a positive correlation between Al2O3 and SO3 found in Viking soils suggest that they also had undergone acid-sulfate dissolution under relatively reducing conditions.

Mixing from below in hydrothermal ore deposits

NASA Astrophysics Data System (ADS)

Bons, Paul D.; Gomez-Rivas, Enrique; Markl, Gregor; Walter, Bejamin

2014-05-01

Unconformity-related hydrothermal ore deposits typically show indications of mixing of two end-member fluids: (a) hot, deep, rock-buffered basement brines and (b) colder fluids derived from the surface or overlying sediments. The hydromechanics of bringing these fluids together from above and below remain unclear. Classical percolative Darcy-flow models are inconsistent with (1) fluid overpressure indicated by fracturing and brecciation, (2) fast fluid flow indicated by thermal disequilibrium, and (3) strong fluid composition variations on the mm-scale, indicated by fluid inclusion analyses (Bons et al. 2012; Fusswinkel et al. 2013). We propose that fluids first descend, sucked down by desiccation reactions in exhumed basement. Oldest fluids reach greatest depths, where long residence times and elevated temperatures allow them the extensively equilibrate with their host rock, reach high salinity and scavenge metals, if present. Youngest fluids can only penetrate to shallower depths and can (partially) retain signatures from their origin, for example high Cl/Br ratios from the dissolution of evaporitic halite horizons. When fluids are released from all levels of the crustal column, these fluids mix during rapid ascent to form hydrothermal ore deposits. Mixing from below provides a viable hydromechanical mechanism to explain the common phenomenon of mixed shallow and deep fluids in hydrothermal ore deposits. Bons, P.D., Elburg, M.A., Gomez-Rivas, E. 2012. A review of the formation of tectonic veins and their microstructures. J. Struct. Geol. doi:10.1016/j.jsg.2012.07.005 Fusswinkel, T., Wagner, T., Wälle, M., Wenzel, T., Heinrich, C.A., Markl, M. 2013. Fluid mixing forms basement-hosted Pb-Zn deposits: Insight from metal and halogen geochemistry of individual fluid inclusions. Geology. doi:10.1130/G34092.1

Origin of the volcanic-hosted Yamansu Fe deposit, Eastern Tianshan, NW China: constraints from pyrite Re-Os isotopes, stable isotopes, and in situ magnetite trace elements

NASA Astrophysics Data System (ADS)

Huang, Xiao-Wen; Zhou, Mei-Fu; Beaudoin, Georges; Gao, Jian-Feng; Qi, Liang; Lyu, Chuan

2018-01-01

The Yamansu Fe deposit (32 Mt at 51% Fe) in the Eastern Tianshan Orogenic Belt of NW China is hosted in early Carboniferous volcano-sedimentary rocks and spatially associated with skarn. The paragenetic sequence includes garnet-diopside (I), magnetite (II), hydrous silicate-sulfide (III), and calcite-quartz (IV) stages. Pyrite associated with magnetite has a Re-Os isochron age of 322 ± 7 Ma, which represents the timing of pyrite and, by inference, magnetite mineralization. Pyrite has δ 34SVCDT values of - 2.2 to + 2.9‰, yielding δ 34SH2S values of - 3.1 to 2‰, indicating the derivation of sulfur from a magmatic source. Calcite from stages II and IV has δ 13CVPDB values from - 2.5 to - 1.2‰, and - 1.1 to 1.1‰, and δ 18OVSMOW values from 11.8 to 12.0‰ and - 7.7 to - 5.2‰, respectively. Calculated δ 13C values of fluid CO2 and water δ 18O values indicate that stage II hydrothermal fluids were derived from magmatic rocks and that meteoric water mixed with the hydrothermal fluids in stage IV. Some ores contain magnetite with obvious chemical zoning composed of dark and light domains in BSE images. Dark domains have higher Mg, Al, Ca, Mn, and Ti but lower Fe and Cr contents than light domains. The chemical zoning resulted from a fluctuating fluid composition and/or physicochemical conditions (oscillatory zoning), or dissolution-precipitation (irregular zoning) via infiltration of magmatic-hydrothermal fluids diluted by late meteoric water. Iron was mainly derived from fluids similar to that in skarn deposits.

Critical elements in sediment-hosted deposits (clastic-dominated Zn-Pb-Ag, Mississippi Valley-type Zn-Pb, sedimentary rock-hosted Stratiform Cu, and carbonate-hosted Polymetallic Deposits): A review: Chapter 12

USGS Publications Warehouse

Marsh, Erin; Hitzman, Murray W.; Leach, David L.

2016-01-01

Some sediment-hosted base metal deposits, specifically the clastic-dominated (CD) Zn-Pb deposits, carbonate-hosted Mississippi Valley-type (MVT) deposits, sedimentary-rock hosted stratiform copper deposits, and carbonate-hosted polymetallic (“Kipushi type”) deposits, are or have been important sources of critical elements including Co, Ga, Ge, and Re. The generally poor data concerning trace element concentrations in these types of sediment-hosted ores suggest that there may be economically important concentrations of critical elements yet to be recognized.

Organic tissues, graphite, and hydrocarbons in host rocks of the Rum Jungle Uranium Field, northern Australia

USGS Publications Warehouse

Foster, C.B.; Robbins, E.I.; Bone, Y.

1990-01-01

The Rum Jungle Uranium field consists of at least six early Proterozoic deposits that have been mined either for uranium and/or the associated base and precious metals. Organic matter in the host rocks of the Whites Formation and Coomalie Dolomite is now predominantly graphite, consistent with the metamorphic history of these rocks. For nine samples, the mean total organic carbon content is high (3.9 wt%) and ranged from 0.33 to 10.44 wt%. Palynological extracts from the host rocks include black, filamentous, stellate (Eoastrion-like), and spherical morphotypes, which are typical of early Proterozoic microbiota. The colour, abundance, and shapes of these morphotypes reflect the thermal history, organic richness, and probable lacustrine biofacies of the host rocks. Routine analysis of rock thin sections and of palynological residues shows that mineral grains in some of the host rocks are coated with graphitized organic matter. The grain coating is presumed to result from ultimate thermal degradation of a petroleum phase that existed prior to metamorphism. Hydrocarbons are, however, still present in fluid inclusions within carbonates of the Coomalie Dolomite and lower Whites Formation. The fluid inclusions fluoresce dull orange in blue-light excitation and their hydrocarbon content is confirmed by gas chromatography of whole-rock extracts. Preliminary analysis of the oil suggests that it is migrated, and because it has escaped graphitization through metamorphism it is probably not of early Proterozoic age. The presence of live oil is consistent with fluid inclusion data that suggest subsequent, low-temperature brine migration through the rocks. The present observations support earlier suggestions that organic matter in the host formations trapped uranium to form protore. Subsequent fluid migrations probably brought additional uranium and other metals to these formations, and the organic matter provided a reducing environment for entrapment. ?? 1990.

N2-fixing legumes are linked to enhanced mineral dissolution and microbiome modulations in Neotropical rainforests

NASA Astrophysics Data System (ADS)

Epihov, Dimitar; Batterman, Sarah; Hedin, Lars; Saltonstall, Kristin; Hall, Jefferson; Leake, Jonathan; Beerling, David

2017-04-01

Legumes represent the dominant family of many tropical forests with estimates of 120 billion legume trees in the Amazon basin alone. Many rainforest legume trees form symbioses with N2-fixing bacteria. In the process of atmospheric N2-fixation large amounts of nitrogen-rich litter are generated, supplying half of all nitrogen required to support secondary rainforest succession. However, it is unclear how N2-fixers affect the biogeochemical cycling of other essential nutrients by affecting the rates of mineral dissolution and rock weathering. Here we show that N2-fixing legumes in young Panamanian rainforests promote acidification and enhance silicate rock weathering by a factor of 2 compared to non-fixing trees. We report that N2-fixers also associate with enhanced dissolution of Al- and Fe-bearing secondary minerals native to tropical oxisols. In legume-rich neighbourhoods, non-fixers benefited from raised weathering rates relative to those of legume-free zones thus suggesting a positive community effect driven by N2-fixers. These changes in weathering potential were tracked by parallel functional and structural changes in the soil and rock microbiomes. Our findings support the view that N2-fixing legumes are central components of biogeochemical cycling, associated with enhanced release of Fe- and Al-bound P and primary mineral products (Mg, Mo). Rainforest legume services therefore bear important implications to short-term C cycling related to forest growth and the long-term C cycle related to marine carbonate deposition fuelled by silicate weathering.

Effect of bacteria and dissolved organics on mineral dissolution kinetics:

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg; Shirokova, Liudmila; Benezeth, Pascale; Zabelina, Svetlana

2010-05-01

Quantification of the effect of microorganisms and associated organic ligands on mineral dissolution rate is one among the last remaining challenges in modeling of water-rock interactions under earth surface and subsurface environments. This is especially true for deep underground settings within the context of CO2 capture, sequestration and storage. First, elevated CO2 pressures create numerous experimental difficulties for performing robust flow-through experiments at a given saturation state. Second, reactivity of main rock-forming minerals in abiotic systems at pCO2 >> 1 atm and circumneutral pH is still poorly constrained. And third, most of microbial habitats of the subsurface biosphere are not suitable for routine culturing in the laboratory, many of them are anaerobic and even strictly anaerobic, and many bacteria and archae cultures can live only in the consortium of microorganisms which is very hard to maintain at a controlled and stable biomass concentration. For experimental modeling of bio-mineral interactions in the laboratory, two other main conceptual challenges exist. Typical concentration of dissolved organic carbon that serves as a main nutrient for heterotrophic bacteria in underground waters rarely exceeds 3-5 mg/L. Typical concentration of DOC in nutrient media used for bacteria culturing is between 100 and 10,000 mg/L. Therefore, performing mineral-bacteria interactions in the laboratory under environmentally-sound conditions requires significant dilution of the nutrient media or the use of flow-through reactors. Concerning the effect of organic ligands and bacterial excudates on rock-forming mineral dissolution, at the present time, mostly empirical (phenomenological) approach can be used. Indeed, the pioneering studies of Stumm and co-workers have established a firm basis for modeling the catalyzing and inhibiting effects of ligands on metal oxide dissolution rate. This approach, very efficient for studying the interaction of organic and inorganic ligands with trivalent metal oxides, is based on applying multiple spectroscopic techniques allowing to reveal the chemical structure of adsorbed complexes. However, due to i) low surface area of most rock-forming minerals (carbonates, non-clay silicates), ii) difficulties of applying surface spectroscopic techniques at elevated pressures, and iii) very complex nature of bacterial exometabolites, it is not possible at the present time, to use rigorous surface complexation approach for rationalizing ligand- and bacteria-affected mineral dissolution under sub-surface CO2 storage environment. In this work, we present examples of overcoming these difficulties via concerted study of olivine, wollastonite and calcite interaction with heterotrophic bacteria and methanogenic archaes.

Preliminary Map of Potentially Karstic Carbonate Rocks in the Central and Southern Appalachian States

USGS Publications Warehouse

Weary, David J.

2008-01-01

Karst is a landscape produced by dissolution of rocks and the development of integrated subterranean drainages dominated by the flow of ground water in solutionally enlarged conduits. Karst landscapes typically include cave entrances, sinkholes, blind valleys, losing streams, springs, and large and small-scale solution features on bedrock surfaces. Water-bearing rocks beneath the surface containing solutionally enlarged pores, fractures, or conduits are referred to as karst aquifers. About 40 percent of all ground water extracted in the United States comes from karst aquifers (Karst Waters Institute). Karst means many things to many people. To most cavers and many speleologists, karst means areas containing caves. To engineers, home builders, local governments, and insurance companies, karst is exemplified by the occurrence of sinkholes and subsidence hazard. To hydrologists, well drillers, and environmental consultants, the focus on karst may be more limited to karst aquifers and springs. Precise figures are not available, but ground collapses in karst areas in the United States require hundreds of millions of dollars in repair and mitigation costs each year. Most karst in the United States is formed in either carbonate or evaporite rocks. This map depicts only areas of carbonate rock outcrop, the chief host for karst formation in the eastern United States. The U.S. Geological Survey (USGS), in cooperation with the National Cave and Karst Research Institute (NCKRI), the National Speleological Society (NSS), and various State geological surveys, is working on a new national karst map that will delineate areas of karst and karst-like features nationwide. This product attempts to identify potentially karstic areas of the Appalachian states as defined by the Appalachian Regional Commission (ARC), with the addition of the state of Delaware. This map is labeled preliminary because there is an expectation that it will be revised and updated as part of a new national karst map.

Lead isotopes and trace metals in dust at Yucca Mountain

USGS Publications Warehouse

Kwak, Loretta; Neymark, Leonid A.; Peterman, Zell E.

2008-01-01

Lead (Pb)-isotope compositions and trace-metal concentrations were determined for samples of dust collected from underground and surface locations at and near the proposed radioactive waste repository at Yucca Mountain, Nevada. Rare earth element concentrations in the dust samples from the underground tunnels are similar to those in wholerock samples of the repository host rocks (Miocene Tiva Canyon Tuff and Topopah Spring Tuff), supporting interpretation that the subsurface dust is mainly composed of rock comminuted during tunnel construction. Other trace metals (arsenic, cadmium, cobalt, chromium, copper, manganese, nickel, lead, antimony, thallium, and zinc) are variably enriched in the subsurface dust samples relative to the average concentrations in the host rocks. Average concentrations of arsenic and lead in dust samples, high concentrations of which can cause corrosion of waste canisters, have enrichment factors from 1.2 to 1.6 and are insignificant relative to the range of concentrations for these metals observed in the host rock samples. Most dust samples from surface sites also are enriched in many of these trace metals relative to average repository host rocks. At least some of these enrichments may be artifacts of sampling. Plotted on a 208Pb/206Pb-207Pb/206Pb graph, Pb-isotope compositions of dust samples from underground sites form a mixing line extending from host-rock Pb-isotope compositions towards compositions of many of the dust samples from surface sites; however, combined Pb concentration and isotope data indicate the presence of a Pbenriched component in the subsurface dust that is not derived from host rock or surface dust and may derive from anthropogenic materials introduced into the underground environment.

Electrokinetic mechanism of wettability alternation at oil-water-rock interface

NASA Astrophysics Data System (ADS)

Tian, Huanhuan; Wang, Moran

2017-12-01

Design of ions for injection water may change the wettability of oil-brine-rock (OBR) system, which has very important applications in enhanced oil recovery. Though ion-tuned wettability has been verified by various experiments, the mechanism is still not clear. In this review paper, we first present a comprehensive summarization of possible wettability alteration mechanisms, including fines migration or dissolution, multicomponent ion-exchange (MIE), electrical double layer (EDL) interaction between rock and oil, and repulsive hydration force. To clarify the key mechanism, we introduce a complete frame of theories to calculate attribution of EDL repulsion to wettability alteration by assuming constant binding forces (no MIE) and rigid smooth surface (no fines migration or dissolution). The frame consists of three parts: the classical Gouy-Chapman model coupled with interface charging mechanisms to describe EDL in oil-brine-rock systems, three methods with different boundary assumptions to evaluate EDL interaction energy, and the modified Young-Dupré equation to link EDL interaction energy with contact angle. The quantitative analysis for two typical oil-brine-rock systems provides two physical maps that show how the EDL interaction influences contact angle at different ionic composition. The result indicates that the contribution of EDL interaction to ion-tuned wettability for the studied system is not quite significant. The classical and advanced experimental work using microfabrication is reviewed briefly on the contribution of EDL repulsion to wettability alteration and compared with the theoretical results. It is indicated that the roughness of real rock surface may enhance EDL interaction. Finally we discuss some pending questions, perspectives and promising applications based on the mechanism.

The effect of electrolytes on dolomite dissolution: nanoscale observations using in situ Atomic Force Microscopy

NASA Astrophysics Data System (ADS)

Urosevic, Maja; Ruiz-Agudo, Encarnacion; Putnis, Christine V.; Cardell, Carolina; Rodriguez-Navarro, Carlos; Putnis, Andrew

2010-05-01

Dissolution of carbonate minerals is one of the main chemical reactions occurring at shallow levels in the crust of the Earth and has a paramount importance for a wide range of geological and biological processes. Calcite (CaCO3), and to a lesser extent dolomite (CaMg(CO3)2), are the major carbonate minerals in sedimentary rocks and building stone materials. The dissolution of calcite has been thoroughly investigated over a range of conditions and solution compositions. In contrast, dolomite dissolution studies have been traditionally hampered by its low reaction rates compared to calcite and its poorly constrained relationship between cation ordering and reactivity (Morse and Arvidson, 2002). Yet important questions like the so-called 'dolomite problem' (e.g. Higgins and Hu, 2005) remain unresolved and more experimental work is needed in order to understand the role of other dissolved species, such as soluble salts, on the kinetics and mechanism of dolomite dissolution and precipitation. We have explored the effect of different electrolytes on the dissolution rate of dolomite by using in situ Atomic Force Microcopy (AFM). Experiments were carried out by passing alkali halide, nitrate and sulfate salt solutions (NaCl, KCl, LiCl, NaI, NaNO3 and Na2SO4) with different ionic strengths (IS = 10-3, 10-2 and 10-1) over dolomite {1014} cleavage surfaces. We show that all electrolytes tested enhance dolomite dissolution. Moreover, the morphology and density of etch pits are controlled by the presence of different ions in solution. The etch pit spreading rate and dolomite dissolution rate depend on both (1) the nature of the electrolyte and (2) the ionic strength. This is in agreement with recent experimental studies on calcite dissolution (Ruiz-Agudo et al., 2010). This study highlights the role of electrolytes in dolomite dissolution and points to a common behavior for carbonate minerals. Our results suggest that soluble salts may play a critical role in the weathering of carbonate rocks, both in the natural environment, as well as in stone buildings and statuary, where the amount of solutes in pore waters is significant and can vary depending on evaporation and condensation phenomena. References Higgins, S.R.; Hu, X. Self-limiting growth on dolomite: Experimental observations with in situ atomic force microscopy. Geochimica et Cosmochimica Acta, 2005, 69 (8), 2085-2094. Morse, J.W.; Arvidson, R.S. The dissolution kinetics of major sedimentary carbonate minerals. Earth-Science Reviews, 2002, 58, 51-84. Ruiz-Agudo, E.; Kowacz, M.; Putnis, C.V.; Putnis, A. The role of background electrolytes on the kinetics and mechanism of calcite dissolution. Geochimica et Cosmochimica Acta, 2010, 74, 1256-1267.

Revisiting classical silicate dissolution rate laws under hydrothermal conditions

NASA Astrophysics Data System (ADS)

Pollet-Villard, Marion; Daval, Damien; Saldi, Giuseppe; Knauss, Kevin; Wild, Bastien; Fritz, Bertrand

2015-04-01

In the context of geothermal energy, the relative intensities of primary mineral leaching and secondary mineral precipitation can affect porosity and permeability of the reservoir, thereby influencing its hydraulic performance and the efficiency of the geothermal power station. That is why the prediction of reaction kinetics of fluid/rock interactions represents a critical issue in this context. Moreover, in several geothermal systems such as the one of Soultz-sous-Forêts (Alsace, France), the circulation of aqueous fluids induces only modest modifications of their chemical composition. Therefore, fluid-rock interactions take place at close-to-equilibrium conditions, where the rate-affinity relations are poorly known and intensively debated [1]. To describe more precisely the dissolution processes, our strategy consists in investigating the dissolution of the main cleavages of K-spar minerals (one of the prevalent primary minerals in the reservoir of Soultz-sous-Forêts geothermal system) over a wide range of Gibbs free energy (ΔG) conditions. The aims are to decipher the impact of crystallographic orientation and microstructural surface modifications on the dissolution kinetics and to propose a relation between K-spar dissolution rate and ΔG. Our experimental work relies on a coupled approach which combines classical experiments of K-spar dissolution monitored by aqueous chemical analyses (ICP-AES) and innovative techniques of nm- to μm-scale characterization of solid surface (SEM, AFM, VSI) [2]. Our results confirm that K-spar dissolution is an anisotropic process: we measure a tenfold factor between the slowest and the fastest-dissolving surfaces. Moreover, the formation of etch pits on surfaces during their alteration has been evidenced on all of the different faces that have been studied. This complex evolution of the surface topography casts doubt of the relevance of a surface model based on shrinking particles and represents a possible cause of an apparent modification of silicate dissolution rate over time. In addition, we evidenced that the relation between K-spar dissolution rate and ΔG depends on the crystallographic orientation of the altered surface, and differs from the transition state theory currently implemented into geochemical codes. Importantly, this theoretical curve overestimates the dissolution rates measured in close-to-equilibrium conditions. Taken together, the new findings show promise as a means for improving the accuracy of geochemical simulations. [1] Schott, J., Pokrovsky, O. S., and Oelkers, E. H., 2009. The Link Between Mineral Dissolution/Precipitation Kinetics and Solution Chemistry. Rev Mineral Geochem 70, 207-258. [2] Daval, D., Hellmann, R., Saldi, G. D., Wirth, R., and Knauss, K. G., 2013. Linking nm-scale measurements of the anisotropy of silicate surface reactivity to macroscopic dissolution rate laws: New insights based on diopside. Geochim Cosmochim Acta 107, 121-134.

Sm-Nd and Rb-Sr isotopic systematics of the Pea Ridge Fe-P deposit and related rocks, southeast Missouri

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

Marikos, M.A.; Barton, M.D.

1993-03-01

Pea ridge is a discordant Middle Proterozoic Fe-P deposit hosted in rhyolite tuffs and flows of the 1.4--1.5 Ga St. Francois terrane. Host rocks and the deposit are cut by basalt and aplite/pegmatite dikes. The deposit overlies a blind pluton which is partially surrounded by a trachytic ring complex. In the deposit, which is mined for Fe, early Qtz+Amph+Mag+Ap rock is cut by Mag+Ap+Qtz rock. Subsequently, portions of the deposit and host rocks were brecciated, oxidized and silicified to produce a complex suite of rocks enriched in Hem+Qtz+Ksp+Mu. Late breccia pipes/dikes cut the complex and were mineralized with Bar+Ksp+Flu+Chl+Cc+REE-phosphates. Sm/Ndmore » and Rb/Sr isotopic systematics have been studied to: (1) constrain source(s) of igneous rocks and deposit components, (2) refine ages of magmatism, mineralization, and later hydrothermal activity, (3) begin regional comparison of isotopic systematics in SE Missouri Fe deposits, and (4) complement ongoing Missouri DGLS/USGS studies. Fourteen combined Sm-Nd and Rb-Sr analyses were done on materials including two host rhyolites, two nearby trachytes, two gneiss samples representing plausible basement, two intramineral dikes, and six samples of mineralization.« less

Effect of oxalate on the dissolution rates of oligoclase and tremolite (journal version)

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

Mast, M.A.; Drever, J.I.

1987-01-01

The effect of oxalate, a strong chelator for Al and other cations, on the dissolution rates of oligoclase feldspar and tremolite amphibole was investigated in a flow-through reactor at 22 deg C. Oxalate at concentrations of 0.5 and 1 mM has essentially no effect on the dissolution rate of tremolite, nor on the steady-state rate of release of Si from oligoclase. The fact that oxalate has no effect on dissolution rate suggests that detachment of Si rather than Al or Mg is the rate-limiting step. At pH 4 and 9, oxalate has no effect on the steady-state rate of releasemore » of Al, and dissolution is congruent. At pH 5 and 7, oligoclase dissolution is congruent in the presence of oxalate, but in the absence of oxalate Al is preferentially retained in the solid relative to Si. The rate of dissolution of tremolite is independent of pH over the pH range 2-5, and decreases at higher pH. The rate of dissolution of oligoclase was independent of pH over the pH range 4-9. Since the dissolution rate of these minerals is independent of pH and organic ligand concentration, the effect of acid deposition from the atmosphere on the rate of supply of cations from weathering of granitic rocks should be minor.« less

Potential Aquifer Vulnerability in Regions Down-Gradient from ...

EPA Pesticide Factsheets

Sandstone-hosted roll-front uranium ore deposits originate when U(VI) dissolved in groundwater is reduced and precipitated as insoluble U(IV) minerals. Groundwater redox geochemistry, aqueous complexation, and solute migration are instrumental in leaching uranium from source rocks and transporting it in low concentrations to a chemical redox interface where it is deposited in an ore zone typically containing the uranium minerals uraninite, pitchblende, and/or coffinite; various iron sulfides; native selenium; clays; and calcite. In situ recovery (ISR) of these uranium ores is a process of contacting the uranium mineral deposit with leaching (lixiviant) fluids via injection of the lixiviant into wells drilled into the subsurface aquifer that hosts uranium ore, while other extraction wells pump the dissolved uranium after dissolution of the uranium minerals. Environmental concerns during and after ISR include water quality impacts from: 1) potential excursions of leaching solutions away from the injection zone into down-dip, underlying, or overlying aquifers; 2) potential migration of uranium and its decay products (e.g., Ra, Rn, Pb); and, 3) potential migration of redox-sensitive trace metals (e.g., Fe, Mn, Mo, Se, V), metalloids (e.g., As), and anions (e.g., sulfate). This review describes the geochemical processes that control roll-front uranium transport and fate in groundwater systems, identifies potential aquifer vulnerabilities to ISR operations, identifies

Mineralogical and geochemical characterization of supergene Cu-Pb-Zn-V ores in the Oriental High Atlas, Morocco

NASA Astrophysics Data System (ADS)

Verhaert, Michèle; Bernard, Alain; Dekoninck, Augustin; Lafforgue, Ludovic; Saddiqi, Omar; Yans, Johan

2017-10-01

In the Moroccan High Atlas, two sulfide deposits hosted by Jurassic dolostones underwent significant weathering. In the Cu deposit of Jbel Klakh, several stages of supergene mineralization are distinguished: (1) the replacement of hypogene sulfides in the protolith (chalcopyrite) by secondary sulfides in the cementation zone (bornite, digenite, chalcocite, covellite), (2) the formation of oxidized minerals in the saprolite (malachite, azurite, brochantite) where the environment becomes more oxidizing and neutral, and (3) the precipitation of late carbonates (calcite) and iron (hydr-)oxides in the laterite. The precipitation of carbonates is related to the dissolution of dolomitic host rocks, which buffers the fluid acidity due to the oxidation of sulfides. In the Jbel Haouanit Pb-Zn deposit, the mineral assemblage is dominated by typical calamine minerals, Cu minerals (chalcocite, covellite, malachite), and a Cu-Pb-Zn vanadate (mottramite). Galena is successively weathered in anglesite and cerussite. Sphalerite is weathered in smithsonite, which is rapidly replaced by hydrozincite. Late iron (hydr-)oxides are mainly found at the top of both deposits (laterite). Both deposits are thus characterized by specific mineral zoning, from laterite to protolith, related to variations in the mineralogy and ore grades and probably caused by varying Eh-pH conditions.

Interface-coupled dissolution-precipitation processes allow a photonic crystal to replace an ionic crystal along lattice planes

NASA Astrophysics Data System (ADS)

Liesegang, Moritz; Milke, Ralf

2015-04-01

Nanocolloidal amorphous silica (SiO2×nH2O) is a major component of environmental aqueous solutions and surface coatings on rocks or mineral grains. Detailed knowledge of amorphous silica formation is indispensable for a better understanding of silicate rock alteration and diagenetic processes. We analyzed a wide range of samples from the Australian precious opal fields in South Australia and Queensland using petrographic microscopy, XRPD, SEM, and EPMA to characterize opaline silica, the mineral assemblage, and the host rock. Over the past 90 Ma the Lower Cretaceous lithologies of central Australia have undergone a weathering regime ranging from sub-tropical to arid, in which pH fluctuated from alkaline to acidic. The prolonged chemical alteration of sedimentary rocks derived from andesitic volcaniclastics and organic matter liberated large volumes of silica into solution, eventually leading to precipitation of nanocolloidal amorphous silica and formation of opal-A. A regular arrangement of close-packed uniform (monodisperse) spheres permits diffraction of white light and gives rise to the famous play-of-color. The opals in this study consist of silica spheres with an average diameter of 100-320 nm and often show a prominent core-shell structure. Two groups are separated by their relative standard deviation (RSD): monodisperse spheres (RSD<6%) and polydisperse spheres (RDS>10%). Monodisperse and polydisperse spheres are separated by their Na/K ratio, restricting the appearance of monodisperse spheres to values <1.2 and polydisperse spheres to values >3.0. We suggest that the Na/K ratio represents significant differences in the overall solution characteristics. The associated minerals (e.g., alunite, gypsum, kaolinite, K feldspar) indicate large variations of fluid composition and pH. Probably, uniform spheres grew at acidic pH, with repulsive forces large enough to arrange them in an ordered array prior to the evaporation of interstitial fluids. The investigation of fossil shells replaced by opal-A reveals clues for the understanding of structural and chemical reorganization mechanisms behind silica pseudomorphism. Fundamental knowledge about the highly selective replacement process is absent so far, impeding an adequate interpretation of the observations. The replacement of calcitic shells by amorphous silica spheres (~300 nm in size) is a unique example for the transformation of an ionic to a photonic crystal accompanied by a large size contrast of ions and spheres, respectively, but preserving lattice planes. The observed replication of polysynthetic twinning and cleavage planes of calcite by opal-A spheres indicates that silicification occurs via dissolution of shell material and immediate precipitation of amorphous silica. This follows the interface-coupled dissolution-precipitation mechanism model (Putnis and Putnis, 2007), but requires some modification to allow for open space necessary to form spheres in the 100s-nm size range with a core-shell structure. While sphere growth by a gravitational ordering process is implausible, we assume that the ordered array of monodisperse spheres forms via layer-by-layer deposition. References: Putnis A. and Putnis C.V. (2007), J. Solid State Chem., 180, 1783-1786

Inferences from Microfractures and Geochemistry in Dynamic Shale-CO2 Packed Bed Experiments

NASA Astrophysics Data System (ADS)

Radonjic, M.; Olabode, A.

2016-12-01

Subsurface storage of large volumes of carbondioxide (CO2) is expected to have long term rock-fluid interactions impact on reservoir and seal rocks properties. Caprocks, particularly sedimentary types, are the ultimate hydraulic barrier in carbon sequestration. The mineralogical components of sedimentary rocks are geochemically active under enormous earth stresses, which generate high pressure and temperature conditions. It has been postulated that in-situ mineralization can lead to flow impedance in natural fractures in the presence of favorable geochemical and thermodynamic conditions. This experimental modelling research investigated the impact of in-situ geochemical precipitation on conductivity of fractures. Geochemical analyses were performed on four different samples of shale rocks, effluent fluids and recovered precipitates both before and after CO2-brine flooding of crushed shale rocks at moderately high temperature and pressure conditions. The results showed that most significant diagenetic changes in shale rocks after flooding with CO2-brine, reflected in the effluent fluid with predominantly calcium based minerals dissolving and precipitating under experimental conditions. Major and trace elements in the effluent (using ICP-OES analysis) indicated that multiple geochemical reactions are occurring with almost all of the constituent minerals participating. The geochemical composition of precipitates recovered after the experiments showed diagenetic carbonates and opal as the main constituents. The bulk rock showed little changes in composition except for sharper and more refined peaks on XRD analysis, suggesting that a significant portion of the amorphous content of the rocks have been removed via dissolution by the slightly acid CO2-brine fluid that was injected. Micro-indentation results captured slight reduction in the hardness of the shale rocks and this reduction appeared dependent on diagenetic quartz content. It can be inferred that convective reactive transport of dissolved minerals are involved in nanoscale precipitation-dissolution processes in shale. This reactive transport of dissolved minerals can occlude micro-fracture flow paths, thereby improving shale caprock seal integrity with respect to leakage risk under CO2 sequestration conditions.

Geology, Geochemistry and Geophysics of Sedimentary Rock-Hosted Au Deposits in P.R. China

USGS Publications Warehouse

Peters, Stephen G.

2002-01-01

This is the second report concerning results of a joint project between the U.S. Geological Survey and the Tianjin Geological Academy to study sedimentary rock-hosted Au deposits in P.R. China. Since the 1980s, Chinese geologists have devoted a large-scale exploration and research effort to the deposits. As a result, there are more than 20 million oz of proven Au reserves in sedimentary rock-hosted Au deposits in P.R. China. Additional estimated and inferred resources are present in over 160 deposits and occurrences, which are undergoing exploration. This makes China second to Nevada in contained ounces of Au in Carlin-type deposits. It is likely that many of the Carlin-type Au ore districts in China, when fully developed, could have resource potential comparable to the multi-1,000-tonne Au resource in northern Nevada. The six chapters of this report describe sedimentary rock-hosted Au deposits that were visited during the project. Chapters 1 and 2 provide an overview of sedimentary rock-hosted Au deposits and Carlin-type Au deposits and also provide a working classification for the sedimentary rock-hosted Au deposits. Chapters 3, 4, and 5 provide descriptions that were compiled from the literature in China in three main areas: the Dian-Qian-Gui, the Qinling fold belt, and Middle-Lower Yangtze River areas. Chapter 6 contains a weights-of-evidence (WofE), GIS-based mineral assessment of sedimentary rock-hosted Au deposits in the Qinling fold belt and Dian-Qian-Gui areas. Appendices contain scanned aeromagnetic (Appendix I) and gravity (Appendix II) geophysical maps of south and central China. Data tables of the deposits (Appendix III) also are available in the first report as an interactive database at http://geopubs.wr.usgs.gov/open-file/of98-466/. Geochemical analysis of ore samples from the deposits visited are contained in Appendix IV.

Mercury isotope constraints on the source for sediment-hosted lead-zinc deposits in the Changdu area, southwestern China

NASA Astrophysics Data System (ADS)

Xu, Chunxia; Yin, Runsheng; Peng, Jiantang; Hurley, James P.; Lepak, Ryan F.; Gao, Jianfeng; Feng, Xinbin; Hu, Ruizhong; Bi, Xianwu

2018-03-01

The Lanuoma and Cuona sediment-hosted Pb-Zn deposits hosted by Upper Triassic limestone and sandstone, respectively, are located in the Changdu area, SW China. Mercury concentrations and Hg isotopic compositions from sulfide minerals and potential source rocks (e.g., the host sedimentary rocks and the metamorphic basement) were investigated to constrain metal sources and mineralization processes. In both deposits, sulfide minerals have higher mercury (Hg) concentrations (0.35 to 1185 ppm) than the metamorphic basement rocks (0.05 to 0.15 ppm) and sedimentary rocks (0.02 to 0.08 ppm). Large variations of mass-dependent fractionation (3.3‰ in δ202Hg) and mass-independent fractionation (0.3‰ in Δ199Hg) of Hg isotopes were observed. Sulfide minerals have Hg isotope signatures that are similar to the hydrothermal altered rocks around the deposit, and similar to the metamorphic basement, but different from barren sedimentary rocks. The variation of Δ199Hg suggests that Hg in sulfides was mainly derived from the underlying metamorphic basement. Mercury isotopes could be a geochemical tracer in understanding metal sources in hydrothermal ore deposits.

Proceedings of the scientific visit on crystalline rock repository development.

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

Mariner, Paul E.; Hardin, Ernest L.; Miksova, Jitka

2013-02-01

A scientific visit on Crystalline Rock Repository Development was held in the Czech Republic on September 24-27, 2012. The visit was hosted by the Czech Radioactive Waste Repository Authority (RAWRA), co-hosted by Sandia National Laboratories (SNL), and supported by the International Atomic Energy Agency (IAEA). The purpose of the visit was to promote technical information exchange between participants from countries engaged in the investigation and exploration of crystalline rock for the eventual construction of nuclear waste repositories. The visit was designed especially for participants of countries that have recently commenced (or recommenced) national repository programmes in crystalline host rock formations.more » Discussion topics included repository programme development, site screening and selection, site characterization, disposal concepts in crystalline host rock, regulatory frameworks, and safety assessment methodology. Interest was surveyed in establishing a %E2%80%9Cclub,%E2%80%9D the mission of which would be to identify and address the various technical challenges that confront the disposal of radioactive waste in crystalline rock environments. The idea of a second scientific visit to be held one year later in another host country received popular support. The visit concluded with a trip to the countryside south of Prague where participants were treated to a tour of the laboratory and underground facilities of the Josef Regional Underground Research Centre.« less

Magmatic interactions as recorded in plagioclase phenocrysts of Chaos Crags, Lassen Volcanic Center, California

USGS Publications Warehouse

Tepley, F. J.; Davidson, J.P.; Clynne, M.A.

1999-01-01

The silicic lava domes of Chaos Crags in Lassen Volcanic National Park contain a suite of variably quenched, hybrid basaltic andesite magmatic inclusions. The inclusions represent thorough mixing between rhyodacite and basalt recharge liquids accompanied by some mechanical disaggregation of the inclusions resulting in crystals mixing into the rhyodacite host preserved by quenching on dome emplacement. 87Sr/86Sr ratios (~0.7037-0.7038) of the inclusions are distinctly lower than those of the host rhyodacite (~0.704-0.7041), which are used to fingerprint the origin of mineral components and to monitor the mixing and mingling process. Chemical, isotopic, and textural characteristics indicate that the inclusions are hybrid magmas formed from the mixing and undercooling of recharge basaltic magma with rhyodacitic magma. All the host magma phenocrysts (biotite, plagioclase, hornblende and quartz crystals) also occur in the inclusions, where they are rimmed by reaction products. Compositional and strontium isotopic data from cores of unresorbed plagioclase crystals in the host rhyodacite, partially resorbed plagioclase crystals enclosed within basaltic andesite inclusions, and partially resorbed plagioclase crystals in the rhyodacitic host are all similar. Rim 87Sr/86Sr ratios of the partially resorbed plagioclase crystals in both inclusions and host are lower and close to those of the whole-rock hybrid basaltic andesite values. This observation indicates that some crystals originally crystallized in the silicic host, were partially resorbed and subsequently overgrown in the hybrid basaltic andesite magma, and then some of these partially resorbed plagioclase crystals were recycled back into the host rhyodacite. Textural evidence, in the form of sieve zones and major dissolution boundaries of the resorbed plagioclase crystals, indicates immersion of crystals into a hotter, more calcic magma. The occurrence of partially resorbed plagioclase together with plagioclase microlites and olivine crystals reflects disaggregation of inclusions and mingling of this material into the silicic host. These processes are commonplace in some orogenic magma systems and may be elucidated by isotopic microsampling and analysis of the plagioclases crystallizing from them.

Genesis and shape of natural solution cavities within salt deposits

NASA Astrophysics Data System (ADS)

Gechter, Daniel; Huggenberger, Peter; Ackerer, Philippe; Waber, H. Niklaus

2008-11-01

Since the genesis and shape of natural deep-seated cavities within a salt body are insufficiently understood, the current study tries to shed some light on this topic. To this end, freshwater was pumped slowly through a horizontal borehole in rock salt cores. Owing to fast halite dissolution kinetics, high solubility, and slow inflow rate, halite dissolution took place only in the inflow of the rock salt cylinder. The shape of the created cavities is an approximately symmetrical half cone with a horizontal base facing upward. A conceptual model is presented that is inspired by the experimental results and based on theoretical hydraulic-geochemical considerations, as well as on field observations. It proposes that triangular prism or conically shaped cavities develop within salt under confined conditions, where aggressive water flows upward along a fracture/conduit from an insoluble aquifer into the soluble stratum. Such cavity enlargements may cause land subsidence and structure collapse.

Fluid Pocket Generation in Response to Heterogeneous Reactivity of a Rock Fracture Under Hydrothermal Conditions

NASA Astrophysics Data System (ADS)

Okamoto, A.; Tanaka, H.; Watanabe, N.; Saishu, H.; Tsuchiya, N.

2017-10-01

Fractures are the location of various water-rock interactions within the Earth's crust; however, the impact of the chemical heterogeneity of fractures on hydraulic properties is poorly understood. We conducted flow-through experiments on the dissolution of granite with a tensile fracture at 350°C and fluid pressure of 20 MPa with confining pressure of 40 MPa. The aperture structures were evaluated by X-ray computed tomography before and after the experiments. Under the experimental conditions, quartz grains dissolve rapidly to produce grain-scale pockets on the fracture surface, whereas altered feldspar grains act as asperities to sustain the open cavities. The fracture contained gouge with large surface area. The feedback between fluid flow and the rapid dissolution of gouge material produced large fluid pockets, whereas permeability did not always increase significantly. Such intense hydrological-chemical interactions could strongly influence the porosity-permeability relationship of fractured reservoirs in the crust.

Modeling low-temperature geochemical processes: Chapter 2

USGS Publications Warehouse

Nordstrom, D. Kirk; Campbell, Kate M.

2014-01-01

This chapter provides an overview of geochemical modeling that applies to water–rock interactions under ambient conditions of temperature and pressure. Topics include modeling definitions, historical background, issues of activity coefficients, popular codes and databases, examples of modeling common types of water–rock interactions, and issues of model reliability. Examples include speciation, microbial redox kinetics and ferrous iron oxidation, calcite dissolution, pyrite oxidation, combined pyrite and calcite dissolution, dedolomitization, seawater–carbonate groundwater mixing, reactive-transport modeling in streams, modeling catchments, and evaporation of seawater. The chapter emphasizes limitations to geochemical modeling: that a proper understanding and ability to communicate model results well are as important as completing a set of useful modeling computations and that greater sophistication in model and code development is not necessarily an advancement. If the goal is to understand how a particular geochemical system behaves, it is better to collect more field data than rely on computer codes.

Investigating the hydrological significance of stalagmite geochemistry (Mg, Sr) using Sr isotope and particulate element records across the Late Glacial-to-Holocene transition

NASA Astrophysics Data System (ADS)

Belli, R.; Borsato, A.; Frisia, S.; Drysdale, R.; Maas, R.; Greig, A.

2017-02-01

The trace element and Sr isotope records in two coeval stalagmites characterized by different growth rates and flow regimes at Savi cave (Grotta Savi, NE Italy) reveal different sources and incorporation mechanisms for Mg and Sr. Mg is sourced primarily from dissolved cave host rock while particulate Mg derived from soil plays a subordinate role. The presence of particulate-borne Mg is inferred from the co-variation of Mg and particle-associated elements (Th, Al and Mn) which are preferentially concentrated in open columnar calcite layers. Variation in Mg concentrations corrected for particle-influenced components, the Mgc parameter, is controlled by water-rock interaction, with higher and lower Mgc during dry and wet phases, respectively. This is thought to reflect incongruent dissolution of Mg-rich phases. Correction of Sr concentrations for contributions from airborne exogenic Sr, based on 87Sr/86Sr ratios, yields the bedrock-only contribution (Src). Src variation in stalagmite calcite is influenced by speleothem growth rate and by variation of the calcite-water Sr partitioning in wet and dry phases, and only to a minor extent by incongruent dissolution of Mg-rich phases. Concentration profiles for Mgc and Srcg (corrected for growth rate effects) show inverse correlations and are inferred to show hydrological significance which is captured in a hydrological index, HI. We suggest HI provides robust information on water-rock interaction related to hydrological changes and can be utilized in both wet and semi-arid environments, provided the corrections for soil Mg and exogenic Sr can be applied with confidence. Application of the HI index allows correction of Grotta Savi oxygen isotope data, to yield a δ18Oc time series that shows when changes in moisture sources and atmospheric reorganization, or changes in moisture amount, were significant. This is especially evident during the Younger Dryas (YD). The Savi record supports the concept of a two-phase YD, marked by an increase of moisture and stronger impact of Adriatic and Mediterranean Sea influences over the northern Adriatic region from 12.3 ka onwards. Then, a large-scale atmospheric reorganization and gradual northward shift of the Polar Front caused a progressive reduction of sea influence over the region from 12.1 ka, supporting the concept of a hemispheric change.

Phosphine from rocks: mechanically driven phosphate reduction?

PubMed

Glindemann, Dietmar; Edwards, Marc; Morgenstern, Peter

2005-11-01

Natural rock and mineral samples released trace amounts of phosphine during dissolution in mineral acid. An order of magnitude more phosphine (average 1982 ng PH3 kg rock and maximum 6673 ng PH3/kg rock) is released from pulverized rock samples (basalt, gneiss, granite, clay, quartzitic pebbles, or marble). Phosphine was correlated to hardness and mechanical pulverization energy of the rocks. The yield of PH3 ranged from 0 to 0.01% of the total P content of the dissolved rock. Strong circumstantial evidence was gathered for reduction of phosphate in the rock via mechanochemical or "tribochemical" weathering at quartz and calcite/marble inclusions. Artificial reproduction of this mechanism by rubbing quartz rods coated with apatite-phosphate to the point of visible triboluminescence, led to detection of more than 70 000 ng/kg PH3 in the apatite. This reaction pathway may be considered a mechano-chemical analogue of phosphate reduction from lightning or electrical discharges and may contribute to phosphine production via tectonic forces and processing of rocks.

Evolution of strength and physical properties of carbonate and ultramafic rocks under hydrothermal conditions

NASA Astrophysics Data System (ADS)

Lisabeth, Harrison Paul

Interaction of rocks with fluids can significantly change mineral assemblage and structure. This so-called hydrothermal alteration is ubiquitous in the Earth's crust. Though the behavior of hydrothermally altered rocks can have planet-scale consequences, such as facilitating oceanic spreading along slow ridge segments and recycling volatiles into the mantle at subduction zones, the mechanisms involved in the hydrothermal alteration are often microscopic. Fluid-rock interactions take place where the fluid and rock meet. Fluid distribution, flux rate and reactive surface area control the efficiency and extent of hydrothermal alteration. Fluid-rock interactions, such as dissolution, precipitation and fluid mediated fracture and frictional sliding lead to changes in porosity and pore structure that feed back into the hydraulic and mechanical behavior of the bulk rock. Examining the nature of this highly coupled system involves coordinating observations of the mineralogy and structure of naturally altered rocks and laboratory investigation of the fine scale mechanisms of transformation under controlled conditions. In this study, I focus on fluid-rock interactions involving two common lithologies, carbonates and ultramafics, in order to elucidate the coupling between mechanical, hydraulic and chemical processes in these rocks. I perform constant strain-rate triaxial deformation and constant-stress creep tests on several suites of samples while monitoring the evolution of sample strain, permeability and physical properties. Subsequent microstructures are analyzed using optical and scanning electron microscopy. This work yields laboratory-based constraints on the extent and mechanisms of water weakening in carbonates and carbonation reactions in ultramafic rocks. I find that inundation with pore fluid thereby reducing permeability. This effect is sensitive to pore fluid saturation with respect to calcium carbonate. Fluid inundation weakens dunites as well. The addition of carbon dioxide to pore fluid enhances compaction and partial recovery of strength compared to pure water samples. Enhanced compaction in CO2-rich fluid samples is not accompanied by enhanced permeability reduction. Analysis of sample microstructures indicates that precipitation of carbonates along fracture surfaces is responsible for the partial restrengthening and channelized dissolution of olivine is responsible for permeability maintenance.

Rare-earth-element minerals in martian breccia meteorites NWA 7034 and 7533: Implications for fluid-rock interaction in the martian crust

NASA Astrophysics Data System (ADS)

Liu, Yang; Ma, Chi; Beckett, John R.; Chen, Yang; Guan, Yunbin

2016-10-01

Paired martian breccia meteorites, Northwest Africa (NWA) 7034 and 7533, are the first martian rocks found to contain rare-earth-element (REE) phosphates and silicates. The most common occurrence is as clusters of anhedral monazite-(Ce) inclusions in apatite. Occasionally, zoned, irregular merrillite inclusions are also present in apatite. Monazite-bearing apatite is sometimes associated with alkali-feldspar and Fe-oxide. Apatite near merrillite and monazite generally contains more F and OH (F-rich region) than the main chlorapatite host and forms irregular boundaries with the main host. Locally, the composition of F-rich regions can reach pure fluorapatite. The chlorapatite hosts are similar in composition to isolated apatite without monazite inclusions, and to euhedral apatite in lithic clasts. The U-Th-total Pb ages of monazite in three apatite are 1.0 ± 0.4Ga (2σ), 1.1 ± 0.5Ga (2σ), and 2.8 ± 0.7Ga (2σ), confirming a martian origin. The texture and composition of monazite inclusions are mostly consistent with their formation by the dissolution of apatite and/or merrillite by fluid at elevated temperatures (>100 °C). In NWA 7034, we observed a monazite-chevkinite-perrierite-bearing benmoreite or trachyandesite clast. Anhedral monazite and chevkinite-perrierite grains occur in a matrix of sub-micrometer REE-phases and silicates inside the clast. Monazite-(Ce) and -(Nd) and chevkinite-perrierite-(Ce) and -(Nd) display unusual La and Ce depletion relative to Sm and Nd. In addition, one xenotime-(Y)-bearing pyrite-ilmenite-zircon clast with small amounts of feldspar and augite occurs in NWA 7034. One xenotime crystal was observed at the edge of an altered zircon grain, and a cluster of xenotime crystals resides in a mixture of alteration materials. Pyrite, ilmenite, and zircon in this clast are all highly altered, zircon being the most likely source of Y and HREE now present in xenotime. The association of xenotime with zircon, low U and Th contents, and the low Yb content relative to Gd and Dy in xenotime suggest the possible formation of xenotime as a byproduct of fluid-zircon reactions. On the basis of relatively fresh apatite grains and lithic clasts in the same samples, we propose that the fluid-rock/mineral reactions occurred in the source rocks before their inclusion in NWA 7034 and 7533. Additionally, monazite-bearing apatite and REE-mineral-bearing clasts are possibly derived from different crustal origins. Thus, our results imply the wide-occurrence of hydrothermal fluids in the martian crust at 1 Ga or older, which were probably induced by impacts or large igneous intrusions.

Geology, distribution, and classification of gold deposits in the western Qinling belt, central China

USGS Publications Warehouse

Mao, J.; Qiu, Yumin; Goldfarb, R.J.; Zhang, Z.; Garwin, S.; Fengshou, R.

2002-01-01

Gold deposits of the western Qinling belt occur within the western part of the Qinling-Dabie-Sulu orogen, which is located between the Precambrian North China and Yangtze cratons and east of the Songpan-Ganzi basin. The early Paleozoic to early Mesozoic orogen can be divided into northern, central, and southern zones, separated by the Shangdan and Lixian-Shanyang thrust fault systems. The northern zone consists of an early Paleozoic arc accreted to the North China craton by ca. 450 Ma. The central zone, which contains numerous orogenic gold deposits, is dominated by clastic rocks formed in a late Paleozoic basin between the converging cratonic blocks. The southern zone is characterized by the easternmost exposure of Triassic sedimentary rocks of the Songpan-Ganzi basin. These Early to Late Triassic turbidities, in part calcareous, of the immense Songpan-Ganzi basin also border the western Qinling belt to the west. Carlinlike gold deposits are abundant (1) along a westward extension of the southern zone defined by a window of early Paleozoic clastic rocks extending into the basin, and (2) within the easternmost margin of the basinal rocks to the south of the extension, and in adjacent cover rocks of the Yangtze craton. Triassic and Early Jurassic synkinematic granitoids are widespread across the western Qinling belt, as well as in the Songpan-Ganzi basin. Orogenic lode gold deposits along brittle-ductile shear zones occur within greenschist-facies, highly deformed, Devonian and younger clastic rocks of the central zone. Mainly coarse-grained gold, along with pyrite, pyrrhotite, arsenopyrite, and minor base metal sulfides, occur in networks of quartz veinlets, brecciated wall rock, and are dissminated in altered wall rock. Isotopic dates suggest that the deposits formed during the Late Triassic to Middle Jurassic as the leading edge of the Yangtze craton was thrust beneath rocks of the western Qinling belt. Many gold-bearing placers are distributed along the river systems that flow south from the lode-bearing central zone. Carlin-like gold deposits have only been identified during the last decade in the southern zone of the western Qinling and in the northeastern corner of the Songpan-Ganzi basin. The deposits mainly contain micron-diameter gold in arsenical pyrite; are characterized by the common occurence of cinnabar, stibnite, realgar, and orpiment; exhibit strong silicification, carbonatization, pyritization, and decalcification dissolution textures; and are structurally controlled. The lack of reactive host lithologies may have prevented development of large (> 100 tones of gold), stratigraphically-controlled orebodies, which are typical of the Carlin deposits in the western USA. These deposits are hosted by Triassic turbidities and shallow-water carbonates, and an early Paleozoic inlier in the Songpan-Ganzi basin that extends in an east-west belt for about 300 km. Rather than true "Carlin" deposits, these Carlin-like deposits may be some type of shallow-crustal (i.e., epithermal) hybrid with features intermediate to Nevada-style Carlin deposits and the orogenic gold deposits to the immediate north. These Carlin-like deposits also overlap in age with the early Mesozoic orogenic gold deposits and, therefore, also formed during the final stages of collision between the cratons and intermediate basin closure.

Modeling transient heat transfer in nuclear waste repositories.

PubMed

Yang, Shaw-Yang; Yeh, Hund-Der

2009-09-30

The heat of high-level nuclear waste may be generated and released from a canister at final disposal sites. The waste heat may affect the engineering properties of waste canisters, buffers, and backfill material in the emplacement tunnel and the host rock. This study addresses the problem of the heat generated from the waste canister and analyzes the heat distribution between the buffer and the host rock, which is considered as a radial two-layer heat flux problem. A conceptual model is first constructed for the heat conduction in a nuclear waste repository and then mathematical equations are formulated for modeling heat flow distribution at repository sites. The Laplace transforms are employed to develop a solution for the temperature distributions in the buffer and the host rock in the Laplace domain, which is numerically inverted to the time-domain solution using the modified Crump method. The transient temperature distributions for both the single- and multi-borehole cases are simulated in the hypothetical geological repositories of nuclear waste. The results show that the temperature distributions in the thermal field are significantly affected by the decay heat of the waste canister, the thermal properties of the buffer and the host rock, the disposal spacing, and the thickness of the host rock at a nuclear waste repository.

Are seismic velocity time-lapse changes due to fluid substitution or matrix dissolution? A CO2 sequestration study at Pohokura Field, New Zealand

NASA Astrophysics Data System (ADS)

Adam, L.; Sim, C. Y.; Macfarlane, J.; van Wijk, K.; Shragge, J. C.; Higgs, K.

2015-12-01

Time-lapse seismic signatures can be used to quantify fluid saturation and pressure changes in a reservoir undergoing CO2 sequestration. However, the injection of CO2 acidifies the water, which may dissolve and/or precipitate minerals. Understanding the impact on the rock frame from field seismic time-lapse changes remains an outstanding challenge. Here, we study the effects of carbonate-CO2-water reactions on the physical and elastic properties of rock samples with variable volumes of carbonate cementation. The effects of fluid substitution alone (brine to CO2) and those due to the combination of fluid substitution and mineral dissolution on time-lapse seismic signatures are studied by combining laboratory data, geophysical well-log data and 1-D seismic modeling. Nine rocks from Pohokura Field (New Zealand) are reacted with carbonic acid. The elastic properties are measured using a high-density laser-ultrasonic setup. We observe that P-wave velocity changes up to -19% and correlate with sandstone grain size. Coarse-grained sandstones show greater changes in elastic wave velocities due to dissolution than fine-grained sandstones. To put this in perspective, this velocity change is comparable to the effect of fluid substitution from brine to CO2. This can potentially create an ambiguity in the interpretation of the physical processes responsible for time-lapse signatures in a CO2injection scenario. The laboratory information is applied onto well-log data to model changes in elastic properties of sandstones at the well-log scale. Well-logs and core petrographic analyses are used to find an elastic model that best describes the observed elastic waves velocities in the cemented reservoir sandstones. The Constant-cement rock physics model is found to predict the elastic behaviour of the cemented sandstones. A possible late-time sequestration scenario is that both mineral dissolution and fluid substitution occur in the reservoir. 1-D synthetic seismograms show that seismic amplitudes can change up to 126% in such a scenario. Our work shows that it is important to consider that time-lapse seismic signatures in carbonate-cemented reservoirs can result not only from fluid and pressure changes but also potentially from chemical reaction between CO2-water mixtures and carbonate cemented sandstones.

Simplified models of rates of CO2 mineralization in Geologic Carbon Storage

NASA Astrophysics Data System (ADS)

DePaolo, D. J.; Zhang, S.

2017-12-01

Geologic carbon storage (GCS) reverses the flow of carbon to the atmosphere, returning the carbon to long-term geologic storage. Models suggest that most of the injected CO2 will be "trapped" in the subsurface by physical means, but the most risk-free and permanent form of carbon storage is as carbonate minerals (Ca,Mg,Fe)CO3. The transformation of CO2 to carbonate minerals requires supply of divalent cations by dissolution of silicate minerals. Available data suggest that rates of transformation are difficult to predict. We show that the chemical kinetic observations and experimental results, when reduced to a single timescale that describes the fractional rate at which cations are released to solution by mineral dissolution, show sufficiently systematic behavior that the rates of mineralization can be estimated with reasonable certainty. Rate of mineralization depends on both the abundance (determined by the reservoir rock mineralogy) and the rate at which cations are released by dissolution into pore fluid that has been acidified with dissolved CO2. Laboratory-measured rates and field observations give values spanning 8 to 10 orders of magnitude, but when evaluated in the context of reservoir-scale reactive transport simulations, this range becomes much smaller. Reservoir scale simulations indicate that silicate mineral dissolution and subsequent carbonate mineral precipitation occur at pH 4.5 to 6, fluid flow velocity less than 5m/yr, and 50-100 years or more after the start of injection. These constraints lead to estimates of 200 to 2000 years for conversion of 60-90% of injected CO2 when the reservoir rock has a sufficient volume fraction of divalent cation-bearing silicate minerals (ca. 20%), and confirms that when reservoir rock mineralogy is not favorable the fraction of CO2 converted to carbonate minerals is minimal over 104 years. A sufficient amount of reactive minerals represents the condition by which the available cations per volume of rock plus pore space exceeds the locally trapped CO2 by a factor of two or more. Our approach may allow for rapid evaluation of mineralization potential of subsurface storage reservoirs, and illustrates how reservoir scale modeling can be integrated with other observations to address key issues for engineering geologic systems.

Strontium isotopes as an indicator for groundwater salinity sources in the Kirkuk region, Iraq.

PubMed

Sahib, Layth Y; Marandi, Andres; Schüth, Christoph

2016-08-15

The Kirkuk region in northern Iraq hosts some of the largest oil fields in the Middle East. Several anticline structures enabled vertical migration and entrapment of the oil. Frequently, complex fracture systems and faults cut across the Eocene and middle Oligocene reservoirs and the cap rock, the Fatha Formation of Miocene age. Seepage of crude oil and oil field brines are therefore a common observation in the anticline axes and contamination of shallow groundwater resources is a major concern. In this study, 65 water samples were collected in the Kirkuk region to analyze and distinguish mixing processes between shallow groundwater resources, uprising oil field brines, and dissolution of gypsum and halite from the Fatha Formation. Hydrochemical analyses of the water samples included general hydrochemistry, stable water isotopes, as well as strontium concentrations and for 22 of the samples strontium isotopes ((87)Sr/(86)Sr). Strontium concentrations increased close to the anticline axes with highest concentrations in the oil field brines (300mg/l). Strontium isotopes proved to be a valuable tool to distinguish mixing processes as isotope signatures of the oil field brines and of waters from the Fatha Formation are significantly different. It could be shown, that mixing of shallow groundwater with oil field brines is occurring close to the major fault zones in the anticlines but high concentrations of strontium in the water samples are mainly due to dissolution from the Fatha Formation. Copyright © 2016 Elsevier B.V. All rights reserved.

Study on effect of L-arginine on solubility and dissolution of Zaltoprofen: Preparation and characterization of binary and ternary cyclodextrin inclusion complexes

NASA Astrophysics Data System (ADS)

Sherje, Atul P.; Patel, Forum; Murahari, Manikanta; Suvarna, Vasanti; Patel, Kavitkumar

2018-02-01

The present study demonstrated the binary and ternary complexes of Zaltoprofen (ZPF) with β-CD and HP-β-CD. The products were characterized using solubility, in vitro dissolution, and DSC studies. The mode of interaction of guest and host was revealed through 1H NMR and FT-IR studies. A significant increase was noticed in the stability constant (Kc) and complexation efficiency (CE) of β-CD and HP-β-CD due to addition of L-Arg in ternary complexes. The ternary complexes showed greater increase in solubility and dissolution of ZPF than binary complexes. Thus, ternary system of ZPF could be an innovative approach for its solubility and dissolution enhancement.

Reactive Transport Modeling of CO2-induced Porosity and Permeability Changes in Heterogeneous Carbonate Rocks

NASA Astrophysics Data System (ADS)

Hao, Y.; Smith, M. M.; Mason, H. E.; Carroll, S.

2015-12-01

It has long been appreciated that chemical interactions have a major effect on rock porosity and permeability evolution and may alter the behavior or performance of both natural and engineered reservoir systems. Such reaction-induced permeability evolution is of particular importance for geological CO2 sequestration and storage associated with enhanced oil recovery. In this study we used a three-dimensional Darcy scale reactive transport model to simulate CO2 core flood experiments in which the CO2-equilibrated brine was injected into dolostone cores collected from the Arbuckle carbonate reservoir, Wellington, Kansas. Heterogeneous distributions of macro pores, fractures, and mineral phases inside the cores were obtained from X-ray computed microtomography (XCMT) characterization data, and then used to construct initial model macroscopic properties including porosity, permeability, and mineral compositions. The reactive transport simulations were performed by using the Nonisothermal Unsaturated Flow and Transport (NUFT) code, and their results were compared with experimental data. It was observed both experimentally and numerically that the dissolution fronts became unstable in highly heterogeneous and less permeable formations, leading to the development of highly porous flow paths or wormholes. Our model results indicate that the continuum-scale reactive transport models are able to adequately capture the evolution of distinct dissolution fronts as observed in carbonate rocks at a core scale. The impacts of rock heterogeneity, chemical kinetics and porosity-permeability relationships were also examined in this study. The numerical model developed in this study will not only help improve understanding of coupled physical and chemical processes controlling carbonate dissolution, but also provide a useful basis for upscaling transport and reaction properties from core scale to field scale. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Provenance, diagenesis, tectonic setting and reservoir quality of the sandstones of the Kareem Formation, Gulf of Suez, Egypt

NASA Astrophysics Data System (ADS)

Zaid, Samir M.

2013-09-01

The Middle Miocene Kareem sandstones are important oil reservoirs in the southwestern part of the Gulf of Suez basin, Egypt. However, their diagenesis and provenance and their impact on reservoir quality, are virtually unknown. Samples from the Zeit Bay Oil Field, and the East Zeit Oil Field represent the Lower Kareem (Rahmi Member) and the Upper Kareem (Shagar Member), were studied using a combination of petrographic, mineralogical and geochemical techniques. The Lower Rahmi sandstones have an average framework composition of Q95F3.4R1.6, and 90% of the quartz grains are monocrystalline. By contrast, the Upper Shagar sandstones are only slightly less quartzose with an average framework composition of Q76F21R3 and 82% of the quartz grains are monocrystalline. The Kareem sandstones are mostly quartzarenite with subordinate subarkose and arkose. Petrographical and geochemical data of sandstones indicate that they were derived from granitic and metamorphic terrains as the main source rock with a subordinate quartzose recycled sedimentary rocks and deposited in a passive continental margin of a syn rift basin. The sandstones of the Kareem Formation show upward decrease in maturity. Petrographic study revealed that dolomite is the dominant cement and generally occurs as fine to medium rhombs pore occluding phase and locally as a grain replacive phase. Authigenic quartz occurs as small euhedral crystals, locally as large pyramidal crystals in the primary pores. Authigenic anhydrites typically occur as poikilotopic rhombs or elongate laths infilling pores but also as vein filling cement. The kaolinite is a by-product of feldspar leaching in the presence of acidic fluid produced during the maturation of organic matter in the adjacent Miocene rocks. Diagenetic features include compaction; dolomite, silica and anhydrite cementation with minor iron-oxide, illite, kaolinite and pyrite cements; dissolution of feldspars, rock fragments. Silica dissolution, grain replacement and carbonate dissolution greatly enhance the petrophysical properties of many sandstone samples.

Tourmaline occurrences within the Penamacor-Monsanto granitic pluton and host-rocks (Central Portugal): genetic implications of crystal-chemical and isotopic features

NASA Astrophysics Data System (ADS)

da Costa, I. Ribeiro; Mourão, C.; Récio, C.; Guimarães, F.; Antunes, I. M.; Ramos, J. Farinha; Barriga, F. J. A. S.; Palmer, M. R.; Milton, J. A.

2014-04-01

Tourmalinization associated with peraluminous granitic intrusions in metapelitic host-rocks has been widely recorded in the Iberian Peninsula, given the importance of tourmaline as a tracer of granite magma evolution and potential indicator of Sn-W mineralizations. In the Penamacor-Monsanto granite pluton (Central Eastern Portugal, Central Iberian Zone), tourmaline occurs: (1) as accessory phase in two-mica granitic rocks, muscovite-granites and aplites, (2) in quartz (±mica)-tourmaline rocks (tourmalinites) in several exocontact locations, and (3) as a rare detrital phase in contact zone hornfels and metapelitic host-rocks. Electron microprobe and stable isotope (δ18O, δD, δ11B) data provide clear distinctions between tourmaline populations from these different settings: (a) schorl-oxyschorl tourmalines from granitic rocks have variable foititic component (X□ = 17-57 %) and Mg/(Mg + Fe) ratios (0.19-0.50 in two-mica granitic rocks, and 0.05-0.19 in the more differentiated muscovite-granite and aplites); granitic tourmalines have constant δ18O values (12.1 ± 0.1 ‰), with wider-ranging δD (-78.2 ± 4.7 ‰) and δ11B (-10.7 to -9.0 ‰) values; (b) vein/breccia oxyschorl [Mg/(Mg + Fe) = 0.31-0.44] results from late, B- and Fe-enriched magma-derived fluids and is characterized by δ18O = 12.4 ‰, δD = -29.5 ‰, and δ11B = -9.3 ‰, while replacement tourmalines have more dravitic compositions [Mg/(Mg + Fe) = 0.26-0.64], close to that of detrital tourmaline in the surrounding metapelitic rocks, and yield relatively constant δ18O values (13.1-13.3 ‰), though wider-ranging δD (-58.5 to -36.5 ‰) and δ11B (-10.2 to -8.8 ‰) values; and (c) detrital tourmaline in contact rocks and regional host metasediments is mainly dravite [Mg/(Mg + Fe) = 0.35-0.78] and oxydravite [Mg/(Mg + Fe) = 0.51-0.58], respectively. Boron contents of the granitic rocks are low (<650 ppm) compared to the minimum B contents normally required for tourmaline saturation in granitic melts, implying loss of B and other volatiles to the surrounding host-rocks during the late-magmatic stages. This process was responsible for tourmalinization at the exocontact of the Penamacor-Monsanto pluton, either as direct tourmaline precipitation in cavities and fractures crossing the pluton margin (vein/breccia tourmalinites), or as replacement of mafic minerals (chlorite or biotite) in the host-rocks (replacement tourmalinites) along the exocontact of the granite. Thermometry based on 18O equilibrium fractionation between tourmaline and fluid indicates that a late, B-enriched magmatic aqueous fluid (av. δ18O ~12.1 ‰, at ~600 °C) precipitated the vein/breccia tourmaline (δ18O ~12.4 ‰) at ~500-550 °C, and later interacted with the cooler surrounding host-rocks to produce tourmaline at lower temperatures (400-450 °C), and an average δ18O ~13.2 ‰, closer to the values for the host-rock. Although B-metasomatism associated with some granitic plutons in the Iberian Peninsula seems to be relatively confined in space, extending integrated studies such as this to a larger number of granitic plutons may afford us a better understanding of Variscan magmatism and related mineralizations.

Microbial Life Driving Low-Temperature Basalt Alteration in the Subsurface: Decoupling Abiotic Processes from Biologically-Mediated Rock Alteration

NASA Astrophysics Data System (ADS)

Moore, R.; Lecoeuvre, A.; Stephant, S.; Dupraz, S.; Ranchou-Peyruse, M.; Ranchou-Peyruse, A.; Gérard, E.; Ménez, B.

2017-12-01

Microorganisms are involved with specific rock alteration processes in the deep subsurface. It is a challenge to link any contribution microbial life may have on rock alteration with specific functions or phyla because many alteration features and secondary minerals produced by metabolic processes can also produce abiotically. Here, two flow-through experiments were designed to mimic the circulation of a CO2-rich fluid through crystalline basalt. In order to identify microbially-mediated alteration and be able to link it with specific metabolisms represented in the subsurface, a relatively fresh crystalline basalt substrate was subsampled, sterilized and used as the substrate for both experiments. In one experiment, the substrate was left sterile, and in the other it was inoculated with an enrichment culture derived from the same aquifer as the rock substrate. Initial results show that the inoculum contained Proteobacteria and Firmicutes, which have diverse metabolic potentials. Fluid and rock analyses before, during, and after the experiments show that mineralogy, fluid chemistry, and dissolution processes differ between the sterile and inoculated systems. In the inoculated experiment iron-rich orthopyroxenes were preferentially dissolved while in the sterile system clinopyroxenes and plagioclases both exhibited a higher degree of dissolution. Additionally, the patterns of CO2 consumption and production over the duration of both experiments is different. This suggest that in a low-temperature basalt system with microorganisms CO2 is either consumed to produce biomass, or that carbonates are produced and then subsequently preserved. This suite of results combined with molecular ecology analyses can be used to conclude that in low-temperature basalts microorganisms play an intrinsic role in rock alteration.

Leaching of boron, arsenic and selenium from sedimentary rocks: I. Effects of contact time, mixing speed and liquid-to-solid ratio.

PubMed

Tabelin, Carlito Baltazar; Hashimoto, Ayaka; Igarashi, Toshifumi; Yoneda, Tetsuro

2014-02-15

Sedimentary rocks of marine origin excavated in tunnel projects were recently identified as potentially hazardous because they could release significant amounts of toxic trace elements when exposed to the environment. This study investigated the leaching characteristics of B, As, Se and the major coexisting ions under various conditions to identify the factors and processes controlling their evolution in the leachate. In addition, we evaluated whether the parameters of the currently used leachability test for excavated rocks were adequate. Although the leachabilities of B, As and Se similarly increased at longer contact times, only those of B and As were influenced by the mixing speed and/or liquid-to-solid ratio (L/S). The majority of trace elements dissolved in the leachate originated from the dissolution of soluble salts formed from seawater of the Cretaceous trapped during the formation of the sedimentary rocks. Moreover, the alkaline pH of the leachates could be attributed to the simultaneous dissolutions at varying degrees of the mineral components of the rocks as well as the precipitation of clay minerals. In the leaching test of excavated rocks for regulatory purposes, the best values of contact time and mixing speed should represent conditions of the highest trace element extractabilities, which in this study were found at longer contact times (>48 h) and the fastest mixing speed (200 rpm). The most appropriate L/S for the leaching test is 10 because it was around this L/S that the extractabilities and leaching concentrations of the trace elements were simultaneously observed at their highest values. Copyright © 2013 Elsevier B.V. All rights reserved.

Production and Application of Olivine Nano-Silica in Concrete

NASA Astrophysics Data System (ADS)

Mardiana, Oesman; Haryadi

2017-05-01

The aim of this research was to produce nano silica by synthesis of nano silica through extraction and dissolution of ground olivine rock, and applied the nano silica in the design concrete mix. The producing process of amorphous silica used sulfuric acid as the dissolution reagent. The separation of ground olivine rock occurred when the rock was heated in a batch reactor containing sulfuric acid. The results showed that the optimum mole ratio of olivine- acid was 1: 8 wherein the weight ratio of the highest nano silica generated. The heating temperature and acid concentration influenced the mass of silica produced, that was at temperature of 90 °C and 3 M acid giving the highest yield of 44.90%. Characterization using Fourier Transform Infrared (FTIR ) concluded that amorphous silica at a wavenumber of 1089 cm-1 indicated the presence of siloxane, Si-O-Si, stretching bond. Characterization using Scanning Electron Microscope - Energy Dispersive Spectroscopy (SEM-EDS) showed the surface and the size of the silica particles. The average size of silica particles was between 1-10 μm due to the rapid aggregation of the growing particles of nano silica into microparticles, caused of the pH control was not fully achieved.

Origin and significance of postore dissolution collapse breccias cemented with calcite and barite at the Meikle gold deposit, Northern Carlin trend, Nevada

USGS Publications Warehouse

Emsbo, P.; Hofstra, A.H.

2003-01-01

The final event in a complicated hydrothermal history at the Meikle gold deposit was gold deficient but caused extensive postore dissolution of carbonate, collapse brecciation, and precipitation of calcite and barite crystals in the resulting cavities. Although previously interpreted to be part of the Carlin-type hydrothermal system, crosscutting relationships and U-Th-Pb geochronology constrain this hydrothermal event to late Pliocene time (ca. 2 Ma), nearly 36 Ma after ore formation. Mineralogic, fluid inclusion, and stable isotope data indicate that postore hydrothermal fluids were reduced, H2S-rich, unevolved meteoric waters ((??18O = -17???) of low temperature (ca. 65??C). The ??18O values of barite and calcite indicate that these minerals were in isotopic equilibrium, requiring that barite SO4 was derived from the oxidation of reduced sulfur; however, preexisting sulfides in breccia cavities were not oxidized. The ??34S (15???) values of barite are higher than those of local bulk sulfide and supergene alunite indicating that SO4 was not derived from supergene oxidation of local sulfide minerals. The 15 per mil ??34S value suggests that the H2S in the fluids may have been leached from sulfur-rich organic matter in the local carbonaceous sedimentary rocks. A reduced H2S-rich fluid is also supported by the bright cathodoluminescence of calcite which indicates that it is Mn rich and Fe poor. Calcite has a narrow range of ??13C values (0.3-1.8???) that are indistinguishable from those of the host Bootstrap limestone, indicating that CO2 in the fluid was from dissolution of the local limestone. These data suggest that dissolution and brecciation of the Bootstrap limestone occurred where H2S-rich fluids encountered more oxidizing fluids and formed sulfuric acid (H2SO4). Intense fracturing in the mine area by previous structural and hydrothermal events probably provided conduits for the descent of oxidized surface water which mixed with the underlying H2S-rich waters to form the dissolving acid. The surface-derived fluid apparently contained sufficient oxygen to produce H2SO4 from H2S but not enough to alter pyrite to Fe oxide. Although H2S is an important gold-transporting ligand, the temperature was too low to transport a significant amount of gold. The presence of analogous calcite- and barite-lined cavities in other Carlin-type deposits suggests that the generation (and oxidation) of H2S-rich meteoric waters was a common phenomenon in north-central Nevada. Previous sulfur isotope studies have also shown that the Paleozoic sedimentary rocks were the principal source of H2S in Devonian sedimentary exhalative-type, Jurassic intrusion-related, Eocene Carlin-type, and Miocene low-sulfidation gold deposits in the region. The similar sulfur source in all of these systems suggests that basin brines, magmatic fluids, and meteoric waters all evolved to be H2S-rich ore fluids by circulation through Paleozoic sedimentary rocks. Thus, although not directly related to gold mineralization, the recent hydrologic history of the deposit provides important clues to earlier ore-forming processes that were responsible for gold mineralization.

Maps showing geology, structure, and geophysics of the central Black Hills, South Dakota

USGS Publications Warehouse

Redden, Jack A.; DeWitt, Ed

2008-01-01

This 1:100,000-scale digital geologic map details the complex Early Proterozoic granitic rocks, Early Proterozoic supracrustal metamorphic rocks, and Archean crystalline basement of the Black Hills. The granitic rocks host pegmatite deposits renowned for their feldspar, mica, spodumene, and beryl. The supracrustal rocks host the Homestake gold mine, which produced more than 40 million ounces of gold over a 125-year lifetime. The map documents the Laramide deformation of Paleozoic and Mesozoic cover rocks; and shows the distribution of Laramide plutonic rocks associated with precious-metals deposits. Four 1:300,000-scale maps summarize Laramide structures; Early Proterozoic structures; aeromagnetic anomalies; and gravity anomalies. Three 1:500,000-scale maps show geophysical interpretations of buried Early Proterozoic to Archean rocks in western South Dakota and eastern Wyoming.

Elemental Geochemistry of Samples From Fault Segments of the San Andreas Fault Observatory at Depth (SAFOD) Drill Hole

NASA Astrophysics Data System (ADS)

Tourscher, S. N.; Schleicher, A. M.; van der Pluijm, B. A.; Warr, L. N.

2006-12-01

Elemental geochemistry of mudrock samples from phase 2 drilling of the San Andreas Fault Observatory at Depth (SAFOD) is presented from bore hole depths of 3066 m to 3169 m and from 3292 m to 3368 m, which contain a creeping section and main trace of the fault, respectively. In addition to preparation and analysis of whole rock sample, fault grains with neomineralized, polished surfaces were hand picked from well-washed whole rock samples, minimizing the potential contamination from drilling mud and steel shavings. The separated fractions were washed in deionized water, powdered using a mortar and pestle, and analyzed using an Inductively Coupled Plasma- Optical Emission Spectrometer for major and minor elements. Based on oxide data results, systematic differences in element concentrations are observed between the whole rock and fault rock. Two groupings of data points are distinguishable in the regions containing the main trace of the fault, a shallow part (3292- 3316 m) and a deeper section (3320-3368 m). Applying the isocon method, assuming Zr and Ti to be immobile elements in these samples, indicates a volume loss of more than 30 percent in the shallow part and about 23 percent in the deep part of the main trace. These changes are minimum estimates of fault-related volume loss, because the whole rock from drilling samples contains variable amount of fault rock as well. Minimum estimates for volume loss in the creeping section of the fault are more than 50 percent when using the isocon method, comparing whole rock to plucked fault rock. The majority of the volume loss in the fault rocks is due to the dissolution and loss of silica, potassium, aluminum, sodium and calcium, whereas (based on oxide data) the mineralized surfaces of fractures appear to be enriched in Fe and Mg. The large amount of element mobility within these fault traces suggests extensive circulation of hydrous fluids along fractures that was responsible for progressive dissolution and leaching of the wall rock during faulting.

Dehydration reactions, mass transfer and rock deformation relationships during subduction of Alpine metabauxites: insights from LIBS compositional profiles between metamorphic veins

NASA Astrophysics Data System (ADS)

Verlaguet, A.; Brunet, F.; Goffe, B.; Menut, D.; Findling, N.; Poinssot, C.

2011-12-01

In subduction zones, the significant amounts of aqueous fluid released in the course of the successive dehydration reactions occurring during prograde metamorphism are expected to strongly influence the rock rheology, as well as kinetics of metamorphic reactions and mass transfer efficiency. Mineralized veins, ubiquitous in metamorphic rocks, can be seen as preserved witnesses of fluid and mass redistribution that partly accommodate the rock deformation (lateral segregation). However, the driving forces and mechanisms of mass transfer towards fluid-filled open spaces remain somewhat unclear. The aim of this study is to investigate the modalities of mass transfer during local fluid-rock interactions, and their links with fluid production and rock deformation. This study focuses on karstic pockets (metre scale) of Triassic metabauxites embedded in thick carbonate units, that have been isolated from large-scale fluid flow during HP-LT Alpine metamorphism (W. Vanoise, French Alps). These rocks display several generations of metamorphic veins containing various Al-bearing minerals, which give particular insights into mass transfer processes. It is proposed that the internally-derived fluid (~13 vol% produced by successive dehydration reactions) has promoted the opening of fluid-filled open spaces (euhedral habits of vein minerals) and served as medium for diffusive mass transfer from rock to vein. Based on mineralogical and textural features, two vein types can be distinguished: (1) some veins are filled with newly formed products of either prograde (chloritoid) or retrograde (chlorite) metamorphic reactions; in this case, fluid-filled open spaces seem to offer energetically favourable nucleation/growth sites; (2) the second vein type is filled with cookeite (Li-Al-rich chlorite) or pyrophyllite, that were present in the host rock prior to the vein formation. In this closed chemical system, mass transfer from rock to vein was achieved through the fluid, in a dissolution-transport-precipitation process, possibly stress-assisted. Cookeite is highly concentrated (40-70 vol%) in regularly spaced veins. Laser Induced Breakdown Spectroscopy profiles show that cookeite is evenly distributed in the rock matrix comprised between two veins. The absence of diffusion profiles suggests that the characteristic diffusion length for Li, Al and Si is greater than or equal to the distance separating two cookeite veins (3-6 cm). This is in agreement with characteristic diffusion lengths calculated from both grain boundary and pore fluid diffusion coefficients, for the estimated duration of the peak of metamorphism. Phyllosilicates have very different morphologies in the rock matrix (fibers) compared to veins (euhedral crystals): fluid-mineral interfacial energy may be maximal in the small matrix pores, which can maintain higher cookeite solubility than in fluid-filled open spaces. Therefore, as soon as veins open, chemical potential gradients may develop and drive cookeite transfer from rock matrix to veins.

Host-guest complexes of 2-hydroxypropyl-β-cyclodextrin/β-cyclodextrin and nifedipine: 1H NMR, molecular modeling, and dissolution studies

NASA Astrophysics Data System (ADS)

de Araújo, Márcia Valéria Gaspar; Vieira, João Victor Francisco; da Silva, Caroline W. P.; Barison, Andersson; Andrade, George Ricardo Santana; da Costa, Nivan Bezerra; Barboza, Fernanda Malaquias; Nadal, Jessica Mendes; Novatski, Andressa; Farago, Paulo Vitor; Zawadzki, Sônia Faria

2017-12-01

Nifedipine (NIF) is a hydrophobic drug widely used for treating cardiovascular diseases. This calcium channel blocker can present a higher apparent solubility by its inclusion into different cyclodextrins (CDs) as host-guest complexes. This paper focused on the structural investigation and dissolution behavior of inclusion complexes prepared with 2-hydroxypropyl-β-cyclodextrin (HPβCD) or β-cyclodextrin (βCD) and NIF. Drug amorphization was observed for HPβCD/NIF and βCD/NIF inclusion complexes by X-ray diffractometry (XRD). The sharp endothermic peak of NIF was not observed for these both host-guest complexes by differential scanning calorimetry (DSC). These results of XRD and DSC provide evidences of complexation between drug and the investigated CDs. 1H and saturation transfer difference nuclear magnetic resonance studies revealed the enhancement in the signal at 2.27 ppm for HPβCD/NIF and βCD/NIF inclusion complexes that corresponded to the methyl groups of NIF from the non-aromatic ring. This result suggested that non-aromatic ring of NIF was inserted into HPβCD and βCD cavities. Considering the mathematical simulations, it was observed that the inclusion process can occur in the both NH-in or NH-out forms. However, since it was used aqueous medium, it is possible to indicate that the obtained host-guest complexes HPβCD/NIF and βCD/NIF are in NH-in form which corresponded to the previous results obtained by 1H NMR experiments. Dissolution assays demonstrated that NIF inclusion complexes improved the drug release nevertheless without changing its biexponential release behavior. These host-guest complexes can be further used as feasible NIF carriers in solid dosage forms.

Dissolved CO2 Increases Breakthrough Porosity in Natural Porous Materials.

PubMed

Yang, Y; Bruns, S; Stipp, S L S; Sørensen, H O

2017-07-18

When reactive fluids flow through a dissolving porous medium, conductive channels form, leading to fluid breakthrough. This phenomenon is caused by the reactive infiltration instability and is important in geologic carbon storage where the dissolution of CO 2 in flowing water increases fluid acidity. Using numerical simulations with high resolution digital models of North Sea chalk, we show that the breakthrough porosity is an important indicator of dissolution pattern. Dissolution patterns reflect the balance between the demand and supply of cumulative surface. The demand is determined by the reactive fluid composition while the supply relies on the flow field and the rock's microstructure. We tested three model scenarios and found that aqueous CO 2 dissolves porous media homogeneously, leading to large breakthrough porosity. In contrast, solutions without CO 2 develop elongated convective channels known as wormholes, with low breakthrough porosity. These different patterns are explained by the different apparent solubility of calcite in free drift systems. Our results indicate that CO 2 increases the reactive subvolume of porous media and reduces the amount of solid residual before reactive fluid can be fully channelized. Consequently, dissolved CO 2 may enhance contaminant mobilization near injection wellbores, undermine the mechanical sustainability of formation rocks and increase the likelihood of buoyance driven leakage through carbonate rich caprocks.

Stability of the Orca Basin Brine Interface Determined Using Radium Isotopes

NASA Astrophysics Data System (ADS)

Peterson, R. N.; Peterson, L.; Montoya, J. P.; Joye, S. B.

2016-02-01

The Orca Basin is an intraslope basin in the northern continental slope of the Gulf of Mexico, and contains a deep (up to 220 m) anoxic, hypersaline brine lake. The brine interface extends from ocean salinity (at a water depth of 2125 m) to a constant salinity of 215 psu below a depth of 2250 m. This interface is considered to be among the most stable interfaces on the planet, and contains distinct zones of macrofaunal and microbial assemblages. The brine lake is supported by continued dissolution of exposed rock salt at an estimated rate of 0.5 million t/yr. Such dissolution of salt should serve as a source of radium isotopes, and given their range of half-lives, these isotopes can serve as unique proxies to the location and rate of salt dissolution into this basin. We have collected a series of radon and radium isotope profiles through this brine lake over the past 4 years, which allow us to assess the spatial and temporal stability of this interface. Throughout the brine lake, we observe strong enrichments in unsupported Ra-224, Rn-222, and Ra-226 in a 10 m thick zone near the base of the brine interface, between 2232 m and 2242 m. The strong enrichment in unsupported Ra-224 in this layer must be supported by a continuous source, presumably the dissolution of exposed salt rock. Various degrees of isotopic enrichment throughout the lake provide an assessment of the rates of lateral and vertical dispersion of salt and associated chemical constituents.

Microbiology of Low Temperature Seafloor Deposits Along a Geochemical Gradient in Lau Basin

NASA Astrophysics Data System (ADS)

sylvan, J. B.; Sia, T. Y.; Haddad, A.; Briscoe, L. J.; Girguis, P. R.; Edwards, K. J.

2011-12-01

The East Lau Spreading Center (ELSC) and Valu Fa Ridge comprise a ridge segment in the southwest Pacific Ocean where rapid transitions in the underlying mantle lenses manifest themselves by gradients in seafloor rock geochemistry. At the spreading center in the north, basaltic host rock extrudes while the influence of subduction in the south creates mainly basaltic andesite host rock. A contuous gradient between these two end members exists along the spreading center. We studied the geology and microbial diversity of three silicate rock samples and three inactive sulfide chimney samples collected along the ELSC and Valu Fa Ridge by X-ray diffraction, elemental analysis, thin section analysis and construction of bacterial 16S rRNA clone libraries. Here, we discuss the geological and biological differences between the collected rocks. We found that the bacterial community composition changed as the host rock mineralogy and chemistry changed from north to south. Also, the bacterial community composition on the silicates is distinct from those on the inactive chimneys, and the interior conduit of an inactive chimney hosts a very different community from the exterior. Basalt from the northern end of the ELSC had high proportions of Alphaproteobacteria and Bacteroidetes. These proportions decreased on the silicates collected further south. Epsilonproteobacteria were also present on the basalt, decreased further south and were absent on the basaltic andesite. Conversely, basaltic andesite rocks from the southern end had high proportions of Chloroflexi, which decreased further north and were absent on basalt. The exterior of inactive sulfide structures were dominated by lineages of sulfur oxidizing Gammaproteobacteria and Epsilonproteobacteria and were less diverse than those on the silicates. The interior of one chimney was dominated by sulfate-reducing Deltaproteobacteria and was the least diverse of all samples. These results support the Mantle to Microbe hypothesis in that different types of Bacteria are selected by the composition of the host rock as determined by the melt lens underlying the hydrothermal vent field.

Rates of mineral dissolution and carbonation in peridotite and basalt

NASA Astrophysics Data System (ADS)

Kelemen, P. B.; Matter, J. M.

2009-12-01

We study natural rates and processes of mineral carbonation in peridotite (olivine-rich rock) in mantle rocks exposed to weathering in northern Oman to learn effective mechanisms from natural processes, and seek ways to accelerate them to achieve significant CO2 capture and storage via mineral carbonation at the lowest possible cost. In our first paper (1), we fit data on mantle olivine carbonation from the DOE Albany Research Center (2,3, ARC). These data, and data from Arizona State University (4, ASU) suggest that a peridotite rock volume heated to 185°C and infused with H2O+CO2 at PCO2 > 75 bars could consume ~ 1 ton CO2 per cubic meter of rock per year. Because it is more abundant than peridotite, other workers focus on carbonation of the most common type of lava on Earth, basalt, whose main mineral constituent is generally labradorite, part of the plagioclase feldspar solid solution series. Our intuition is that labradorite carbonation is much slower than mantle olivine carbonation. To quantify this, we compiled data on dissolution of mantle olivine, labradorite, crystalline basalt, and basaltic glass in aqueous fluids, as well as data on mantle olivine carbonation. The dissolution data are calibrated as a function of surface area (i.e., grain size and shape) and pH, as well as temperature, whereas most of the ARC and ASU experiments were done at a single pH and grain size. Thus, for comparison, we calculated dissolution rates for 70 micron spheres at pH 8, close to the ARC and ASU experimental conditions. At these conditions, olivine carbonation observed by ARC and ASU is 100 to 1000 times faster than labradorite and crystalline basalt, and faster than conventionally measured olivine dissolution rates. The ARC and ASU experiments were different from conventional dissolution experiments in several ways that could lead to an enhancement in olivine reaction rates: (a) they may have lower a(Mg) in fluid due to solid MgCO3 (magnesite) precipitation, (b) they used a relatively high ratio of olivine:fluid (1:4), (c) they generally used high fluid NaCl contents, and (d) they consistently used high NaHCO3 and/or KHCO3 (alkali-bicarbonate) concentrations. In agreement with the ASU group, we consider that alkali-bicarbonate is the crucial catalyst, provided PCO2 is high.This raises the question of whether alkali-carbonate could also catalyze labradorite and basalt carbonation. ARC and ASU data extrapolated to low T and low PCO2 agree with natural carbonation rates in Oman. Our geological observations suggest that higher temperature peridotite carbonation went to completion (all Mg as MgCO3, all Si as quartz), perhaps because reaction-driven cracking maintained reactive surface area and permeability despite formation of reaction products in pore space and armoring of remaining olivine reactants. We are not aware of comparable observations on present-day carbonation of basalt. (1) Kelemen & Matter, PNAS 2008 (2) O’Connor et al., DOE Final Report ARC-TR-04-002, 2004 (3) Gerdemann et al., Environ. Sci. Technol. 2007 (4) Chizmeshya et al., DOE Final Report 924162, 2007

Mineral potential modelling of gold and silver mineralization in the Nevada Great Basin - a GIS-based analysis using weights of evidence

USGS Publications Warehouse

Mihalasky, Mark J.

2001-01-01

The distribution of 2,690 gold-silver-bearing occurrences in the Nevada Great Basin was examined in terms of spatial association with various geological phenomena. Analysis of these relationships, using GIS and weights of evidence modelling techniques, has predicted areas of high mineral potential where little or no mining activity exists. Mineral potential maps for sedimentary (?disseminated?) and volcanic (?epithermal?) rock-hosted gold-silver mineralization revealed two distinct patterns that highlight two sets of crustal-scale geologic features that likely control the regional distribution of these deposit types. The weights of evidence method is a probability-based technique for mapping mineral potential using the spatial distribution of known mineral occurrences. Mineral potential maps predicting the distribution of gold-silver-bearing occurrences were generated from structural, geochemical, geomagnetic, gravimetric, lithologic, and lithotectonic-related deposit-indicator factors. The maps successfully predicted nearly 70% of the total number of known occurrences, including ~83% of sedimentary and ~60% of volcanic rock-hosted types. Sedimentary and volcanic rockhosted mineral potential maps showed high spatial correlation (an area cross-tabulation agreement of 85% and 73%, respectively) with expert-delineated mineral permissive tracts. In blind tests, the sedimentary and volcanic rock-hosted mineral potential maps predicted 10 out of 12 and 5 out of 5 occurrences, respectively. The key mineral predictor factors, in order of importance, were determined to be: geology (including lithology, structure, and lithotectonic terrane), geochemistry (indication of alteration), and geophysics. Areas of elevated sedimentary rock-hosted mineral potential are generally confined to central, north-central, and north-eastern Nevada. These areas form a conspicuous ?V?-shape pattern that is coincident with the Battle Mountain-Eureka (Cortez) and Carlin mineral trends and a segment of the Roberts Mountain thrust front, which bridges the southern ends of the trends. This pattern appears to delineate two well-defined, sub-parallel, northwest?southeast-trending crustal-scale structural zones. These features, here termed the ?Carlin? and ?Cortez? structural zones, are believed to control the regional-scale distribution of the sedimentary rock-hosted occurrences. Mineralizing processes were focused along these structural zones and significant ore deposits exist where they intersect other tectonic zones, favorable host rock-types, and (or) where appropriate physio-chemical conditions were present. The origin and age of the Carlin and Cortez structural zones are not well constrained, however, they are considered to be transcurrent features representing a long-lived, deep-crustal or mantle-rooted zone of weakness. Areas of elevated volcanic rock-hosted mineral potential are principally distributed along two broad and diffuse belts that trend (1) northwest-southeast across southwestern Nevada, parallel to the Sierra Nevada, and (2) northeast-southwest across northern Nevada, extending diagonally from the Sierra Nevada to southern Idaho. The first belt corresponds to the Walker Lane shear zone, a wide region of complex strike-slip faulting. The second, here termed the ?Humboldt shear(?) zone?, may represent a structural zone of transcurrent movement. Together, the Walker Lane and Humboldt shear(?) zones are believed to control the regional-scale distribution of volcanic rock-hosted occurrences. Volcanic rock-hosted mineralization was closely tied to the southward and westward migration of Tertiary magmatism across the region (which may have been mantle plume-driven). Both magmatic and mineralizing processes were localized and concentrated along these structural zones. The Humboldt shear(?) zone may have also affected the distribution of sedimentary rock-hosted mineralization along the Battle Mountain?Eureka (C

Lithium isotopic systematics of submarine vent fluids from arc and back-arc hydrothermal systems in the western Pacific

NASA Astrophysics Data System (ADS)

Araoka, Daisuke; Nishio, Yoshiro; Gamo, Toshitaka; Yamaoka, Kyoko; Kawahata, Hodaka

2016-10-01

The Li concentration and isotopic composition (δ7Li) in submarine vent fluids are important for oceanic Li budget and potentially useful for investigating hydrothermal systems deep under the seafloor because hydrothermal vent fluids are highly enriched in Li relative to seawater. Although Li isotopic geochemistry has been studied at mid-ocean-ridge (MOR) hydrothermal sites, in arc and back-arc settings Li isotopic composition has not been systematically investigated. Here we determined the δ7Li and 87Sr/86Sr values of 11 end-member fluids from 5 arc and back-arc hydrothermal systems in the western Pacific and examined Li behavior during high-temperature water-rock interactions in different geological settings. In sediment-starved hydrothermal systems (Manus Basin, Izu-Bonin Arc, Mariana Trough, and North Fiji Basin), the Li concentrations (0.23-1.30 mmol/kg) and δ7Li values (+4.3‰ to +7.2‰) of the end-member fluids are explained mainly by dissolution-precipitation model during high-temperature seawater-rock interactions at steady state. Low Li concentrations are attributable to temperature-related apportioning of Li in rock into the fluid phase and phase separation process. Small variation in Li among MOR sites is probably caused by low-temperature alteration process by diffusive hydrothermal fluids under the seafloor. In contrast, the highest Li concentrations (3.40-5.98 mmol/kg) and lowest δ7Li values (+1.6‰ to +2.4‰) of end-member fluids from the Okinawa Trough demonstrate that the Li is predominantly derived from marine sediments. The variation of Li in sediment-hosted sites can be explained by the differences in degree of hydrothermal fluid-sediment interactions associated with the thickness of the marine sediment overlying these hydrothermal sites.

Carbonate-silicate liquid immiscibility in the mantle propels kimberlite magma ascent

NASA Astrophysics Data System (ADS)

Kamenetsky, Vadim S.; Yaxley, Gregory M.

2015-06-01

Kimberlite is a rare volcanic rock renowned as the major host of diamonds and originated at the base of the subcontinental lithospheric mantle. Although kimberlite magmas are dense in crystals and deeply-derived rock fragments, they ascend to the surface extremely rapidly, enabling diamonds to survive. The unique physical properties of kimberlite magmas depend on the specific compositions of their parental melts that, in absence of historical eruptions and due to pervasive alteration of kimberlite rocks, remain highly debatable. We explain exceptionally rapid ascent of kimberlite magma from mantle depths by combining empirical data on the essentially carbonatite composition of the kimberlite primary melts and experimental evidence on interaction of the carbonate liquids with mantle minerals. Our experimental study shows that orthopyroxene is completely dissolved in a Na2CO3 melt at 2.0-5.0 GPa and 1000-1200 °C. The dissolution of orthopyroxene results in homogeneous silicate-carbonate melt at 5.0 GPa and 1200 °C, and is followed by unmixing of carbonate and carbonated silicate melts and formation of stable magmatic emulsion at lower pressures and temperatures. The dispersed silicate melt has a significant capacity for storing a carbonate component in the deep mantle (13 wt% CO2 at 2.0 GPa). We envisage that this component reaches saturation and is gradually released as CO2 bubbles, as the silicate melt globules are transported upwards through the lithosphere by the carbonatite magma. The globules of unmixed, CO2-rich silicate melt are continuously produced upon further reaction between the natrocarbonatite melt and mantle peridotite. On decompression the dispersed silicate melt phase ensures a continuous supply of CO2 bubbles that decrease density and increase buoyancy and promote rapid ascent of the magmatic emulsion.

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.

Geochemical models of metasomatism in ultramafic systems: Serpentinization, rodingitization, and sea floor carbonate chimney precipitation

USGS Publications Warehouse

Palandri, J.L.; Reed, M.H.

2004-01-01

In a series of water-rock reaction simulations, we assess the processes of serpentinization of harzburgite and related calcium metasomatism resulting in rodingite-type alteration, and seafloor carbonate chimney precipitation. At temperatures from 25 to 300??C (P = 10 to 100 bar), using either fresh water or seawater, serpentinization simulations produce an assemblage commonly observed in natural systems, dominated by serpentine, magnetite, and brucite. The reacted waters in the simulations show similar trends in composition with decreasing water-rock ratios, becoming hyper-alkaline and strongly reducing, with increased dissolved calcium. At 25??C and w/r less than ???32, conditions are sufficiently reducing to yield H2 gas, nickel-iron alloy and native copper. Hyperalkalinity results from OH- production by olivine and pyroxene dissolution in the absence of counterbalancing OH- consumption by alteration mineral precipitation except at very high pH; at moderate pH there are no stable calcium minerals and only a small amount of chlorite forms, limited by aluminum, thus allowing Mg2+ and Ca2+ to accumulate in the aqueous phase in exchange for H+. The reducing conditions result from oxidation of ferrous iron in olivine and pyroxene to ferric iron in magnetite. Trace metals are computed to be nearly insoluble below 300??C, except for mercury, for which high pH stabilizes aqueous and gaseous Hg??. In serpentinization by seawater at 300??C, Ag, Au, Pd, and Pt may approach ore-forming concentrations in sulfide complexes. Simulated mixing of the fluid derived from serpentinization with cold seawater produces a mineral assemblage dominated by calcite, similar to recently discovered submarine, ultramafic rock-hosted, carbonate mineral deposits precipitating at hydrothermal vents. Simulated reaction of gabbroic or basaltic rocks with the hyperalkaline calcium- and aluminum-rich fluid produced during serpentinization at 300??C yields rodingite-type mineral assemblages, including grossular, clinozoisite, vesuvianite, prehnite, chlorite, and diopside. ?? 2004 Elsevier Ltd.

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.

Deformation-resembling microstructure created by fluid-mediated dissolution-precipitation reactions.

PubMed

Spruzeniece, Liene; Piazolo, Sandra; Maynard-Casely, Helen E

2017-01-27

Deformation microstructures are widely used for reconstructing tectono-metamorphic events recorded in rocks. In crustal settings deformation is often accompanied and/or succeeded by fluid infiltration and dissolution-precipitation reactions. However, the microstructural consequences of dissolution-precipitation in minerals have not been investigated experimentally. Here we conducted experiments where KBr crystals were reacted with a saturated KCl-H 2 O fluid. The results show that reaction products, formed in the absence of deformation, inherit the general crystallographic orientation from their parents, but also display a development of new microstructures that are typical in deformed minerals, such as apparent bending of crystal lattices and new subgrain domains, separated by low-angle and, in some cases, high-angle boundaries. Our work suggests that fluid-mediated dissolution-precipitation reactions can lead to a development of potentially misleading microstructures. We propose a set of criteria that may help in distinguishing such microstructures from the ones that are created by crystal-plastic deformation.

Effect of oxalate on the dissolution rates of oligoclase and tremolite

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

Mast, M.A.; Drever, J.I.

1987-09-01

The effect of oxalate, a strong chelator for Al and other cations, on the dissolution rates of oligoclase feldspar and tremolite amphibole was investigated in a flow-through reactor at 22/sup 0/C. Oxalate at concentrations of 0.5 and 1 mM has essentially no effect on the dissolution rate of tremolite, nor on the steady-state rate of release of Si from oligoclase. The fact that oxalate has no effect on dissolution rate suggests that detachment of Si rather than Al or Mg is the rate-limiting step. At pH 4 and 9, oxalate has no effect on the steady-state rate of release ofmore » Al, and dissolution is congruent. At pH 5 and 7, oligoclase dissolution is congruent in the presence of oxalate, but in the absence of oxalate Al is preferentially retained in the solid relative to Si. Large transient spikes of Al or Si are observed when oxalate is added to or removed from the system. The cause of the spikes is unknown; the authors suggest adsorption feldspar surfaces away from sites of active dissolution as a possibility. The rate of dissolution of tremolite is independent of pH over the pH range 2-5, and decreases at higher pH. The rate of dissolution of oligoclase in these experiments was independent of pH over the pH range 4-9. Since the dissolution rate of these minerals is independent of pH and organic ligand concentration, the effect of acid deposition from the atmosphere on the rate of supply of cations from weathering of granitic rocks should be minor.« less

Rock-magnetic changes with reduction diagenesis in Japan Sea sediments and preservation of geomagnetic secular variation in inclination during the last 30,000 years

NASA Astrophysics Data System (ADS)

Yamazaki, T.; Abdeldayem, A. L.; Ikehara, K.

2003-06-01

A rock-magnetic and paleomagnetic study was conducted on a sediment core of about 4.4 m long taken from the northeastern part of the Japan Sea. The core covers the last about 30 kyrs, which was dated by nineteen radiocarbon (14C) ages. Remanent magnetization is carried dominantly by magnetite. Reductive dissolution of magnetic minerals occurs between 1.2 and 1.6 m in depth (about 5-8 ka in age). A rapid downcore decrease of anhysteretic remanent magnetization (ARM) begins at the shallowest depth. Saturation isothermal remanent magnetization (SIRM) follows, and a decrease of magnetic susceptibility (k) takes place at the deepest. Within this zone, coercivity of natural remanent magnetization (NRM) and the ratios of ARM to k and SIRM to k also decreases with depth. These observations indicate that finer magnetic grains were lost earlier than larger grains. A decrease of S ratios, wasp-waisted hysteresis curves, and a deviation from a mixing trend of single-domain and multi-domain grains in a Day plot occur as the dissolution proceeds, which suggests that high coercivity minerals like hematite are more resistive to dissolution than low coercivity minerals like magnetite. The start of the dissolution at 1.2 m in depth is synchronous with increases in organic-carbon and total-sulfur contents, but the horizon does not coincide with the present Fe-redox boundary at about 0.02 m below the sediment-water interface. From low-temperature magnetometry, it is estimated that magnetites with maghemite skin are reduced to pure magnetites prior to dissolution. There is no evidence for precipitation of secondary magnetic phases and acquisition of chemical remanent magnetization (CRM). Neither pyrrhotite nor greigite was detected. Information of paleomagnetic directions have survived the reductive dissolution. Inclination variations of this core resembles closely to the secular variation records available around Japan. Well-dated records older than 10 ka are still very rare, and hence our new record could be useful for establishing regional secular variations.

Role of fiber dissolution in biological activity in rats.

PubMed

Eastes, W; Hadley, J G

1994-12-01

This report deals with the role of dissolution in removing long fibers from the lung and with a mathematical model that predicts chronic effects in rats following inhalation or intraperitoneal (i.p.) injection of fibers. Results of intratracheal instillation studies and inhalation studies in rats demonstrate clearly that long vitreous fibers dissolve in vivo at about the same rate measured in vitro in fluid designed to stimulate the extracellular lung fluid. For the glass, rock, and slag wool fibers tested, dissolution removed most of the fibers longer than 20 microns inhaled into the rats' lungs within 6 months after both short-term (5 days) and long-term (1 to 2 years) exposures. A mathematical model was developed that is based on fiber dissolution and allows one to predict the development of chronic lung diseases in rats. The model predicted the incidence of fibrosis and lung tumors in a series of recent inhalation studies and tumors following ip injection to within about the error of the experiments. The model suggests that all fibers, regardless of their dissolution rate in lung fluid, can produce tumors after ip injection because the dose can be unlimited by this route. After inhalation, in contrast, dissolution of many types of long vitreous fibers occurs rapidly, and disease does not ensue for these fibers.

Hyperacid volcano-hydrothermal fluids from Copahue volcano, Argentina: Analogs for "subduction zone fluids"?

NASA Astrophysics Data System (ADS)

Varekamp, J. C.

2007-12-01

Hyperacid concentrated Chlorine-Sulfate brines occur in many young arc volcanoes, with pH values <1, high concentrations of volcanogenic elements (S, Cl, F, As, B) and the main rock forming elements (Ca, Al, Mg, K, Na, P). Sulfur isotope data and Silica thermometry from such fluids sampled over a ten year period from the Copahue volcanic system (Argentina) suggest reservoir temperatures of 175-300 oC, whereas the surface fluids do not exceed local boiling temperatures. These fluids are generated at much lower P-T conditions than fluids associated with a dehydrating subducted sediment complex below arc volcanoes, but their fundamental chemical compositions may have similarities. Incompatible trace element, major element concentrations and Pb isotope compositions of the fluids were used to determine the most likely rock protoliths for these fluids. Mean rock- normalized trace element diagrams then indicate which elements are quantitatively extracted from the rocks and which are left behind or precipitated in secondary phases. Most LILE show flat rock-normalized patterns, indicating close to congruent dissolution, whereas Ta-Nb-Ti show strong depletions in the rock-normalized diagrams. These HFSE are either left behind in the altered rock protolith or were precipitated along the way up. The behavior of U and Th is almost identical, suggesting that in these low pH fluids with abundant ligands Th is just as easily transported as U, which is not the case in more dilute, neutral fluids. Most analyzed fluids have steeper LREE patterns than the rocks and have negative Eu anomalies similar to the rocks. Fluids that interacted with newly intruded magma e.g., during the 2000 eruption, have much less pronounced Eu anomalies, which was most likely caused by the preferential dissolution of plagioclase when newly intruded magma interacted with the acid fluids. The fluids show a strong positive correlation between Y and Cd (similar to MORB basalts, Yi et al., JGR, 2000), suggesting that Cd is mainly a rock-derived element that may not show chalcophilic behavior. The fluids are strongly enriched (relative to rock) in As, Zn and Pb, suggesting that these elements were carried with the volcanic gas phase into the system. In summary, if these fluids are broadly similar to fluids from dehydrating subducted sediments, they tend to transport preferently the LILE, LREE, U as well as Th, while the HFSE are left behind.

Coper Isotope Fractionation in Porphyry Copper Deposits: A Controlled Experiment

NASA Astrophysics Data System (ADS)

Ruiz, J.; Mathur, R.; Uhrie, J. L.; Hiskey, B.

2001-12-01

Previous studies have shown that copper is fractionated in the environment. However, the mechanisms for isotope fractionation and the role of organic and inorganic processes in the fractionation are not well understood. Here we used the well controlled experiments used by Phelps Dodge Corporation aimed at leaching copper from their ore deposits to constrain the mechanism of copper isotope fractionation in natural systems. The isotope data were collected on a Micromass Isoprobe. High temperature copper sulfides from ore deposits in Chile and Arizona yield delta 65Cu near 0 permil. The reproducibility of the data is better that 0.1 permil. Controlled experiments consisting of large columns of rocks were fed solutions containing bacteria such as Thiobacillus ferroxidans and Leptospirrilium ferroxidan. Solutions fom the columns were sampled for sixty days and analyzed for copper concentrations, oxidation potential, ferrous/ferric ratios and pH. The results indicate that the bacterially aided dissolution of copper fractionated copper. Preliminary experiments of copper dissolution not using bacteria show no isotope fractionation The original rock in the experiment has a delta 65Cu of -2.1. The first solutions that were collected from the columns had a delta 65Cu of -5.0 per mil. The liquid changed its isotopic composition from -50 to -10 during the sixty days of sampling. The greatest shift in the isotope ratios occurred the first 30 days when the copper recovered was less than 40% and the ferrous/ferric ratios were somewhat constant. At approximately 35 days after the start of the experiments, the copper recovery increases the ferrousferric ratio decreased and the copper isotope ratio of the fluids remained fairly constant. The data suggest that the bacteria are required to effectively fractionate copper isotopes in natural systems and that the mechanisms of bacterial aided copper dissolution may include a direct dissolution of the sulfides by the bacteria. Experiments underway with enzimes without the bacteria may confirm this hypothesis. The data obtained in these experiments will provide some constraints in the use of copper isotopes as proxy for life in the rock record.

Effects of Bacillus subtilis endospore surface reactivity on the rate of forsterite dissolution

NASA Astrophysics Data System (ADS)

Harrold, Z.; Gorman-Lewis, D.

2013-12-01

Primary mineral dissolution products, such as silica (Si), calcium (Ca) and magnesium (Mg), play an important role in numerous biologic and geochemical cycles including microbial metabolism, plant growth and secondary mineral precipitation. The flux of these and other dissolution products into the environment is largely controlled by the rate of primary silicate mineral dissolution. Bacteria, a ubiquitous component in water-rock systems, are known to facilitate mineral dissolution and may play a substantial role in determining the overall flux of dissolution products into the environment. Bacterial cell walls are complex and highly reactive organic surfaces that can affect mineral dissolution rates directly through microbe-mineral adsorption or indirectly by complexing dissolution products. The effect of bacterial surface adsorption on chemical weathering rates may even outweigh the influence of active processes in environments where a high proportion of cells are metabolically dormant or cell metabolism is slow. Complications associated with eliminating or accounting for ongoing metabolic processes in long-term dissolution studies have made it challenging to isolate the influence of cell wall interactions on mineral dissolution rates. We utilized Bacillus subtilis endospores, a robust and metabolically dormant cell type, to isolate and quantify the effects of bacterial surface reactivity on forsterite (Mg2SiO4) dissolution rates. We measured the influence of both direct and indirect microbe-mineral interactions on forsterite dissolution. Indirect pathways were isolated using dialysis tubing to prevent mineral-microbe contact while allowing free exchange of dissolved mineral products and endospore-ion adsorption. Homogenous experimental assays allowed both direct microbe-mineral and indirect microbe-ion interactions to affect forsterite dissolution rates. Dissolution rates were calculated based on silica concentrations and zero-order dissolution kinetics. Additional analyses including Mg concentrations, microprobe and BET analyses support mineral dissolution rate calculations and stoichiometry considerations. All experimental assays containing endospores show increased forsterite dissolution rates relative to abiotic controls. Forsterite dissolution rates increased by approximately one order of magnitude in dialysis bound, biotic experiments relative to abiotic assays. Homogenous biotic assays exhibited a more complex dissolution rate profile that changes over time. All microbially mediated forsterite dissolution rates returned to abiotic control rates after 10 to 15 days of incubation. This shift in dissolution rate likely corresponds to maximum endospore surface adsorption capacity. The Bacillus subtilis endospore surface serves as a first-order proxy for studying the effect of metabolizing microbe surfaces on silicate dissolution rates. Comparisons with published abiotic, microbial, and organic acid mediated forsterite dissolution rates will provide insight on the importance of bacterial surfaces in primary mineral dissolution processes.

[Difference of Karst Carbon Sink Under Different Land Use and Land Cover Areas in Dry Season].

PubMed

Zhao, Rui-yi; Liang, Zuo-bing; Wang, Zun-bo; Yu, Zheng-liang; Jiang, Ze-li

2015-05-01

In order to identify the distinction of soil CO2 consumed by carbonate rock dissolution, Baishuwan spring, Lanhuagou spring and Hougou spring were selected as objects to monitor the hydrochemistry from November 2013 to May 2014. The results showed that the highest HCO3- concentration was observed in Baishuwan spring which is covered by pine forest, while the lowest HCO3- concentration was observed in Hougou spring which is mainly covered by cultivated land. In Baishuwan spring, HCO3- was mainly derived from carbonic acid dissolving carbonate rock and the molar ratio between Ca(2+) + Mg2+ and HCO3- was close to 0. 5; while the molar ratio between Ca(2+) + Mg2+ and HCO3- exceeded 0.5 because the carbonate rock in Lanhuagou spring and Hougou spring was mainly dissolved by nitric acid and sulfuric acid. Because of the input of litter and the fact that gas-permeability of soil was limited in Baishuwan spring catchment, most of soil CO2 was dissolved in infiltrated water and reacted with bedrock. However, in Lanhuagou spring catchment and Hougou spring catchment, porous soil made soil CO2 easier to return to the atmosphere in the form of soil respiration. Therefore, in order to accurately estimate karst carbon sink, it was required to clarify the distinction of CO2 consumption by carbonate rock dissolution under different land use and land cover areas.

Stable isotopic evidence for anaerobic maintained sulphate discharge in a polythermal glacier

NASA Astrophysics Data System (ADS)

Ansari, A. H.

2016-03-01

To understand the sources and sinks of sulphate and associated biogeochemical processes in a High Arctic environment, late winter snowpacks, the summer melt-waters and rock samples were collected and analysed for major ions and stable isotope tracers (δ18O, δ34S). The SO42bar/Clbar ratio reveal that more than 87% of sulphate (frequently > 95%) of total sulphate carried by the subglacial runoff and proglacial streams was derived from non-snowpack sources. The proximity of non-snowpack sulphate δ34S (∼8-19‰) to the δ34S of the major rocks in the vicinity (∼-6 to +18‰) suggest that the non-snowpack sulphate was principally derived from rock weathering. Furthermore, Ca2++Mg2+/SO42ˉ molar shows that sulphate acquisition in the meltwaters was controlled by two major processes: 1) coupled-sulphide carbonate weathering (molar ratio ∼ 2) and, 2) re-dissolution of secondary salts (molar ratio ∼ 1). The δ34S-SO4 = +19.4‰ > δ34S-S of rock, accompanied by increased sulphate concentration also indicates an input from re-dissolution of secondary salts. Overall, δ18O composition of these non-snowpack sulphate (-11.9 to -2.2‰) mostly stayed below the threshold δ18O value (-6.7 to -3.3‰) for minimum O2 condition, suggesting that certain proportion of sulphate was regularly supplied from anaerobic sulphide oxidation.

Alteration of fault rocks by CO2-bearing fluids with implications for sequestration

NASA Astrophysics Data System (ADS)

Luetkemeyer, P. B.; Kirschner, D. L.; Solum, J. G.; Naruk, S.

2011-12-01

Carbonates and sulfates commonly occur as primary (diagenetic) pore cements and secondary fluid-mobilized veins within fault zones. Stable isotope analyses of calcite, formation fluid, and fault zone fluids can help elucidate the carbon sources and the extent of fluid-rock interaction within a particular reservoir. Introduction of CO2 bearing fluids into a reservoir/fault system can profoundly affect the overall fluid chemistry of the reservoir/fault system and may lead to the enhancement or degradation of porosity within the fault zone. The extent of precipitation and/or dissolution of minerals within a fault zone can ultimately influence the sealing properties of a fault. The Colorado Plateau contains a number of large carbon dioxide reservoirs some of which leak and some of which do not. Several normal faults within the Paradox Basin (SE Utah) dissect the Green River anticline giving rise to a series of footwall reservoirs with fault-dependent columns. Numerous CO2-charged springs and geysers are associated with these faults. This study seeks to identify regional sources and subsurface migration of CO2 to these reservoirs and the effect(s) faults have on trap performance. Data provided in this study include mineralogical, elemental, and stable isotope data for fault rocks, host rocks, and carbonate veins that come from two localities along one fault that locally sealed CO2. This fault is just tens of meters away from another normal fault that has leaked CO2-charged waters to the land surface for thousands of years. These analyses have been used to determine the source of carbon isotopes from sedimentary derived carbon and deeply sourced CO2. XRF and XRD data taken from several transects across the normal faults are consistent with mechanical mixing and fluid-assisted mass transfer processes within the fault zone. δ13C range from -6% to +10% (PDB); δ18O values range from +15% to +24% (VSMOW). Geochemical modeling software is used to model the alteration productions of fault rocks from fluids of various chemistries coming from several different reservoirs within an active CO2-charged fault system. These results are compared to data obtained in the field.

Preliminary Numerical Simulations of Nozzle Formation in the Host Rock of Supersonic Volcanic Jets

NASA Astrophysics Data System (ADS)

Wohletz, K. H.; Ogden, D. E.; Glatzmaier, G. A.

2006-12-01

Recognizing the difficulty in quantitatively predicting how a vent changes during an explosive eruption, Kieffer (Kieffer, S.W., Rev. Geophys. 27, 1989) developed the theory of fluid dynamic nozzles for volcanism, utilizing a highly developed predictive scheme used extensively in aerodynamics for design of jet and rocket nozzles. Kieffer's work shows that explosive eruptions involve flow from sub to supersonic conditions through the vent and that these conditions control the erosion of the vent to nozzle shapes and sizes that maximize mass flux. The question remains how to predict the failure and erosion of vent host rocks by a high-speed, multiphase, compressible fluid that represents an eruption column. Clearly, in order to have a quantitative model of vent dynamics one needs a robust computational method for a turbulent, compressible, multiphase fluid. Here we present preliminary simulations of fluid flowing from a high-pressure reservoir through an eroding conduit and into the atmosphere. The eruptive fluid is modeled as an ideal gas, the host rock as a simple incompressible fluid with sandstone properties. Although these simulations do not yet include the multiphase dynamics of the eruptive fluid or the solid mechanics of the host rock, the evolution of the host rock into a supersonic nozzle is clearly seen. Our simulations show shock fronts both above the conduit, where the gas has expanded into the atmosphere, and within the conduit itself, thereby influencing the dynamics of the jet decompression.

Epigenetic formation of amethyst-bearing geodes from Los Catalanes gemological district, Artigas, Uruguay, southern Paraná Magmatic Province

NASA Astrophysics Data System (ADS)

Duarte, L. C.; Hartmann, L. A.; Vasconcellos, M. A. Z.; Medeiros, J. T. N.; Theye, T.

2009-07-01

Giant geodes (up to 4 m long) in the massive central portions of altered basalt lavas from the Paraná Magmatic Province, southern Brazil and Uruguay, form a world-class source of amethyst and agate. Although the origin of the cavities has been ascribed to degassing of the lava at > 1150 °C, field evidence is conclusive that the giant amethyst-agate-filled geodes were formed by hydrothermal processes at low temperatures. We propose an epigenetic and hydrothermal model for the origin of giant geodes. This model includes hydrothermal brecciation during an early brittle stage and the late formation of the cavities (geodes). In the brittle stage an overpressured aqueous fluid affected the basalt in a P, T field delimited by temperatures between 100 and 150 °C and vapor pressures between 1.2 and 5.5 bar. The fluids were capable of lifting the roof and fracturing the host rock along new subhorizontal and subvertical fractures and breccias in the massive lava. The formation of these structures occurred at shallow depths, unit-by-unit. To open the cavities, dissolution of the now altered basalt to clay minerals is necessary. The process is closely linked to the highest alteration grade of mineralized lavas in Los Catalanes gemological district. Dissolution processes are observed in micrometer-scale in the studied basalts. The primary mineralogy, consisting of labradorite (± andesine) +augite + pigeonite + mesostasis (K-rich), was altered during the interaction of large volumes of hot aqueous fluid with the rock. The alteration of pigeonite and its replacement by smectite is observed around the cavities, followed by the precipitation of amorphous silica and microcrystalline quartz in clay-rich sites. Associated zeolites (heulandite + clinoptilolite) fill the newly formed cavities in progressive stages of hydrothermal alteration. Our data indicate that the temperatures were less than 200 °C and probably less than 150 °C; cavity formation occurred after alteration of the basalt to more than 60 vol.% clay minerals. We thus suggest that cavities related to geode formation are of epigenetic origin.

Fracturing of doleritic intrusions and associated contact zones: Implications for fluid flow in volcanic basins

NASA Astrophysics Data System (ADS)

Senger, Kim; Buckley, Simon J.; Chevallier, Luc; Fagereng, Åke; Galland, Olivier; Kurz, Tobias H.; Ogata, Kei; Planke, Sverre; Tveranger, Jan

2015-02-01

Igneous intrusions act as both carriers and barriers to subsurface fluid flow and are therefore expected to significantly influence the distribution and migration of groundwater and hydrocarbons in volcanic basins. Given the low matrix permeability of igneous rocks, the effective permeability in- and around intrusions is intimately linked to the characteristics of their associated fracture networks. Natural fracturing is caused by numerous processes including magma cooling, thermal contraction, magma emplacement and mechanical disturbance of the host rock. Fracturing may be locally enhanced along intrusion-host rock interfaces, at dyke-sill junctions, or at the base of curving sills, thereby potentially enhancing permeability associated with these features. In order to improve our understanding of fractures associated with intrusive bodies emplaced in sedimentary host rocks, we have investigated a series of outcrops from the Karoo Basin of the Eastern Cape province of South Africa, where the siliciclastic Burgersdorp Formation has been intruded by various intrusions (thin dykes, mid-sized sheet intrusions and thick sills) belonging to the Karoo dolerite. We present a quantified analysis of fracturing in- and around these igneous intrusions based on five outcrops at three individual study sites, utilizing a combination of field data, high-resolution lidar virtual outcrop models and image processing. Our results show a significant difference between the three sites in terms of fracture orientation. The observed differences can be attributed to contrasting intrusion geometries, outcrop geometry (for lidar data) and tectonic setting. Two main fracture sets were identified in the dolerite at two of the sites, oriented parallel and perpendicular to the contact respectively. Fracture spacing was consistent between the three sites, and exhibits a higher degree of variation in the dolerites compared to the host rock. At one of the study sites, fracture frequency in the surrounding host rock increases slightly toward the intrusion at approximately 3 m from the contact. We conclude by presenting a conceptual fluid flow model, showing permeability enhancement and a high potential for fluid flow-channeling along the intrusion-host rock interfaces.

Geochemistry of groundwater in the Beaver and Camas Creek drainage basins, eastern Idaho

USGS Publications Warehouse

Rattray, Gordon W.; Ginsbach, Michael L.

2014-01-01

The U.S. Geological Survey (USGS), in cooperation with the U.S. Department of Energy, is studying the fate and transport of waste solutes in the eastern Snake River Plain (ESRP) aquifer at the Idaho National Laboratory (INL) in eastern Idaho. This effort requires an understanding of the natural and anthropogenic geochemistry of groundwater at the INL and of the important physical and chemical processes controlling the geochemistry. In this study, the USGS applied geochemical modeling to investigate the geochemistry of groundwater in the Beaver and Camas Creek drainage basins, which provide groundwater recharge to the ESRP aquifer underlying the northeastern part of the INL. Data used in this study include petrology and mineralogy from 2 sediment and 3 rock samples, and water-quality analyses from 4 surface-water and 18 groundwater samples. The mineralogy of the sediment and rock samples was analyzed with X-ray diffraction, and the mineralogy and petrology of the rock samples were examined in thin sections. The water samples were analyzed for field parameters, major ions, silica, nutrients, dissolved organic carbon, trace elements, tritium, and the stable isotope ratios of hydrogen, oxygen, carbon, sulfur, and nitrogen. Groundwater geochemistry was influenced by reactions with rocks of the geologic terranes—carbonate rocks, rhyolite, basalt, evaporite deposits, and sediment comprised of all of these rocks. Agricultural practices near and south of Dubois and application of road anti-icing liquids on U.S. Interstate Highway 15 were likely sources of nitrate, chloride, calcium, and magnesium to groundwater. Groundwater geochemistry was successfully modeled in the alluvial aquifer in Camas Meadows and the ESRP fractured basalt aquifer using the geochemical modeling code PHREEQC. The primary geochemical processes appear to be precipitation or dissolution of calcite and dissolution of silicate minerals. Dissolution of evaporite minerals, associated with Pleistocene Lake Terreton, is an important contributor of solutes in the Mud Lake-Dubois area. Oxidation-reduction reactions are important influences on the chemistry of groundwater at Camas Meadows and the Camas National Wildlife Refuge. In addition, mixing of different groundwaters or surface water with groundwater appears to be an important physical process influencing groundwater geochemistry in much of the study area, and evaporation may be an important physical process influencing the groundwater geochemistry of the Camas National Wildlife Refuge. The mass-balance modeling results from this study provide an explanation of the natural geochemistry of groundwater in the ESRP aquifer northeast of the INL, and thus provide a starting point for evaluating the natural and anthropogenic geochemistry of groundwater at the INL.

Clay alteration and gold deposition in the genesis and blue star deposits, Eureka County, Nevada

USGS Publications Warehouse

Drews-Armitage, S. P.; Romberger, S.B.; Whitney, C.G.

1996-01-01

The Genesis and Blue Star sedimentary rock-hosted gold deposits occur within the 40-mile-long Carlin trend and are located in Eureka County, Nevada. The deposits are hosted within the Devonian calcareous Popovich Formation, the siliciclastic Rodeo Creek unit and the siliciclastic Vinini Formation. The host rocks have undergone contact metamorphism, decalcification, silicification, argillization, and supergene oxidation. Detailed characterization of the alteration patterns, mineralogy, modes of occurrence, and associated geochemistry of clay minerals resulted in the following classifications: least altered rocks, found distal to the orebody, consisting of both metamorphosed and unmetamorphosed host rock that has not been completely decalcified; and altered rocks, found proximal to the orebody that have been decalcified. Altered rocks are classified further into the following groups based on clay mineral content: silicic, 1 to 10 percent clay; silicicargillic, 10 to 35 percent clay; and argillic, 35 to 80 percent clay. Clay species identified are 1M illite, 2M1 illite, kaolinite, halloysite, and dioctahedral smectite. An early hydrothermal event resulted in the precipitation of euhedral kaolinite and at least one generation of silica. This event occurred contemporaneously with decalcification which increased rock permeability and porosity. A second clay alteration event resulted in the precipitation of hydrothermal 1M illite which replaced hydrothermal kaolinite and is associated with gold deposition. Silver and silica deposition is also associated with this phase of hydrothermal alteration. Hydrothermal alteration was followed by supergene alteration which resulted in the formation of supergene kaolinite, halloysite, and smectite as well as the oxidation of iron-bearing minerals. Supergene clays are concentrated along faults, dike margins, and within rocks containing carbonate. Gold mineralization is not associated with supergene clay minerals within the Genesis and Blue Star deposits. Rocks classified as silicic-argillic in the Popovich Formation represent the most significant gold host. Silicicargillic rocks commonly exhibit bedding-parallel alteration zones. This pattern of alteration indicates that stratigraphy as well as northwest-trending structures played a significant role in the migration of gold-bearing fluids. Based on K-Ar age determinations of hydrothermal 1M illite associated with gold, the main event of mineralization in the Genesis and Blue Star deposits occurred between 93 and 100 Ma, during mid-Cretaceous time.

Carbon dioxide sequestration induced mineral precipitation healing of fractured reservoir seals

NASA Astrophysics Data System (ADS)

Welch, N.; Crawshaw, J.

2017-12-01

Initial experiments and the thermodynaic basis for carbon dioxide sequestration induced mineral precipitation healing of fractures through reservoir seals will be presented. The basis of this work is the potential exists for the dissolution of reservoir host rock formation carbonate minerals in the acidified injection front of CO2 during sequestration or EOR. This enriched brine and the bulk CO2 phase will then flow through the reservoir until contact with the reservoir seal. At this point any fractures present in the reservoir seal will be the preferential flow path for the bulk CO2 phase as well as the acidified brine front. These fractures would currently be filled with non-acidified brine saturated in seal formation brine. When the acidifeid brine from the host formation and the cap rock brine mix there is the potential for minerals to fall out of solution, and for these precipitated minerals to decrease or entirely cut off the fluid flow through the fractures present in a reservoir seal. Initial equilibrium simulations performed using the PHREEQC1 database drived from the PHREEQE2 database are used to show the favorable conditions under which this mineral precipitation can occurs. Bench scale fluid mixing experiments were then performed to determine the kinetics of the mineral precipitation process, and determine the progress of future experiemnts involving fluid flow within fractured anhydrite reservoir seal samples. 1Parkhurst, D.L., and Appelo, C.A.J., 2013, Description of input and examples for PHREEQC version 3—A computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations: U.S. Geological Survey Techniques and Methods, book 6, chap. A43, 497 p., available only at https://pubs.usgs.gov/tm/06/a43/. 2Parkhurst, David L., Donald C. Thorstenson, and L. Niel Plummer. PHREEQE: a computer program for geochemical calculations. No. 80-96. US Geological Survey, Water Resources Division,, 1980.

Fe (hydro) oxide controls Mo isotope fractionation during the weathering of granite

NASA Astrophysics Data System (ADS)

Wang, Zhibing; Ma, Jinlong; Li, Jie; Wei, Gangjian; Zeng, Ti; Li, Lei; Zhang, Le; Deng, Wenfeng; Xie, Luhua; Liu, Zhifeng

2018-04-01

Understanding the fractionation mechanisms of Mo isotopes and seeking the main hosts of light δ98/95Mo during chemical weathering of continental rocks is a prerequisite for constraining heavy δ98/95Mo input into rivers. This study investigates the Mo concentrations and δ98/95Mo values of bulk samples, chemical extractions, and clay fractions of weathering products in a granite weathering profile in Guangdong province, South China, as well as in surrounding stream water. Results from bulk samples show that the τ MoTiO2 values systematically decrease from 59.1% to -77.0%, and δ98/95Mo values systematically increase from -1.46‰ to -0.17‰, upwards in the profile (from 30 to 0 m depth). Atmospheric input has a limited effect on δ98/95Mo variations in the weathering profile. Adsorption and desorption processes of Fe (hydro) oxide are the dominant factors controlling the variations in δ98/95Mo, with light Mo isotopes preferentially adsorbed by Fe (hydro) oxide, and released during desorption process, whereas the incongruent dissolution of primary minerals has little effect. Organic materials and the clay fraction are not the main hosts of light δ98/95Mo, as indicated by the results of chemical extractions, which show that a large proportion (41.5-86.2%) of total Mo with light δ98/95Mo (-1.57‰ to -0.59‰) is associated with Fe (hydro) oxide. Moreover, a significant positive correlation exists between Mo concentrations and δ98/95Mo in the Fe (hydro) oxide extractions from bulk samples. Finally, δ98/95Mo in stream water indicates the release of heavier δ98/95Mo into river water during the chemical weathering of granite rock. The results advance our understanding the mechanisms of Mo isotope fractionation during chemical weathering and its isotopic mass balance in Earth's surface system.

Subsurface drainage erodes forested granitic terrane

Treesearch

Philip Durgin

1984-01-01

Abstract - Solution and landsliding, the dominant erosion processes in undisturbed forested mountainous watersheds, are both influenced by subsurface drainage. Biological processes that generate organic acids accelerate loss of dissolved solids by promoting the dissolution of primary minerals in granitic rock. These organic acids can also disperse the secondary...

A dissolution-precipitation mechanism is at the origin of concrete creep in moist environments

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

Pignatelli, Isabella; Kumar, Aditya; Alizadeh, Rouhollah

Long-term creep (i.e., deformation under sustained load) is a significant material response that needs to be accounted for in concrete structural design. However, the nature and origin of concrete creep remain poorly understood and controversial. Here, we propose that concrete creep at relative humidity ≥ 50%, but fixed moisture content (i.e., basic creep), arises from a dissolution-precipitation mechanism, active at nanoscale grain contacts, as has been extensively observed in a geological context, e.g., when rocks are exposed to sustained loads, in liquid-bearing environments. Based on micro-indentation and vertical scanning interferometry data and molecular dynamics simulations carried out on calcium–silicate–hydrate (C–S–H),more » the major binding phase in concrete, of different compositions, we show that creep rates are correlated with dissolution rates—an observation which suggests a dissolution-precipitation mechanism as being at the origin of concrete creep. C–S–H compositions featuring high resistance to dissolution, and, hence, creep are identified. Analyses of the atomic networks of such C–S–H compositions using topological constraint theory indicate that these compositions present limited relaxation modes on account of their optimally connected (i.e., constrained) atomic networks.« less

A dissolution-precipitation mechanism is at the origin of concrete creep in moist environments.

PubMed

Pignatelli, Isabella; Kumar, Aditya; Alizadeh, Rouhollah; Le Pape, Yann; Bauchy, Mathieu; Sant, Gaurav

2016-08-07

Long-term creep (i.e., deformation under sustained load) is a significant material response that needs to be accounted for in concrete structural design. However, the nature and origin of concrete creep remain poorly understood and controversial. Here, we propose that concrete creep at relative humidity ≥ 50%, but fixed moisture content (i.e., basic creep), arises from a dissolution-precipitation mechanism, active at nanoscale grain contacts, as has been extensively observed in a geological context, e.g., when rocks are exposed to sustained loads, in liquid-bearing environments. Based on micro-indentation and vertical scanning interferometry data and molecular dynamics simulations carried out on calcium-silicate-hydrate (C-S-H), the major binding phase in concrete, of different compositions, we show that creep rates are correlated with dissolution rates-an observation which suggests a dissolution-precipitation mechanism as being at the origin of concrete creep. C-S-H compositions featuring high resistance to dissolution, and, hence, creep are identified. Analyses of the atomic networks of such C-S-H compositions using topological constraint theory indicate that these compositions present limited relaxation modes on account of their optimally connected (i.e., constrained) atomic networks.

Magmatic sulphides in Quaternary Ecuadorian arc magmas

NASA Astrophysics Data System (ADS)

Georgatou, Ariadni; Chiaradia, Massimo; Rezeau, Hervé; Wälle, Markus

2018-01-01

New petrographic and geochemical data on magmatic sulphide inclusions (MSIs) are presented and discussed for 15 Quaternary volcanic centers of the Ecuadorian frontal, main and back volcanic arc. MSIs occur mostly in Fe-Ti oxides (magnetite and/or magnetite-ilmenite pair) and to a lesser extent in silicate minerals (amphibole, plagioclase, and pyroxene). MSIs are present in all volcanic centers ranging in composition from basalt to dacite (SiO2 = 50-67 wt.%), indicating that sulphide saturation occurs at various stages of magmatic evolution and independently from the volcano location along the volcanic arc. MSIs also occur in dioritic, gabbroic and hornblenditic magmatic enclaves of the volcanic rocks. MSIs display variable sizes (1-30 μm) and shapes (globular, ellipsoidal, angular, irregular) and occur mostly as polymineralic inclusions composed of Fe-rich and Cu-poor (pyrrhotite) and Cu-rich (mostly chalcopyrite) phases. Aerial sulphide relative abundances range from 0.3 to 7 ppm in volcanic host rocks and from 13 to 24 ppm in magmatic enclaves. Electron microprobe analyses of MSIs indicate maximum metal contents of Cu = 65.7 wt.%, Fe = 65.2 wt.%, Ni = 10.1 wt.% for those hosted in the volcanic rocks and of Cu = 57.7 wt.%, Fe = 60.9 wt.%, Ni = 5.1 wt.%, for those hosted in magmatic enclaves. Relationships of the sulphide chemistry to the host whole rock chemistry show that with magmatic differentiation (e.g., increasing SiO2) the Cu and Ni content of sulphides decrease whereas the Fe and S contents increase. The opposite behavior is observed with the increase of Cu in the whole rock, because the latter is anti-correlated with the SiO2 whole rock content. Laser ablation ICP-MS analyses of MSIs returned maximum values of PGEs and noble metals of Pd = 30 ppm, Rh = 8.1 ppm, Ag = 92.8 ppm and Au = 0.6 ppm and Pd = 43 ppm, Rh = 22.6 ppm, Ag = 89 ppm and Au = 1 ppm for those hosted in volcanic rocks and magmatic enclaves, respectively. These PGE contents display a different range of values with respect to those in previously investigated magmatic sulphides. MSIs that are Cu- and PGE/Cu-rich are found in less evolved rocks (i.e., lower SiO2 contents) that also display a lower amount of sulphide inclusions. Cu-rich sulphide phases (chalcopyrite ± bornite) are mostly hosted by magnetite, whereas PGE-rich ones consist of a Cu-poor phase (pyrrhotite) hosted by plagioclase. However, no systematic changes in the chemistry of the host silicate mineral are observed in coincidence with the occurrence of MSIs. We use the results of our study to draw some implications on Cu (and other chalcophile elements) behavior during arc magmatic processes potentially associated with the formation of porphyry-type deposits.

Experimental investigation of CO2-brine-rock interactions at simulated in-situ conditions

NASA Astrophysics Data System (ADS)

Słomski, Piotr; Lutyński, Marcin; Mastalerz, Maria; Szczepański, Jacek; Derkowski, Arkadiusz; Topór, Tomasz

2017-04-01

Geological sequestration of carbon dioxide (CO2) in deep formations (e.g. saline aquifers, oil and gas reservoirs and coalbeds) is one of the most promising options for reducing concentration of this anthropogenic greenhouse gas in the atmosphere. CO2 injected into the rock formations can be trapped by several mechanisms including structural and stratigraphic trapping, capillary CO2 trapping, dissolution trapping and mineral trapping. During dissolution trapping, CO2 dissolves in the formation brine and sinks in the reservoir as the CO2-enriched brine has an increased density. In comparison, in mineral trapping, CO2 is bound by precipitating new carbonate minerals. The latter two mechanisms depend on the temperature, pressure, and the mineralogy of the reservoir rock and the chemical composition of the brine. This study discusses laboratory scale alterations of Ordovician and Silurian shale rocks from potential CO2 sequestration site B1 in the Baltic Basin. In the reported experiment, rocks submerged in brine in specially constructed reactors were subjected to CO2 pressure of 30-35 MPa for 30-45 days at temperature of 80 oC. Shale samples were analyzed in terms of mineral composition and mesopore surface area and volume, before and after experiments, by means of X-ray diffraction and N2 low-pressure adsorption, respectively, for possible CO2 induced changes. Comparison of mineral composition before and after experiments demonstrated subtle mineral changes. The most conspicuous was a release of Fe in the form of Fe-oxyhydroxides, most probably related to the decomposition of Fe-bearing minerals like pyrite, chlorite and, less frequently, ankerite. With regard to porosity, interestingly, the most significant increase in mesopore surface area and mesopore volume was observed in samples with the largest drop of chlorite amount. The less significant mineral changes were associated with formation of kaolinite related to breakdown of feldspars and dissolution of carbonate minerals represented by calcite, dolomite, and ankerite. In the analyzed samples, no new carbonate minerals were formed during the experiments. An increase of carbonates was recorded only in three out of 13 samples. However, concentration of carbonates in these three samples is too low to conclude CO2 mineral trapping in new carbonate phases. Acknowledgments: the study was supported from grant SHALESEQ (No PL12-0109) funded by the National Centre for Research and Development.

Coatings on Atacama Desert Basalt: A Possible Analog for Coatings on Gusev Plains Basalt

NASA Technical Reports Server (NTRS)

Sutter, B.; Golden, D. C.; Amundson, R.; Chong-Diaz, G.; Ming, D. W.

2007-01-01

Surface coatings on Gusev Plains basalt have been observed and may contain hematite and nanophase Fe-oxides along with enrichments in P, S, Cl, and K relative to the underlying rock. The Gusev coatings may be derived from the dissolution of adhering soil and/or parent rock along with the addition of S and Cl from outside sources. Transient water for dissolution could be sourced from melting snow during periods of high obliquity, acid fog, and/or ground water (Haskin et al., 2005). Coatings on basalt in the hyper-arid (less than 2mm y(sup -1)) Atacama Desert may assist in understanding the chemistry, mineralogy and formation mechanisms of the Gusev basalt coatings. The Atacama Desert climate is proposed to be analogous to a paleo-Mars climate that was characterized by limited aqueous activity when the Gusev coatings could have formed. The objectives of this work are to (i) determine the chemical nature and extent of surface coatings on Atacama Desert basalt, and (ii) assess coating formation mechanisms in the Atacama Desert. Preliminary backscattered electron imaging of Atacama basalt thin-sections indicated that the coatings are as thick as 20 m. The boundary between the coating and the basalt labradorite, ilmenite, and augite grains was abrupt indicating that the basalt minerals underwent no chemical dissolution. The Atacama coatings have been added to the basalt instead of being derived from basalt chemical weathering. Semi-quantitative energy dispersive spectroscopy shows the coatings to be chemically homogeneous. The coating is depleted in Ca (0.9 wt% CaO) and enriched in K (1.3 wt.% K2O) and Si (69.1 wt.% SiO2) relative to the augite and labradorite grains. A dust source enriched in Si (e.g., poorly crystalline silica) and K and depleted in Ca appears to have been added to the basalt surface. Unlike the Gusev coatings, no P, S, and Cl enrichment was observed. However, Fe (3.2 wt.% FeO) was present in the Atacama coatings suggesting the present of Fe-oxides. While the chemistry of Atacama coating does not mirror the Gusev coating, the coating formation mechanism may be similar. The Atacama coatings of surface basalt are derived completely from exogenous sources. If surface Mars rocks have experienced limited wetting conditions as in the Atacama, then Mars coatings may be derived only from dissolution of material adhering to rock.

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

Earl D Mattson; Ghanashyam Neupane; Mitchell Plummer

Long-term sustainability of fracture conductivity is critical for commercial success of engineered geothermal system (EGS) and hydrogeothermal field sites. The injection of proppants has been suggested as a means to enhance the conductivity in these systems. Several studies have examined the chemical behavior of proppants that are not at chemical equilibrium with the reservoir rock and water. These studies have suggested that in geothermal systems, geochemical reactions can lead to enhance proppant dissolution and deposition alteration minerals. We hypothesize that proppant dissolution will decrease the strength of the proppant and can potentially reduce the conductivity of the fracture. To examinemore » the geomechanical strength of proppants, we have performed modified crushing tests of proppants and reservoir rock material that was subjected to geothermal reservoir temperature conditions. The batch reactor experiments heated crushed quartz monzonite rock material, proppants (either quartz sand, sintered bauxite or kryptospheres) with Raft River geothermal water to 250 ºC for a period of 2 months. Solid and liquid samples were shipped to University of Utah for chemical characterization with ICP-OES, ICP-MS, and SEM. A separate portion of the rock/proppant material was subjected to a modified American Petroleum Institute ISO 13503-2 proppant crushing test. This test is typically used to determine the maximum stress level that can be applied to a proppant pack without the occurrence of unacceptable proppant crushing. We will use the test results to examine potential changes in proppant/reservoir rock geomechanical properties as compared to samples that have not been subjected to geothermal conditions. These preliminary results will be used to screen the proppants for long term use in EGS and hot hydrogeothermal systems.« less

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.

Modeling Thermal Pressurization Around Shallow Dikes Using Temperature-Dependent Hydraulic Properties: Implications for Deformation Around Intrusions

NASA Astrophysics Data System (ADS)

Townsend, Meredith R.

2018-01-01

Pressurization and flow of groundwater around igneous intrusions depend in part on the hydraulic diffusivity of the host rocks and processes that enhance diffusivity, such as fracturing, or decrease diffusivity, such as mineral precipitation during chemical alteration. Characterizing and quantifying the coupled effects of alteration, pore pressurization, and deformation have significant implications for deformation around intrusions, geothermal energy, contact metamorphism, and heat transfer at mid-ocean ridges. Fractures around dikes at Ship Rock, New Mexico, indicate that pore pressures in the host rocks exceeded hydrostatic conditions by at least 15 MPa following dike emplacement. Hydraulic measurements and petrographic analysis indicate that mineral precipitation clogged the pores of the host rock, reducing porosity from 0.25 to <0.10 and reducing permeability by 5 orders of magnitude. Field data from Ship Rock are used to motivate and constrain numerical models for thermal pore fluid pressurization adjacent to a meter-scale dike, using temperature-dependent hydraulic properties in the host rock as a proxy for porosity loss by mineral precipitation during chemical alteration. Reduction in permeability by chemical alteration has a negligible effect on pressurization. However, reduction in porosity by mineral precipitation increases fluid pressure by constricting pore volume and is identified as a potentially significant source of pressure. A scaling relationship is derived to determine when porosity loss becomes important; if permeability is low enough, pressurization by porosity loss outweighs pressurization by thermal expansion of fluids.

Alteration minerals in impact-generated hydrothermal systems - Exploring host rock variability

NASA Astrophysics Data System (ADS)

Schwenzer, Susanne P.; Kring, David A.

2013-09-01

Impact-generated hydrothermal systems have been previously linked to the alteration of Mars’ crust and the production of secondary mineral assemblages seen from orbit. The sensitivity of the resultant assemblages has not yet been evaluated as a function of precursor primary rock compositions. In this work, we use thermochemical modeling to explore the variety of minerals that could be produced by altering several known lithologies based on martian meteorite compositions. For a basaltic host rock lithology (Dhofar 378, Humphrey) the main alteration phases are feldspar, zeolite, pyroxene, chlorite, clay (nontronite, kaolinite), and hematite; for a lherzolithic host rock lithology (LEW 88516) the main alteration phases are amphibole, serpentine, chlorite, clay (nontronite, kaolinite), and hematite; and for an ultramafic host rock lithology (Chassigny) the main minerals are secondary olivine, serpentine, magnetite, quartz, and hematite. These assemblages and proportions of phases in each of those cases depend on W/R and temperature. Integrating geologic, hydrologic and alteration mineral evidence, we have developed a model to illustrate the distribution of alteration assemblages that occur in different levels of an impact structure. At the surface, hot, hydrous alteration affects the ejecta and melt sheet producing clay and chlorite. Deeper in the subsurface and depending on the permeability of the rock, a variety of minerals - smectite, chlorite, serpentine, amphiboles and hematite - are produced in a circulating hydrothermal system. These modeled mineral distributions should assist with interpretation of orbital observations and help guide surface exploration by rovers and sample return assets.

Pore-Scale Geochemical Reactivity Associated with CO2 Storage: New Frontiers at the Fluid-Solid Interface.

PubMed

Noiriel, Catherine; Daval, Damien

2017-04-18

The reactivity of carbonate and silicate minerals is at the heart of porosity and pore geometry changes in rocks injected with CO 2 , which ultimately control the evolution of flow and transport properties of fluids in porous and/or fractured geological reservoirs. Modeling the dynamics of CO 2 -water-rock interactions is challenging because of the resulting large geochemical disequilibrium, the reservoir heterogeneities, and the large space and time scales involved in the processes. In particular, there is a lack of information about how the macroscopic properties of a reservoir, e.g., the permeability, will evolve as a result of geochemical reactions at the molecular scale. Addressing this point requires a fundamental understanding of how the microstructures influence the macroscopic properties of rocks. The pore scale, which ranges from a few nanometers to centimeters, has stood out as an essential scale of observation of geochemical processes in rocks. Transport or surface reactivity limitations due to the pore space architecture, for instance, are best described at the pore scale itself. It can be also considered as a mesoscale for aggregating and increasing the gain of fundamental understanding of microscopic interfacial processes. Here we focus on the potential application of a combination of physicochemical measurements coupled with nanoscale and microscale imaging techniques during laboratory experiments to improve our understanding of the physicochemical mechanisms that occur at the fluid-solid interface and the dynamics of the coupling between the geochemical reactions and flow and transport modifications at the pore scale. Imaging techniques such as atomic force microscopy, vertical scanning interferometry, focused ion beam transmission electron microscopy, and X-ray microtomography, are ideal for investigating the reactivity dynamics of these complex materials. Minerals and mineral assemblages, i.e., rocks, exhibit heterogeneous and anisotropic reactivity, which challenges the continuum description of porous media and assumptions required for reactive transport modeling at larger scales. The conventional approach, which consists of developing dissolution rate laws normalized to the surface area, should be revisited to account for both the anisotropic crystallographic structure of minerals and the transport of chemical species near the interface, which are responsible for the intrinsic evolution of the mineral dissolution rate as the reaction progresses. In addition, the crystal morphology and the mineral assemblage composition, texture, and structural heterogeneities are crucial in determining whether the permeability and transport properties of the reservoir will be altered drastically or maintain the sealing properties required to ensure the safe sequestration of CO 2 for hundreds of years. Investigating the transport properties in nanometer- to micrometer-thick amorphous Si-rich surface layers (ASSLs), which develop at the fluid-mineral interface in silicates, provides future direction, as ASSLs may prevent contact between the dissolving solids and the pore fluid, potentially inhibiting the dissolution/carbonation process. Equally, at a larger scale, the growth of micrometer- to millimeter-thick alteration layers, which result from the difference in reactivity between silicates and carbonates, slows the transport in the vicinity of the fluid-solid interface in polymineralic rocks, thus limiting the global reactivity of the carbonate matrix. In contrast, in pure limestone, the global reactivity of the monomineralic rock decreases because the flow localization promotes the local reactivity within the forming channels, thus enhancing permeability changes compared with more homogeneous dissolution of the rock matrix. These results indicate that the transformation of the rock matrix should control the evolution of the transport properties in reservoirs injected with CO 2 to the same extent as the intrinsic chemical reactivity of the minerals and the reservoir hydrodynamics. This process, which is currently not captured by large-scale modeling of reactive transport, should benefit from the increasing capabilities of noninvasive and nondestructive characterization tools for pore-scale processes, ultimately constraining reactive transport modeling and improving the reliability of predictions.

Arsenic release from arsenopyrite weathering: insights from sequential extraction and microscopic studies.

PubMed

Basu, Ankan; Schreiber, Madeline E

2013-11-15

At a former As mine site, arsenopyrite oxidation has resulted in formation of scorodite and As-bearing iron hydroxide, both in host rock and mine tailings. Electron microprobe analysis documents that arsenopyrite weathers along two pathways: one that involves formation of sulfur, and one that does not. In both pathways, arsenopyrite oxidizes to form scorodite, which dissolves incongruently to form As-bearing iron hydroxides. From a mass balance perspective, arsenopyrite oxidation to scorodite conserves As, but as scorodite dissolves incongruently to iron hydroxides, As is released to solution, resulting in elevated As concentrations in the headwater stream adjacent to the site. The As-bearing iron hydroxide is the dominant solid phase reservoir of As in mine tailings and stream sediment, as suggested by sequential extraction. This As-bearing iron hydroxide is stable under the aerobic and pH 4-6 conditions at the site; however, changes in biogeochemical conditions resulting from sediment burial or future remedial efforts, which could promote As release from this reservoir due to reductive dissolution, should be avoided. Copyright © 2012 Elsevier B.V. All rights reserved.

Cobalt—Styles of deposits and the search for primary deposits

USGS Publications Warehouse

Hitzman, Murray W.; Bookstrom, Arthur A.; Slack, John F.; Zientek, Michael L.

2017-11-30

Cobalt (Co) is a potentially critical mineral. The vast majority of cobalt is a byproduct of copper and (or) nickel production. Cobalt is increasingly used in magnets and rechargeable batteries. More than 50 percent of primary cobalt production is from the Central African Copperbelt. The Central African Copperbelt is the only sedimentary rock-hosted stratiform copper district that contains significant cobalt. Its presence may indicate significant mafic-ultramafic rocks in the local basement. The balance of primary cobalt production is from magmatic nickel-copper and nickel laterite deposits. Cobalt is present in several carbonate-hosted lead-zinc and copper districts. It is also variably present in Besshi-type volcanogenic massive sulfide and siliciclastic sedimentary rock-hosted deposits in back arc and rift environments associated with mafic-ultramafic rocks. Metasedimentary cobalt-copper-gold deposits (such as Blackbird, Idaho), iron oxide-copper-gold deposits, and the five-element vein deposits (such as Cobalt, Ontario) contain different amounts of cobalt. None of these deposit types show direct links to mafic-ultramafic rocks; the deposits may result from crustal-scale hydrothermal systems capable of leaching and transporting cobalt from great depths. Hydrothermal deposits associated with ultramafic rocks, typified by the Bou Azzer district of Morocco, represent another type of primary cobalt deposit.In the United States, exploration for cobalt deposits may focus on magmatic nickel-copper deposits in the Archean and Proterozoic rocks of the Midwest and the east coast (Pennsylvania) and younger mafic rocks in southeastern and southern Alaska; also, possibly basement rocks in southeastern Missouri. Other potential exploration targets include—The Belt-Purcell basin of British Columbia (Canada), Idaho, Montana, and Washington for different styles of sedimentary rock-hosted cobalt deposits;Besshi-type VMS deposits, such as the Greens Creek (Alaska) deposit and the Ducktown (Tennessee) waste and tailings; andKnown five-element vein districts in Arizona and New Mexico, as well as in the Yukon-Tanana terrane of Alaska; and hydrothermal deposits associated with ultramafic rocks along the west coast, in Alaska, and in the Appalachian Mountains.

Inverse Modeling of Water-Rock-CO2 Batch Experiments: Potential Impacts on Groundwater Resources at Carbon Sequestration Sites.

PubMed

Yang, Changbing; Dai, Zhenxue; Romanak, Katherine D; Hovorka, Susan D; Treviño, Ramón H

2014-01-01

This study developed a multicomponent geochemical model to interpret responses of water chemistry to introduction of CO2 into six water-rock batches with sedimentary samples collected from representative potable aquifers in the Gulf Coast area. The model simulated CO2 dissolution in groundwater, aqueous complexation, mineral reactions (dissolution/precipitation), and surface complexation on clay mineral surfaces. An inverse method was used to estimate mineral surface area, the key parameter for describing kinetic mineral reactions. Modeling results suggested that reductions in groundwater pH were more significant in the carbonate-poor aquifers than in the carbonate-rich aquifers, resulting in potential groundwater acidification. Modeled concentrations of major ions showed overall increasing trends, depending on mineralogy of the sediments, especially carbonate content. The geochemical model confirmed that mobilization of trace metals was caused likely by mineral dissolution and surface complexation on clay mineral surfaces. Although dissolved inorganic carbon and pH may be used as indicative parameters in potable aquifers, selection of geochemical parameters for CO2 leakage detection is site-specific and a stepwise procedure may be followed. A combined study of the geochemical models with the laboratory batch experiments improves our understanding of the mechanisms that dominate responses of water chemistry to CO2 leakage and also provides a frame of reference for designing monitoring strategy in potable aquifers.

Detachment of particulate iron sulfide during shale-water interaction

NASA Astrophysics Data System (ADS)

Emmanuel, S.; Kreisserman, Y.

2017-12-01

Hydraulic fracturing, a commonly used technique to extract oil and gas from shales, is controversial in part because of the threat it poses to water resources. The technique involves the injection into the subsurface of large amounts of fluid, which can become contaminated by fluid-rock interaction. The dissolution of pyrite is thought to be a primary pathway for the contamination of fracturing fluids with toxic elements, such as arsenic and lead. In this study, we use direct observations with atomic force microscopy to show that the dissolution of carbonate minerals in Eagle Ford shale leads to the physical detachment of embedded pyrite grains. To simulate the way fluid interacts with a fractured shale surface, we also reacted rock samples in a flow-through cell, and used environmental scanning electron microscopy to compare the surfaces before and after interaction with water. Crucially, our results show that the flux of particulate iron sulfide into the fluid may be orders of magnitude higher than the flux of pyrite from chemical dissolution. This result suggests that mechanical detachment of pyrite grains could be the dominant mode by which arsenic and other inorganic elements are mobilized in the subsurface. Thus, during hydraulic fracturing operations and in groundwater systems containing pyrite, the transport of many toxic species may be controlled by the transport of colloidal iron sulfide particles.

On the neutralization of acid rock drainage by carbonate and silicate minerals

NASA Astrophysics Data System (ADS)

Sherlock, E. J.; Lawrence, R. W.; Poulin, R.

1995-02-01

The net result of acid-generating and-neutralizing reactions within mining wastes is termed acid rock drainage (ARD). The oxidation of sulfide minerals is the major contributor to acid generation. Dissolution and alteration of various minerals can contribute to the neutralization of acid. Definitions of alkalinity, acidity, and buffer capacity are reviewed, and a detailed discussion of the dissolution and neutralizing capacity of carbonate and silicate minerals related to equilibium conditions, dissolution mechanism, and kinetics is provided. Factors that determine neutralization rate by carbonate and silicate minerals include: pH, PCO 2, equilibrium conditions, temperature, mineral composition and structure, redox conditions, and the presence of “foreign” ions. Similar factors affect sulfide oxidation. Comparison of rates shows sulfides react fastest, followed by carbonates and silicates. The differences in the reaction mechanisms and kinetics of neutralization have important implications in the prediction, control, and regulation of ARD. Current static and kinetic prediction methods upon which mine permitting, ARD control, and mine closure plans are based do not consider sample mineralogy or the kinetics of the acid-generating and-neutralizing reactions. Erroneous test interpretations and predictions can result. The importance of considering mineralogy for site-specific interpretation is highlighted. Uncertainty in prediction leads to difficulties for the mine operator in developing satisfactory and cost-effective control and remediation measures. Thus, the application of regulations and guidelines for waste management planning need to beflexible.

Impact of early diagenesis and bulk particle grain size distribution on estimates of relative geomagnetic palaeointensity variations in sediments from Lama Lake, northern Central Siberia

NASA Astrophysics Data System (ADS)

Nowaczyk, Norbert R.; Harwart, Stefanie; Melles, Martin

2001-04-01

High-resolution analyses of rock magnetic and sedimentological parameters were conducted on an 11m long sediment core from Lama Lake, Northern Siberia, which encompasses the late Pleistocene and the Holocene epochs. The results reveal a strong link between the median grain size of the magnetic particles, identified as magnetite, and the oxidation state of the sediment. Reducing conditions associated with a relative high total organic carbon (TOC) content of the sediment characterize the upper 7m of the core (~Holocene), and these have led to a partial dissolution of detrital magnetite grains, and a homogenization of grain-size-related rock magnetic parameters. The anoxic sediments are characterized by significantly larger median magnetic grain sizes, as indicated, for example, by lower median destructive fields of the natural remanent magnetization (MDFNRM) and lower ratios of saturation remanence to saturation magnetization (MSR/MS). Consequently, estimates of relative geomagnetic palaeointensity variations yielded large amplitude shifts associated with anoxic/oxic boundaries. Despite the partial reductive dissolution of magnetic particles within the anoxic section, and consequent minimal variations in magnetic concentration and grain size, palaeointensity estimates for this part of the core were still lithologically distorted by the effects of particle size (and subsidiary TOC) variations. Anomalously high values coincide with an interval of significantly more fine-grained sediment, which is also associated with a decrease in TOC content, which may thus imply a decreased level of magnetite dissolution in this interval. Calculation of relative palaeointensity estimates therefore seems to be compromised by a combined effect of shifts in the particle size distribution of the bulk sediment and by partial magnetite dissolution varying in association with the TOC content of the sediment.

Gypsum scarps and asymmetric fluvial valleys in evaporitic terrains. The role of river migration, landslides, karstification and lithology (Ebro River, NE Spain)

NASA Astrophysics Data System (ADS)

Guerrero, J.; Gutiérrez, F.

2017-11-01

Most of the Spanish fluvial systems excavated in Tertiary evaporitic gypsum formations show asymmetric valleys characterized by a stepped sequence of fluvial terraces on one valley flank and kilometric-long and > 100-m high prominent river scarp on the opposite side of the valley. Scarp undermining by the continuous preferential lateral migration of the river channel toward the valley margin leads to vertical to overhanging unstable slopes affected by a large number of slope failures that become the main geological hazard for villages located at the toe of the scarps. Detailed mapping of the gypsum scarps along the Ebro and Huerva Rivers gypsum scarps demonstrates that landslides and lateral spreading processes are predominant when claystones crop out at the base of the scarp, while rockfalls and topples become the dominant movement in those reaches where the rock mass is mainly constituted by evaporites. The dissolution of gypsum nodules, seasonal swelling and shrinking, and dispersion processes contribute to a decrease in the mechanical strength of claystones. The existence of dissolution-enlarged joints, sinkholes, and severely damaged buildings at the toe of the scarp from karstic subsidence demonstrates that the interstratal karstification of evaporites becomes a triggering factor in the instability of the rock mass. The genesis of asymmetric valleys and river gypsum scarps in the study area seem to be caused by the random migration of the river channel in the absence of lateral tilting related to tectonics or dissolution-induced subsidence. Once the scarp is developed, its preservation depends on the physicochemical properties of the substratum, the ratio between bedrock erosion and river incision rates, and climatic conditions that favour runoff erosion versus dissolution.

Danburite in evaporites of the Paradox basin, Utah.

USGS Publications Warehouse

Raup, O.B.; Madsen, B.M.

1986-01-01

Danburite (CaB2Si2O8) has been found as nodules in Pennsylvanian age marine evaporites. The occurrence of danburite and its relation to the host rock in the Paradox basin evaporites indicates that it most likely formed by diagenetic reaction of boron-rich, high-salinity brines with constituents in the anhydrite host rock.-from Authors

Processes of high-T fluid-rock interaction during gold mineralization in carbonate-bearing metasediments: the Navachab gold deposit, Namibia

NASA Astrophysics Data System (ADS)

Dziggel, A.; Wulff, K.; Kolb, J.; Meyer, F. M.

2009-08-01

The Navachab gold deposit in the Damara belt of central Namibia is hosted by a near-vertical sequence of amphibolite facies shelf-type metasediments, including marble, calc-silicate rock, and biotite schist. Petrologic and geochemical data were collected in the ore, alteration halos, and the wall rock to evaluate transport of elements and interaction between the wall rock and the mineralizing fluid. The semi-massive sulfide lenses and quartz-sulfide veins are characterized by a complex polymetallic ore assemblage, comprising pyrrhotite, chalcopyrite, sphalerite, and arsenopyrite, native bismuth, gold, bismuthinite, and bismuth tellurides. Mass balance calculations indicate the addition of up to several orders of magnitude of Au, Bi, As, Ag, and Cu. The mineralized zones also record up to eightfold higher Mn and Fe concentrations. The semi-massive sulfide lenses are situated in the banded calc-silicate rock. Petrologic and textural data indicate that they represent hydraulic breccias that contain up to 50 vol.% ore minerals, and that are dominated by a high-temperature (T) alteration assemblage of garnet-clinopyroxene-K-feldspar-quartz. The quartz-sulfide veins crosscut all lithological units. Their thickness and mineralogy is strongly controlled by the composition and rheological behavior of the wall rocks. In the biotite schist and calc-silicate rock, they are up to several decimeters thick and quartz-rich, whereas in the marble, the same veins are only a few millimeters thick and dominated by sulfides. The associated alteration halos comprise (1) an actinolite-quartz alteration in the biotite schist, (2) a garnet-clinopyroxene-K-feldspar-quartz alteration in the marble and calc-silicate rock, and (3) a garnet-biotite alteration that is recorded in all rock types except the marble. The hydrothermal overprint was associated with large-scale carbonate dissolution and a dramatic increase in CO2 in the ore fluid. Decarbonation of wall rocks, as well as a low REE content of the ore fluid resulted in the mobilization of the REE, and the decoupling of the LREE from the HREE. The alteration halos not only parallel the mineralized zones, but may also follow up single layers away from the mineralization. Alteration is far more pronounced facing upward, indicating that the rocks were steep when veining occurred. The petrologic and geochemical data indicate that the actinolite-quartz- and garnet-clinopyroxene-K-feldspar-quartz alterations formed in equilibrium with a fluid (super-) saturated in Si, and were mainly controlled by the composition of the wall rocks. In contrast, the garnet-biotite alteration formed by interaction with a fluid undersaturated in Si, and was mainly controlled by the fluid composition. This points to major differences in fluid-rock ratios and changes in fluid composition during alteration. The alteration systematics and geometry of the hydrothermal vein system are consistent with cyclic fluctuations in fluid pressure during fault valve action.

Petrographic, geochemical and isotopic evidence of crustal assimilation processes in the Ponte Nova alkaline mafic-ultramafic massif, SE Brazil

NASA Astrophysics Data System (ADS)

Azzone, Rogério Guitarrari; Montecinos Munoz, Patricio; Enrich, Gaston Eduardo Rojas; Alves, Adriana; Ruberti, Excelso; Gomes, Celsode Barros

2016-09-01

Crustal assimilation plus crystal fractionation processes of different basanite magma batches control the evolution of the Ponte Nova cretaceous alkaline mafic-ultramafic massif in SE Brazil. This massif is composed of several intrusions, the main ones with a cumulate character. Disequilibrium features in the early-crystallized phases (e.g., corrosion and sieve textures in cores of clinopyroxene crystals, spongy-cellular-textured plagioclase crystals, gulf corrosion texture in olivine crystals) and classical hybridization textures (e.g., blade biotite and acicular apatite crystals) provide strong evidence of open-system behavior. All samples are olivine- and nepheline-normative rocks with basic-ultrabasic and potassic characters and variable incompatible element enrichments. The wide ranges of whole-rock 87Sr/86Sri and 143Nd/144Ndi ratios (0.70432-0.70641 and 0.512216-0.512555, respectively) are indicative of crustal contribution from the Precambrian basement host rocks. Plagioclase and apatite 87Sr/86Sr ratios (0.70422-0.70927) obtained for the most primitive samples of each intrusion indicate disequilibrium conditions from early- to principal-crystallization stages. Isotope mixing-model curves between the least contaminated alkaline basic magma and heterogeneous local crustal components indicate that each intrusion of the massif is differentiated from the others by varied degrees of crustal contribution. The primary mechanisms of crustal contribution to the Ponte Nova massif involve the assimilation of host rock xenoliths during the development of the chamber environment and the assimilation of partial melts from the surrounding host rocks. Thermodynamic models using the melts algorithm indicate that parental alkaline basic magmas can be strongly affected by contamination processes subsequently to their initial stages of crystallization when there is sufficient energy to assimilate partial melts of crustal host rocks. The assimilation processes are considered to be responsible for the increse in the K2O/Na2O, Ba/Sr and Rb/Sr ratios. This enrichment was associated with the relevant role of biotite breakdown in the assimilated host rock partial melts. The petrological model for the Ponte Nova massif is explained as repeated influxes of antecryst-laden basanite magmas that deposited most of their suspended crystals on the floor of the upper-crust magma chamber. Each intrusion is representative of relatively primitive olivine- and clinopyroxene-phyric basanites that had assimilated different degrees of partial melts of heterogeneous host rocks. This study reveals the relevant role of crustal assimilation processes in the magmatic evolution of nepheline-normative rocks, especially in upper-crust chamber environments.

Lung Biopersistence and in Vitro Dissolution Rate Predict the Pathogenic Potential of Synthetic Vitreous Fibers.

PubMed

Hesterberg, T W; Hart, G A

2000-01-01

Here we review the past decade of research on inorganic fiber toxicology, which demonstrates that fiber biopersistence and in vitro dissolution rate correlate well with fiber pathogenicity. Test fibers for these studies included eight synthetic vitreous fibers (SVFs)-refractory ceramic fiber (RCF1), four fiber glasses (FCs), rock wool, slag wool, HT stone wool-and two asbestos types (crocidolite and amosite). Fiber toxicology and biopersistence were investigated using rodents exposed by inhalation. To evaluate chronic inhalation toxicity, rodents were exposed nose-only to ∼ 100 fibers >20 µm in length (F > 20 µm)/cm(3), 6 h/day, 5 days/wk, for 2 yr (rats) or 1½ yr (hamsters). To evaluate lung biopersistence, rats were exposed nose-only for 5 days to fiber aerosol; lung burdens were then analyzed during 1 yr postexposure. In vitro dissolution rate was evaluated in a flow-through system using physiological solutions that mimic the inorganic components of extra- and intracellular lung fluids. The 10 test fibers encompassed a range of respiratory toxicities, from transient inflammation only to carcinogenesis. Lung clearance weighted half-times (WT½) for F > 20 µm were 6-15 days for stonewool, building insulation FCs, and slag wool; 50-80 days for rock wool, 2 special-application FCs, and RCFI; and >400 days for asbestos. WT½ correlated with pathogenicity: The rapidly clearing fibers were innocuous (insulation FCs, slag wool, and stonewool), but the more biopersistent fibers were fibrogenic (rock wool) or fibrogenic and carcinogenic (special-application FCs, RCFI, amosite and crocidolite asbestos). In vitro dissolution rates (k dis= ng/cm(2)/h) of the 10 fibers at pH 7.4 or 4.5 ranged from < 1 to >600. Fibers that dissolved rapidly in vitro also cleared quickly from the lung and induced only transient inflammation in the chronic studies. In contrast, fibers that dissolved slowly in vitro were biopersistent in the lung and tended to induce permanent pathogenicity. Other in vitro studies of fiber degradation suggest that, in addition to fiber dissolution, fiber leaching and subsequent transverse breakage may also be important mechanisms in lung biopersistence and hence pathogenicity. The validity of using lung biopersistence for predicting the potential pathogenicity of SVFs is confirmed by this research. The research also supports the use of in vitro fiber degradation at pH 7.4 and/or pH 4.5 as an indicator of SVF potential pathogenicity.

Hydrothermal reequilibration of igneous magnetite in altered granitic plutons and its implications for magnetite classification schemes: Insights from the Handan-Xingtai iron district, North China Craton

NASA Astrophysics Data System (ADS)

Wen, Guang; Li, Jian-Wei; Hofstra, Albert H.; Koenig, Alan E.; Lowers, Heather A.; Adams, David

2017-09-01

Magnetite is a common mineral in igneous rocks and has been used as an important petrogenetic indicator as its compositions and textures reflect changing physiochemical parameters such as temperature, oxygen fugacity and melt compositions. In upper crustal settings, igneous rocks are often altered by hydrothermal fluids such that the original textures and compositions of igneous magnetite may be partly or completely obliterated, posing interpretive problems in petrological and geochemical studies. In this paper, we present textural and compositional data of magnetite from variably albitized granitoid rocks in the Handan-Xingtai district, North China Craton to characterize the hydrothermal reequilibration of igneous magnetite. Four types of magnetite have been identified in the samples studied: pristine igneous magnetite (type 1), reequilibrated porous magnetite (type 2), reequilibrated nonporous magnetite (type 3), and hydrothermal magnetite (type 4). Pristine igneous magnetite contains abundant well-developed ilmenite exsolution lamellae that are largely replaced by titanite during subsequent hydrothermal alteration. The titanite has a larger molar volume than its precursor ilmenite and thus causes micro-fractures in the host magnetite grains, facilitating dissolution and reprecipitation of magnetite. During sodic alteration, the igneous magnetite is extensively replaced by type 2 and type 3 magnetite via fluid-induced dissolution and reprecipitation. Porous type 2 magnetite is the initial replacement product of igneous magnetite and is subsequently replaced by the nonoporous type 3 variety as its surface area is reduced and compositional equilibrium with the altering fluid is achieved. Hydrothermal type 4 magnetite is generally euhedral and lacks exsolution lamellae and porosity, and is interpreted to precipitate directly from the ore-forming fluids. Hydrothermal reequilibration of igneous magnetite has led to progressive chemical purification, during which trace elements such as Ti, Al, Mg, Zn, and Cr contents decrease dramatically (up to 2-3 orders of magnitude different), coupled with significant increase in iron concentrations from less than 64 wt.% to higher than 70 wt.%. Results presented here show that magnetite is much more susceptible to textural and compositional reequilibration than previously thought. The reequilibrated magnetite has geochemical patterns that may be distinctively different from its precursor, making existing discrimination plots questionable when applied to genetic interpretation. Based on textural characterization and high-resolution in situ compositional analyses, we propose that the Fe versus V/Ti diagram can be more confidently used to discriminate between pristine igneous magnetite, reequilibrated magnetite, and hydrothermal magnetite.

Mineral and energy resources of the BLM Roswell Resource Area, east-central New Mexico

USGS Publications Warehouse

Bartsch-Winkler, Susan B.

1992-01-01

The sedimentary formations of the Roswell Resource Area have significant mineral and energy resources. Some of the pre-Pennsylvanian sequences in the Northwestern Shelf of the Permian Basin are oil and gas reservoirs, and Pennsylvanian rocks in Tucumcari basin are reservoirs of oil and gas as well as source rocks for oil and gas in Triassic rocks. Pre-Permian rocks also contain minor deposits of uranium and vanadium, limestone, and associated gases. Hydrocarbon reservoirs in Permian rocks include associated gases such as carbon dioxide, helium, and nitrogen. Permian rocks are mineralized adjacent to the Lincoln County porphyry belt, and include deposits of copper, uranium, manganese, iron, polymetallic veins, and Mississippi-valley-type (MVT) lead-zinc. Industrial minerals in Permian rocks include fluorite, barite, potash, halite, polyhalite, gypsum, anhydrite, sulfur, limestone, dolomite, brine deposits (iodine and bromine), aggregate (sand), and dimension stone. Doubly terminated quartz crystals, called "Pecos diamonds" and collected as mineral specimens, occur in Permian rocks along the Pecos River. Mesozoic sedimentary rocks are hosts for copper, uranium, and small quantities of gold-silver-tellurium veins, as well as significant deposits of oil and gas, COa, asphalt, coal, and dimension stone. Mesozoic rocks contain limited amounts of limestone, gypsum, petrified wood, dinosaur remains, and clays. Tertiary rocks host ore deposits commonly associated with intrusive rocks, including platinum group elements, iron skarns, manganese, uranium and vanadium, molybdenum, polymetallic vein deposits, gold-silver- tellurium veins, and thorium-rare earth veins. Museum-quality quartz crystals in Lincoln County were formed in association with intrusive rocks in the Lincoln County porphyry belt. Industrial minerals in Tertiary rocks include fluorite, vein- and bedded-barite, caliche, limestone, and aggregate. Tertiary and Quaternary sediments host important placer deposits of gold and titanium, and minor silver, uranium occurrences, as well as important industrial commodities, including caliche, limestone and dolomite, and aggregate (sand). Quaternary basalt contains sub-ore-grade uranium, scoria, and clay deposits.

Mineral and energy resources of the Roswell Resource Area, East-Central New Mexico

USGS Publications Warehouse

Bartsch-Winkler, Susan B.; Donatich, Alessandro J.

1995-01-01

The sedimentary formations of the Roswell Resource Area have significant mineral and energy resources. Some of the pre-Pennsylvanian sequences in the Northwestern Shelf of the Permian Basin are oil and gas reservoirs, and Pennsylvanian rocks in Tucumcari Basin are reservoirs of oil and gas as well as source rocks for oil and gas in Triassic rocks. Pre-Permian rocks also contain minor deposits of uranium and vanadium, limestone, and gases. Hydrocarbon reservoirs in Permian rocks include associated gases such as carbon dioxide, helium, and nitrogen. Permian rocks are mineralized adjacent to the Lincoln County porphyry belt, and include deposits of copper, uranium, manganese, iron, polymetallic veins, and Mississippi-Valley-type lead-zinc. Industrial minerals in Permian rocks include fluorite, barite, potash, halite, polyhalite, gypsum, anhydrite, sulfur, limestone, dolomite, brine deposits (iodine and bromine), aggregate (sand), and dimension stone. Doubly terminated quartz crystals, called 'Pecos diamonds' and collected as mineral specimens, occur in Permian rocks along the Pecos River. Mesozoic sedimentary rocks are hosts for copper, uranium, and small quantities of gold-silver-tellurium veins, as well as significant deposits of oil and gas, carbon dioxide, asphalt, coal, and dimension stone. Mesozoic rocks contain limited amounts of limestone, gypsum, petrified wood, and clay. Tertiary rocks host ore deposits commonly associated with intrusive rocks, including platinum-group elements, iron skarns, manganese, uranium and vanadium, molybdenum, polymetallic vein deposits, gold-silver-tellurium veins, and thorium-rare-earth veins. Museum-quality quartz crystals are associated with Tertiary intrusive rocks. Industrial minerals in Tertiary rocks include fluorite, vein- and bedded-barite, caliche, limestone, and aggregate. Tertiary and Quaternary sediments host important placer deposits of gold and titanium, and occurrences of silver and uranium. Important industrial commodities include caliche, limestone and dolomite, and aggregate. Quaternary basalt contains sub-ore-grade uranium, scoria, and clay deposits.

10 CFR 960.3-1-2 - Diversity of rock types.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 10 Energy 4 2011-01-01 2011-01-01 false Diversity of rock types. 960.3-1-2 Section 960.3-1-2... NUCLEAR WASTE REPOSITORY Implementation Guidelines § 960.3-1-2 Diversity of rock types. Consideration... sites for characterization shall have different types of host rock. ...

10 CFR 960.3-1-2 - Diversity of rock types.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 10 Energy 4 2013-01-01 2013-01-01 false Diversity of rock types. 960.3-1-2 Section 960.3-1-2... NUCLEAR WASTE REPOSITORY Implementation Guidelines § 960.3-1-2 Diversity of rock types. Consideration... sites for characterization shall have different types of host rock. ...

10 CFR 960.3-1-2 - Diversity of rock types.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 10 Energy 4 2014-01-01 2014-01-01 false Diversity of rock types. 960.3-1-2 Section 960.3-1-2... NUCLEAR WASTE REPOSITORY Implementation Guidelines § 960.3-1-2 Diversity of rock types. Consideration... sites for characterization shall have different types of host rock. ...

10 CFR 960.3-1-2 - Diversity of rock types.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 10 Energy 4 2012-01-01 2012-01-01 false Diversity of rock types. 960.3-1-2 Section 960.3-1-2... NUCLEAR WASTE REPOSITORY Implementation Guidelines § 960.3-1-2 Diversity of rock types. Consideration... sites for characterization shall have different types of host rock. ...

Lithogeochemical character of the near-surface bedrock in the Connecticut, Housatonic, and Thames River Basins

USGS Publications Warehouse

Robinson, Gilpin R.; Peper, John D.; Steeves, Peter A.; Desimone, Leslie A.

1999-01-01

This data layer shows the generalized lithologic and geochemical (lithogeochemical) character of near-surface bedrock in the Connecticut, Housatonic, and Thames River Basins and several other small basins that drain into Long Island Sound from Connecticut. The area includes most of Connecticut, western Massachusetts, eastern Vermont, western New Hampshire, and small parts of Rhode Island, New York, and Quebec, Canada.Bedrock geologic rock units are classified into 29 lithogeochemical rock units, on the basis of the relative reactivity of their constituent minerals to dissolution and other weathering reactions and the presence of carbonate or sulfide minerals. The 29 lithogeochemical units (28 of which can be found in the study area) can be grouped into 6 major categories: (1) carbonate-rich rocks, (2) carbonate-poor, clastic sedimentary rocks restricted to distinct depositional basins, (3) metamorphosed, clastic sedimentary rocks (primarily noncalcareous), (4) mafic igneous rocks and their metamorphic equivalents, (5) ultramafic rocks, and (6) felsic igneous and plutonic rocks and their metamorphic equivalents. The lithogeochemical rock units also are grouped into nine lithologic and physiographic provinces (lithophysiographic domains), which can be further grouped into three major regions: (1) western highlands and lowlands, (2) central lowlands, and (3) eastern highlands.

A model for interpretation of brine-dependent spontaneous imbibition experiments

NASA Astrophysics Data System (ADS)

Evje, S.; Hiorth, A.

2011-12-01

Previous experimental results for spontaneous imbibition experiments in the context of chalk cores have revealed a rather puzzling behavior: the oil recovery curves, both the shape as well as the steady state level which is reached, depend strongly on the brine composition. In particular, it has been demonstrated that Mg,SO42-, and Ca 2+ play a central role in this physico-chemical system. A good theoretical understanding of these experimental results, in terms of mathematical models that can suggest possible explanations of the lab experiments as well as predict behavior not yet tested in the lab, seems to still be lacking. The purpose of this paper is to try to shed light on some important modeling aspects. The model we propose is an extended version of the classical Buckley-Leverett (BL) equation for two-phase spontaneous imbibition where the water saturation equation has been coupled to a system of reaction-diffusion (RD) equations describing water-rock chemistry relevant for chalk core plugs. As far as water-rock chemistry is concerned we focus in this work on the combined effect of transport and dissolution/precipitation of calcite, magnesite, and anhydrite. The line we pursue is to couple changes of the wetting state, expressed in terms of the relative permeability and capillary pressure functions, to the water-rock chemistry behavior. More precisely, we build into the model the mechanism that the rock surface will become more water-wet at the places where dissolution of calcite takes place. In particular, we illustrate and analyze how different compositions of the imbibing brine then lead to different water-rock interaction scenarios which in turn gives qualitative and quantitative differences in the solution of the saturation equation describing spontaneous imbibition. Comparison with relevant experimental behavior is included as well as illustration of some possible interesting and non-trivial characteristic features of the model reflecting the nonlinear coupling mechanisms between the RD model for the water-rock chemistry and the BL equation for the water-oil transport.

Radium isotope quartet in groundwater as a proxy for identification of aquifer rocks and mechanisms of water-rock interactions: examples from the Negev, Israel

NASA Astrophysics Data System (ADS)

Vengosh, A.; Pery, N.; Paytan, A.; Haquin, G.; Elhanani, S.; Pankratov, I.

2006-05-01

Many aquifer systems are composed of multiple rock types. Previous attempts to evaluate the specific aquifer rocks that control the groundwater chemistry and possible flow paths within these multiple lithological systems have used major ion chemistry and isotopic tracers (e.g., strontium isotopes). Here we propose an additional isotopic proxy that is based on the distribution of radium isotopes in groundwater. Radium has four radioactive isotopes that are part of the decay chains of uranium-238, thorium-232, and uranium-235. The abundance of radium isotope quartet (226Ra-half life 1600 y; 228Ra-5.6 y; 224Ra-3.6 d; 223Ra-11.4 d) in groundwater reflects the Th/U ratios in the rocks. Investigation of groundwater from the Negev, Israel, enabled us to discriminate between groundwaters flowing in the Lower Cretaceous Nubian Sandstone and the Upper Cretaceous Judea Group carbonate aquifers. Groundwater flowing in the sandstone aquifer has distinguishably high 228Ra/226Ra and 224Ra/223Ra ratios due to the high Th/U ratio in sandstone. In contrast, the predominance of uranium in carbonate rocks results in low 228Ra/226Ra and 224Ra/223Ra ratios in the associated groundwater. We show that the radium activity in groundwater in the two-aquifer systems is correlated with temperature, dissolved oxygen, and salinity. The increase of radium activity is also associated with changes in the isotopic ratios; 228Ra/226Ra ratios increase and decrease in the sandstone and carbonate aquifers, respectively. Given that the dissolution of radium isotopes depends on their decay constants, the use of the four radium isotopes with different decay constants enabled us to distinguish between dissolution (higher abundance of the long-lived isotopes) and recoil (predominance of the short-lived isotopes) processes. In spite of these isotopic fractionations, the radium isotopic discrimination between carbonate and sandstone aquifers is significant.

Models and Experiments of Melt-Rock Interaction in the Lower Oceanic Crust

NASA Astrophysics Data System (ADS)

Orton, W. H., II; Liang, Y.; Sanfilippo, A.

2017-12-01

Understanding the processes of melt-rock interaction in the lower oceanic crust isimportant to the interpretation of mid-ocean ridge basalt (MORB) and the petrogenesis of lowercrustal cumulates. Petrologic and geochemical studies of cumulates from the lower crustalregions of oceanic lithosphere have identified a number of textural and chemical features that arepertinent to melt-rock reaction (e.g., high-Mg# clinopyroxene oikocrysts within local gabbroicregions in troctolite bodies). The purpose of the present study is to provide some referenceexamples of MORB melt and cumulate mush interaction under controlled conditions. Suchsimple experiments are useful in sorting out crystallization, dissolution, re-precipitation, anddiffusion processes in the cumulate mush and in developing better models for melt transport andmelt-rock interaction in the lower oceanic crust.We performed piston cylinder experiments at 0.5-0.7 GPa and 1000-1250°C reacting anolivine or olivine + plagioclase cumulate mush and an intruding MORB melt in a graphite-linedmolybdenum capsule. Our experiments consist of two steps: (1) reaction at 1250°C for 10 to 24hours; and (2) reactive crystallization to a lower temperature through controlled cooling overseveral days. Cooling promotes in situ crystallization of interstitial melts, allowing us to bettercharacterize the mineral compositional trends produced and observed by melt-rock reaction andcrystallization. Reaction at 1250°C produced an olivine + melt mush with small rounded crystalscharacteristic of dissolution. Significant crystal settling was also observed at large melt-to- rockratio. Cooling with continued reaction resulted in the formation of a plagioclase matrix withpoikilitic clinopyroxene oikocrysts containing plagioclase and relict olivine as chadacrysts.Clinopyroxenes were in a reaction relationship with both plagioclase and olivine. In somesamples, multiple phases of clinopyroxene and plagioclase were present, each with differentcompositions, similar to those observed in the field-based studies. With these insights, a modelfor melt transport and melt-rock interaction in the lower oceanic crust has been developed andwill be used to study major and trace element fractionation during reactive melt migration in thecumulate mush.

Use of structural geology in exploration for and mining of sedimentary rock-hosted Au deposits

USGS Publications Warehouse

Peters, Stephen G.

2001-01-01

Structural geology is an important component in regional-, district- and orebody-scale exploration and development of sedimentary rock-hosted Au deposits.Identification of timing of important structural events in an ore district allows analysis and classification of fluid conduits and construction of genetic models for ore formation.The most practical uses of structural geology deal with measurement and definition of various elements that comprise orebodies, which can then be directly applied to ore-reserve estimation,ground control,grade control, safety issues,and mine planning.District- and regional-scale structural studies are directly applicable to long-term strategic planning,economic analysis,and land ownership. Orebodies in sedimentary rock-hosted Au deposits are discrete, hypogene, epigenetic masses usually hosted in a fault zone,breccia mass, or lithologic bed or unit. These attributes allow structural geology to be directly applied to the mining and exploration of sedimentary rock-hosted Au deposits. Internal constituents in orebodies reflect unique episodes relating to ore formation.The main internal constituents in orebodies are ore minerals, gangue, and alteration minerals that usually are mixed with one another in complex patterns, the relations among which may be used to interpret the processes of orebody formation and control.Controls of orebody location and shape usually are due to structural dilatant zones caused by changes in attitude, splays, lithologic contacts,and intersections of the host conduit or unit.In addition,conceptual parameters such as district fabric,predictable distances, and stacking also are used to understand the geometry of orebodies.Controls in ore districts and location and geometry of orebodies in ore districts can be predicted to various degrees by using a number of qualitative concepts such as internal and external orebody plunges,district plunge, district stacking, conduit classification, geochemical, geobarometric and geothermal gradients, and tectonic warps. These concepts have practical and empirical application in most mining districts where they are of use in the exploration for ore, but are of such broad and general application that they may not represent known or inferred ore formation processes. Close spatial relation among some sedimentary rock- hosted Au deposits and their host structures suggests that the structures and the orebodies are genetically linked because they may have shared the same developmental history. Examples of probable syn-deformational genesis and structural control of sedimentary rock-hosted Au deposits are in the large Betze deposit in the Carlin trend, Nevada and in the Lannigou, Jinlongshan, and Maanqiao Au deposits, China.

Mineralogical and geochemical studies on the Central Seruyan Pb-Zn deposits in Central Kalimantan, Indonesia

NASA Astrophysics Data System (ADS)

Choi, Y.; Lee, I.; Choi, B.; KIM, Y.; Moon, I.

2017-12-01

The Central Seruyan Pb-Zn deposit is located in Seruyan, Central Kalimantan Province in Indonesia. This deposit has been developed since last year and is still being investigated. The Pb-Zn deposit consists of two formations, Pinoh and Kuayan formation. The former is a metamorphic unit hosting schist, phyllite and gneiss, and the latter is a pyroclastic and volcanic unit includes intermediate volcanic rocks such as dacite, tuff and breccia. Most host rocks of the deposit is composed of the silicified porphyritic dacite and silicified phyllite and covered by silicified tuff. The joints and fractures within the wall rock has E-W trends. The Seruyan Pb-Zn deposit is considered as hydrothermal breccia type.In this study, we observe ore minerals and host rocks to understand the genesis of the Pb-Zn deposit with geochemical data. Pyrite, chalcopyrite, sphalerite and galena are major ore minerals and covellite and bornite are also observed as minor sulfide minerals. These ore minerals, except pyrite, usually occur within quartz or calcite veins indicating the influence of hydrothermal fluid. In the host rocks, dacite, has the altered minerals like sericite, chlorite, epidote and some clay minerals of hydrothermal origin. All minerals occur as massive form. Only some pyrites have an euhedral form. Small amount of Au, Ag and Mo are detected in major ore minerals in the EPMA (electron probe X-ray microanalyzer) analyses.

A Compilation of Rate Parameters of Water-Mineral Interaction Kinetics for Application to Geochemical Modeling

DTIC Science & Technology

2004-03-01

equilibria among fluids, gases, and alteration minerals is a valid assumption in many volcanic-hosted hydrothermal systems (Arnórsson, 1983; Arnórsson et al...order n with respect to P(CO2). e. Sedimentary (disordered) dolomite. f. Hydrothermal (ordered) dolomite. 3.9 Sulfates Dissolution rate data...carbonate in sea water IV. Theory of calcite dissolution. Am. J. Sci. 274, 108-134. Bertrand C., Fritz B., and Sureau J. F. (1994) Hydrothermal

Evolution of major and trace elements and volatile contents of selected magmas in the Campi Flegrei and Procida volcanic fields, Italy, based on melt inclusion

NASA Astrophysics Data System (ADS)

Esposito, R.; Badescu, K.; Steele-MacInnis, M.; Lima, A.; De Vivo, B.; Cannatelli, C.; Manning, C. E.; Bodnar, R. J.

2017-12-01

The active Campi Flegrei (CF) volcanic field in southern Italy has been intensively studied owing to the volcanic risk to which the 1.5 million people in the area are exposed. The volcanic Island of Procida (IP) is located just southwest from CF but shows no signs of volcanic activity today. The IP volcanic products are the most primitive volcanic products of these two related volcanic fields. In this study, the major and minor element and volatile (H2O, CO2, S, Cl and F) compositions of melt inclusions (MI) hosted in sanidine, clinopyroxene, plagioclase and olivine were determined. MI data from this study and from the literature were compared with bulk rock data to test for agreement between MI compositions and compositions of CF and IP magmas determined by bulk rock analyses. Although MI compositions overlap with those of the bulk rock, some MI show anomalous compositions for one or a combination of Al2O3, FeO, P2O5, and TiO2. These MI represent melts produced by dissolution-reaction-mixing and were not included for the interpretation of volatile contents. Major elements and volatile concentrations of bubble-free MI that are interpreted to be representative of CF and IP were compared to crystal host compositions and to melt compositions obtained using rhyolite-MELTS simulations. Data suggest that less evolved magmas beneath the studied area crystallize either isobarically at ≥200 MPa (≥7.5 km) or polybarically during ascent to shallow depths under volatile-saturated conditions. Bubble-free MI representative of the least differentiated magmas can be divided into two groups. One group of MI is representative of simple fractional crystallization under volatile-saturated conditions from a primitive trachybasaltic melt. The other group of MI is representative of recharge of a primitive basaltic magma mixing with the preexisting primitive trachybasaltic magma before eruption. We suggest that the mixing process occurred at relatively great depth. Extensive isobaric crystallization of the trachybasaltic magmas beneath CF at 7.5 km may have generated trachy-phonolitic magmas, such as those associated with the Neapolitan Yellow Tuff that is characterized by a relatively high H2O content. These volatile saturated trachy-phonolitic magmas ascend through the crust and trigger high-magnitude eruptions.

Path Selection in the Growth of Wormholes

NASA Astrophysics Data System (ADS)

Yang, Yi; Bruns, Stefan; Stipp, Susan; Sørensen, Henning

2017-04-01

Spontaneous growth of wormholes in natural porous media often leads to generation of highly complex flow systems with fractal morphologies. Despite extensive investigations, the underpinning mechanism for path selection during wormholing remains elusive. Here we introduce the concept of cumulative surface (CS) and show that the trajectory of a growing wormhole is one with minimum CS. Theoretical analysis shows that the CS determines the position of the dissolution front. We then show, using numerical simulation based on greyscale data of the fine grained carbonate rock chalk, that the tip of an advancing pore always follows the migration of the most far reaching dissolution front determined from the CS. The predicted dissolution behavior was verified by experimental observation of wormhole growth in chalk using in situ microtomography. The results suggest that wormholing is deterministic in nature rather than stochastic. This insight sheds light on engineering of artificial flow systems in geologic formations by exploiting self-organization in natural porous materials.

Characteristics of streams and aquifers and processes affecting the salinity of water in the upper Colorado River basin, Texas

USGS Publications Warehouse

Slade, R.M.; Buszka, P.M.

1994-01-01

The chemical characteristics of the saline water in streams and shallow aquifers in the study area were compared to characteristics of water that would result from the probable processes affecting the salinity of water, such as evapotranspiration, mineral dissolution, and mixing of water from streams and shallow-aquifer water with brines from deep aquifers. Dissolution of halite or mixing with deep-aquifer water was the most common cause of increased salinity in 48.0 percent of 77 water samples from shallow aquifers, as classified using salt-norm analysis; the second most common cause was the weathering and dissolution of sulfur-bearing minerals. Mixing with water from soil-mineral dissolution was classified as the principal source of chloride in 28.4 percent of 67 water samples from shallow aquifers with nitrate determinations. Trace-species/chloride ratios indicated that mixing with water from deep aquifers in rocks of the Pennsylvanian System was the principal source of chloride in 24.4 percent of 45 shallow-aquifer samples lacking nitrate determinations.

Determination of the carbonate dissolution mechanism of Lactococcus sp.

NASA Astrophysics Data System (ADS)

Yanmiş, Derya; Orhan, Furkan; Güllüce, Medine; Şahin, Fikrettin

2017-04-01

Magnesite, the main source for magnesium and magnesium derivatives, are also commonly used in the production of caustic, dead-burned and fused magnesia. World magnesite resources are estimated to be at 12 billion tonnes mostly located in China, Russia, North Korea, Australia and Turkey. Turkey is the second producer of the magnesite. Magnesite deposits in Turkey are sedimentary magnesite which have been formed in specific conditions as high concentrations of MgSO4 and CO2 and presence of certain organic salts or created by hot or cold dissolution connected with carbonate rocks mainly with dolomites. According to the genesis of magnesite deposits, they have some impurities as calcium, quartz, iron, etc. Impurities of magnesite, especially CaCO3, reduce its economic value and industrial usability. In our previous study, we have performed biotechnologically enrichment of magnesite by Lactococcus sp., which gave significantly important results. However, we had no information about carbonate dissolution mechanism of bacteria. Therefore, it is aimed to reveal the metabolites of Lactococcus sp. and mechanism leading to the carbonate dissolution (MgCO3 and CaCO3).

Returning from the deep: Archean atmospheric fingerprints in modern hotspot lavas (Invited)

NASA Astrophysics Data System (ADS)

Jackson, M. G.; Cabral, R. A.; Rose-Koga, E. F.; Koga, K. T.; Whitehouse, M. J.; Antonelli, M. A.; Farquhar, J.; Day, J. M.; Hauri, E. H.

2013-12-01

Ocean plates transport surface materials, including oceanic crust and sediment, into the mantle at subduction zones. However, the fate of the subducted package--oceanic crust and sediment--in the mantle is poorly understood. A long-standing hypothesis maintains that subducted materials reside in the mantle for an extended, but unknown, period of time and are then recycled back to the Earth's surface in regions of buoyantly upwelling mantle and melted beneath hotspots. Sulfur isotopes provide an important new tool to evaluate the presence of ancient recycled materials in hotspot lavas. Widespread terrestrial mass independently fractionated sulfur (MIF-S) isotope signatures were generated exclusively through atmospheric photochemical reactions until ~2.45 Ga. In fact, the only significant reservoirs of MIF-S containing rocks documented so far are sediments and hydrothermal rocks older than ~2.45 Ga. Armed with this insight, we examined sulfur isotopes in olivine phenocrysts and olivine-hosted sulfides in lavas from the island of Mangaia, Cook Islands. Lavas from this location host unusually radiogenic Pb-isotopic compositions--referred to as a HIMU (high U/Pb) component--and this has been attributed to ancient recycled oceanic crust in the mantle source. In Cabral et al. (2013), we report MIF-S in olivine phenocrysts and olivine-hosted sulfides. The discovery of MIF-S isotopic signatures in young hotspot lavas appears to provide a "timestamp" and "signature" for preservation of subducted Archean surface materials in the mantle sourcing Mangaia lavas. We report new sulfur isotope data on olivine-hosted sulfides from the Mangaia lavas that reinforce our discovery of MIF-S anomalies reported in Cabral et al. (2013). We also report new sulfur isotopic data on Mangaia whole rock powders, and we find no evidence of MIF-S signatures. It is not yet clear why the individual Mangaia sulfides and the olivine separates have more extreme MIF-S than the whole rocks. We consider it likely that the MIF-S anomaly measured in the olivine separates was diminished relative to the olivine-hosted sulfides by incorporation of modern sulfur into the olivine separates by low-temperature processes operating on the rocks during the 20 Ma since eruption: The absence of a MIF-S anomaly in the whole rock that has olivine-hosted sulfides with MIF-S anomalies may be a result of near-complete replacement of the magmatic sulfur (with a MIF-S anomaly) with modern sulfur (with no MIF-S anomaly) during surficial weathering over 20 Ma. The sulfur in the olivine-hosted sulfides with the largest MIF-S anomalies represents a very small proportion of the sulfur in a bulk basaltic rock and therefore do not impart a clear MIF-S anomaly on the bulk rock analysis. Very few data are available to evaluate this hypothesis. Therefore, pairing sulfur isotope measurements with whole rocks, mineral separates and olivine-hosted sulfides with careful petrographic and electron probe analyses of the samples will be critical for evaluating the origin of the sulfides--primary magmatic or secondary--and the origin and distribution of the sulfur-isotopic signatures in OIB.

Earthquake rupture at focal depth, part II: mechanics of the 2004 M2.2 earthquake along the Pretorius Fault, TauTona Mine, South Africa

USGS Publications Warehouse

Heesakkers, V.; Murphy, S.; Lockner, D.A.; Reches, Z.

2011-01-01

We analyze here the rupture mechanics of the 2004, M2.2 earthquake based on our observations and measurements at focal depth (Part I). This event ruptured the Archean Pretorius fault that has been inactive for at least 2 Ga, and was reactivated due to mining operations down to a depth of 3.6 km depth. Thus, it was expected that the Pretorius fault zone will fail similarly to an intact rock body independently of its ancient healed structure. Our analysis reveals a few puzzling features of the M2.2 rupture-zone: (1) the earthquake ruptured four, non-parallel, cataclasite bearing segments of the ancient Pretorius fault-zone; (2) slip occurred almost exclusively along the cataclasite-host rock contacts of the slipping segments; (3) the local in-situ stress field is not favorable to slip along any of these four segments; and (4) the Archean cataclasite is pervasively sintered and cemented to become brittle and strong. To resolve these observations, we conducted rock mechanics experiments on the fault-rocks and host-rocks and found a strong mechanical contrast between the quartzitic cataclasite zones, with elastic-brittle rheology, and the host quartzites, with damage, elastic–plastic rheology. The finite-element modeling of a heterogeneous fault-zone with the measured mechanical contrast indicates that the slip is likely to reactivate the ancient cataclasite-bearing segments, as observed, due to the strong mechanical contrast between the cataclasite and the host quartzitic rock.

Thermo-mechanical modelling of salt caverns due to fluctuating loading conditions.

NASA Astrophysics Data System (ADS)

Böttcher, N.

2015-12-01

This work summarizes the development and application of a numerical model for the thermo-mechanical behaviour of salt caverns during cyclic gas storage. Artificial salt caverns are used for short term energy storage, such as power-to-gas or compressed air energy storage. Those applications are characterized by highly fluctuating operation pressures due to the unsteady power levels of power plants based on renewable energy. Compression and expansion of the storage gases during loading and unloading stages lead to rapidly changing temperatures in the host rock of the caverns. This affects the material behaviour of the host rock within a zone that extends several meters into the rock mass adjacent to the cavern wall, and induces thermo-mechanical stresses and alters the creep response.The proposed model features the thermodynamic behaviour of the storage medium, conductive heat transport in the host rock, as well as temperature dependent material properties of rock salt using different thermo-viscoplastic material models. The utilized constitutive models are well known and state-of-the-art in various salt mechanics applications. The model has been implemented into the open-source software platform OpenGeoSys. Thermal and mechanical processes are solved using a finite element approach, coupled via a staggered coupling scheme. The simulation results allow the conclusion, that the cavern convergence rate (and thus the efficiency of the cavern) is highly influenced by the loading cycle frequency and the resulting gas temperatures. The model therefore allows to analyse the influence of operation modes on the cavern host rock or on neighbouring facilities.

Potential for leaching of arsenic from excavated rock after different drying treatments.

PubMed

Li, Jining; Kosugi, Tomoya; Riya, Shohei; Hashimoto, Yohey; Hou, Hong; Terada, Akihiko; Hosomi, Masaaki

2016-07-01

Leaching of arsenic (As) from excavated rock subjected to different drying methods is compared using sequential leaching tests and rapid small-scale column tests combined with a sequential extraction procedure. Although the total As content in the rock was low (8.81 mg kg(-1)), its resulting concentration in the leachate when leached at a liquid-to-solid ratio of 10 L kg(-1) exceeded the environmental standard (10 μg L(-1)). As existed mainly in dissolved forms in the leachates. All of the drying procedures applied in this study increased the leaching of As, with freeze-drying leading to the largest increase. Water extraction of As using the two tests showed different leaching behaviors as a function of the liquid-to-solid ratio, and achieved average extractions of up to 35.7% and 25.8% total As, respectively. Dissolution of As from the mineral surfaces and subsequent re-adsorption controlled the short-term release of As; dissolution of Fe, Al, and dissolved organic carbon played important roles in long-term As leaching. Results of the sequential extraction procedure showed that use of 0.05 M (NH4)2SO4 underestimates the readily soluble As. Long-term water extraction removed almost all of the non-specifically sorbed As and most of the specifically sorbed As. The concept of pollution potential indices, which are easily determined by the sequential leaching test, is proposed in this study and is considered for possible use in assessing efficacy of treatment of excavated rocks. Copyright © 2016 Elsevier Ltd. All rights reserved.

EGS rock reactions with Supercritical CO2 saturated with water and water saturated with Supercritical CO2

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

Earl D. Mattson; Travis L. McLing; William Smith

2013-02-01

EGS using CO2 as a working fluid will likely involve hydro-shearing low-permeability hot rock reservoirs with a water solution. After that process, the fractures will be flushed with CO2 that is maintained under supercritical conditions (> 70 bars). Much of the injected water in the main fracture will be flushed out with the initial CO2 injection; however side fractures, micro fractures, and the lower portion of the fracture will contain connate water that will interact with the rock and the injected CO2. Dissolution/precipitation reactions in the resulting scCO2/brine/rock systems have the potential to significantly alter reservoir permeability, so it ismore » important to understand where these precipitates form and how are they related to the evolving ‘free’ connate water in the system. To examine dissolution / precipitation behavior in such systems over time, we have conducted non-stirred batch experiments in the laboratory with pure minerals, sandstone, and basalt coupons with brine solution spiked with MnCl2 and scCO2. The coupons are exposed to liquid water saturated with scCO2 and extend above the water surface allowing the upper portion of the coupons to be exposed to scCO2 saturated with water. The coupons were subsequently analyzed using SEM to determine the location of reactions in both in and out of the liquid water. Results of these will be summarized with regard to significance for EGS with CO2 as a working fluid.« less

Distinction between epigenic and hypogenic maze caves

NASA Astrophysics Data System (ADS)

Palmer, Arthur N.

2011-11-01

Certain caves formed by dissolution of bedrock have maze patterns composed of closed loops in which many intersecting fractures or pores have enlarged simultaneously. Their origin can be epigenic (by shallow circulation of meteoric groundwater) or hypogenic (by rising groundwater or production of deep-seated solutional aggressiveness). Epigenic mazes form by diffuse infiltration through a permeable insoluble caprock or by floodwater supplied by sinking streams. Most hypogenic caves involve deep sources of aggressiveness. Transverse hypogenic cave origin is a recently proposed concept in which groundwater of mainly meteoric origin rises across strata in the distal portions of large flow systems, to form mazes in soluble rock sandwiched between permeable but insoluble strata. The distinction between maze types is debated and is usually based on examination of diagnostic cave features and relation of caves to their regional setting. In this paper, the principles of mass transfer are applied to clarify the limits of each model, to show how cave origin is related to groundwater discharge, dissolution rate, and time. The results show that diffuse infiltration and floodwater can each form maze caves at geologically feasible rates (typically within 500 ka). Transverse hypogenic mazes in limestone, to enlarge significantly within 1 Ma, require an unusually high permeability of the non-carbonate beds (generally ≥ 10-4 cm/s), large discharge, and calcite saturation no greater than 90%, which is rare in deep diffuse flow in sedimentary rocks. Deep sources of aggressiveness are usually required. The origin of caves by transverse hypogenic flow is much more favorable in evaporite rocks than in carbonate rocks.

10 CFR 960.4-2-3 - Rock characteristics.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 10 Energy 4 2013-01-01 2013-01-01 false Rock characteristics. 960.4-2-3 Section 960.4-2-3 Energy... REPOSITORY Postclosure Guidelines § 960.4-2-3 Rock characteristics. (a) Qualifying condition. The present and expected characteristics of the host rock and surrounding units shall be capable of accommodating the...

Kimberlite-related metasomatism recorded in MARID and PIC mantle xenoliths

NASA Astrophysics Data System (ADS)

Fitzpayne, Angus; Giuliani, Andrea; Phillips, David; Hergt, Janet; Woodhead, Jon D.; Farquhar, James; Fiorentini, Marco L.; Drysdale, Russell N.; Wu, Nanping

2018-05-01

MARID (Mica-Amphibole-Rutile-Ilmenite-Diopside) and PIC (Phlogopite-Ilmenite-Clinopyroxene) xenoliths are thought to be formed by intense "primary" mantle metasomatism. These rocks also display secondary features, such as cross-cutting veins and geochemical zonation of matrix minerals, which probably reflect later metasomatic events. To investigate the nature and origin(s) of these secondary features, 28 MARID and PIC xenoliths from southern African kimberlites and orangeites have been studied. MARID-hosted veins contain both carbonate and Ti-rich phases (e.g., titanite, phlogopite), suggesting that they formed by the infiltration of a carbonated silicate melt. Elevated TiO2 contents in MARID matrix mineral rims are spatially associated with carbonate-dominated veins, suggesting a genetic relationship between vein formation and geochemical zonation. Spongy rims around primary MARID and PIC clinopyroxene are depleted in Na2O and Al2O3 relative to their cores, possibly reflecting mineral dissolution in the xenoliths during ascent and emplacement of the entraining kimberlite. The preservation of compositional differences between primary and secondary phases in MARID and PIC xenoliths indicates that metasomatism occurred shortly before, or broadly coeval with, kimberlite/orangeite magmatism; otherwise, at typical mantle temperatures, such features would have quickly re-equilibrated. Increased Na2O in some mineral rims (e.g., K-richterite) may therefore reflect equilibration with a more Na-enriched primitive kimberlite melt composition than is commonly suggested. Vein-hosted clinopyroxene 87Sr/86Sri (0.70539 ± 0.00079) in one MARID sample is intermediate between primary clinopyroxene in the sample (0.70814 ± 0.00002) and the host Bultfontein kimberlite (0.70432 ± 0.00005), suggesting that vein minerals are derived from interactions between primary MARID phases and kimberlite-related melts/fluids. Sulfur isotope compositions of barite (δ34SVCDT = +4.69 ‰) and sulfides (δ34SVCDT = -0.69 ‰) in carbonate veins reflect equilibration at temperatures of 850-900 °C, consistent with sulfur-rich melt/fluid infiltration in the lithospheric mantle. In contrast, vein carbonate C-O isotope systematics (δ13CVPDB = -9.18 ‰; δ18OVSMOW = +17.22 ‰) are not typical of kimberlites or other mantle carbonates (δ13CVPDB = -3 to -8 ‰; δ18OVSMOW = 6 to 9 ‰), and may represent post-emplacement hydrothermal interactions of the cooling kimberlite with crustal fluids. These constraints suggest protracted metasomatism of MARID rocks shortly before and during entrainment by the host kimberlite.

Note: CO₂-mineral dissolution experiments using a rocking autoclave and a novel titanium reaction cell.

PubMed

Purser, Gemma; Rochelle, Christopher A; Wallis, Humphrey C; Rosenqvist, Jörgen; Kilpatrick, Andrew D; Yardley, Bruce W D

2014-08-01

A novel titanium reaction cell has been constructed for the study of water-rock-CO2 reactions. The reaction cell has been used within a direct-sampling rocking autoclave and offers certain advantages over traditional "flexible gold/titanium cell" approaches. The main advantage is robustness, as flexible cells are prone to rupture on depressurisation during gas-rich experiments. The reaction cell was tested in experiments during an inter-laboratory comparison study, in which mineral kinetic data were determined. The cell performed well during experiments up to 130 °C and 300 bars pressure. The data obtained were similar to those of other laboratories participating in the study, and also to previously published data.

Isotopic and trace element compositions of upper mantle and lower crustal xenoliths, Cima volcanic field, California: Implications for evolution of the subcontinental lithospheric mantle

USGS Publications Warehouse

Mukasa, S.B.; Wilshire, H.G.

1997-01-01

Ultramafic and mafic xenoliths from the Cima volcanic field, southern California, provide evidence of episodic modification of the upper mantle and underplating of the crust beneath a portion of the southern Basin and Range province. The upper mantle xenoliths include spinel peridotite and anhydrous and hydrous pyroxenite, some cut by igneous-textured pyroxenite-gabbro veins and dikes and some by veins of amphibole ?? plagioclase. Igneous-textured pyroxenites and gabbros like the dike rocks also occur abundantly as isolated xenoliths inferred to represent underplated crust. Mineral and whole rock trace element compositions among and within the different groups of xenoliths are highly variable, reflecting multiple processes that include magma-mantle wall rock reactions, episodic intrusion and it filtration of basaltic melts of varied sources into the mantle wall rock, and fractionation. Nd, Sr, and Pb isotopic compositions mostly of clinopyroxene and plagioclase mineral separates show distinct differences between mantle xenoliths (??Nd = -5.7 to +3.4; 87Sr/86Sr = 0.7051 - 0.7073; 206Pb/204Pb = 19.045 - 19.195) and the igneous-textured xenoliths (??Nd = +7.7 to +11.7; 87Sr/86Sr = 0.7027 - 0.7036 with one carbonate-affected outlier at 0.7054; and 206Pb/204Pb = 18.751 - 19.068), so that they cannot be related. The igneous-textured pyroxenites and gabbros are similar in their isotopic compositions to the host basaltic rocks, which have ??Nd of+5.1 to +9.3; 87Sr/86Sr of 0.7028 - 0.7050, and 206Pb/204Pb of 18.685 - 21.050. The igneous-textured pyroxenites and gabbros are therefore inferred to be related to the host rocks as earlier cogenetic intrusions in the mantle and in the lower crust. Two samples of peridotite, one modally metasomatized by amphibole and the other by plagioclase, have isotopic compositions intermediate between the igneous-textured xenoliths and the mantle rock, suggesting mixing, but also derivation of the metasomatizing magmas from two separate and distinct sources. Sm-Nd two-mineral "isochrons" yield apparent ages for petrographically identical rocks believed to be coeval ranging from -0 to 113 ?? 26 Ma, indicating the unreliability of dating these rocks with this method. Amphibole and plagioclase megacrysts are isotopically like the host basalts and probably originate by mechanical breakup of veins comagmatic with the host basaltic rocks. Unlike other Basin and Range localities, Cima Cr-diopside group isotopic compositions do not overlap with those of the host basalts. Copyright 1997 by the American Geophysical Union.

Insights on the injection mechanisms inferred from AMS fabrics of sand injectites in a turbiditic system, the exemple of Bevon area of the SE Basin (France).

NASA Astrophysics Data System (ADS)

Robion, Philippe; Mehl, Caroline

2016-04-01

We propose to investigate the set up mechanisms of sands injection in the case of dykes injected in host marls of Aptian-Albian age in the Vocontian basin (SE France). Several models have been proposed for a downward injection of the dyke in the Bevons area and we guess that AMS fabric investigations can be used to infer the flow direction. 144 drill cores distributed on 14 sites were sampled, among which 8 sites in the injectites and 6 sites in the host rocks. The studied dykes are generally of a few decimeters thick and are setting up in both in vertical or oblique position with respect to the subhorizontal bedding of the host rocks. There were sampled from one side to the other in order to track the flow direction by identification of imbricated fabric. Magnetic mineralogy, i.e. unblocking temperature inferred from IRM 3 axes demagnetization, indicates that the ferromagnetics s.l. mineralogy is dominated by an assemblage of magnetite (unblocking temperature Tub=580°C) and pyrrhotite (Tub=325°C). Magnetic susceptibility is low, typical for siliciclastic rocks, ranging from 4x10-5 up to 1.7x10-4 SI. Degree of magnetic anisotropy is likely representative of AMS measurements in sedimentary rocks with weak values, below than 5 %. In marly host rocks magnetic mineralogy is dominated by pyrrhotite associated with magnetite and both the magnetic susceptibility and degree of anisotropy are slightly lower than for injectites. Regarding magnetic fabric axes distribution, despite some dispersion, the results show that minimum axes of AMS (K3) are parallel to the dyke plane, and maximum axes (K1) are roughly in horizontal position. In marly host rocks, the magnetic fabric is related to tectonic shortening. We interpret that the host rocks have recorded the regional tectonic imprint while the magnetic fabric of the injectites are related to early sedimentary processes. The mechanism of set up proposed to explain the magnetic fabric in the Bevon injectites is a step-by-step process of filling the pre-existing fractures with highly fluidized sand and a compaction direction parallel to dyke plane. A late diagenetic cementation affecting the injectites network prevents any further deformation during tectonic inversion.

Effect of brine salinity and guar gum on the transport of barium through dolomite rocks: Implications for unconventional oil and gas wastewater disposal.

PubMed

Ebrahimi, Pouyan; Vilcáez, Javier

2018-05-15

This research aimed to elucidate the effect of brine salinity and guar gum on the sorption and transport of Ba in dolomite rocks collected from the Arbuckle formation in Oklahoma, USA. Guar gum represents the most important organic additive used in viscosified fracturing fluids, and Ba constitutes the most common and abundant heavy metal found in unconventional oil and gas (UOG) wastewater. Batch experiments conducted using powdered dolomite rocks (500-600 μm particle size) revealed that at brine salinities of UOG wastewater, chloro-complexation reactions between Ba and Cl ions and pH changes that results from dolomite dissolution are the controlling factors of Ba sorption on dolomite. Competition of Ba with common cations (Ca and Mg) for hydration sites of dolomite, plays a secondary role. Core-flooding experiments conducted to analyze the transport of Ba through natural and synthetic dolomite core plugs are in agreement with the batch sorption experimental results. The transport of Ba through dolomite rocks, increases with increasing brine salinity (0-180,000 mg-NaCl/L). The presence guar gum (50-500 mg/L) does not affect the transport of Ba through dolomite rocks of high flow properties (25-29.6% porosity, 9.6-13.7 mD permeability). However, core-flooding experiments conducted using tight dolomite rocks (6.5-8.6% porosity, 0.06-0.3 mD permeability), revealed that guar gum can retard the transport of Ba by clogging high permeability/porosity regions of tight dolomite rocks. The mechanism of Ba sorption on dolomite can be represented by a sorption model that accounts for both surface complexation reactions on three distinct hydration sites (>CaOH o , >MgOH o , and >CO 3 H o ), and the kinetic dissolution of dolomite. These results are important in understanding and predicting the fate of Ba present in UOG wastewater disposed into deep dolomite saline aquifers. Copyright © 2018 Elsevier Ltd. All rights reserved.

No Martian soil component in shergottite meteorites

NASA Astrophysics Data System (ADS)

Barrat, J. A.; Jambon, A.; Ferrière, L.; Bollinger, C.; Langlade, J. A.; Liorzou, C.; Boudouma, O.; Fialin, M.

2014-01-01

We report on the major and trace element geochemistry of the impact melts contained in some shergottite meteorites. It has been previously proposed that some of these impact melts formed from a mixture of the host rock and a Martian soil component (e.g., Rao et al., 1999) or from partially weathered portions of the host rock (Chennaoui Aoudjehane et al., 2012). Our results contradict both of these theories. Trace element abundances of a glass pod from the EETA 79001A meteorite are identical to those of the host lithology, and indicate that no additional component is required in this case. The impact melts in Tissint share the same trace element features as the host rock, and no secondary phases produced by Martian secondary processes are involved. The light rare earth enrichments displayed by two small samples of Tissint (Chennaoui Aoudjehane et al., 2012) are possibly the result of some contamination of small stones on desert soil before the recovery of the meteorites.

INFLUENCE OF PH AND OXIDATION-REDUCTION (EH) POTENTIAL ON THE DISSOLUTION OF MERCURY-CONTAINING MINE WASTES FROM THE SULFUR BANK MERCURY MINE

EPA Science Inventory

Mine waste rock and roaster tailings were collected from the Sulfur Bank Mercury Mine (SBMM) located in Clearlake Oaks, California. The site has been under investigation as a Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) site. Characterization an...

The Origin of Fibrous Calcite Veins: Aragonite?

NASA Astrophysics Data System (ADS)

Elburg, M. A.; Bons, P. D.

2005-12-01

Truly fibrous calcite veins occur mainly in carbonaceous shales and are characterised by high length:width ratios of their fibres (>10). Previous studies on their Sr isotopic geochemistry (Elburg et al., 2002: Geol. Soc. London Spec. Publ. 200, 103-118; Hilgers and Sindern, 2005: Geofluids, in press) have shown that some of the material could be derived from the local wall rock. These studies also showed that the veins were always enriched in Sr compared to the calcite in the host rocks. Aragonite can contain significantly more Sr than calcite, while it also tends to have a fibrous crystal habit. It is therefore possible that the fibrous habit of these veins, which now consist of calcite, are a reflection of their initial aragonitic mineralogy, rather than of any special tectonic regime during their formation. This idea was investigated by analysing the major and trace element geochemistry of selected fibrous and non-fibrous calcite veins from Arkaroola (northern Flinders Ranges, Australia). The fibrous vein analysed for major elements contains less than 1% MgCO3, whereas calcite in the host rock, with which it is in Sr isotopic equilibrium, contains 18% MgCO3. Calcite can contain significant Mg, whereas the aragonitic structure cannot accomodate this ion, so this result is consistent with the idea of an original aragonitic mineralogy of the veins. The fibrous veins show an enrichment in the middle rare earth elements (REE) compared to the calcite in the host rock and blocky veins. In a Post-Archean Average Shale normalised diagram, Eu is more strongly enriched compared to its neighbouring elements in the fibrous veins, but not in the host calcite, blocky veins, or in the silicate fraction of the host rock, suggesting more reducing conditions during fibrous vein formation. This data cannot be used as direct evidence for the fibrous veins' aragonitic mineralogy. It does, however, show that significant differences exist between calcite in host rocks, blocky and fibrous calcite veins, and this data should be incorporated in any model explaining the origin of fibrous veins.

Consequences of the Thermal Transient on the Evolution of the Damaged Zone Around a Repository for Heat-Emitting High-Level Radioactive Waste in a Clay Formation: a Performance Assessment Perspective

NASA Astrophysics Data System (ADS)

Yu, Li; Weetjens, Eef; Sillen, Xavier; Vietor, Tim; Li, Xiangling; Delage, Pierre; Labiouse, Vincent; Charlier, Robert

2014-01-01

A proper evaluation of the perturbations of the host rock induced by the excavation and the emplacement of exothermic wastes is essential for the assessment of the long-term safety of high-level radioactive waste disposals in clay formations. The impact of the thermal transient on the evolution of the damaged zone (DZ) has been explored in the European Commission project TIMODAZ (thermal impact on the damaged zone around a radioactive waste disposal in clay host rocks, 2006-2010). This paper integrates the scientific results of the TIMODAZ project from a performance assessment (PA) point of view, showing how these results support and justify key PA assumptions and the values of PA model parameters. This paper also contextualises the significance of the thermal impact on the DZ from a safety case perspective, highlighting how the project outcomes result into an improved understanding of the thermo-hydro-mechanical behaviour of the clay host rocks. The results obtained in the TIMODAZ project strengthen the assessment basis of the safety evaluation of the current repository designs. There was no evidence throughout the TIMODAZ experimental observations of a temperature-induced additional opening of fractures nor of a significant permeability increase of the DZ. Instead, thermally induced plasticity, swelling and creep seem to be beneficial to the sealing of fractures and to the recovery of a very low permeability in the DZ, close to that of an undisturbed clay host rock. Results from the TIMODAZ project indicate that the favourable properties of the clay host rock, which guarantee the effectiveness of the safety functions of the repository system, are expected to be maintained after the heating-cooling cycle. Hence, the basic assumptions usually made in PA calculations so far are expected to remain valid, and the performance of the system should not be affected in a negative way by the thermal evolution of the DZ around a radioactive waste repository in clay host rock.

In vitro dynamic solubility test: influence of various parameters.

PubMed Central

Thélohan, S; de Meringo, A

1994-01-01

This article discusses the dissolution of mineral fibers in simulated physiological fluids (SPF), and the parameters that affect the solubility measurement in a dynamic test where an SPF runs through a cell containing fibers (Scholze and Conradt test). Solutions simulate either the extracellular fluid (pH 7.6) or the intracellular fluid (pH 4.5). The fibers have various chemical compositions and are either continuously drawn or processed as wool. The fiber solubility is determined by the amount of SiO2 (and occasionally other ions) released in the solution. Results are stated as percentage of the initial silica content released or as dissolution rate v in nm/day. The reproducibility of the test is higher with the less soluble fibers (10% solubility), than with highly soluble fibers (20% solubility). The influence of test parameters, including SPF, test duration, and surface area/volume (SA/V), has been studied. The pH and the inorganic buffer salts have a major influence: industrial glasswool composition is soluble at pH 7.6 but not at pH 4.5. The opposite is true for rock- (basalt) wool composition. For slightly soluble fibers, the dissolution rate v remains constant with time, whereas for highly soluble fibers, the dissolution rate decreases rapidly. The dissolution rates believed to occur are v1, initial dissolution rate, and v2, dissolution rate of the residual fibers. The SA of fibers varies with the mass of the fibers tested, or with the fiber diameter at equal mass. Volume, V, is the chosen flow rate. An increase in the SA/V ratio leads to a decrease in the dissolution rate.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7882964

In vitro dynamic solubility test: influence of various parameters.

PubMed

Thélohan, S; de Meringo, A

1994-10-01

This article discusses the dissolution of mineral fibers in simulated physiological fluids (SPF), and the parameters that affect the solubility measurement in a dynamic test where an SPF runs through a cell containing fibers (Scholze and Conradt test). Solutions simulate either the extracellular fluid (pH 7.6) or the intracellular fluid (pH 4.5). The fibers have various chemical compositions and are either continuously drawn or processed as wool. The fiber solubility is determined by the amount of SiO2 (and occasionally other ions) released in the solution. Results are stated as percentage of the initial silica content released or as dissolution rate v in nm/day. The reproducibility of the test is higher with the less soluble fibers (10% solubility), than with highly soluble fibers (20% solubility). The influence of test parameters, including SPF, test duration, and surface area/volume (SA/V), has been studied. The pH and the inorganic buffer salts have a major influence: industrial glasswool composition is soluble at pH 7.6 but not at pH 4.5. The opposite is true for rock- (basalt) wool composition. For slightly soluble fibers, the dissolution rate v remains constant with time, whereas for highly soluble fibers, the dissolution rate decreases rapidly. The dissolution rates believed to occur are v1, initial dissolution rate, and v2, dissolution rate of the residual fibers. The SA of fibers varies with the mass of the fibers tested, or with the fiber diameter at equal mass. Volume, V, is the chosen flow rate. An increase in the SA/V ratio leads to a decrease in the dissolution rate.(ABSTRACT TRUNCATED AT 250 WORDS)

Effects of Irradiation on Albite's Chemical Durability.

PubMed

Hsiao, Yi-Hsuan; La Plante, Erika Callagon; Krishnan, N M Anoop; Le Pape, Yann; Neithalath, Narayanan; Bauchy, Mathieu; Sant, Gaurav

2017-10-19

Albite (NaAlSi 3 O 8 ), a framework silicate of the plagioclase feldspar family and a common constituent of felsic rocks, is often present in the siliceous mineral aggregates that compose concrete. When exposed to radiation (e.g., in the form of neutrons) in nuclear power plants, the crystal structure of albite can undergo significant alterations. These alterations may degrade its chemical durability. Indeed, careful examinations of Ar + -implanted albite carried out using Fourier transform infrared spectroscopy (FTIR) and molecular dynamics simulations show that albite's crystal structure, upon irradiation, undergoes progressive disordering, resulting in an expansion in its molar volume (i.e., a reduction of density) and a reduction in the connectivity of its atomic network. This loss of network connectivity (i.e., rigidity) results in an enhancement of the aqueous dissolution rate of albite-measured using vertical scanning interferometry (VSI) in alkaline environments-by a factor of 20. This enhancement in the dissolution rate (i.e., reduction in chemical durability) of albite following irradiation has significant impacts on the durability of felsic rocks and of concrete containing them upon their exposure to radiation in nuclear power plant (NPP) environments.

The role of mineral heterogeneity on the hydrogeochemical response of two fractured reservoir rocks in contact with dissolved CO2

NASA Astrophysics Data System (ADS)

Garcia Rios, Maria; Luquot, Linda; Soler, Josep M.; Cama, Jordi

2017-04-01

In this study we compare the hydrogeochemical response of two fractured reservoir rocks (limestone composed of 100 wt.% calcite and sandstone composed of 66 wt.% calcite, 28 wt.% quartz and 6 wt.% microcline) in contact with CO2-rich sulfate solutions. Flow-through percolation experiments were performed using artificially fractured limestone and sandstone cores and injecting a CO2-rich sulfate solution under a constant volumetric flow rate (from 0.2 to 60 mL/h) at P = 150 bar and T = 60 °C. Measurements of the pressure difference between the inlet and the outlet of the samples and of the aqueous chemistry enabled the determination of fracture permeability changes and net reaction rates. Additionally, X-ray computed microtomography (XCMT) was used to characterize and localized changes in fracture volume induced by dissolution and precipitation reactions. In all reacted cores an increase in fracture permeability and in fracture volume was always produced even when gypsum precipitation happened. The presence of inert silicate grains in sandstone samples favored the occurrence of largely distributed dissolution structures in contrast to localized dissolution in limestone samples. This phenomenon promoted greater dissolution and smaller precipitation in sandstone than in limestone experiments. As a result, in sandstone reservoirs, the larger increase in fracture volume as well as the more extended distribution of the created volume would favor the CO2 storage capacity. The different distribution of created volume between limestone and sandstone experiments led to a different variation in fracture permeability. The progressive stepped permeability increase for sandstone would be preferred to the sharp permeability increase for limestone to minimize risks related to CO2 injection, favor capillary trapping and reduce energetic storage costs. 2D reactive transport simulations that reproduce the variation in aqueous chemistry and the fracture geometry (dissolution pattern) were performed using CrunchFlow. The calcite reactive surface area had to be diminished with respect to the geometric surface area in order to account for the transport control of the calcite dissolution reaction at pH < 5. The fitted reactive surface area was higher under faster flow conditions, reflecting a decrease in transport control and a more distributed reaction in sandstone compared to limestone.

Interaction Between CO2-Rich Sulfate Solutions and Carbonate Reservoir Rocks from Atmospheric to Supercritical CO2 Conditions: Experiments and Modeling

NASA Astrophysics Data System (ADS)

Cama, J.; Garcia-Rios, M.; Luquot, L.; Soler Matamala, J. M.

2014-12-01

A test site for CO2 geological storage is situated in Hontomín (Spain) with a reservoir rock that is mainly composed of limestone. During and after CO2 injection, the resulting CO2-rich acid brine gives rise to the dissolution of carbonate minerals (calcite and dolomite) and gypsum (or anhydrite at depth) may precipitate since the reservoir brine contains sulfate. Experiments using columns filled with crushed limestone or dolostone were conducted under different P-pCO2 conditions (atmospheric: 1-10-3.5 bar; subcritical: 10-10 bar; and supercritical: 150-34 bar), T (25, 40 and 60 ºC) and input solution compositions (gypsum-undersaturated and gypsum-equilibrated solutions). We evaluated the effect of these parameters on the coupled reactions of calcite/dolomite dissolution and gypsum/anhydrite precipitation. The CrunchFlow and PhreeqC (v.3) numerical codes were used to perform reactive transport simulations of the experiments. Under the P-pCO2-T conditions, the volume of precipitated gypsum was smaller than the volume of dissolved carbonate minerals, yielding an increase in porosity (Δporosity up to ≈ 4%). A decrease in T favored limestone dissolution regardless of pCO2 owing to increasing undersaturation with decreasing temperature. However, gypsum precipitation was favored at high T and under atmospheric pCO2 conditions but not at high T and under 10 bar of pCO2 conditions. The increase in limestone dissolution with pCO2 was directly attributed to pH, which was more acidic at higher pCO2. Increasing pCO2, carbonate dissolution occurred along the column whereas it was localized in the very inlet under atmospheric conditions. This was due to the buffer capacity of the carbonic acid, which maintains pH at around 5 and keeps the solution undersaturated with respect to calcite and dolomite along the column. 1D reactive transport simulations reproduced the experimental data (carbonate dissolution and gypsum precipitation for different P-pCO2-T conditions). Drawing on reaction rate laws in the literature, we used the reactive surface area to fit the models to the experimental data. The values of the reactive surface area were much smaller than those calculated of the geometric areas.

Geochemical transformations and modeling of two deep-well injected hazardous wastes

USGS Publications Warehouse

Roy, W.R.; Seyler, B.; Steele, J.D.; Mravik, S.C.; Moore, D.M.; Krapac, I.G.; Peden, J.M.; Griffin, R.A.

1991-01-01

Two liquid hazardous wastes (an alkaline brine-like solution and a dilute acidic waste) were mixed with finely ground rock samples of three injection-related lithologies (sandstone, dolomite, and siltstone) for 155 to 230 days at 325??K-10.8 MPa. The pH and inorganic chemical composition of the alkaline waste were not significantly altered by any of the rock samples after 230 days of mixing. The acidic waste was neutralized as a consequence of carbonate dissolution, ion exchange, or clay-mineral dissolution, and hence was transformed into a nonhazardous waste. Mixing the alkaline waste with the solid phases yielded several reaction products: brucite, Mg(OH)2; calcite, CaCO3; and possibly a type of sodium metasilicate. Clay-like minerals formed in the sandstone, and hydrotalcite, Mg6Al2-CO3(OH)16??4H2O, may have formed in the siltstone at trace levels. Mixing the alkaline waste with a synthetic brine yielded brucite, calcite, and whewellite (CaC2O4??H2O). The thermodynamic model PHRQPITZ predicted that brucite and calcite would precipitate from solution in the dolomite and siltstone mixtures and in the alkaline waste-brine system. The dilute acidic waste did not significantly alter the mineralogical composition of the three rock types after 155 days of contact. The model PHREEQE indicated that the calcite was thermodynamically stable in the dolomite and siltstone mixtures.

Dissolution of Olivine, Siderite, and Basalt at 80 Deg C in 0.1 M H2SO4 in a Flow Through Process: Insights into Acidic Weathering on Mars

NASA Technical Reports Server (NTRS)

Golden, D. C.; Ming, D. W.; Hausrath, E. M.; Morris, R. V.; Niles, P. B.; Achilles, C. N.; Ross, D. K.; Cooper, B. L.; Gonzalex, C. P.; Mertzman, S. A.

2012-01-01

The occurrence of jarosite, other sulfates (e.g., Mg-and Ca-sulfates), and hematite along with silicic-lastic materials in outcrops of sedimentary materials at Meridiani Planum (MP) and detection of silica rich deposits in Gusev crater, Mars, are strong indicators of local acidic aqueous processes [1,2,3,4,5]. The formation of sediments at Meridiani Planum may have involved the evaporation of fluids derived from acid weathering of Martian basalts and subsequent diagenesis [6,7]. Also, our previous work on acid weathering of basaltic materials in a closed hydro-thermal system was focused on the mineralogy of the acid weathering products including the formation of jarosite and gray hematite spherules [8,9,10]. The object of this re-search is to extend our earlier qualitative work on acidic weathering of rocks to determine acidic dissolution rates of Mars analog basaltic materials at 80 C using a flow-thru reactor. We also characterized residual phases, including poorly crystalline or amorphous phases and precipitates, that remained after the treatments of olivine, siderite, and basalt which represent likely MP source rocks. This study is a stepping stone for a future simulation of the formation of MP rocks under a range of T and P.

Pore water colloid properties in argillaceous sedimentary rocks.

PubMed

Degueldre, Claude; Cloet, Veerle

2016-11-01

The focus of this work is to evaluate the colloid nature, concentration and size distribution in the pore water of Opalinus Clay and other sedimentary host rocks identified for a potential radioactive waste repository in Switzerland. Because colloids could not be measured in representative undisturbed porewater of these host rocks, predictive modelling based on data from field and laboratory studies is applied. This approach allowed estimating the nature, concentration and size distributions of the colloids in the pore water of these host rocks. As a result of field campaigns, groundwater colloid concentrations are investigated on the basis of their size distribution quantified experimentally using single particle counting techniques. The colloid properties are estimated considering data gained from analogue hydrogeochemical systems ranging from mylonite features in crystalline fissures to sedimentary formations. The colloid concentrations were analysed as a function of the alkaline and alkaline earth element concentrations. Laboratory batch results on clay colloid generation from compacted pellets in quasi-stagnant water are also reported. Experiments with colloids in batch containers indicate that the size distribution of a colloidal suspension evolves toward a common particle size distribution independently of initial conditions. The final suspension size distribution was found to be a function of the attachment factor of the colloids. Finally, calculations were performed using a novel colloid distribution model based on colloid generation, aggregation and sedimentation rates to predict under in-situ conditions what makes colloid concentrations and size distributions batch- or fracture-size dependent. The data presented so far are compared with the field and laboratory data. The colloid occurrence, stability and mobility have been evaluated for the water of the considered potential host rocks. In the pore water of the considered sedimentary host rocks, the clay colloid concentration is expected to be very low (<1ppb, for 10-100nm) which restricts their relevance for radionuclide transport. Copyright © 2016. Published by Elsevier B.V.

Dehydration reactions, mass transfer and rock deformation relationships during subduction of Alpine metabauxites: insights from LIBS compositional profiles between metamorphic veins

NASA Astrophysics Data System (ADS)

Verlaguet, Anne; Brunet, Fabrice; Goffé, Bruno; Menut, Denis; Findling, Nathaniel; Poinssot, Christophe

2013-04-01

In subduction zones, the significant amounts of aqueous fluid released in the course of the successive dehydration reactions occurring during prograde metamorphism are expected to strongly influence the rock rheology, as well as kinetics of metamorphic reactions and mass transfer efficiency. Mineralized veins, ubiquitous in metamorphic rocks, can be seen as preserved witnesses of fluid and mass redistribution that partly accommodate the rock deformation (lateral segregation). However, the driving forces and mechanisms of mass transfer towards fluid-filled open spaces remain somewhat unclear. The aim of this study is to investigate the vein-forming processes and the modalities of mass transfer during local fluid-rock interactions, and their links with fluid production and rock deformation, with new insights from Laser Induced Breakdown Spectroscopy (LIBS) profiles. This study focuses on karstic pockets (metre scale) of Triassic metabauxites embedded in thick carbonate units, that have been isolated from large-scale fluid flow during HP-LT Alpine metamorphism (W. Vanoise, French Alps). These rocks display several generations of metamorphic veins containing various Al-bearing minerals, which give particular insights into mass transfer processes. It is proposed that the internally-derived fluid (~13 vol% produced by successive dehydration reactions) has promoted the opening of fluid-filled open spaces (euhedral habits of vein minerals) and served as medium for diffusive mass transfer from rock to vein. Based on mineralogical and textural features, two vein types can be distinguished: (1) some veins are filled with newly formed products of either prograde (chloritoid) or retrograde (chlorite) metamorphic reactions; in this case, fluid-filled open spaces seem to offer energetically favourable nucleation/growth sites; (2) the second vein type is filled with cookeite (Li-Al-rich chlorite) or pyrophyllite, that were present in the host rock prior to the vein formation. In this closed chemical system, mass transfer from rock to vein was achieved through the fluid, in a dissolution-transport-precipitation process, possibly stress-assisted. To investigate the modalities of mass transfer towards this second vein type, LIBS profiles were performed in the rock matrix, taking Li concentration as a proxy for cookeite distribution. Cookeite is highly concentrated (40-70 vol%) in regularly spaced veins, and the LIBS profiles show that cookeite is evenly distributed in the rock matrix comprised between two veins. The absence of diffusion profiles suggests that the characteristic diffusion length for Li, Al and Si is greater than or equal to the distance separating two cookeite veins (3-6 cm). This is in agreement with characteristic diffusion lengths calculated from both grain boundary and pore fluid diffusion coefficients, for the estimated duration of the peak of metamorphism. Concerning mass transfer driving forces, phyllosilicates have very different morphologies in the rock matrix (fibers) compared to veins (euhedral crystals): fluid-mineral interfacial energy may be maximal in the small matrix pores, which can maintain higher cookeite solubility than in fluid-filled open spaces. Therefore, as soon as veins open, chemical potential gradients may develop and drive cookeite transfer from rock matrix to veins.

The effect of CO2-fluid-rock interactions on the porosity and permeability of calcite-bearing sandstone

NASA Astrophysics Data System (ADS)

Lamy-Chappuis, B.; Yardley, B.; Grattoni, C.

2013-12-01

Brine acidification following CO2 dissolution will initiate fluid-rock interactions that could significantly modify porosity, permeability and therefore the capacity and injectivity of a reservoir. We have investigated experimentally the dissolution of calcite in sandstone cores injected with CO2-saturated brine, and the effect this has on permeability. A series of CT (Computerized Tomography) - monitored experiments were conducted on a Jurassic sandstone (porosity = 30%, permeability = 10mD, calcite content = 5% in the form of dispersed shell fragments). Brine saturated with CO2 at pressures up to 1 MPa was injected into 5cm long, 3.75cm diameter cores at a flow rate of 1 ml/min and room temperature. The data showed quasi-instantaneous dissolution of the calcite even at low CO2 concentrations (0.15 Molar) and high fluid interstitial velocities (1mm/s), with the migration of a calcite dissolution front through the core recorded by successive CT scans. The resulting permeability increase was 60 - 80% whereas the predicted permeability change for the observed increase in porosity is only 10 - 20% using the Kozeny-Carman relationship. This result is particularly significant because the effect of porosity increase on permeability is usually modelled with this relationship, irrespective of the mechanism of porosity increase. Micro-CT scans (pixel resolution: 2.5 microns) of unreacted cores were used to generate 3D porosity models with calcite either treated as solid (pre-reaction model) or converted to pores (post-reaction model). FLUENT simulations performed using these models predicted the observed large relative changes in permeability with calcite dissolution but overestimated absolute permeability by an order of magnitude. This was probably due to the scan resolution being too coarse to correctly model pore throats. The observed large change in permeability for a small change in porosity may have resulted from increase in connectivity, focused dissolution at the pore throats or reduction in tortuosity. SEM (Scanning Electron Microscope) imaging demonstrates dissolution of relatively large isolated shell fragments but this had little effect on the overall connectivity. No calcite cement was observed at the pore throats in the unreacted specimens. The micro-CT scans indicate a modest tortuosity decrease from 2.00 to 1.85 when calcite is dissolved, but this change in tortuosity results from the opening of new flow paths as the dissolution of discrete grains opened new flow paths and created shortcuts, not from changes to the sinuosity of existing pathways. We suggest that the marked discrepancy in the effect of calcite dissolution on permeability between our experimental data and standard models arises because of the very different way in which the porosity is increased (new pathways rather than inflation). While our results cast doubt on the general applicability of standard models for porosity-permeability relationships for situations in which porosity changes by grain-specific reactions, it is encouraging that pore scale modelling is able to reproduce the experimental relationships.

Concentration gradients at the mineral-solution interface: implications for understanding dissolution mechanisms

NASA Astrophysics Data System (ADS)

Ruiz-Agudo, Encarnacion; Patiño-López, Luis David; Putnis, Christine V.; Rodriguez-Navarro, Carlos; Putnis, Andrew

2014-05-01

Dissolution is a key process in fluid-rock interactions, such as in chemical weathering, CO2 carbonation reactions, metasomatism, and metamorphism. Many multicomponent rock-forming minerals are reported to dissolve incongruently, because the elemental molar ratios, measured in the fluid during dissolution experiments, that differ from those in the solid. This frequently results in the formation of chemically and structurally altered zones at the fluid-solid interface of varying thickness that are depleted in some elements relative to the bulk mineral composition. Although the mechanisms of the formation of these altered layers is still a matter of debate (see e.g. Ruiz-Agudo et al. 2012 and Schott et al. 2012), recent AFM studies on the dissolution of two multicomponent minerals, dolomite, Ca0.5Mg0.5CO3 (Urosevic et al. 2012), and wollastonite, CaSiO3 (Ruiz-Agudo et al. 2012), provide experimental evidence showing that these layers are formed in a two-step process: (i) stoichiometric dissolution of the pristine mineral surfaces and (ii) precipitation of a secondary phase. This occurs despite the fact that the bulk solution is undersaturated with respect to such a phase. It has been suggested that after stoichiometric dissolution of the mineral, a boundary layer of fluid in contact with the surface becomes supersaturated with respect to a secondary phase that then precipitates. Here we present in situ observations of the evolution of the fluid composition at the interface during dissolution in acidic solutions (pH 1.5) of dolomite and wollastonite using real-time phase-shift interferometry. We show that immediately when the sparingly soluble dolomite or wollastonite crystals are in contact with the solution, the refractive index of the solution at the crystal surface sharply increases. A steep refractive index gradient (i.e., concentration gradient) develops as a consequence of mineral dissolution producing an interfacial fluid with a different composition to the bulk. Similar observations have been made during the replacement of KBr by KCl (Putnis et al. 2005). Thus, it seems that incongruent dissolution is essentially similar to any other mineral-fluid equilibration process: when a fluid interacts with a mineral with which it is out of equilibrium the mineral will tend to dissolve. Depending on the fluid composition, the interfacial fluid may become supersaturated with respect to a secondary phase that will eventually nucleate on the parent mineral surface. Ruiz-Agudo E., Putnis, C.V., Rodríguez-Navarro, C. and Putnis A. (2012) Geology 40, 947-950 (2012) Urosevic M., Rodríguez-Navarro C., Putnis C.V., Cardell C., Putnis A. and Ruiz Agudo, E. (2012) In Geochimica et Cosmochimica Acta 80, 1-13 Schott J., Pokrovsky O.S., Spalla O., Devreux F., Gloter A. and Mielczarski J.A. (2012) Geochimica et Cosmochimica Acta 98, 259-281 Putnis C.V., Tsukamoto K. and Nishimura Y. (2005) American Mineralogist 90, 1909-1912

Potential aquifer vulnerability in regions down-gradient from uranium in situ recovery (ISR) sites.

PubMed

Saunders, James A; Pivetz, Bruce E; Voorhies, Nathan; Wilkin, Richard T

2016-12-01

Sandstone-hosted roll-front uranium ore deposits originate when U(VI) dissolved in groundwater is reduced and precipitated as insoluble U(IV) minerals. Groundwater redox geochemistry, aqueous complexation, and solute migration are important in leaching uranium from source rocks and transporting it in low concentrations to a chemical redox interface where it is deposited in an ore zone typically containing the uranium minerals uraninite, pitchblende, and/or coffinite; various iron sulfides; native selenium; clays; and calcite. In situ recovery (ISR) of uranium ores is a process of contacting the uranium mineral deposit with leaching and oxidizing (lixiviant) fluids via injection of the lixiviant into wells drilled into the subsurface aquifer that hosts uranium ore, while other extraction wells pump the dissolved uranium after dissolution of the uranium minerals. Environmental concerns during and after ISR include water quality degradation from: 1) potential excursions of leaching solutions away from the injection zone into down-gradient, underlying, or overlying aquifers; 2) potential migration of uranium and its decay products (e.g., Ra, Rn, Pb); and, 3) potential mobilization and migration of redox-sensitive trace metals (e.g., Fe, Mn, Mo, Se, V), metalloids (e.g., As), and anions (e.g., sulfate). This review describes the geochemical processes that control roll-front uranium transport and fate in groundwater systems, identifies potential aquifer vulnerabilities to ISR operations, identifies data gaps in mitigating these vulnerabilities, and discusses the hydrogeological characterization involved in developing a monitoring program. Published by Elsevier Ltd.

The fate of iron on Mars: Mechanism of oxidation of basaltic minerals to ferric-bearing assemblages

NASA Technical Reports Server (NTRS)

Burns, Roger G.

1992-01-01

Perhaps the most conspicuous indication that chemical weathering has occurred on the surface of Mars is the overall color of the red planet and the spectroscopic features that identify ferric-bearing assemblages in the martian regolith. Apparently, Fe(2+) ions in primary minerals in parent igneous rocks on the martian surface have been oxidized to ferric iron, which occurs in degradation products that now constitute the regolith. The mineralogy of the unweathered igneous rocks prior to weathering on the martian surface is reasonably well constrained, mainly as a result of petrographic studies of the SNC meteorites. However, the alteration products resulting from oxidative weathering of these rocks are less well-constrained. The topics covered include the following: primary rocks subjected to chemical weathering; dissolution processes; oxidation of dissolved Fe(2+); mechanism of polymerization of hydrous ferric oxides; terrestrial occurrences of ferromagnesian smectites; and dehydroxylated Mg-Fe smectites on Mars.

Reactive Transport in a Pipe in Soluble Rock: a Theoretical and Experimental Study

NASA Astrophysics Data System (ADS)

Li, W.; Opolot, M.; Sousa, R.; Einstein, H. H.

2015-12-01

Reactive transport processes within the dominant underground flow pathways such as fractures can lead to the widening or narrowing of rock fractures, potentially altering the flow and transport processes in the fractures. A flow-through experiment was designed to study the reactive transport process in a pipe in soluble rock to serve as a simplified representation of a fracture in soluble rock. Assumptions were made to formulate the problem as three coupled, one-dimensional partial differential equations: one for the flow, one for the transport and one for the radius change due to dissolution. Analytical and numerical solutions were developed to predict the effluent concentration and the change in pipe radius. The positive feedback of the radius increase is captured by the experiment and the numerical model. A comparison between the experiment and the simulation results demonstrates the validity of the analytical and numerical models.

A mechanistic understanding of plagioclase dissolution based on Al occupancy and T-O bond length: from geologic carbon sequestration to ambient conditions.

PubMed

Yang, Yi; Min, Yujia; Jun, Young-Shin

2013-11-14

A quantitative description of how the bulk properties of aluminosilicates affect their dissolution kinetics is important in helping people understand the regulation of atmospheric CO2 concentration by silicate weathering and predict the fate and transport of geologically sequestered CO2 through brine-rock interactions. In this study, we employed a structure model based on the C1 space group to illustrate how differences in crystallographic properties of aluminosilicates, such as T-O (Tetrahedral site-Oxygen) bond length and Al/Si ordering, can result in quantifiable variations in mineral dissolution rates. The dissolution rates of plagioclases were measured under representative geologic carbon sequestration (GCS) conditions (90 °C, 100 atm of CO2, 1.0 M NaCl, and pH ∼ 3.1), and used to validate the model. We found that the logarithm of the characteristic time of the breakdown of Al-O-Si linkages in plagioclases follows a good linear relation with the mineral's aluminum content (nAl). The Si release rates of plagioclases can be calculated based on an assumption of dissolution congruency or on the regularity of Al/Si distribution in the constituent tetrahedra of the mineral. We further extended the application of our approach to scenarios where dissolution incongruency arises because of different linkage reactivities in the solid matrix, and compared the model predictions with published data. The application of our results enables a significant reduction of experimental work for determining the dissolution rates of structurally related aluminosilicates, given a reaction environment.

Geologic setting, genesis and transformation of sulfide deposits in the northern part of Khetri copper belt, Rajasthan, India — an outline

NASA Astrophysics Data System (ADS)

Sarkar, S. C.; Dasgupta, Somnath

1980-07-01

The present study is confined to the northern part of the Khetri copper belt that extends for about 100 km in northern Rajasthan. Mineralization is more or less strata-bound and is confined to the garnetiferous chlorite schist and banded amphibolite quartzite, occurring towards the middle of the Proterozoic Delhi Supergroup. Preserved sedimentary features and re-estimation of the composition of the pre-metamorphic rocks suggest that the latter were deposited in shallow marine environment characterized by tidal activity. Cordierite-orthoamphibole-cummingtonite rock occurring in the neighbourhood of the ores is discussed, and is suggested to be isochemically metamorphosed sediment. The rocks together with the ores were deformed in two phases and metamorphosed in two progressive and one retrogressive events of metamorphism. Study of the host rocks suggests that the maximum temperature and pressure attained during metamorphism are respectively 550 600°C and < 5.5 kb. Principal ore minerals in Madan Kudan are chalcopyrite, pyrrhotite, pyrite and locally magnetite. In Kolihan these are chalcophyrite, pyrrhotite and cubanite. Subordinate phases are sphalerite, ilmenite, arsenopyrite, mackinawite, molybdenite, cobaltite and pentlandite. The last two are very rare. Gangue minerals comprise quartz, chlorite, garnet, amphiboles, biotite, scapolite, plagioclase and graphite. The ores are metamorphosed at temperatures > 491°C. Sulfide assemblages are explained in terms of fS 2 during metamorphism. Co-folding of the ore zone with the host rocks, confinement of the ores to the carbonaceous pelites or semi-pelitic rocks, strata-bound and locally even stratiform nature of the orebodies, lack of finite ‘wall rock alteration’, metamorphism of the ores in the thermal range similar to that for the host rocks, absence of spatial and temporal relationship with the granitic rocks of the region led the authors to conclude that the entire mineralization was originally sedimentary-diagenetic. Any loss of primitive features and development of incongruency are due to subsequent deformation and metamorphism to which the ores and their hosts were together subjected.

The evolution of fabric with displacement in natural brittle faults

NASA Astrophysics Data System (ADS)

Mittempergher, S.; Di Toro, G.; Gratier, J.; Aretusini, S.; Boullier-Bertrand, A.

2011-12-01

In experiments performed at room temperature on gouges, a characteristic clast size distribution (CSD) is produced with increasing strain, and shear localization is documented to begin after few millimetres of sliding. But in natural faults active at depth in the crust, mechanical processes are associated with fluid-rock interactions, which might control the deformation and strength recovery. We aim to investigate the microstructural, geochemical and mineralogical evolution of low-displacement faults with increasing shear strain. The faults (cataclasite- and pseudotachylyte-bearing) are hosted in tonalite and were active at 9-11 km and 250-300°C. The samples were collected on a large glacier-polished outcrop, where major faults (accommodating up to 4300 mm of displacement) exploit pre-existing magmatic joints and are connected by a network of secondary fractures and faults (accommodating up to 500 mm of displacement) breaking intact tonalite. We performed optical and cathodoluminescence (CL) microscope, Scanning Electron Microscope (SEM), Energy Dispersive X-ray Spectroscopy (EDS), Rietveld X-Ray Powder Diffraction and microprobe chemical analysis in deformation zones of secondary faults with various offsets in order to evaluate the transfer of chemical species between dissolution zones and protected zones. Image analysis techniques were applied on SEM-BSE and optical microscope images to compute the CSD in samples, which experienced an increasing amount of strain. The secondary fractures are up to 5 mm thick. Within the first 20 mm of displacement, shear localizes along Y and R1 surfaces and a cataclastic foliation develops. The CSD evolves from a fractal dimension D of 1.3 in fractures without visible displacement to values above 2 after the first 500 mm of displacement. Chemical maps and CL images indicate that the foliation in cataclasite results from the rotation and fragmentation of clasts, with dissolution of quartz and passive concentration of Ti oxides and titanite in the foliation planes. The cataclasites are cemented by pervasive precipitation of K-feldspar plagues and idiomorphic, randomly oriented, epidote and chlorite. We conclude that the textures of these small displacement (< 500 mm) faults are controlled by brittle processes (fracture propagation and cataclastic comminution) similar to those reproduced in friction experiments performed on granite gouge (e.g., Beeler et al., 1996; Logan, 2007). Then progressively, stress driven fluid-rock reactions develop as fracturing and grain size reduction allows the kinetics of these reactions to be more efficient and fracture interconnection allows fluid infiltration. Healing of microfractures and fault rock cementation caused a rapid posteismic recovery of fault strength. References Beeler, N.M., Tullis, T.E., Blanpied, L., Weeks, J.D., 1996. Frictional behaviour of large displacement experimental faults. Journal of Geophysical Research 101, B4, 8697-8715. Logan, J.M., 2007. The progression from damage to localization of displacement observed in laboratory testing of porous rocks, in Lewis, H., and Couples, G.D. (eds.) The relationship between damage and localization. Geological Society of London Special Publication 289, 75-87.

Evidence from Opportunity's Microscopic Imager for water on Meridiani Planum.

PubMed

Herkenhoff, K E; Squyres, S W; Arvidson, R; Bass, D S; Bell, J F; Bertelsen, P; Ehlmann, B L; Farrand, W; Gaddis, L; Greeley, R; Grotzinger, J; Hayes, A G; Hviid, S F; Johnson, J R; Jolliff, B; Kinch, K M; Knoll, A H; Madsen, M B; Maki, J N; McLennan, S M; McSween, H Y; Ming, D W; Rice, J W; Richter, L; Sims, M; Smith, P H; Soderblom, L A; Spanovich, N; Sullivan, R; Thompson, S; Wdowiak, T; Weitz, C; Whelley, P

2004-12-03

The Microscopic Imager on the Opportunity rover analyzed textures of soils and rocks at Meridiani Planum at a scale of 31 micrometers per pixel. The uppermost millimeter of some soils is weakly cemented, whereas other soils show little evidence of cohesion. Rock outcrops are laminated on a millimeter scale; image mosaics of cross-stratification suggest that some sediments were deposited by flowing water. Vugs in some outcrop faces are probably molds formed by dissolution of relatively soluble minerals during diagenesis. Microscopic images support the hypothesis that hematite-rich spherules observed in outcrops and soils also formed diagenetically as concretions.

New data on carbonatites of the Il'mensky-Vishnevogorsky alkaline complex, the southern Urals, Russia

NASA Astrophysics Data System (ADS)

Nedosekova, I. L.

2007-04-01

Carbonatites that are hosted in metamorphosed ultramafic massifs in the roof of miaskite intrusions of the Il’mensky-Vishnevogorsky alkaline complex are considered. Carbonatites have been revealed in the Buldym, Khaldikha, Spirikha, and Kagan massifs. The geological setting, structure of carbonatite bodies, distribution of accessory rare-metal mineralization, typomorphism of rock-forming minerals, geochemistry, and Sr and Nd isotopic compositions are discussed. Dolomite-calcite carbonatites hosted in ultramafic rocks contain tetraferriphlogopite, richterite, accessory zircon, apatite, magnetite, ilmenite, pyrrhotite, pyrite, and pyrochlore. According to geothermometric data and the composition of rock-forming minerals, the dolomite-calcite carbonatites were formed under K-feldspar-calcite, albite-calcite, and amphibole-dolomite-calcite facies conditions at 575-300°C. The Buldym pyrochlore deposit is related to carbonatites of these facies. In addition, dolomite carbonatites with accessory Nb and REE mineralization (monazite, aeschynite, allanite, REE-pyrochlore, and columbite) are hosted in ultramafic massifs. The dolomite carbonatites were formed under chlorite-sericite-ankerite facies conditions at 300-200°C. The Spirikha REE deposit is related to dolomite carbonatite and alkaline metasomatic rocks. It has been established that carbonatites hosted in ultramafic rocks are characterized by high Sr, Ba, and LREE contents and variable Nb, Zr, Ti, V, and Th contents similar to the geochemical attributes of calcio-and magnesiocarbonatites. The low initial 87Sr/86Sr = 0.7044-0.7045 and ɛNd ranging from 0.65 to -3.3 testify to their derivation from a deep mantle source of EM1 type.

4D XMT of Reaction in Carbonates: Reactive Transport Dynamics at Multiples Scales

NASA Astrophysics Data System (ADS)

Menke, H. P.; Reynolds, C. A.; Andrew, M. G.; Nunes, J. P. P.; Bijeljic, B.; Blunt, M. J.

2016-12-01

Upscaling pore scale rock-fluid interaction processes for predictive modelling poses a challenge to underground carbon storage. We have completed experiments and flow modelling to investigate the impact of pore-space heterogeneity and scale on the dissolution of two limestones at both the mm and cm scales. Two samples were reacted with reservoir condition CO2-saturated brine at both scales and scanned dynamically as dissolution took place. First, 1-cm long 4-mm diameter micro cores were scanned during reactive flow at a 4-μm resolution between 4 and 40 times using 4D X-ray micro-tomography over the course of 1.5 hours using a laboratory μ-CT. Second, 3.8-cm diameter, 8-cm long macro cores were reacted at the same conditions inside a reservoir condition flow rig and imaged using a medical CT scanner. Each sample was imaged 10 times over the course of 1.5 hours at a 250 x 250 x 500-μm resolution. The reacted macro cores were then scanned inside a μ-CT at a 27-μm resolution to assess the alteration in pore-scale reaction-induced heterogeneity. It was found that both limestones showed channel formation at the pore-scale and progressive high porosity pathway dissolution at the core-scale with the more heterogeneous rock having dissolution progressing along direction of flow more quickly. Additionally, upon analysis of the high-resolution macro core images it was found that the dissolution pathways contained a distinct microstructure that was not visible at the resolution of the medical CT, where the reactive fluid had not completely dissolved the internal pore-structure. Flow was modelled in connected pathways, the flow streamlines were traced and streamline density for each voxel was calculated. It was found that the streamline density was highest in the most well-connected pathways and that density increased with increasing heterogeneity as the number of connected pathways decreased and flow was consolidated along fewer pathways. This work represents the first study of scale dependency using reservoir condition 4D X-ray tomography and provides insight into the mechanisms that control local reaction rates at multiple scales.

Understanding the roles of ligand promoted dissolution, water column saturation and hydrological properties on intense basalt weathering using reactive transport and watershed-scale hydrologic modeling

NASA Astrophysics Data System (ADS)

Perez Fodich, A.; Walter, M. T.; Derry, L. A.

2016-12-01

The interaction of rocks with rainwater generates physical and chemical changes, which ultimately culminates in soil development. The addition of catalyzers such as plants, atmospheric gases and hydrological properties will result in more intense and/or faster weathering transformations. The intensity of weathering across the Island of Hawaii is strongly correlated with exposure age and time-integrated precipitation. Intense weathering has resulted from interaction between a thermodynamically unstable lithology, high water/rock ratios, atmospheric gases (O2, CO2) and biota as an organic acid and CO2 producer. To further investigate the role of different weathering agents we have developed 1-D reactive transport models (RTM) to understand mineralogical and fluid chemistry changes in the initially basaltic porous media. The initial meso-scale heterogeneity of porosity makes it difficult for RTMs to capture changes in runoff/groundwater partitioning. Therefore, hydraulic properties (hydraulic conductivity and aquifer depth) are modeled as a watershed parameter appropriate for this system where sub-surface hydraulic data is scarce(1). Initial results agree with field data in a broad sense: different rainfall regimes and timescales show depletion of mobile cations, increasingly low pH, congruent dissolution of olivine and pyroxene, incongruent dissolution of plagioclase and basaltic glass, precipitation of non-crystalline allophane and ferrihydrite, and porosity changes due to dissolution and precipitation of minerals; ultimately Al and Fe are also exported from the system. RTM is used to examine the roles of unsaturation in the soil profile, ligand promoted dissolution of Al- and Fe-bearing phases, and Fe-oxide precipitation at the outcrop scale. Also, we aim to test the use of recession flow analysis to model watershed-scale hydrological properties to extrapolate changes in the runoff/groundwater partitioning. The coupling between weathering processes and hydrologic properties is a fundamental driver of the evolution of volcanic landscapes and weathering fluxes. 1. G. F. Mendoza, T. S. Steenhuis, M. T. Walter, J. Y. Parlange, Estimating basin-wide hydraulic parameters of a semi-arid mountainous watershed by recession-flow analysis. Journal of Hydrology 279, 57-69 (2003).

Experimental observation and modelling of rock - water interaction in a landslide-prone loess area of Hungary

NASA Astrophysics Data System (ADS)

Udvardi, Beatrix; Szabó, Zsuzsanna; Freiler, Ágnes; Kónya, Péter; Jerabek, Csaba; Pálfi, Éva; Kovács, István; Nagy, Péter; Halupka, Gábor

2017-04-01

It is well known that water from precipitation or other sources (e.g. groundwater, river) contributes to the triggering of landslides by means of infiltration into the slope, which causes an increase in the pore pressure and a reduction in the strength of the involved material. The physical failure is commonly coupled with chemical changes in landslides due the fact that soluble components dissolve in the pore water and others precipitate during rock-water interaction. Thus the composition of sediments and water chemistry are used jointly as indicators of the development of landslides. Rock-water interaction, however, takes a long time, and depends on hydrology and geochemistry of the landslide area; therefore, many researchers have focused on numerical simulation and laboratory experiment for setting up a landslide early warning system. Since water chemistry can change over time in landslides due to the seasonal rainfall pattern, groundwater fluctuation and flood events, the intensity of rock-water interaction (e.g. dissolution, precipitation) may also vary. Thus, the physicochemical processes cannot be elucidated precisely without understanding both the solution evolution and the mineral alteration in landslides. From this aspect, field survey, mineralogical (XRD, FTIR, DTG) and chemical measurements (ICP-OES), and geochemical modelling (PHREEQC) were conducted in a landslide-prone loess area along the River Danube (Hungary). Water from the River Danube and three springs were sampled during four field campaigns at Kulcs over a year. Additionally, landslide deposits including sliding surface and secondary precipitations were collected at Kulcs and Dunaújváros. In combination with previous hydrochemical analyses of the area and average rainfall composition of Hungary, it is possible to model the kinetic dissolution and precipitation of minerals during rainfall events and flooding periods of the river. The chemistry of springs shows that the Mg-Ca-HCO3 facies with high electrical conductivity (898 - 1227 µS/cm) may occur due to the dissolution of carbonates and silicates throughout the year. During occasional rainstorms in summer, however, it is found that the pH of the springs slightly increased while their electrical conductivity decreased tenfold. This can be attributed to the rapid infiltration of rainwater through fractures and holes of the loess deposit. Similar process can take place at Dunaújváros, however, larger subsidence happened there than at Kulcs. The secondary precipitations indicate that dissolved components in groundwater precipitate as calcite at the foot of the Dunaújváros landslide. Furthermore, the comparison between model of loess-river water and loess-spring water interaction suggests that the dissolution of dolomite, Ca-montmorillonite and chlorite is stronger during flooding than during low water level of the river. Therefore, frequency and duration of rainstorms and floodings may have deeper consequences for loess landslides.

Effect of the size of nanoparticles on their dissolution within metal-glass nanocomposites under sustained irradiation

NASA Astrophysics Data System (ADS)

Vu, T. H. Y.; Ramjauny, Y.; Rizza, G.; Hayoun, M.

2016-01-01

We investigate the dissolution law of metallic nanoparticles (NPs) under sustained irradiation. The system is composed of isolated spherical gold NPs (4-100 nm) embedded in an amorphous silica host matrix. Samples are irradiated at room temperature in the nuclear stopping power regime with 4 MeV Au ions for fluences up to 8 × 1016 cm-2. Experimentally, the dependence of the dissolution kinetics on the irradiation fluence is linear for large NPs (45-100 nm) and exponential for small NPs (4-25 nm). A lattice-based kinetic Monte Carlo (KMC) code, which includes atomic diffusion and ballistic displacement events, is used to simulate the dynamical competition between irradiation effects and thermal healing. The KMC simulations allow for a qualitative description of the NP dissolution in two main stages, in good agreement with the experiment. Moreover, the perfect correlation obtained between the evolution of the simulated flux of ejected atoms and the dissolution rate in two stages implies that there exists an effect of the size of NPs on their dissolution and a critical size for the transition between the two stages. The Frost-Russell model providing an analytical solution for the dissolution rate, accounts well for the first dissolution stage but fails in reproducing the data for the second stage. An improved model obtained by including a size-dependent recoil generation rate permits fully describing the dissolution for any NP size. This proves, in particular, that the size effect on the generation rate is the principal reason for the existence of two regimes. Finally, our results also demonstrate that it is justified to use a unidirectional approximation to describe the dissolution of the NP under irradiation, because the solute concentration is particularly low in metal-glass nanocomposites.

Differential thermal response within inshore vs. offshore congeneric scleractinian coral species in Palau.

NASA Astrophysics Data System (ADS)

Hoadley, K. D.; Lewis, A.; Wham, D.; Pettay, D. T.; Kemp, D.; Warner, M.; Lajeunesse, T.

2016-02-01

The rock island reef habitats of Palau are an ideal location to study climate change effects to reefs, as corals there are exposed to average temperature and pCO2 conditions well above levels experienced at offshore reef locations. We examined the response of 6 coral species, Acropora muricata, Goniastrea sp, Porities rus, Cyphastrea sp, Porites cylindrical and Pachyseris sp, from both rock island and offshore habitats to high temperature (32 Celsius) for 15 days. With the exception of P. rus and P. cylindrica which harbored Symbiodinium C15 at both locations, other rock island corals harbored the thermally tolerant species Symbiodinium trenchii, whereas offshore colonies harbored clade C symbionts. A total of 15 separate host and symbiont physiological variables were utilized to assess thermal acclimation/stress response within each host/symbiont combination. Differences in photophysiology, algal cell volume and biochemical composition were observed for Symbiodinium trenchii within different host species, reflecting the importance of the host organism in mitigating the symbiont response. Similarly, the host thermal response was also dependent on symbiont type, with greater reductions in symbiont density occurring within the offshore colonies. Overall, prior exposure to warmer temperatures, elevated nutrient and pCO2 conditions, along with association with more robust symbionts allowed rock island corals to exhibit greater thermal tolerance toward high temperature. Importantly, the results herein for Symbiodinium trenchii physiological plasticity and thermal mitigation provides useful insight into the potential of scleractinian corals to acclimatize under future climate change scenarios.

Diagenetic Crystal Growth in the Murray Formation, Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Kah, L. C.; Kronyak, R. E.; Ming, D. W.; Grotzinger, J. P.; Schieber, J.; Sumner, D. Y.; Edgett, K. S.

2015-01-01

The Pahrump region (Gale Crater, Mars) marks a critical transition between sedimentary environments dominated by alluvial-to-fluvial materials associated with the Gale crater rim, and depositional environments fundamentally linked to the crater's central mound, Mount Sharp. At Pahrump, the Murray formation consists of an approximately 14-meter thick succession dominated by massive to finely laminated mudstone with occasional interbeds of cross-bedded sandstone, and is best interpreted as a dominantly lacustrine environment containing tongues of prograding fluvial material. Murray formation mudstones contain abundant evidence for early diagenetic mineral precipitation and its subsequent removal by later diagenetic processes. Lenticular mineral growth is particularly common within lacustrine mudstone deposits at the Pahrump locality. High-resolution MAHLI images taken by the Curiosity rover permit detailed morphological and spatial analysis of these features. Millimeter-scale lenticular features occur in massive to well-laminated mudstone lithologies and are interpreted as pseudomorphs after calcium sulfate. The distribution and orientation of lenticular features suggests deposition at or near the sediment-water (or sediment-air) interface. Retention of chemical signals similar to host rock suggests that original precipitation was likely poikilotopic, incorporating substantial amounts of the primary matrix. Although poikilotopic crystal growth is common in burial environments, it also occurs during early diagenetic crystal growth within unlithified sediment where high rates of crystal growth are common. Loss of original calcium sulfate mineralogy suggests dissolution by mildly acidic, later-diagenetic fluids. As with lenticular voids observed at Meridiani by the Opportunity Rover, these features indicate that calcium sulfate deposition may have been widespread on early Mars; dissolution of depositional and early diagenetic minerals is a likely source for both calcium and sulfate ion-enrichment in burial fluids that precipitated in ubiquitous late-stage hydrofracture veins

Tectono-metamorphic evolution of the Jomolhari massif: Variations in timing of syn-collisional metamorphism across western Bhutan

NASA Astrophysics Data System (ADS)

Regis, Daniele; Warren, Clare J.; Young, David; Roberts, Nick M. W.

2014-03-01

Our current understanding of the rates and timescales of mountain-building processes is largely based on information recorded in U-bearing accessory minerals such as monazite, which is found in low abundance but which hosts the majority of the trace element budget. Monazite petrochronology was used to investigate the timing of crustal melting in migmatitic metasedimentary rocks from the Jomolhari massif (NW Bhutan). The samples were metamorphosed at upper amphibolite to granulite facies conditions (~ 0.85 GPa, ~ 800 °C), after an earlier High-Pressure stage (P > 1.4 GPa), and underwent partial melting through dehydration melting reactions involving muscovite and biotite. In order to link the timing of monazite growth/dissolution to the pressure-temperature (P-T) evolution of the samples, we identified 'chemical fingerprints' in major and accessory phases that were used to back-trace specific metamorphic reactions. Variations in Eu anomaly and Ti in garnet were linked to the growth and dissolution of major phases (e.g. growth of K-feldspar and dehydration melting of muscovite/biotite). Differences in M/HREE and Y from garnet core to rim were instead related to apatite breakdown and monazite-forming reactions. Chemically zoned monazite crystals reacted multiple times during the metamorphic evolution suggesting that the Jomolhari massif experienced a prolonged high-temperature metamorphic evolution from 36 Ma to 18 Ma, significantly different from the P-T-time path recorded in other portions of the Greater Himalayan Sequence (GHS) in Bhutan. Our data demonstrate unequivocally that the GHS in Bhutan consists of units that experienced independent high-grade histories and that were juxtaposed across different tectonic structures during exhumation. The GHS may have been exhumed in response to (pulsed) mid-crustal flow but cannot be considered a coherent block.

Quantification of elements essential for habitability: the case of the nakhlite hydrothermal brine

NASA Astrophysics Data System (ADS)

Schwenzer, S. P.; Bridges, J.

2013-12-01

Hypervelocity impact events deposit a high amount of energy in the target - devastating to the existing environment in a few seconds, but in the long term aftermath the morphological changes and the deposited heat offer new habitable environments. If water is available in the target, impact-generated hydrothermal activity will result. To assess the habitability of this new site, information on fluid chemistry is critical, but not readily available by observing final products of rock alteration. The nakhlite Martian meteorites contain such impact-generated alteration mineral assemblages, which reveal detailed information about their formation conditions (Changela and Bridges, 2010, MAPS, 45: 1847-1865). Combining the mineralogical observations with thermochemical modeling (code: CHILLER, Mark Reed and co-workers, U Oregon) we quantify the solution concentration of a variety of elements essential for habitability: C, P, S, Na, K, Ca, Mg. For this we use our previous model (Bridges and Schwenzer, 2012, EPSL, 359-360: 117-123) at W/R of 100, T of 50 °C and 0.1 mole CO2. This leads to the formation of nontronite (77 wt%), carbonate (14 wt%), quartz (5 wt%) and kaolinite (4 wt%). Of the 0.1 mole CO2, 97% is precipitated as carbonates using cations from the 10 g of altered Lafayette in the presence of 1 kg of water, and this is equivalent to 4 g CO2 being sequestered. While the CO2 is sourced from the fluid, S and P are contained in Lafayette, leading to 27 x 10-9 g of P and 0.06 g of S available in the fluid after dissolution and precipitation of alteration minerals. Other cations important for habitability, e.g., Na, K, Ca, and Mg, are present in solution in varying amounts. 100 % of Na and K, equal to 0.004 and 0.001 moles of Na and K, respectively, from the dissolving rock stay in solution. In contrast, Fe dissolved from the host rock does not stay in solution, but is almost entirely precipitated in the nontronite and carbonate. The situation is more complex for other cations: 1.4 % of Ca (0.0003 moles), and 3.3 % of Mg (0.003 moles) are available in dissolved form. As this specific example shows, with accurate mineralogical information on the dissolving host rock and most importantly alteration minerals, it is possible to determine formation conditions of the alteration phases. With that it is then possible to quantify the sinks and mobility of key elements for habitability. This is especially interesting for near- and subsurface environments on Mars, where a multitude of processes from diagenesis to hydrothermal alteration has occurred in the past and could have provided habitable sites, if life ever existed on Mars (Cockell et al. 2012, Icarus, 217: 184-193). Further, those results are applicable to other medium- to high-temperature hydrous processes and also transferrable to other celestial bodies with (basaltic) rock-water interaction.

Phosphates in some Missouri refractory clays

USGS Publications Warehouse

Halley, Robert B.; Foord, Eugene E.; Keller, David J.; Keller, Walter D.

1997-01-01

This paper describes in detail phosphate minerals occurring in refractory clays of Missouri and their effect on the refractory degree of the clays. The minerals identified include carbonate-fluorapatite (francolite), crandallite, goyazite, wavellite, variscite and strengite. It is emphasized that these phosphates occur only in local isolated concentrations, and not generally in Missouri refractory clays.The Missouri fireclay region comprises 2 districts, northern and southern, separated by the Missouri River. In this region, clay constitutes a major part of the Lower Pennsylvanian Cheltenham Formation. The original Cheltenham mud was an argillic residue derived from leaching and dissolution of pre-Pennsylvanian carbonates. The mud accumulated on a karstic erosion surface truncating the pre-Cheltenham rocks. Fireclays of the northern district consist mainly of poorly ordered kaolinite, with variable but minor amounts of illite, chlorite and fine-grained detrital quartz. Clays of the southern district were subjected to extreme leaching that produced well-ordered kaolinite flint clays. Local desilication formed pockets of diaspore, or more commonly, kaolinite, with oolite-like nubs or burls of diaspore (“burley”" clay).The phosphate-bearing materials have been studied by X-ray diffraction (XRD), scanning electron microscopy-energy dispersive spectral analysis (SEM-EDS) and chemical analysis. Calcian goyazite was identified in a sample of diaspore, and francolite in a sample of flint clay. A veinlet of wavellite occurs in flint clay at one locality, and a veinlet of variscite-strengite at another locality.The Missouri flint-clay-hosted francolite could not have formed in the same manner as marine francolite. The evidence suggests that the Cheltenham francolite precipitated from ion complexes in pore water, nearly simultaneously with crystallization of kaolinite flint clay from an alumina-silica gel. Calcian goyazite is an early diagenetic addition to its diaspore host. The wavellite and variscite-strengite veinlets are secondary, precipitated from ion complexes in ground water percolating along cracks in the flint clay. The flint clay host of the variscite-strengite veinlet contains strontian crandallite. All of the phosphates contain significant amounts of strontium. The source of P, Ca and Sr was the marine carbonates. Dissolution of these carbonates produced the argillic residue that became the primordial Cheltenham paludal mud, which ultimately altered to fireclay.Preliminary firing tests show that the presence of phosphates lowers fusion temperature. However, it is not clear whether poor refractoriness is due to the presence of phosphates, per se, or to Ca, Sr and other alkaline elements present in the phosphates.

CO2-brine-mineral Reactions in Geological Carbon Storage: Results from an EOR Experiment

NASA Astrophysics Data System (ADS)

Chapman, H.; Wigley, M.; Bickle, M.; Kampman, N.; Dubacq, B.; Galy, A.; Ballentine, C.; Zhou, Z.

2012-04-01

Dissolution of CO2 in brines and reactions of the acid brines ultimately dissolving silicate minerals and precipitating carbonate minerals are the prime long-term mechanisms for stabilising the light supercritical CO2 in geological carbon storage. However the rates of dissolution are very uncertain as they are likely to depend on the heterogeneity of the flow of CO2, the possibility of convective instability of the denser CO2-saturated brines and on fluid-mineral reactions which buffer brine acidity. We report the results of sampling brines and gases during a phase of CO2 injection for enhanced oil recovery in a small oil field. Brines and gases were sampled at production wells daily for 3 months after initiation of CO2 injection and again for two weeks after 5 months. Noble gas isotopic spikes were detected at producing wells within days of initial CO2 injection but signals continued for weeks, and at some producers for the duration of the sampling period, attesting to the complexity of gas-species pathways. Interpretations are complicated by the previous history of the oil field and re-injection of produced water prior to injection of CO2. However water sampled from some producing wells during the phase of CO2 injection showed monotonic increases in alkalinity and in concentrations of major cations to levels in excess of those in the injected water. The marked increase in Na, and smaller increases in Ca, Mg, Si, K and Sr are interpreted primarily to result from silicate dissolution as the lack of increase in S and Cl concentrations preclude additions of more saline waters. Early calcite dissolution was followed by re-precipitation. 87Sr/86Sr ratios in the waters apparently exceed the 87Sr/86Sr ratios of acetic and hydrochloric acid leaches of carbonate fractions of the reservoir rocks and the silicate residues from the leaching. This may indicate incongruent dissolution of Sr or larger scale isotopic heterogeneity of the reservoir. This is being investigated further by analyses of rock and mineral clasts from core. A surprising result of this study is the extent to which CO2 has dissolved in brines to drive fluid-rock reactions during the short duration of this experiment. However, simple one-dimensional flow modelling with lateral diffusion of CO2 into brines demonstrates that the natural heterogeneities in permeability in the reservoir on the scale of ~ 1 m are sufficient to cause extensive fingering of the CO2 along the highest permeability horizons. Because flow of brines is fastest in the relatively high permeability layers adjacent to the CO2-bearing layers, production of this more CO2-rich water dominates the output from production wells.

Autotrophic denitrification supported by biotite dissolution in crystalline aquifers (1): New insights from short-term batch experiments.

PubMed

Aquilina, Luc; Roques, Clément; Boisson, Alexandre; Vergnaud-Ayraud, Virginie; Labasque, Thierry; Pauwels, Hélène; Pételet-Giraud, Emmanuelle; Pettenati, Marie; Dufresne, Alexis; Bethencourt, Lorine; Bour, Olivier

2018-04-01

We investigate denitrification mechanisms through batch experiments using crushed rock and groundwater from a granitic aquifer subject to long term pumping (Ploemeur, France). Except for sterilized experiments, extensive denitrification reaction induces NO 3 decreases ranging from 0.3 to 0.6mmol/L. Carbon concentrations, either organic or inorganic, remain relatively stable and do not document potential heterotrophic denitrification. Batch experiments show a clear effect of mineral dissolution which is documented through cation (K, Na, Ca) and Fluoride production. These productions are tightly related to denitrification progress during the experiment. Conversely, limited amounts of SO 4 , systematically lower than autotrophic denitrification coupled to sulfur oxidation stoichiometry, are produced during the experiments which indicates that sulfur oxidation is not likely even when pyrite is added to the experiments. Analysis of cation ratios, both in isolated minerals of the granite and within water of the batch, allow the mineral dissolution during the experiments to be quantified. Using cation ratios, we show that batch experiments are characterized mainly by biotite dissolution. As biotite contains 21 to 30% of Fe and 0.3 to 1.7% of F, it constitutes a potential source for these two elements. Denitrification could be attributed to the oxidation of Fe(II) contained in biotite. We computed the amount of K and F produced through biotite dissolution when entirely attributing denitrification to biotite dissolution. Computed amounts show that this process may account for the observed K and F produced. We interpret these results as the development of microbial activity which induces mineral dissolution in order to uptake Fe(II) which is used for denitrification. Although pyrite is probably available, SO 4 and cation measurements favor a large biotite dissolution reaction which could account for all the observed Fe production. Chemical composition of groundwater produced from the Ploemeur site indicates similar denitrification processes although original composition shows mainly plagioclase dissolution. Copyright © 2017 Elsevier B.V. All rights reserved.

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

Perry, Frank Vinton; Kelley, Richard E.

The DOE Spent Fuel and Waste Technology (SWFT) R&D Campaign is supporting research on crystalline rock, shale (argillite) and salt as potential host rocks for disposal of HLW and SNF in a mined geologic repository. The distribution of these three potential repository host rocks is limited to specific regions of the US and to different geologic and hydrologic environments (Perry et al., 2014), many of which may be technically suitable as a site for mined geologic disposal. This report documents a regional geologic evaluation of the Pierre Shale, as an example of evaluating a potentially suitable shale for siting amore » geologic HLW repository. This report follows a similar report competed in 2016 on a regional evaluation of crystalline rock that focused on the Superior Province of the north-central US (Perry et al., 2016).« less

CO2 Driven Mineral Transformations in Fractured Reservoir

NASA Astrophysics Data System (ADS)

Schaef, T.

2015-12-01

Engineering fracture systems in low permeable formations to increase energy production, accelerate heat extraction, or to enhance injectivity for storing anthropogenic CO2, is a challenging endeavor. To complicate matters, caprocks, essential components of subsurface reservoirs, need to maintain their sealing integrity in this modified subsurface system. Supercritical CO2 (scCO2), a proposed non-aqueous based working fluid, is capable of driving mineral transformations in fracture environments. Water dissolution in scCO2 significantly impacts the reactivity of this fluid, largely due to the development of thin adsorbed H2O films on the surfaces of exposed rocks and minerals. Adsorbed H2O films are geochemically complex microenvironments that host mineral dissolution and precipitation processes that could be tailored to influence overall formation permeability. Furthermore, manipulating the composition of injected CO2 (e.g., moisture content and/or reactive gases such as O2, NOx, or SOx) could stimulate targeted mineral transformations that enhance or sustain reservoir performance. PNNL has developed specialized experimental techniques that can be used to characterize chemical reactions occurring between minerals and pressurized gases. For example, hydration of a natural shale sample (Woodford Shale) has been characterized by an in situ infrared spectroscopic technique as water partitions from the scCO2 onto the shale. Mineral dissolution and carbonate precipitation reactions were tracked by monitoring changes of Si-O and C-O stretching bands, respectively Structural changes indicated expandable clays in the shale such as montmorillonite are intercalated with scCO2, a process not observed with the non-expandable kaolinite component. Extreme scale ab initio molecular dynamics simulations were used in conjunction with model mineral systems to identify the driving force and mechanism of water films. They showed that the film nucleation and formation on minerals is driven by both enthalpic and entropic requirements. Collectively, the synergy between laboratory observations, state-of-the-art atomistic simulations and reservoir modeling has generated important insights for the design and engineering of subsurface reservoirs for CO2 storage and energy extraction.

Experimental Constraints on Fluid-Rock Reactions during Incipient Serpentinization of Harzburgite

NASA Astrophysics Data System (ADS)

Klein, F.; Grozeva, N. G.; Seewald, J.; McCollom, T. M.; Humphris, S. E.; Moskowitz, B. M.; Berquo, T. S.; Kahl, W. A.

2014-12-01

The exposure of mantle peridotite to water at crustal levels leads to a cascade of interconnected dissolution-precipitation and reduction-oxidation reactions - a process referred to as serpentinization. These reactions have major implications for microbial life through the provision of hydrogen (H2). To simulate incipient serpentinization and the release of H2 under well-constrained conditions, we reacted uncrushed harzburgite with chemically modified seawater at 300°C and 35 MPa for ca. 1.5 years (13441 hours), monitored changes in fluid chemistry over time, and examined the secondary mineralogy at the termination of the experiment. Approximately 4 mol % of the protolith underwent alteration forming serpentine, accessory magnetite, chlorite, and traces of calcite and heazlewoodite. Alteration textures bear remarkable similarities to those found in partially serpentinized abyssal peridotites. Neither brucite nor talc precipitated during the experiment. Given that the starting material contained ~3.8 times more olivine than orthopyroxene on a molar basis, mass balance requires that dissolution of orthopyroxene was significantly faster than dissolution of olivine. However, the H2 release rate was not uniform, slowing from ~2 nmol H2(aq) gperidotite-1 s-1 at the beginning of the experiment to ~0.2 nmol H2(aq) gperidotite-1 s-1 at its termination. Serpentinization consumed water but did not release significant amounts of dissolved species (other than H2) suggesting that incipient hydration reactions involved a volume increase of ~40%. The reduced access of water to olivine surfaces due to filling of fractures and coating of primary minerals with alteration products led to decreased rates of serpentinization and H2 release. While this concept might seem at odds with completely serpentinized seafloor peridotites, reaction-driven fracturing offers an intriguing solution to the seemingly self-limiting nature of serpentinization. Indeed, the reacted sample revealed a number of textural features diagnostic of incipient reaction-driven fracturing. Reaction-driven and tectonic fracturing must have far reaching impacts on the release rate of H2 in peridotite-hosted hydrothermal systems and therefore represent key mechanisms in regulating the supply of reduced gases to microbial ecosystems.

Fluid inclusion chemistry of adularia-sericite epithermal Au-Ag deposits of the southern Hauraki Goldfield, New Zealand

USGS Publications Warehouse

Simpson, Mark P.; Strmic Palinkas, Sabina; Mauk, Jeffrey L.; Bodnar, Robert J.

2015-01-01

LA-ICP-MS analyses show that in some cases different fluid inclusion assemblages (FIAs) within a single sample trapped fluids with variable chemistries. These differences likely reflect modification of a single parent fluid through mineral dissolution and precipitation, water/rock interactions, boiling and vapor loss, conductive cooling, and mixing.

Geological and environmental implications of the evaporite karst in Spain

NASA Astrophysics Data System (ADS)

Gutiérrez, F.; Calaforra, J. M.; Cardona, F.; Ortí, F.; Durán, J. J.; Garay, P.

2008-01-01

In Spain, evaporite outcrops cover approximately 7% of the total area of the country. Most of the evaporitic formations are made up of Ca-sulfates (gypsum/anhydrite) or Ca-sulfates and halite. Certain Paleogene marine evaporites also contain K-Mg-chlorides, and some Tertiary continental formations bear substantial amounts of Na-sulfates in the subsurface (glauberite and thenardite). Mesozoic evaporitic formations commonly wedge out towards the ground surface, passing into condensed sequences and dissolution-collapse breccias. Some of these highly porous breccias constitute major regional aquifers. In several areas, interstratal karstification of the evaporites has given rise to gravitational deformations such as basin structures, monoclines, and collapse structures covering several square kilometers that record a cumulative subsidence in excess of 200 m (Teruel and Calatayud Grabens). A widespread consequence of evaporite dissolution processes in Spain is the hydrochemical degradation of surface waters. Some of the largest and most outstanding lake systems, from an environmental perspective, occur in karstic depressions developed in evaporitic formations (Fuente de Piedra, Gallocanta, Bujaraloz, and Bañolas lakes). Sinkhole activity is a major geohazard in several evaporite karst areas. The sinkhole risk has a particularly high impact in sectors where Tertiary evaporites are overlain by Quaternary alluvial aquifers (Calatayud, Zaragoza, and Madrid areas). Some of the detrimental effects of subsidence include severe damage to historical monuments (Calatayud), the demolition of a whole village (Puilatos), or the derailment of a freight train (Zaragoza area). The deepest gypsum caves are found in Triassic diapiric structures (El Sumidor Cave, 210 m deep), and the longest ones are developed in horizontally lying Neogene sequences (Sorbas caves, and Estremera maze cave). The Cardona diapir hosts salt caves up to 4,300 m long whose genesis is related to flooding of mine galleries caused by the interception of a phreatic conduit. The main anthropogenic impacts on the endokarstic systems are related to the disposal of wastewaters and the destruction of caves by quarrying. The fluvial valleys that cross Tertiary evaporitic outcrops commonly show peculiar geological characteristics related to dissolution-induced synsedimentary subsidence phenomena: (1) Thickened alluvium filling dissolution basins up to several tens of kilometers long and more than 100 m deep. The largest thickenings are found in areas where the bedrock contains halite and glauberite. (2) Superimposed alluvial units locally bounded by angular unconformities. (3) Abundant deformational structures and paleosinkholes related to the rockhead and/or interstratal karstification of the substratum. These fluvial valleys typically are flanked by a prominent gypsum escarpment. Rock-falls favored by the dissolutional enlargement of joints derived from these scarps are the type of mass movement which has caused the highest number of casualties in Spain.

Origin of halides (Cl- and Br-) and of their stable isotopes (d37Cl and d81Br) at the Tournemire URL (France) - Experimental and numerical approach

NASA Astrophysics Data System (ADS)

Bachir-Bey, Nassim; Matray, Jean-Michel

2014-05-01

This work is part of research conducted by the Institute of Radiological and Nuclear Safety (IRSN) on the geological disposal of High-Level and Intermediate-Level Long-Lived (HL-ILLL) radioactive waste in deep clayrocks. In France, the choice of the potential host rock for the geological storage is focused on the Callovian-Oxfordian (COx) of Meuse/Haute-Marne from its low permeability, capacity for self- sealing, high sorption and ability to radionuclide (RN) transport by diffusion. IRSN, which plays an expert role for ASN has its own underground research laboratory in a clayrock which has strong analogies to the COx. This is the Toarcian/Domerian clayrock located at Tournemire in southern Aveyron in France. The purpose of this study was to assess the transfer of RN in the Tournemire clayrock through the study of halides contents and of their stable isotopes (Cl-, Br-, Cl-/Br-, d37Cl, d81Br). The approach used was multiple and consisted for halides to: 1) Assess their stock in different fractions of the rock by applying several techniques including i) alkaline fusion for their total stock, ii) leaching to access their stock in porewater and to mineral phases sensitive to dissolution iii) cubic diffusion for their stock in porewater, 2) Get their diffusive transport parameters of a selection of samples from the upper Toarcian by cubic diffusion experiments modelled using the Hytec transport code developed by Mines ParisTech and 3) Model their transport after palaeohydrogeological known changes of the Tournemire massif. The experimental approach, conducted at the LAME lab, did not lead to an operational protocol for the alkaline fusion due to an incomplete rock dissolution. Leaching was used to characterize the concentrations of halides in the fractions of pore water and of minerals sensitive to dissolution. The results show levels of halides much higher than those of pore water with very low Cl/Br ratios likely resulting from the dissolution of mineral species. The cubic diffusion produced the pore diffusion coefficients for Cl and Br as well as their concentration in the porewater. Cubic diffusion also allowed to estimate a Cl to Br pore diffusion coefficient ratio, necessary to calculate the profiles of Cl/Br. These estimates have required the use of the transport code Hytec i) for dimensioning and implementing the experiment in a time frame compatible with the work period, ii) for analysing the sensitiveness of the model to the accessible porosity and to the diffusion coefficient which act respectively to the steady phase and transient phase of the experiments, and finally, iii ) for adjusting the pore diffusion coefficients of Cl and Br to an accessible porosity of 3-4%. The Hytec code was then used to check the consistency of the current profiles of chlorides, bromides, 35Cl , 37Cl , d37Cl, Cl/Br in 1D, a fake drilling assumed crossing the entire clayrock. The assumption is that halides have undergone a diffusive transport between seawater trapped during sedimentation and meteoric waters infiltrated at different times to domain boundaries. Four scenarios were tested according to the paleohydrogeological history of the massif. All tracers and scenarios are consistent with a unique marine source of halides more or less diluted by meteoric waters. The duration of the diffusive exchange initially suggested 85 ± 10 Ma (Bensenouci, 2010) is never contradicted despite uncertainties related to changes in boundary conditions. This body of evidence would suggest that molecular diffusion is the transport process which has affected and still affect the Tournemire clayrock, outside fault zones. The d37Cl results expected on the surrounding carbonated aquifers, leachates and fracture waters (including d81Br values) should help to refine the models and the results.

Tracking hydrothermal alteration and mineralization in rock-forming and accessory minerals from the Lyon Mountain Granite and related iron oxide apatite (IOA) ores from the Adirondack Mountains, New York State

NASA Astrophysics Data System (ADS)

Buchanan, A.; Hanchar, J. M.; Steele-MacInnis, M. J.; Crowley, J. L.; Valley, P. M.; Fisher, C. M.; Fedo, C.; Piccoli, P. M.; Fournelle, J.

2012-12-01

The Lyon Mountain granite (LMG) is located in the northeastern Adirondack Mountains in New York State and hosts several low-titanium iron oxide apatite (IOA) ore deposits. The ores are predominately hosted by perthite bearing granite, which has been extensively altered to albite and microcline granite by Na and K metasomatism. This alteration results in several distinct groups of rocks that are dominated by either K or Na addition and a group composed of mixed Na and K addition. The different groups of altered perthite also lie on a trend suggestive of addition of Fe to each, consistent with a secondary mineralization origin. Previous work showed that the host rocks of the IOA ores have zircon with ~1150 Ma cores and 1060-1050 Ma rims and whole grains. This study aims to further constrain the timing of LMG emplacement, subsequent hydrothermal alteration, and Fe mineralization through geochemical analysis of the major, minor, and accessory phases and geochronology of accessory phases. SIMS analyses of zircon from several of the IOA ores reveal at least two periods of growth after LMG magmatism, at 1039 +/- 4.4 Ma and 1016 +/- 7 Ma to 1000 +/- 9 Ma. In situ EMPA and LA-ICPMS trace element analyses of the zircon rims and cores reveal that in two samples the zircon rims are enriched in rare earth elements (REE) compared to their cores, potentially pointing to a hydrothermal origin. Apatite has unusually high REE and Y concentrations (some total REE2O3 > 20 wt. % oxide and up to 8 wt. % oxide Y2O3), as does titanite, which allowed for the in situ analysis of Sm-Nd in apatite and titanite by LA-MC-ICP-MS. Initial Nd isotopic composition of both ore and host rock apatite and host rock titanite are consistent with published Adirondack initial Nd whole rock data, suggesting a local source for REE in these ores. EMPA and LA-ICPMS trace-element analyses of the major rock-forming minerals indicate that the feldspar have undergone Na-metasomatism and are depleted in REEs, perhaps signifying the "local source" and the mechanism of the REE enrichment in the LMG apatite in the IOA ores and host rocks. In contrast, the minor- and trace-element compositions of the other major rock-forming minerals (e.g., clinopyroxene and fayalite) as well as the zircon, and fluorite in the LMG have average igneous granitic trace- and minor-element compositions. To better understand the timing and origin of these post ~1050 Ma events, U-Pb ID-TIMS dating of apatite and titanite, and in situ LA-MC-ICPMS Sm-Nd analysis were done on the ore and host rock samples. Apatite dates range from 1050 to 850 Ma and titanite dates range from ~1015 to 970 Ma. There is significant age variation within samples and within grains. Titanite does not have sufficient spread for accurate Sm-Nd isochron dating and two ore-apatite samples have homogenous initial Nd isotopic and Sm-Nd elemental ratios, precluding calculation of Sm-Nd dates. A third ore sample shows a large spread in Sm-Nd and yields a Sm-Nd isochron date of ~850 Ma, in close agreement with U-Pb apatite dates. The Sm-Nd isochron and U-Pb apatite dates may reflect cooling recorded in these minerals or a younger hydrothermal mineralization event.

The Impact of Mineralogy on the Geochemical Alteration of Shales During Hydraulic Fracturing Operations

NASA Astrophysics Data System (ADS)

Maher, K.; Harrison, A. L.; Jew, A. D.; Dustin, M. K.; Kiss, A. M.; Kohli, A. H.; Thomas, D.; Joe-Wong, C. M.; Brown, G. E.; Bargar, J.

2016-12-01

The extraction of oil and gas resources from low permeability shale reservoirs using hydraulic fracturing techniques has increased significantly in recent years. During hydraulic fracturing, large volumes of fluid are injected into subsurface shale formations, which drives substantial fluid-rock interaction that can release contaminants and alter rock permeability. Here, a combined experimental, imaging, and modeling approach was employed to systematically evaluate the impact of shale mineralogy on its physical and chemical alteration when exposed to fracturing fluids of different composition. Batch reactor experiments contained different shales with unique mineralogical compositions that were exposed to simulated hydraulic fracturing fluid. Experiments revealed that the balance between fluid acidity and acid neutralizing capacity of the rock was the strongest control on the evolution of fluid and rock chemistry. Carbonate mineral-rich shales rapidly recovered solution pH to circum-neutral conditions, whereas fluids in contact with carbonate mineral-poor shales remained acidic. The dissolution of shale minerals released metal contaminants, yet the precipitation of Fe(III)-bearing secondary phases helped to attenuate their release via co-precipitation or sorption. Post-reaction imaging illustrated that selective dissolution of carbonate minerals generated secondary porosity, the connectivity of which was dictated by initial carbonate distribution. Conversely, the precipitation of secondary Al- and Fe-bearing phases may occlude porosity, potentially inhibiting transport of water, contaminants, and hydrocarbons. The maturation of secondary Fe-bearing phases from amorphous to crystalline over time suggests that porosity will continue to evolve even after oxidation reactions have effectively ceased. These experiments reveal that the relative abundance and distribution of carbonate minerals is the master variable dictating both porosity alteration and contaminant release from shale formations, implying that the response of a reservoir to hydraulic fracturing can be better assessed using robust mineralogical data.

Rock fracture processes in chemically reactive environments

NASA Astrophysics Data System (ADS)

Eichhubl, P.

2015-12-01

Rock fracture is traditionally viewed as a brittle process involving damage nucleation and growth in a zone ahead of a larger fracture, resulting in fracture propagation once a threshold loading stress is exceeded. It is now increasingly recognized that coupled chemical-mechanical processes influence fracture growth in wide range of subsurface conditions that include igneous, metamorphic, and geothermal systems, and diagenetically reactive sedimentary systems with possible applications to hydrocarbon extraction and CO2 sequestration. Fracture processes aided or driven by chemical change can affect the onset of fracture, fracture shape and branching characteristics, and fracture network geometry, thus influencing mechanical strength and flow properties of rock systems. We are investigating two fundamental modes of chemical-mechanical interactions associated with fracture growth: 1. Fracture propagation may be aided by chemical dissolution or hydration reactions at the fracture tip allowing fracture propagation under subcritical stress loading conditions. We are evaluating effects of environmental conditions on critical (fracture toughness KIc) and subcritical (subcritical index) fracture properties using double torsion fracture mechanics tests on shale and sandstone. Depending on rock composition, the presence of reactive aqueous fluids can increase or decrease KIc and/or subcritical index. 2. Fracture may be concurrent with distributed dissolution-precipitation reactions in the hostrock beyond the immediate vicinity of the fracture tip. Reconstructing the fracture opening history recorded in crack-seal fracture cement of deeply buried sandstone we find that fracture length growth and fracture opening can be decoupled, with a phase of initial length growth followed by a phase of dominant fracture opening. This suggests that mechanical crack-tip failure processes, possibly aided by chemical crack-tip weakening, and distributed solution-precipitation creep in the hostrock can independently affect fracture opening displacement and thus fracture aperture profiles and aperture distribution.

Rock-weathering rates as functions of time

USGS Publications Warehouse

Colman, Steven M.

1981-01-01

The scarcity of documented numerical relations between rock weathering and time has led to a common assumption that rates of weathering are linear. This assumption has been strengthened by studies that have calculated long-term average rates. However, little theoretical or empirical evidence exists to support linear rates for most chemical-weathering processes, with the exception of congruent dissolution processes. The few previous studies of rock-weathering rates that contain quantitative documentation of the relation between chemical weathering and time suggest that the rates of most weathering processes decrease with time. Recent studies of weathering rinds on basaltic and andesitic stones in glacial deposits in the western United States also clearly demonstrate that rock-weathering processes slow with time. Some weathering processes appear to conform to exponential functions of time, such as the square-root time function for hydration of volcanic glass, which conforms to the theoretical predictions of diffusion kinetics. However, weathering of mineralogically heterogeneous rocks involves complex physical and chemical processes that generally can be expressed only empirically, commonly by way of logarithmic time functions. Incongruent dissolution and other weathering processes produce residues, which are commonly used as measures of weathering. These residues appear to slow movement of water to unaltered material and impede chemical transport away from it. If weathering residues impede weathering processes then rates of weathering and rates of residue production are inversely proportional to some function of the residue thickness. This results in simple mathematical analogs for weathering that imply nonlinear time functions. The rate of weathering becomes constant only when an equilibrium thickness of the residue is reached. Because weathering residues are relatively stable chemically, and because physical removal of residues below the ground surface is slight, many weathering features require considerable time to reach constant rates of change. For weathering rinds on volcanic stones in the western United States, this time is at least 0.5 my. ?? 1981.

Structural controls and evolution of gold-, silver-, and REE-bearing copper-cobalt ore deposits, Blackbird district, east-central Idaho: Epigenetic origins

USGS Publications Warehouse

Lund, K.; Tysdal, Russell G.; Evans, Karl V.; Kunk, Michael J.; Pillers, Renee M.

2011-01-01

Textural data at all scales indicate that the host sites for veins and the tectonic evolution of both host rocks and mineral deposits were kinematically linked to Late Cretaceous regional thrust faulting. Heat, fluids, and conduits for generation and circulation of fluids were part of the regional crustal thickening. The faulting also juxtaposed metaevaporite layers in the Mesoproterozoic Yellowjacket Formation over Blackbird district host rocks. We conclude that this facilitated chemical exchange between juxtaposed units resulting in leaching of critical elements (Cl, K, B, Na) from metaevaporites to produce brines, scavenging of metals (Co, Cu, etc) from rocks in the region, and, finally, concentrating metals in the lower-plate ramp structures. Although the ultimate source of the metals remains undetermined, the present Cu-Co ± Au (± Ag ± Ni ± REE) Blackbird ore deposits formed during Late Cretaceous compressional deformation.

Self-Organizing Fluid Convection Patterns in an en Echelon Fault Array

NASA Astrophysics Data System (ADS)

Patterson, James W.; Driesner, Thomas; Matthai, Stephan K.

2018-05-01

We present three-dimensional numerical simulations of natural convection in buried, vertical en echelon faults in impermeable host rock. Despite the fractures being hydraulically disconnected, convection within each fracture alters the temperature field in the surrounding host rock, altering convection in neighboring fractures. This leads to self-organization of coherent patterns of upward/downward flow and heating/cooling of the host rock spanning the entire fault array. This "synchronization" effect occurs when fracture spacing is less than the width of convection cells within the fractures, which is controlled by fracture transmissivity (permeability times thickness) and heterogeneity. Narrow fracture spacing and synchronization enhance convective fluid flow within fractures and cause convection to initiate earlier, even lowering the critical transmissivity necessary for convection initiation. Heat flow through the en echelon region, however, is enhanced only in low-transmissivity fractures, while heat flow in high-permeability fractures is reduced due to thermal interference between fractures.

Changes in geophysical properties caused by fluid injection into porous rocks: analytical models: Geophysical changes in porous rocks

DOE PAGES

Pride, Steven R.; Berryman, James G.; Commer, Michael; ...

2016-08-30

Analytical models are provided that describe how the elastic compliance, electrical conductivity, and fluid-flow permeability of rocks depend on stress and fluid pressure. In order to explain published laboratory data on how seismic velocities and electrical conductivity vary in sandstones and granites, the models require a population of cracks to be present in a possibly porous host phase. The central objective is to obtain a consistent mean-field analytical model that shows how each modeled rock property depends on the nature of the crack population. We describe the crack populations by a crack density, a probability distribution for the crack aperturesmore » and radii, and the averaged orientation of the cracks. The possibly anisotropic nature of the elasticity, conductivity, and permeability tensors is allowed for; however, only the isotropic limit is used when comparing to laboratory data. For the transport properties of conductivity and permeability, the percolation effect of the crack population linking up to form a connected path across a sample is modeled. But, this effect is important only in crystalline rock where the host phase has very small conductivity and permeability. In general, the importance of the crack population to the transport properties increases as the host phase becomes less conductive and less permeable.« less

Changes in geophysical properties caused by fluid injection into porous rocks: analytical models: Geophysical changes in porous rocks

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

Pride, Steven R.; Berryman, James G.; Commer, Michael

Analytical models are provided that describe how the elastic compliance, electrical conductivity, and fluid-flow permeability of rocks depend on stress and fluid pressure. In order to explain published laboratory data on how seismic velocities and electrical conductivity vary in sandstones and granites, the models require a population of cracks to be present in a possibly porous host phase. The central objective is to obtain a consistent mean-field analytical model that shows how each modeled rock property depends on the nature of the crack population. We describe the crack populations by a crack density, a probability distribution for the crack aperturesmore » and radii, and the averaged orientation of the cracks. The possibly anisotropic nature of the elasticity, conductivity, and permeability tensors is allowed for; however, only the isotropic limit is used when comparing to laboratory data. For the transport properties of conductivity and permeability, the percolation effect of the crack population linking up to form a connected path across a sample is modeled. But, this effect is important only in crystalline rock where the host phase has very small conductivity and permeability. In general, the importance of the crack population to the transport properties increases as the host phase becomes less conductive and less permeable.« less

Multi-stage evolution of the lithospheric mantle beneath the westernmost Mediterranean: Geochemical constraints from peridotite xenoliths in the eastern Betic Cordillera (SE Spain)

NASA Astrophysics Data System (ADS)

Marchesi, Claudio; Konc, Zoltán; Garrido, Carlos J.; Bosch, Delphine; Hidas, Károly; Varas-Reus, María Isabel; Acosta-Vigil, Antonio

2017-04-01

Spinel (± plagioclase) peridotite xenoliths from the Tallante and Los Perez volcanic centres in the eastern Betics (SE Spain) range from depleted (clinopyroxene-poor) harzburgites to fertile (clinopyroxene-rich) lherzolites and orthopyroxene-free wehrlites. Significantly, only one harzburgite, which is depleted in heavy rare earth elements (HREE), retains the imprint of ca. 20% ancient melting of an original garnet lherzolite source. In contrast, REE abundances of other harzburgites and lherzolites from the eastern Betics have been increased by melt-rock reaction. The whole-rock and mineral compositions of these mantle rocks are largely controlled by three types of modal metasomatism: 1) common clinopyroxene-orthopyroxene addition and olivine consumption which increased FeOt, SiO2 and Al2O3, and decreased MgO compared to the refractory melting products; 2) subordinate orthopyroxene dissolution and precipitation of clinopyroxene and olivine, which led to higher FeOt and MgO and lower SiO2 than in common (orthopyroxene-rich) lherzolites; and 3) rare orthopyroxene consumption and olivine addition that caused higher FeOt and lower SiO2 compared to the original melting residues. These mineral modal and major element variations have been produced mostly by interactions with relatively FeOt-rich/SiO2-poor melts, likely derived from a peridotite-pyroxenite lithospheric mantle with a highly heterogeneous isotopic composition. Melting of the lithospheric mantle in the western Mediterranean was triggered by upwelling of the asthenosphere induced by back-arc extension in the Late Oligocene-Early Miocene. Trapping of small fractions of exotic melts in whole-rocks - likely the parental magmas of Miocene back-arc dykes that intruded the Betic crust - caused local disequilibrium between the trace element signatures and Pb isotopic compositions of clinopyroxene and whole-rock. Subsequent interaction with SiO2-undersaturated magmas, similar to the parental melts of the Pliocene alkali basalts that host the xenoliths, promoted orthopyroxene consumption and clinopyroxene-olivine enrichment at locations close to magma conduits, and finally generated orthopyroxene-free wehrlites. This event constitutes the last episode of the Cenozoic magmatic evolution of the westernmost Mediterranean which is recorded in the mantle xenoliths from the eastern Betics.

Genesis of the Touissit-Bou Beker Mississippi valley-type district (Morocco-Algeria) and its relationship to the Africa-Europe collision

USGS Publications Warehouse

Bouabdellah, M.; Sangster, D.F.; Leach, D.L.; Brown, A.C.; Johnson, C.A.; Emsbo, P.

2012-01-01

The Mississippi Valley-type deposits of the Touissit-Bou Beker district are hosted by a 25 m thick sequence of diagenetically and hydrothermally dolomitized carbonate platform rocks of Aalenian-Bajocian age. The sulfide mineralization consists principally of galena and sphalerite and occurs as open-space fillings of voids and moderate to massive replacement of the medium- to coarse-grained host dolostone. Five types of dolomite have been distinguished, two of which (D 1 and D 2) are of replacement origin, whereas HD 1, HD 2, HD 3 occurring as open-space filling are of hydrothermal affiliation. Main ore controls include stratigraphy and lithology, carbonate dissolution, paleogeography, faults or faulted rocks, and availability of organic matter. Fluid inclusion data, along with Na-Cl-Br leachate, indicate that the ore-forming fluids correspond to evolved NaCl-CaCl 2-KCl-MgCl 2 basin-derived hot (100?? ?? 20??C) saline brines (>20 wt% NaCl equiv) that acquired their high salinities and Ca/Na ratios through evaporation of seawater, and subsequent dolomitization and fluid-rock interactions. Stable isotope data for replacement and hydrothermal dolomites are tightly clustered and overlapping, with ?? 18O and ?? 13C values from 20.5 to 21.2 and 0.2 to 0.7%, respectively. Similarly, sulfides yield ?? 34S values between 11.2 and 1.9%, whereas those corresponding to the nearby Triassic gypsum cluster yield around 14%. Altogether, these isotopic compositions are consistent with a basinal-type fluid with reduced sulfur very likely being derived through thermochemical reduction of dissolved sulfate, resulting in metal precipitation, and carbon of mainly marine Aalenian-Bajocian carbonate origin with a minor biogenic component. 87Sr/ 86Sr values of replacement dolostone are similar to those of ore-related hydrothermal dolomites, ranging from 0.70746 to 0.70833 and from 0.70769 to 0.70828, respectively, and are different from those of the Visean rhyodacite (0.71849-0.72167). Lead isotope ratios ( 206Pb/ 204Pb = 18.319-18.390; 207Pb/ 204Pb = 15.620. 15.680; 208Pb/ 204Pb = 38.452-38.650) of sulfides are consistent with Pb being derived from the Visean rhyodacite and associated volcaniclastic rocks. The intimate link between faults and mineralization suggests the strong possibility of brine flow along both ENE-trending regional-scale faults and NW-SW-trending local-scale faults. The data suggest that MVT mineralization was emplaced during the late Neogene-Quaternary (i.e., ca. 15.0 Ma), possibly as a result of subsurface gravity-driven fluid flow in response to the collision between the African and Eurasian plates. ?? 2012 Society of Economic Geologists, Inc.

Genesis of the Touissit-Bou Beker Mississippi Valley-type district (Morocco-Algeria) and its relation to the Africa-Europe collision

USGS Publications Warehouse

Bouabdellah, Mohammed; Sangster, Donald F.; Leach, David L.; Brown, Alex C.; Johnson, Craig A.; Emsbo, Poul

2012-01-01

The Mississippi Valley-type deposits of the Touissit-Bou Beker district are hosted by a 25 m thick sequence of diagenetically and hydrothermally dolomitized carbonate platform rocks of Aalenian-Bajocian age. The sulfide mineralization consists principally of galena and sphalerite and occurs as open-space fillings of voids and moderate to massive replacement of the medium- to coarse-grained host dolostone. Five types of dolomite have been distinguished, two of which (D1 and D2) are of replacement origin, whereas HD1, HD2, HD3 occurring as open-space filling are of hydrothermal affiliation. Main ore controls include stratigraphy and lithology, carbonate dissolution, paleogeography, faults or faulted rocks, and availability of organic matter. Fluid inclusion data, along with Na-Cl-Br leachate, indicate that the ore-forming fluids correspond to evolved NaCl-CaCl2-KCl-MgCl2 basin-derived hot (100° ± 20°C) saline brines (>20 wt % NaCl equiv) that acquired their high salinities and Ca/Na ratios through evaporation of seawater, and subsequent dolomitization and fluid-rock interactions. Stable isotope data for replacement and hydrothermal dolomites are tightly clustered and overlapping, with δ18O and δ13C values from 20.5 to 21.2 and 0.2 to 0.7‰, respectively. Similarly, sulfides yield δ34S values between 11.2 and 1.9‰, whereas those corresponding to the nearby Triassic gypsum cluster yield around 14‰. Altogether, these isotopic compositions are consistent with a basinal-type fluid with reduced sulfur very likely being derived through thermochemical reduction of dissolved sulfate, resulting in metal precipitation, and carbon of mainly marine Aalenian-Bajocian carbonate origin with a minor biogenic component. 87Sr/86Sr values of replacement dolostone are similar to those of ore-related hydrothermal dolomites, ranging from 0.70746 to 0.70833 and from 0.70769 to 0.70828, respectively, and are different from those of the Visean rhyodacite (0.71849–0.72167). Lead isotope ratios (206Pb/204Pb = 18.319–18.390; 207Pb/204Pb = 15.620–15.680; 208Pb/204Pb = 38.452–38.650) of sulfides are consistent with Pb being derived from the Visean rhyodacite and associated volcaniclastic rocks. The intimate link between faults and mineralization suggests the strong possibility of brine flow along both ENE-trending regional-scale faults and NW-SW-trending local-scale faults. The data suggest that MVT mineralization was emplaced during the late Neogene-Quaternary (i.e., ca. 15–0 Ma), possibly as a result of subsurface gravity-driven fluid flow in response to the collision between the African and Eurasian plates.

TEM study of a silicate-carbonate-microbe interface prepared by focused ion beam milling

NASA Astrophysics Data System (ADS)

Benzerara, Karim; Menguy, Nicolas; Guyot, François; Vanni, Christian; Gillet, Philippe

2005-03-01

The biogeochemical alteration of an Mg-Fe orthopyroxene, reacted for 70 yr under arid conditions in a desert environment, was studied by transmission electron microscopy. For this purpose, an electron transparent cross-section of the interface between a single microorganism, an orthopyroxene and nanometer-sized calcite crystals, was prepared with a focused ion beam system. X-ray energy dispersive spectrometry and electron energy loss spectroscopy allowed one to clearly distinguish the microorganism en route to fossilization from the nanometer-sized calcite crystals, showing the usefulness of such a protocol for identifying unambiguously traces of life in rocks. A 100-nm-deep depression was observed in the orthopyroxene close to the microorganism, suggesting an enhanced dissolution mediated by the microbe. However, an Al- and Si-rich amorphous altered layer restricted to the area just below the microorganism could be associated with decreased silicate dissolution rates at this location, suggesting complex effects of the microorganism on the silicate dissolution process. The close association observed between silicate dissolution and carbonate formation at the micrometer scale suggests that Urey-type CO 2 sequestration reactions could be mediated by microorganisms under arid conditions.

15 CFR 922.102 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-01-01

... genetic matter, or genetic matter from another species, has been transferred in order that the host organism acquires the genetic traits of the transferred genes. Live rock means any Coral, basalt rock, or...

15 CFR 922.102 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-01-01

... genetic matter, or genetic matter from another species, has been transferred in order that the host organism acquires the genetic traits of the transferred genes. Live rock means any Coral, basalt rock, or...

Brine history indicated by argon, krypton, chlorine, bromine, and iodine analyses of fluid inclusions from the Mississippi Valley type lead-fluorite-barite deposits at Hansonburg, New Mexico

USGS Publications Warehouse

Böhlke, J.K.; Irwin, J.J.

1992-01-01

Argon, krypton, chlorine, bromine, and iodine were measured in a homogeneous population of high-salinity hydrothermal fluid inclusions from the Tertiary-age Mississippi Valley-type (MVT) lead-fluorite-barite deposits at Hansonburg, New Mexico to establish new types of evidence for the history of both the fluid and the major dissolved salts. Noble gases and halogens in fluid inclusions containing 10−10–10−9 L of brine (Cl= 3 molal) were analyzed by laser microprobe noble-gas mass spectrometry (lmngms) on neutron-irradiated samples.The concentrations of36Ar (4.7 × 10−8 molal) and84Kr1.8 × 10−9 molal) in the fluid inclusions are equal to those of fresh surface waters in equilibrium with air at approximately20 ± 5°. The mole ratios ofBr/Cl (1.2 × 10−4) andI/Cl (1–2 × 10−6) are among the lowest measured in any natural waters, similar to those of modern brines formed by dissolution of Permian NaCl-bearing evaporites in southeast New Mexico.40Ar/36Ar ratios (600) are twice that of air, and indicate that the fluid inclusions had excess radiogenic40Ar (1.4 × 10−5 molal) when trapped. The amount of excess40Ar appears to be too large to have been acquired with Cl by congruent dissolution of halite-bearing evaporites, and possibly too small to have been acquired with Pb by congruent dissolution of granitic basement rocks with Proterozoic KAr ages.From thelmngms data, combined with published Pb and S isotope data, we infer the following sequence of events in the history of the Hansonburg MVT hydrothermal brine: (1) the brine originated as relatively dilute meteoric water, and it did not gain or lose atmospheric Ar or Kr after recharge; (2) the originally dilute fluid acquired the bulk of its Cl and sulfate in the subsurface after recharge by dissolving halite-bearing Permian? marine evaporites; (3) the high salinity brine then acquired most of its Pb and excess radiogenic40Ar from interactions with aquifer rocks other than evaporites, possibly clastic sedimentary rocks or basement rocks with Phanerozoic KAr “ages”; and (4) the brine deposited fluorite without having boiled or degassed.

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.

The roles of organic matter in the formation of uranium deposits in sedimentary rocks

USGS Publications Warehouse

Spirakis, C.S.

1996-01-01

Because reduced uranium species have a much smaller solubility than oxidized uranium species and because of the strong association of organic matter (a powerful reductant) with many uranium ores, reduction has long been considered to be the precipitation mechanism for many types of uranium deposits. Organic matter may also be involved in the alterations in and around tabular uranium deposits, including dolomite precipitation, formation of silicified layers, iron-titanium oxide destruction, dissolution of quartz grains, and precipitation of clay minerals. The diagenetic processes that produced these alterations also consumed organic matter. Consequently, those tabular deposits that underwent the more advanced stages of diagenesis, including methanogenesis and organic acid generation, display the greatest range of alterations and contain the smallest amount of organic matter. Because of certain similarities between tabular uranium deposits and Precambrian unconformity-related deposits, some of the same processes might have been involved in the genesis of Precambrian unconformity-related deposits. Hydrologic studies place important constraints on genetic models of various types of uranium deposits. In roll-front deposits, oxidized waters carried uranium to reductants (organic matter and pyrite derived from sulfate reduction by organic matter). After these reductants were oxidized at any point in the host sandstone, uranium minerals were reoxidized and transported further down the flow path to react with additional reductants. In this manner, the uranium ore migrated through the sandstone at a rate slower than the mineralizing ground water. In the case of tabular uranium deposits, the recharge of surface water into the ground water during flooding of lakes carried soluble humic material to the water table or to an interface where humate precipitated in tabular layers. These humate layers then established the chemical conditions for mineralization and related alterations. In the case of Precambrian unconformity-related deposits, free thermal convection in the thick sandstones overlying the basement rocks carried uranium to concentrations of organic matter in the basement rocks.

Cu-Mo-Au mineralization in Qarachilar area, Qaradagh batholith (NW Iran): Fluid inclusion and stable isotope studies and Re-Os dating

NASA Astrophysics Data System (ADS)

Simmonds, Vartan; Moazzen, Mohssen

2015-04-01

The Qaradagh batholith is located in NW Iran, neighboring the Meghri-Ordubad granitoid in southern Armenia. This magmatic complex is emplaced in the northwestern part of the Urumieh-Dokhtar magmatic arc, which formed through north-eastward subduction of Neo-Tethyan oceanic crust beneath the central Iranian domain in the late-Mesozoic and early-Cenozoic and hosts most of the porphyry copper deposits and prospects in Iran, such as Sarcheshmeh and Sungun. The Qaradagh batholith is comprised of Eocene-Oligocene intrusive rocks occurring as multi-episode stocks, where the dominant rock type is granodiorite. Hydrothermal alterations have also occurred in these rocks including potassic, phyllic-sericitic, argillic and propylitic alterations and silicification. These alterations are accompanied by vein-type and disseminated Cu, Mo and Au mineralization. The Qarachilar area is located in the central part of the Qaradagh batholith, which hosts mono-mineralic and quartz-sulfide veins and veinlets (several mm to <1 m thick and 50-700 m long) and silicic zones containing Cu-Mo-Au-Ag ore minerals (mainly pyrite, chalcopyrite and molybdenite). Microthermometric studies on the fluid inclusions of quartz-sulfide veins-veinlets show that the salinity ranges between 15-70 wt% NaCl, with the highest peak between 35-40 wt% NaCl. The homogenization temperature for primary 2-phase and multi-phase inclusions ranges between 220 and 540 °C. Two-phase inclusions homogenizing by vapor disappearance have TH values between 280 and 440 °C (mainly between 300 and 360 °C). A few of them homogenize into vapor state with TH values of 440-540 °C. Multi-phase inclusions show 3 types of homogenization. Most of them homogenize by simultaneous disappearance of vapor bubble and dissolution of halite daughter crystal, for which the TH value is 240-420 °C (mostly between 260 and 340 °C). Those homogenizing by halite dissolution show TH values about 220-360 °C and a few homogenizing by vapor disappearance display TH values between 300 and 360 °C. The data-point trend in TH(L-V)-Salinity plot may signify boiling of low-salinity fluids and distillation by superficial fluids. Therefore, it can be concluded that the ore-forming magmatic-hydrothermal aqueous fluids have most likely experienced boiling and also mixed with low temperature and low salinity superficial fluids. Occurrence of boiling is also supported by the coexistence of liquid-rich and vapor-rich 2-phase inclusions as well as multi-phase halite-bearing inclusions which homogenize in a similar range of TH. The calculated minimum pressure at the time of entrapment is estimated about 50 to 120 bar, which is equal to the hydrostatic depth of 500-1100 m. Stable isotope studies of O, H and S on the quartz and sulfide samples taken from quartz-sulfide veins-veinlets reveal a magmatic origin for the ore-bearing fluid and its sulfur content. The δ18O values for quartz and fluid are about 11.13-12.47 ‰ and 5.78-6.89 ‰ (SMOW), respectively, the δD values are about -93 and -50 ‰ and the δ34S values of sulfide minerals are about -1.37-0.49‰ (VCDT). Re-Os model ages calculated for molybdenite samples range between 25.19±0.19 and 31.22±0.28 Ma, referring to middle-late Oligocene, contemporaneous with the third metallogenic epoch in the Lesser Caucasus (especially Kadjaran and Paragachai PCDs in South Armenian Block).

Experimental layering development by indenter technique and application to fault rheology differentiation

NASA Astrophysics Data System (ADS)

Gratier, J. P.; Noiriel, C. N.; Renard, F.

2014-12-01

Natural deformation of rocks is often associated with differentiation processes leading to irreversible transformations of their microstructural thus leading in turn to modifications of their rheological properties. The mechanisms of development of such processes at work during diagenesis, metamorphism or fault differentiation are poorly known as they are not easy to reproduce in the laboratory due to the long duration required for most of chemically controlled differentiation processes. Here we show that experimental compaction with layering development, similar to what happens in natural deformation, can be obtained in the laboratory by indenter techniques. Samples of plaster mixed with clay and samples of diatomite loosely interbedded with clays were loaded during several months at 40°C (plaster) and 150°C (diatomite) in presence of their saturated solutions. High-resolution X-ray tomography and SEM studies show that the layering development is a self-organized process. Stress driven dissolution of the soluble minerals (gypsum in plaster, silica in diatomite) is initiated in the zones initially richer in clays because the kinetics of diffusive mass transfer along the clay/soluble mineral interfaces is much faster than along the healed boundaries of the soluble minerals. The passive concentration of the clay minerals amplifies the localization of the dissolution along some layers oriented perpendicular to the maximum compressive stress component. Conversely, in the areas with initial low content in clay and clustered soluble minerals, dissolution is more difficult as the grain boundaries of the soluble species are healed together. These areas are less deformed and they act as rigid objects that concentrate the dissolution near their boundaries thus amplifying the differentiation. Applications to fault processes are discussed: i) localized pressure solution and sealing processes may lead to fault rheology differentiation with a partition between two end-member behaviors: seismic (in sealed zones) and aseismic (in dissolved zones); ii) tectonic layering may lead to highly anisotropic structures with a drastic decrease of the rock strength parallel to the layering.

Quantification of a maximum injection volume of CO2 to avert geomechanical perturbations using a compositional fluid flow reservoir simulator

NASA Astrophysics Data System (ADS)

Jung, Hojung; Singh, Gurpreet; Espinoza, D. Nicolas; Wheeler, Mary F.

2018-02-01

Subsurface CO2 injection and storage alters formation pressure. Changes of pore pressure may result in fault reactivation and hydraulic fracturing if the pressure exceeds the corresponding thresholds. Most simulation models predict such thresholds utilizing relatively homogeneous reservoir rock models and do not account for CO2 dissolution in the brine phase to calculate pore pressure evolution. This study presents an estimation of reservoir capacity in terms of allowable injection volume and rate utilizing the Frio CO2 injection site in the coast of the Gulf of Mexico as a case study. The work includes laboratory core testing, well-logging data analyses, and reservoir numerical simulation. We built a fine-scale reservoir model of the Frio pilot test in our in-house reservoir simulator IPARS (Integrated Parallel Accurate Reservoir Simulator). We first performed history matching of the pressure transient data of the Frio pilot test, and then used this history-matched reservoir model to investigate the effect of the CO2 dissolution into brine and predict the implications of larger CO2 injection volumes. Our simulation results -including CO2 dissolution- exhibited 33% lower pressure build-up relative to the simulation excluding dissolution. Capillary heterogeneity helps spread the CO2 plume and facilitate early breakthrough. Formation expansivity helps alleviate pore pressure build-up. Simulation results suggest that the injection schedule adopted during the actual pilot test very likely did not affect the mechanical integrity of the storage complex. Fault reactivation requires injection volumes of at least about sixty times larger than the actual injected volume at the same injection rate. Hydraulic fracturing necessitates much larger injection rates than the ones used in the Frio pilot test. Tested rock samples exhibit ductile deformation at in-situ effective stresses. Hence, we do not expect an increase of fault permeability in the Frio sand even in the presence of fault reactivation.

Reactive transport under stress: Permeability evolution in deformable porous media

NASA Astrophysics Data System (ADS)

Roded, R.; Paredes, X.; Holtzman, R.

2018-07-01

We study reactive transport in a stressed porous media, where dissolution of the solid matrix causes two simultaneous, competing effects: pore enlargement due to chemical deformation, and pore compaction due to mechanical weakening. We use a novel, mechanistic pore-scale model to simulate flooding of a sample under fixed confining stress. Our simulations show that increasing the stress inhibits the permeability enhancement, increasing the injected volume required to reach a certain permeability, in agreement with recent experiments. We explain this behavior by stress concentration downstream, in the less dissolved (hence stiffer) outlet region. As this region is also less conductive, even its small compaction has a strong bottleneck effect that curbs the permeability. Our results also elucidate that the impact of stress depends on the dissolution regime. Under wormholing conditions (slow injection, i.e. high Damkohler number, Da), the development of a sharp dissolution front and high porosity contrast accentuates the bottleneck effect. This reduces transport heterogeneity, promoting wormhole competition. Once the outlet starts eroding, the extreme focusing of transport and hence dissolution-characteristic of wormholing-becomes dominant, diminishing the bottleneck effect and hence the impact of stress at breakthrough. In contrast, at high flow rates (low Da), incomplete reaction upstream allows some of the reactant to traverse the sample, causing a more uniform dissolution. The continuous dissolution and its partial counteraction by compaction at the outlet provides a steady, gradual increase in the effect of stress. Consequently, the impact of stress is more pronounced at high Da during early stages (low permeability), and at low Da close breakthrough. Our work promotes understanding of the interplay between dissolution and compaction and its effect on the hydromechanical property evolution, with important implications for processes ranging from diagenesis and weathering of rocks, to well stimulation and carbon sequestration.

A kinetic rate model for crystalline basalt dissolution at temperature and pressure conditions relevant for geologic CO2 sequestration

NASA Astrophysics Data System (ADS)

Pollyea, R.; Rimstidt, J. D.

2016-12-01

Geologic carbon sequestration in terrestrial basalt reservoirs is predicated on permanent CO2 trapping through CO2-water-rock dissolution reactions followed by carbonate precipitation. Bench-scale experiments have shown these reaction paths to be rapid, occurring on a timescale 100 - 102 years. Moreover, recent results from the CarbFix basalt sequestration pilot project in Iceland demonstrate >95% CO2 isolation two years after a small-scale injection. In order to assess the viability of basalt sequestration worldwide (e.g., Deccan Traps, Columbia Plateau, etc.), flexible simulation tools are required that distill the dissolution reactions into a user-friendly format that is readily transmissible to existing reactive transport numerical simulators. In the present research, we combine experimental results extant in the literature for Icelandic basalt to develop kinetic rate models describing the pH-dependent dissolution of (1) basaltic glass and (2) an aggregate mineral assemblage for crystalline basalt comprising olivine, pyroxene, and plagioclase phases. In order to utilize these kinetic rate models with numerical simulation, a thermodynamic solubility model for each phase is developed for use with the reactive transport simulation code, TOUGHREACT. We use reactive transport simulation in a simple 1-D reactor to compare dissolution of the aggregate crystalline basalt phase with the traditional formulation comprising individual mineral phases for the crystalline basalt. Simulation results are in general agreement, illustrating the efficacy of this simplified approach for modeling basalt dissolution at temperature and pressure conditions typical of geologic CO2 reservoirs. Moreover, this approach may be of value to investigators seeking dissolution models for crystalline basalt in other mafic provinces.

Metallogeny of the midcontinent rift system of North America

USGS Publications Warehouse

Nicholson, S.W.; Cannon, W.F.; Schulz, K.J.

1992-01-01

The 1.1 Ga Midcontinent rift system of North America is one of the world's major continental rifts and hosts a variety of mineral deposits. The rocks and mineral deposits of this 2000 km long rift are exposed only in the Lake Superior region. In the Lake Superior region, the rift cuts across Precambrian basement terranes ranging in age from ??? 1850 Ma to more than 3500 Ma. Where exposed, the rift consists of widespread tholeiitic basalt flows with local interlayered rhyolite and clastic sedimentary rocks. Beneath the center of Lake Superior the volcanic and sedimentary rocks are more than 30 km deep as shown by recent seismic reflection profiles. This region hosts two major classes of mineral deposits, magmatic and hydrothermal. All important mineral production in this region has come from hydrothermal deposits. Rift-related hydrothermal deposits include four main types: (1) native copper deposits in basalts and interflow sediments; (2) sediment-hosted copper sulfide and native copper; (3) copper sulfide veins and lodes hosted by rift-related volcanic and sedimentary rocks; and (4) polymetallic (five-element) veins in the surrounding Archean country rocks. The scarcity of sulfur within the rift rocks resulted in the formation of very large deposits of native metals. Where hydrothermal sulfides occur (i.e., shale-hosted copper sulfides), the source of sulfur was local sedimentary rocks. Magmatic deposits have locally supported exploration and minor production, but most are subeconomic presently. These deposits occur in intrusions exposed near the margins of the rift and include CuNiPGE and TiFe (V) in the Duluth Complex, U-REE-Nb in small carbonatites, and breccia pipes resulting from local hydrothermal activity around small felsic intrusions. Mineralization associated with some magmatic bodies resulted from the concentration of incompatible elements during fractional crystallization. Most of the sulfide deposits in intrusions, however, contain sulfur derived from country rocks; the interaction between magma and country rocks was important in generation of the magmatic CuNi sulfide deposits. A mantle plume origin has been proposed for the formation of the Midcontinent rift. More than 1 million km3 of mafic magma was erupted in the rift and a comparable volume of mafic intrusions are inferred beneath the rift, providing a ready and structurally confined supply of mafic source rocks that were available for leaching of metals by basinal brines. These brines were heated by a steep geothermal gradient that resulted from the melting and underplating of magma derived from the plume. Hydrothermal deposits were emplaced for at least 30-40 m.y. after rift magmatism and extension ceased. This time lag may reflect either the time required to heat deeply buried rocks and fluids within the rift, or may be due to the timing of post-rift compression that may have provided the driving mechanism for expulsion of hydrothermal fluids from deep portions of the rift. ?? 1992.

Magmatic evolution of lunar highland rocks estimated from trace elements in plagioclase: A new bulk silicate Moon model with sub-chondritic Ti/Ba, Sr/Ba, and Sr/Al ratios

NASA Astrophysics Data System (ADS)

Togashi, Shigeko; Kita, Noriko T.; Tomiya, Akihiko; Morishita, Yuichi

2017-08-01

The compositions of host magmas of ferroan anorthosites (FAN-host magmas) were estimated from secondary ion mass spectrometry analyses of plagioclase in lunar highland rocks. The evolution of the magmas was investigated by considering phase relations based on the MELTS algorithm and by re-examining partition coefficients for trace elements between plagioclase and melts. Data little affected by post-magmatic processes were selected by using plagioclase with relatively primitive Sc and Co contents. The FAN-host magma contained 90-174 ppm Sr, 40-119 ppm Ba and 0.5-1.3% TiO2, and had sub-chondritic Sr/Ba and Ti/Ba ratios. It is difficult to account for the formation of FAN-host magma on the basis of magma evolution processes of previously proposed bulk silicate Moon models with chondritic ratios for refractory elements at global scale. Therefore, the source of the FAN-host magma must have had primordial sub-chondritic Sr/Ba and Ti/Ba ratios. The FAN-host magmas were consistent in refractory elements with the estimated host mafic magma for feldspathic crust based on lunar meteorites, and some very-low-Ti mare rocks from lunar meteorites. Here, we propose an alternative bulk silicate Moon model (the cBSM model), which is enriched in crustal components of proto-bodies relative to the present whole Earth-Moon system.

Uranium-bearing breccia pipes of northwestern Arizona - an overview

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

Chenoweth, W.L.

During the 1950s and 1960s, the uranium deposits in breccia pipes of the Grand Canyon region were regarded as geologic curiosities. Today this area is the site of numerous exploration projects for ore-bearing pipes. The classic example of the older mines is the Orphan Lode, a patented claim within Grand Canyon National Park. Between 1956 and 1969, this deposit produced 4.26 million lb U/sub 3/O/sub 8/. Exploration since the mid-1970s has developed numerous new deposits in the Grand Canyon region. The Hack 1, 2, and 3, Pigeon, Kanab North, Canyon, and Pinenut deposits are, or will be, mined. The pipesmore » are circular and originated by dissolution of the Mississippian Redwall Limestone and collapse of the overlying strata. Uraninite ore occurs in both the pipe fill and in association with the peripheral shear zone. The principal host rocks are the Coconino Sandstone, Hermit Shale, and Esplanade Sandstone. Although small (3 to 5 million lb U/sub 3/O/sub 8/), the high grade (60 to 70% U/sub 3/O/sub 8/) of the deposits makes the pipes attractive exploration targets.« less

Excavation Induced Hydraulic Response of Opalinus Clay - Investigations of the FE-Experiment at the Mont Terri URL in Switzerland

NASA Astrophysics Data System (ADS)

Vogt, T.; Müller, H. R.; Garitte, B.; Sakaki, T.; Vietor, T.

2013-12-01

The Full-Scale Emplacement (FE) Experiment at the Mont Terri underground research laboratory in Switzerland is a full-scale heater test in a clay-rich formation (Opalinus Clay). Based on the Swiss disposal concept it simulates the construction, emplacement, backfilling, and post-closure thermo-hydro-mechanical (THM) evolution of a spent fuel / vitrified high-level waste (SF / HLW) repository tunnel in a realistic manner. The main aim of this experiment is to investigate SF / HLW repository-induced THM coupled effects mainly in the host rock but also in the engineered barrier system (EBS), which consists of bentonite pellets and blocks. A further aim is to gather experience with full-scale tunnel construction and associated hydro-mechanical (HM) processes in the host rock. The entire experiment implementation (in a 50 m long gallery with approx. 3 m diameter) as well as the post-closure THM evolution will be monitored using a network of several hundred sensors (state-of-the-art sensors and measurement systems as well as fiber-optic sensors). The sensors are distributed in the host rock's near- and far-field, the tunnel lining, the EBS, and on the heaters. The heater emplacement and backfilling has not started yet, therefore only the host rock instrumentation is installed at the moment and is currently generating data. We will present the instrumentation concept and rationale as well as the first monitoring results of the excavation and ventilation phase. In particular, we investigated the excavation induced hydraulic response of the host rock. Therefore, the spatiotemporal evolution of porewater-pressure time series was analyzed to get a better understanding of HM coupled processes during and after the excavation phase as well as the impact of anisotropic geomechanic and hydraulic properties of the clay-rich formation on its hydraulic behavior. Excavation related investigations were completed by means of inclinometer data to characterize the non-elastic and time-dependent deformations. In addition, we evaluated the effect of drainage and suction processes during the ventilation phase on the pressure distribution in the host rock. Based on our results the conceptual models of HM processes and hydraulic behavior of clay rich formations during excavation and ventilation phases could be improved.

Occurrence of Mesocestoides canislagopodis (Rudolphi, 1810) (Krabbe, 1865) in mammals and birds in Iceland and its molecular discrimination within the Mesocestoides species complex.

PubMed

Skirnisson, Karl; Jouet, Damien; Ferté, Hubert; Nielsen, Ólafur K

2016-07-01

The life cycle of Mesocestoides tapeworms (Cestoda: Cyclophyllidea: Mesocestoididae) requires three hosts. The first intermediate host is unknown but believed to be an arthropod. The second intermediate host is a vertebrate. The primary definitive host is a carnivore mammal, or a bird of prey, that eats the tetrathyridium-infected second intermediate host. One representative of the genus, Mesocestoides canislagopodis, has been reported from Iceland. It is common in the arctic fox (Vulpes lagopus) and has also been detected in domestic dogs (Canis familiaris) and cats (Felis domestica). Recently, scolices of a non-maturing Mesocestoides sp. have also been detected in gyrfalcon (Falco rusticolus) intestines, and tetrathyridia in the body cavity of rock ptarmigan (Lagopus muta). We examined the taxonomic relationship of Mesocestoides from arctic fox, gyrfalcon, and rock ptarmigan using molecular methods, both at the generic level (D1 domain LSU ribosomal DNA) and at the specific level (cytochrome c oxidase subunit I (COI) and 12S mitochondrial DNA). All stages belonged to Mesocestoides canislagopodis. Phylogenetic analysis of the combined 12S-COI at the specific level confirmed that M. canislagopodis forms a distinct clade, well separated from three other recognized representatives of the genus, M. litteratus, M. lineatus, and M. corti/vogae. This is the first molecular description of this species. The rock ptarmigan is a new second intermediate host record, and the gyrfalcon a new primary definitive host record. However, the adult stage seemed not to be able to mature in the gyrfalcon, and successful development is probably restricted to mammalian hosts.

Geologic Site Characterization of the North Korean Nuclear Test Site at Punggye-Ri: A Reconnaissance Mapping Redux

DTIC Science & Technology

2013-11-30

at the “South Portal”) is evidently located in host rock that is similar to that used in association with the latter two tests (but perhaps having... using image processing algorithms). As the authors point out: “Drainage patterns can provide substantial information on the nature of rock ... metamorphic rocks , with lesser amounts of sedimentary rocks . The metamorphic rocks are mostly schists, fewer types of gneiss, and some

Long-Term Modeling of Coupled Processes in a Generic Salt Repository for Heat-Generating Nuclear Waste: Analysis of the Impacts of Halite Solubility Constraints

NASA Astrophysics Data System (ADS)

Blanco Martin, L.; Rutqvist, J.; Battistelli, A.; Birkholzer, J. T.

2015-12-01

Rock salt is a potential medium for the underground disposal of nuclear waste because it has several assets, such as its ability to creep and heal fractures and its water and gas tightness in the undisturbed state. In this research, we focus on disposal of heat-generating nuclear waste and we consider a generic salt repository with in-drift emplacement of waste packages and crushed salt backfill. As the natural salt creeps, the crushed salt backfill gets progressively compacted and an engineered barrier system is subsequently created [1]. The safety requirements for such a repository impose that long time scales be considered, during which the integrity of the natural and engineered barriers have to be demonstrated. In order to evaluate this long-term integrity, we perform numerical modeling based on state-of-the-art knowledge. Here, we analyze the impacts of halite dissolution and precipitation within the backfill and the host rock. For this purpose, we use an enhanced equation-of-state module of TOUGH2 that properly includes temperature-dependent solubility constraints [2]. We perform coupled thermal-hydraulic-mechanical modeling and we investigate the influence of the mentioned impacts. The TOUGH-FLAC simulator, adapted for large strains and creep, is used [3]. In order to quantify the importance of salt dissolution and precipitation on the effective porosity, permeability, pore pressure, temperature and stress field, we compare numerical results that include or disregard fluids of variable salinity. The sensitivity of the results to some parameters, such as the initial saturation within the backfill, is also addressed. References: [1] Bechthold, W. et al. Backfilling and Sealing of Underground Repositories for Radioactive Waste in Salt (BAMBUS II Project). Report EUR20621 EN: European Atomic Energy Community, 2004. [2] Battistelli A. Improving the treatment of saline brines in EWASG for the simulation of hydrothermal systems. Proceedings, TOUGH Symposium 2012, Lawrence Berkeley National Laboratory, Berkeley, California, Sept. 17-19, 2012. [3] Blanco-Martín L, Rutqvist J, Birkholzer JT. Long-term modelling of the thermal-hydraulic-mechanical response of a generic salt repository for heat generating nuclear waste. Eng Geol 2015;193:198-211. doi:10.1016/j.enggeo.2015.04.014.

Deformation behaviour of feldspar in greenschist facies granitoide shear zones from the Austroalpine basement to the south of the western Tauern window, Eastern Alps

NASA Astrophysics Data System (ADS)

Hentschel, Felix; Trepmann, Claudia

2015-04-01

Objective of this study is to elucidate the feldspar deformation behaviour at greenschist facies conditions relevant for the long-term rheological properties of continental crust. Uncertainties in models for the rheological properties are partly due to a poor knowledge of the deformation mechanisms taking place in granitoid rocks at inaccessible depth. The deformation behaviour of feldspar, the most abundant mineral in the continental crust, is characterized by an interaction of brittle, dissolution-precipitation and crystal-plastic processes, which is difficult to evaluate in experiments given the problematic extrapolation of experimental conditions to reasonable natural conditions. However, microfabrics of metamorphic granitoid rocks record the grain-scale deformation mechanisms and involved chemical reactions proceeding during their geological history. This usually includes deformation and modification through several stages in space (depth, i.e., P, T conditions) and/or time. For deciphering the rock's record this implies both, challenge and chance to resolve these different stages. Here, we use the deformation record of mylonitic pegmatites from the Austroalpine basement south to the western Tauern window. The structural, crystallographic and chemical characteristics of the feldspar microfabrics are determined via micro-analytical techniques (polarized light microscopy, scanning electron microscopy, SEM, electron back scatter diffraction, EBSD) to identify the relevant deformation mechanisms and deformation conditions. The pegmatites represent a relatively simple Ca-poor granitoid system, mineralogically dominated by albite-rich plagioclase, K-feldspar and quartz. The matrix of the mylonitic pegmatites is composed of alternating monomineralic albite and quartz ribbons defining the foliation. Fragmented tourmaline and K-feldspar porphyroclasts occur isolated within the matrix. At sites of dilation along the stretching lineation K-feldspar porphyroclasts show serrated boundaries to matrix albite grains. In intragranular zones within K-feldspar porphyroclasts, small albite but also K-feldspar grains and "subgrains" (K-feldspar domains with a small misorientation angle to the host K-feldspar porphyroclast) occur. Strain shadows around porphyroclasts are composed of polymineralic aggregates of albite, K-feldspar and quartz. The albite grains in ribbons show a shape preferred orientation (SPO) with a long axis of about 50-100 µm in the foliation plane and EBSD data reveal an absent to very weak crystallographic orientation (CPO). These microfabrics show indication of a sequence of brittle behaviour, localized dislocation glide-controlled deformation and dissolution-precipitation creep of feldspar. Monomineralic quartz ribbons and shear bands show evidence of dislocation glide by a pronounced CPO, implying dislocation creep. The microfabric is interpreted to have evolved during different stages of episodic deformation at transient high stresses with subsequent viscous flow at decreasing stresses.

Geochemistry of the acid Kawah Putih lake, Patuha Volcano, West Java, Indonesia

NASA Astrophysics Data System (ADS)

Sriwana, T.; van Bergen, M. J.; Varekamp, J. C.; Sumarti, S.; Takano, B.; van Os, B. J. H.; Leng, M. J.

2000-04-01

Kawah Putih is a summit crater of Patuha volcano, West Java, Indonesia, which contains a shallow, ∼300 m-wide lake with strongly mineralized acid-sulfate-chloride water. The lake water has a temperature of 26-34°C, pH=<0.5-1.3, Stot=2500-4600 ppm and Cl=5300-12 600 ppm, and floating sulfur globules with sulfide inclusions are common. Sulfur oxyanion concentrations are unusually high, with S4O62-+S5O62-+S6O62-=2400 - 4200 ppm. Subaerial fumaroles (<93°C) on the lake shore have low molar SO2/H2S ratios (<2), which is a favorable condition to produce the observed distribution of sulfur oxyanion species. Sulfur isotope data of dissolved sulfate and native sulfur show a significant 34S fractionation (ΔSO4-Se of ⩾20‰), probably the result of SO2 disproportionation in or below the lake. The lake waters show strong enrichments in 18O and D relative to local meteoric waters, a result of the combined effects of mixing between isotopically heavy fluids of deep origin and meteoric water, and evaporation-induced fractionation at the lake surface. The stable-isotope systematics combined with energy-balance considerations support very rapid fluid cycling through the lake system. Lake levels and element concentrations show strong seasonal fluctuations, indicative of a short water residence time in the lake as well. Thermodynamic modeling of the lake fluids indicates that the lake water is saturated with silica phases, barite, pyrite and various Pb, Sb, Cu, As, Bi-bearing sulfides when sulfur saturation is assumed. Precipitating phases predicted by the model calculations are consistent with the bulk chemistry of the sulfur-rich bottom sediments and their identified mineral phases. Much of the lake water chemistry can be explained by congruent rock dissolution in combination with preferential enrichments from entering fumarolic gases or brines and element removal by precipitating mineral phases, as indicated by a comparison of the fluids, volcanic rocks and lake bed sediment. Flank springs on the mountain at different elevations vary in composition, and are consistent with local rock dissolution as a dominant factor and pH-dependent element mobility. Discharges of warm sulfate- and chloride-rich water at the highest elevation and a near-neutral spring at lower level may contain a small contribution of crater-lake water. The acid fluid-induced processes at Patuha have led to the accumulation of elements that are commonly associated with volcano-hosted epithermal ore deposits. The dispersal of heavy metals and other potentially toxic elements from the volcano via the local drainage system is a matter of serious environmental concern.

Mineral storage of CO2/H2S gas mixture injection in basaltic rocks

NASA Astrophysics Data System (ADS)

Clark, D. E.; Gunnarsson, I.; Aradottir, E. S.; Oelkers, E. H.; Sigfússon, B.; Snæbjörnsdottír, S. Ó.; Matter, J. M.; Stute, M.; Júlíusson, B. M.; Gíslason, S. R.

2017-12-01

Carbon capture and storage is one solution to reducing CO2 emissions in the atmosphere. The long-term geological storage of buoyant supercritical CO2 requires high integrity cap rock. Some of the risk associated with CO2 buoyancy can be overcome by dissolving CO2 into water during its injection, thus eliminating its buoyancy. This enables injection into fractured rocks, such as basaltic rocks along oceanic ridges and on continents. Basaltic rocks are rich in divalent cations, Ca2+, Mg2+ and Fe2+, which react with CO2 dissolved in water to form stable carbonate minerals. This possibility has been successfully tested as a part of the CarbFix CO2storage pilot project at the Hellisheiði geothermal power plant in Iceland, where they have shown mineralization occurs in less than two years [1, 2]. Reykjavik Energy and the CarbFix group has been injecting a mixture of CO2 and H2S at 750 m depth and 240-250°C since June 2014; by 1 January 2016, 6290 tons of CO2 and 3530 tons of H2S had been injected. Once in the geothermal reservoir, the heat exchange and sufficient dissolution of the host rock neutralizes the gas-charged water and saturates the formation water respecting carbonate and sulfur minerals. A thermally stable inert tracer was also mixed into the stream to monitor the subsurface transport and to assess the degree of subsurface carbonation and sulfide precipitation [3]. Water and gas samples have been continuously collected from three monitoring wells and geochemically analyzed. Based on the results, mineral saturation stages have been defined. These results and tracer mass balance calculations are used to evaluate the rate and magnitude of CO2 and H2S mineralization in the subsurface, with indications that mineralization of carbon and sulfur occurs within months. [1] Gunnsarsson, I., et al. (2017). Rapid and cost-effective capture and subsurface mineral storage of carbon and sulfur. Manuscript submitted for publication. [2] Matter, J., et al. (2016). Rapid carbon mineralization for permanent disposal of anthropogenic carbon dioxide emissions. Science 352 (6291), 1312-1314. [3] Snæbjörnsdottír, S.O., et al. (2017). The chemistry and saturation states of subsurface fluids during the in-situ mineralisation of CO2 and H2S at the CarbFix site in SW-Iceland. International Journal of Greenhouse Gas Control 58, 87-102.

Generation, migration, and entrapment of Precambrian oils in the Eastern Flank Heavy Oil province, south Oman

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

Konert, G.; Van Den Brink, H.A.; Visser, W.

1991-08-01

The prolific Eastern Flank Heavy Oil province east of the South Oman Salt basin is unique because of the widespread occurrence of Precambrian source rocks from which the hydrocarbons originated. Fission-track analysis and burial studies suggest that most of these source rocks became mature and generated hydrocarbons in the Ordovician; subsequently, the source beds were uplifted and did not re-enter the oil window. Its uniqueness is also based on the all-important role played by Precambrian salt. The traps in Palaeozoic clastics were initially structured by halokinesis, and subsequently by salt dissolution. The latter process gradually removed the salt from themore » area is largely responsible for the present-day structure with palaeo-withdrawal basins inverted in present-day turtles. Present-day traps are mainly post-Late Jurassic in age, significantly post-dating the time of oil generation. Detailed field studies indicate that charge phases appear to correlate with periods of increased salt dissolution in the Late Jurassic-Early Cretaceous, Late Cretaceous, and Tertiary. Oil was probably stored in intermediate traps below and within the salt. It was gradually released upon progressive tilting of the basin flank; it migrated updip toward the basinward retreating salt edge, and subsequently (back) spilled into the stratigraphically younger traps. Also, removal of the top seal of intra-salt and sub-salt traps by salt dissolution allowed upward remigration. It follows that charge concepts in the Eastern Flank Heavy Oil province depend on defining salt-edge-related hydrocarbon release areas, rather than on kitchen modeling.« less

From conservative to reactive transport under diffusion-controlled conditions

NASA Astrophysics Data System (ADS)

Babey, Tristan; de Dreuzy, Jean-Raynald; Ginn, Timothy R.

2016-05-01

We assess the possibility to use conservative transport information, such as that contained in transit time distributions, breakthrough curves and tracer tests, to predict nonlinear fluid-rock interactions in fracture/matrix or mobile/immobile conditions. Reference simulated data are given by conservative and reactive transport simulations in several diffusive porosity structures differing by their topological organization. Reactions includes nonlinear kinetically controlled dissolution and desorption. Effective Multi-Rate Mass Transfer models (MRMT) are calibrated solely on conservative transport information without pore topology information and provide concentration distributions on which effective reaction rates are estimated. Reference simulated reaction rates and effective reaction rates evaluated by MRMT are compared, as well as characteristic desorption and dissolution times. Although not exactly equal, these indicators remain very close whatever the porous structure, differing at most by 0.6% and 10% for desorption and dissolution. At early times, this close agreement arises from the fine characterization of the diffusive porosity close to the mobile zone that controls fast mobile-diffusive exchanges. At intermediate to late times, concentration gradients are strongly reduced by diffusion, and reactivity can be captured by a very limited number of rates. We conclude that effective models calibrated solely on conservative transport information like MRMT can accurately estimate monocomponent kinetically controlled nonlinear fluid-rock interactions. Their relevance might extend to more advanced biogeochemical reactions because of the good characterization of conservative concentration distributions, even by parsimonious models (e.g., MRMT with 3-5 rates). We propose a methodology to estimate reactive transport from conservative transport in mobile-immobile conditions.

Host rocks and their alterations as related to uranium-bearing veins in the United States

USGS Publications Warehouse

Walker, George W.

1956-01-01

This paper, dealing with the different kinds of host rocks and their alterations associated with uranium-bearing veins in the United States, is a chapter of a comprehensive report entitled , "Geology of uranium-bearing vein deposits in the United States," in preparation by George W. Walker, Frank W. Osterwald, and others. The comprehensive report will include detailed information on tectonic and structural setting, kinds of host rocks, wall-rock alteration, mineralogy, physical characteristics, processes of deposition, and concepts of origin of uraniferous veins; but, because it will not be completed until sometime in the future, some chapters of the report are being transmitted as they are finished. Part of an introductory chapter to the comprehensive report entitled, "Classification and distribution of uranium-bearing veins in the United States" (Walker and Osterwald, 1956) has already been transmitted; several of the terms used herein are defined in the introductory chapter. Data included in this chapter demonstrate that uranium-bearing veins are: 1) in rocks of nearly all textural, chemical, and mineralogic types; 2) most abundant in holocrystalline, commonly equigranular, igeneous and metamorphic rocks characterized by a moderate to high silica content and and by similar physical properties. Although some of the physiochemical properties of the host rocks are discussed in terms of favorability or nonfavoribility for uranium deposition, the principal purpose of this chapter is to establish the petroloic environment in which uranium-bearing veins have been found. Because favorability or nonfavorability of host rocks is related complexly to the chemistry of ore solutions and to methods or uranium transport and deposition, several hypothetical processes of transport and deposition have been referred to briefly; these and other hypotheses will be outlines and discussed in greater detail in a subsequent chapter. The compilation of data leading to this report and its preparation by a member of the Uranium Research and Resource Section, U.S. Geological Survey, was done on behalf of the Division of Raw Materials, U.S. Atomic Energy Commission. The report is based on both published and unpublished information collected principally by personnel of the U.S. Geological Survey, the U.S. Atomic Energy Commission or its predecessor organization, the Manhattan Engineer District, and to a lesser extent by staff members of other Federal or State agencies and by geologists in private industry. Information concerning foreign uranium-bearing vein deposits has been extracted almost exclusively from published reports; references to these and other data are included at appropriate places.

Carbonate mineral dissolution kinetics in high pressure experiments

NASA Astrophysics Data System (ADS)

Dethlefsen, F.; Dörr, C.; Schäfer, D.; Ebert, M.

2012-04-01

The potential CO2 reservoirs in the North German Basin are overlain by a series of Mesozoic barrier rocks and aquifers and finally mostly by Tertiary and Quaternary close-to-surface aquifers. The unexpected rise of stored CO2 from its reservoir into close-to-surface aquifer systems, perhaps through a broken well casing, may pose a threat to groundwater quality because of the acidifying effect of CO2 dissolution in water. The consequences may be further worsening of the groundwater quality due to the mobilization of heavy metals. Buffer mechanisms counteracting the acidification are for instance the dissolution of carbonates. Carbonate dissolution kinetics is comparably fast and carbonates can be abundant in close-to-surface aquifers. The disadvantages of batch experiments compared to column experiments in order to determine rate constants are well known and have for instance been described by v. GRINSVEN and RIEMSDIJK (1992). Therefore, we have designed, developed, tested, and used a high-pressure laboratory column system to simulate aquifer conditions in a flow through setup within the CO2-MoPa project. The calcite dissolution kinetics was determined for CO2-pressures of 6, 10, and 50 bars. The results were evaluated by using the PHREEQC code with a 1-D reactive transport model, applying a LASAGA (1984) -type kinetic dissolution equation (PALANDRI and KHARAKA, 2004; eq. 7). While PALANDRI and KHARAKA (2004) gave calcite dissolution rate constants originating from batch experiments of log kacid = -0.3 and log kneutral = -5.81, the data of the column experiment were best fitted using log kacid = -2.3 and log kneutral = -7.81, so that the rate constants fitted using the lab experiment applying 50 bars pCO2 were approximately 100 times lower than according to the literature data. Rate constants of experiments performed at less CO2 pressure (pCO2 = 6 bars: log kacid = -1.78; log kneutral = -7.29) were only 30 times lower than literature data. These discrepancies in the reaction kinetics should be acknowledged when using reactive transport models, especially when modeling kinetically controlled pH-buffering processes between a CO2 leakage an a receptor like a ground water well. Currently, further experiments for the determination of the dolomite dissolution kinetics are being performed. Here, the knowledge of the dissolution rate constants can be even more important compared to the (still) fast calcite dissolution. This study is being funded by the German Federal Ministry of Education and Research (BMBF), EnBW Energie Baden-Württemberg AG, E.ON Energie AG, E.ON Gas Storage AG, RWE Dea AG, Vattenfall Europe Technology Research GmbH, Wintershall Holding AG and Stadtwerke Kiel AG as part of the CO2-MoPa joint project in the framework of the Special Program GEOTECHNOLOGIEN. Literature Lasaga, A. C., 1984. Chemical Kinetics of Water-Rock Interactions. Journal of Geophysical Research 89, 4009-4025. Palandri, J. L. and Kharaka, Y. K., 2004. A compilation of rate parameters of water-mineral interaction kinetics for application to geochemical modeling. USGS, Menlo Park, CA, USA. v. Grinsven, J. J. M. and Riemsdijk, W. H., 1992. Evaluation of batch and column techniques to measure weathering rates in soils. Geoderma 52, 41-57.

A relationship between porosity and permeability of carbonate rock reservoirs

NASA Astrophysics Data System (ADS)

Lee, J.; Park, Y.; Jo, Y.; Jeong, J.; Eom, S.

2009-12-01

Most of oil reservoirs in the world occur in carbonate rocks. Thus, characterization of the carbonate reservoirs, including understanding the correlation between porosity and permeability is essentially required to enhance oil recovery. Compared with the other sedimentary rocks such as sandstone and shale, the carbonate rocks would exhibit a wide variety of vertical and horizontal heterogeneities. In general, pores of the carbonate rocks can be affected by mineral dissolution, replacement by other minerals and re-crystallization, which are the post-depositional processes. Permeability has been estimated at a wide scale by thin section image analysis, rock core experiments, geophysical well logging data and large scale aquifer tests. For the same porosity, the permeability might show a wide variation. In this study, a large number of the porosity and the permeability data pairs for world wide carbonate rocks (reservoirs) were collected from many literatures. The porosity and permeability data were grouped according to test scale, the reservoir location and the rock types. As is already known, the relation showed a rather scattered distribution also in this study, not monotonous, which indicates that higher porosity does not mean higher permeability of the rock formation. This study provides the analysis results and implications for oil production of the carbonate reservoirs. This research was funded by Energy Efficiency and Resources Program of KETEP (Korea Institute of Energy Technology Evaluation and Planning), Grant No. 2009T100200058.

Bioremediation in fractured rock: 2. Mobilization of chloroethene compounds from the rock matrix

USGS Publications Warehouse

Shapiro, Allen M.; Tiedeman, Claire; Imbrigiotta, Thomas; Goode, Daniel J.; Hsieh, Paul A.; Lacombe, Pierre; DeFlaun, Mary F.; Drew, Scott R.; Curtis, Gary P.

2018-01-01

A mass balance is formulated to evaluate the mobilization of chlorinated ethene compounds (CE) from the rock matrix of a fractured mudstone aquifer under pre- and postbioremediation conditions. The analysis relies on a sparse number of monitoring locations and is constrained by a detailed description of the groundwater flow regime. Groundwater flow modeling developed under the site characterization identified groundwater fluxes to formulate the CE mass balance in the rock volume exposed to the injected remediation amendments. Differences in the CE fluxes into and out of the rock volume identify the total CE mobilized from diffusion, desorption, and nonaqueous phase liquid dissolution under pre- and postinjection conditions. The initial CE mass in the rock matrix prior to remediation is estimated using analyses of CE in rock core. The CE mass mobilized per year under preinjection conditions is small relative to the total CE mass in the rock, indicating that current pump-and-treat and natural attenuation conditions are likely to require hundreds of years to achieve groundwater concentrations that meet regulatory guidelines. The postinjection CE mobilization rate increased by approximately an order of magnitude over the 5 years of monitoring after the amendment injection. This rate is likely to decrease and additional remediation applications over several decades would still be needed to reduce CE mass in the rock matrix to levels where groundwater concentrations in fractures achieve regulatory standards.

Experimental Study of Porosity Changes in Shale Caprocks Exposed to Carbon Dioxide-Saturated Brine II: Insights from Aqueous Geochemistry

DOE PAGES

Miller, Quin R. S.; Wang, Xiuyu; Kaszuba, John P.; ...

2016-07-18

Laboratory experiments evaluated two shale caprock formations, the Gothic Shale and Marine Tuscaloosa Formation, at conditions relevant to carbon dioxide (CO 2) sequestration. Both rocks were exposed to CO 2-saturated brines at 160°C and 15 MPa for ~45 days. Baseline experiments for both rocks were pressurized with argon to 15 MPa for ~35 days. Varying concentrations of iron, aqueous silica, sulfate, and initial pH decreases coincide with enhanced carbonate and silicate dissolution due to reaction between CO 2-saturated brine and shale. Saturation indices were calculated and activity diagrams were constructed to gain insights into sulfate, silicate, and carbonate mineral stabilities.more » We found that upon exposure to CO 2-saturated brines, the Marine Tuscaloosa Formation appeared to be more reactive than the Gothic Shale. Evolution of aqueous geochemistry in the experiments is consistent with mineral precipitation and dissolution reactions that affect porosity. Finally, this study highlights the importance of tracking fluid chemistry to clarify downhole physicochemical responses to CO 2 injection and subsequent changes in sealing capacity in CO 2 storage and utilization projects.« less

Basic data report for drillhole WIPP 30 (Waste Isolation Pilot Plant - WIPP)

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

Not Available

1980-04-01

WIPP 30 was drilled in east-central Eddy County, New Mexico, in NW 1/4, Sec. 33, T21S, R31E, to obtain drill core for the study of dissolution of near-surface rocks. The borehole encountered from top to bottom, the Dewey Lake Red Beds (449' including artificial fill for drill pad), Rustler Formation (299'), and the upper 160' of the Salado Formation. Continuous core was cut from the surface to total depth. Geophysical logs were taken the full length of the borehole to measure acoustic velocities, density, and distribution of potassium and other radioactive elements. Information from this borehole will be included inmore » an interpretive report on dissolution in Nash Draw based on combined borehole data, surface mapping and laboratory analyses of rocks and fluids. The WIPP is to demonstrate (through limited operations) disposal technology for transuranic defense wastes and to then be converted to a repository. The WIPP will also provide research facilities for interactions between high-level waste and salt. Administration policy as of February 1980 is to hold the WIPP site in reserve until the first disposal site can be chosen from several potential sites, including the WIPP.« less

Conceptual model analysis of interaction at a concrete-Boom Clay interface

NASA Astrophysics Data System (ADS)

Liu, Sanheng; Jacques, Diederik; Govaerts, Joan; Wang, Lian

In many concepts for deep disposal of high-level radioactive waste, cementitious materials are used in the engineered barriers. For example, in Belgium the engineered barrier system is based on a considerable amount of cementitious materials as buffer and backfill in the so-called supercontainer embedded in the hosting geological formation. A potential hosting formation is Boom Clay. Insight in the interaction between the high-pH pore water of the cementitious materials and neutral-pH Boom Clay pore water is required. Two problems are quite common for modeling of such a system. The first one is the computational cost due to the long timescale model assessments envisaged for the deep disposal system. Also a very fine grid (in sub-millimeter), especially at interfaces has to be used in order to accurately predict the evolution of the system. The second one is whether to use equilibrium or kinetic reaction models. The objectives of this paper are twofold. First, we develop an efficient coupled reactive transport code for this diffusion-dominated system by making full use of multi-processors/cores computers. Second, we investigate how sensitive the system is to chemical reaction models especially when pore clogging due to mineral precipitation is considered within the cementitious system. To do this, we selected two portlandite dissolution models, i.e., equilibrium (fastest) and diffusion-controlled model with precipitation of a calcite layer around portlandite particles (diffusion-controlled dissolution). The results show that with shrinking core model portlandite dissolution and calcite precipitation are much slower than with the equilibrium model. Also diffusion-controlled dissolution smooths out dissolution fronts compared to the equilibrium model. However, only a slight difference with respect to the clogging time can be found even though we use a very small diffusion coefficient (10-20 m2/s) in the precipitated calcite layer.

Sulfur mass-independent fractionation in subsurface fracture waters indicates a long-standing sulfur cycle in Precambrian rocks.

PubMed

Li, L; Wing, B A; Bui, T H; McDermott, J M; Slater, G F; Wei, S; Lacrampe-Couloume, G; Lollar, B Sherwood

2016-10-27

The discovery of hydrogen-rich waters preserved below the Earth's surface in Precambrian rocks worldwide expands our understanding of the habitability of the terrestrial subsurface. Many deep microbial ecosystems in these waters survive by coupling hydrogen oxidation to sulfate reduction. Hydrogen originates from water-rock reactions including serpentinization and radiolytic decomposition of water induced by decay of radioactive elements in the host rocks. The origin of dissolved sulfate, however, remains unknown. Here we report, from anoxic saline fracture waters ∼2.4 km below surface in the Canadian Shield, a sulfur mass-independent fractionation signal in dissolved sulfate. We demonstrate that this sulfate most likely originates from oxidation of sulfide minerals in the Archaean host rocks through the action of dissolved oxidants (for example, HO · and H 2 O 2 ) themselves derived from radiolysis of water, thereby providing a coherent long-term mechanism capable of supplying both an essential electron donor (H 2 ) and a complementary acceptor (sulfate) for the deep biosphere.

Wind Carved Rock

NASA Image and Video Library

2016-10-19

The distinctively fluted surface and elongated hills in this image in Medusae Fossae are caused by wind erosion of a soft fine-grained rock. Called yardangs, these features are aligned with the prevailing wind direction. This wind direction would have dominated for a very long time to carve these large-scale features into the exposed rock we see today. Yardangs not only reveal the strength and direction of historic winds, but also reveal something of the host rock itself. Close inspection by HiRISE shows an absence of boulders or rubble, especially along steep yardang cliffs and buttresses. The absence of rubble and the scale of the yardangs tells us that the host rock consists only of weakly cemented fine granules in tens of meters or more thick deposits. Such deposits could have come from extended settling of volcanic ash, atmospheric dust, or accumulations of wind deposited fine sands. After a time these deposits became cemented and cohesive, illustrated by the high standing relief and exposed cliffs. http://photojournal.jpl.nasa.gov/catalog/PIA21111

Sulfur mass-independent fractionation in subsurface fracture waters indicates a long-standing sulfur cycle in Precambrian rocks

PubMed Central

Li, L.; Wing, B. A.; Bui, T. H.; McDermott, J. M.; Slater, G. F.; Wei, S.; Lacrampe-Couloume, G.; Lollar, B. Sherwood

2016-01-01

The discovery of hydrogen-rich waters preserved below the Earth's surface in Precambrian rocks worldwide expands our understanding of the habitability of the terrestrial subsurface. Many deep microbial ecosystems in these waters survive by coupling hydrogen oxidation to sulfate reduction. Hydrogen originates from water–rock reactions including serpentinization and radiolytic decomposition of water induced by decay of radioactive elements in the host rocks. The origin of dissolved sulfate, however, remains unknown. Here we report, from anoxic saline fracture waters ∼2.4 km below surface in the Canadian Shield, a sulfur mass-independent fractionation signal in dissolved sulfate. We demonstrate that this sulfate most likely originates from oxidation of sulfide minerals in the Archaean host rocks through the action of dissolved oxidants (for example, HO· and H2O2) themselves derived from radiolysis of water, thereby providing a coherent long-term mechanism capable of supplying both an essential electron donor (H2) and a complementary acceptor (sulfate) for the deep biosphere. PMID:27807346

Air and groundwater flow at the interface between fractured host rock and a bentonite buffer

NASA Astrophysics Data System (ADS)

Dessirier, B.; Jarsjo, J.; Frampton, A.

2014-12-01

Designs of deep geological repositories for spent nuclear fuel include several levels of confinement. The Swedish and Finnish concept KBS-3 targets for example sparsely fractured crystalline bedrock as host formation and would have the waste canisters embedded in an engineered buffer of compacted MX-80 bentonite. The host rock is a highly heterogeneous dual porosity material containing fractures and a rock matrix. Bentonite is a complex expansive porous material. Its water content and mechanical properties are interdependent. Beyond the specific physics of unsaturated flow and transport in each medium, the interface between them is critical. Detailed knowledge of the transitory two-phase flow regime, induced by the insertion of the unsaturated buffer in a saturated rock environment, is necessary to assess the performance of planned KBS-3 deposition holes. A set of numerical simulations based on the equations of two-phase flow for water and air in porous media were conducted to investigate the dynamics of air and groundwater flow near the rock/bentonite interface in the period following installation of the unsaturated bentonite buffer. We assume state of the two-phase flow parameter values for bentonite from laboratory water uptake tests and typical fracture and rock properties from the Äspö Hard rock laboratory (Sweden) gathered under several field characterization campaigns. The results point to desaturation of the rock domain as far as 10 cm away from the interface into matrix-dominated regions for up to 160 days. Similar observations were made during the Bentonite Rock Interaction Experiment (BRIE) at the Äspö HRL, with a desaturation sustained for even longer times. More than the mere time to mechanical and hydraulic equilibrium, the occurrence of sustained unsaturated conditions opens the possibility for biogeochemical processes that could be critical in the safety assessment of the planned repository.

Septate-tubular textures in 2.0-Ga pillow lavas from the Pechenga Greenstone Belt: a nano-spectroscopic approach to investigate their biogenicity.

PubMed

Fliegel, D; Wirth, R; Simonetti, A; Furnes, H; Staudigel, H; Hanski, E; Muehlenbachs, K

2010-12-01

Pillow lava rims and interpillow hyaloclastites from the upper part of the Pechenga Greenstone Belt, Kola Peninsula, N-Russia contain rare tubular textures 15-20 μm in diameter and up to several hundred μm long in prehnite-pumpellyite to lower greenschist facies meta-volcanic glass. The textures are septate with regular compartments 5-20 μm across and exhibit branching, stopping and no intersecting features. Synchrotron micro-energy dispersive X-ray was used to image elemental distributions; scanning transmission X-ray microscopy, Fe L-edge and C K-edge were used to identify iron and carbon speciation at interfaces between the tubular textures and the host rock. In situ U-Pb radiometric dating by LA-MC-ICP-MS (laser ablation multicollector inductively coupled plasma mass spectrometry) of titanite from pillow lavas yielded a metamorphic age of 1790 ± 89 Ma. Focused ion-beam milling combined with transmission electron microscopy was used to analyze the textures in three dimensions. Electron diffraction showed that the textures are mineralized by orientated pumpellyite. On the margins of the tubes, an interface between mica or chlorite and the pumpellyite shows evidence of dissolution reactions where the pumpellyite is replaced by mica/chlorite. A thin poorly crystalline Fe-phase, probably precipitated out of solution, occurs at the interface between pumpellyite and mica/chlorite. This sequence of phases leads to the hypothesis that the tubes were initially hollow, compartmentalized structures in volcanic glass that were mineralized by pumpellyite during low-grade metamorphism. Later, a Fe-bearing fluid mineralized the compartments between the pumpellyite and lastly the pumpellyite was partially dissolved and replaced by chlorite during greenschist metamorphism. The most plausible origin for a septate-tubular texture is a progressive etching of the host matrix by several generations of microbes and subsequently these tubes were filled by authigenic mineral precipitates. This preserves the textures in the rock record over geological time. The micro textures reported here thus represent a pumpellyite-mineralized trace fossil that records a Paleoproterozoic sub-seafloor biosphere. © 2010 Blackwell Publishing Ltd.

Fault-zone structure and weakening processes in basin-scale reverse faults: The Moonlight Fault Zone, South Island, New Zealand

NASA Astrophysics Data System (ADS)

Alder, S.; Smith, S. A. F.; Scott, J. M.

2016-10-01

The >200 km long Moonlight Fault Zone (MFZ) in southern New Zealand was an Oligocene basin-bounding normal fault zone that reactivated in the Miocene as a high-angle reverse fault (present dip angle 65°-75°). Regional exhumation in the last c. 5 Ma has resulted in deep exposures of the MFZ that present an opportunity to study the structure and deformation processes that were active in a basin-scale reverse fault at basement depths. Syn-rift sediments are preserved only as thin fault-bound slivers. The hanging wall and footwall of the MFZ are mainly greenschist facies quartzofeldspathic schists that have a steeply-dipping (55°-75°) foliation subparallel to the main fault trace. In more fissile lithologies (e.g. greyschists), hanging-wall deformation occurred by the development of foliation-parallel breccia layers up to a few centimetres thick. Greyschists in the footwall deformed mainly by folding and formation of tabular, foliation-parallel breccias up to 1 m wide. Where the hanging-wall contains more competent lithologies (e.g. greenschist facies metabasite) it is laced with networks of pseudotachylyte that formed parallel to the host rock foliation in a damage zone extending up to 500 m from the main fault trace. The fault core contains an up to 20 m thick sequence of breccias, cataclasites and foliated cataclasites preserving evidence for the progressive development of interconnected networks of (partly authigenic) chlorite and muscovite. Deformation in the fault core occurred by cataclasis of quartz and albite, frictional sliding of chlorite and muscovite grains, and dissolution-precipitation. Combined with published friction and permeability data, our observations suggest that: 1) host rock lithology and anisotropy were the primary controls on the structure of the MFZ at basement depths and 2) high-angle reverse slip was facilitated by the low frictional strength of fault core materials. Restriction of pseudotachylyte networks to the hanging-wall of the MFZ further suggests that the wide, phyllosilicate-rich fault core acted as an efficient hydrological barrier, resulting in a relatively hydrous footwall and fault core but a relatively dry hanging-wall.

Experimentally determined rock-fluid interactions applicable to a natural hot dry rock geothermal system

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

Charles, R.W.; Holley, C.E. Jr.; Tester, J.W.

1980-02-01

The Los Alamos Scientific Laboratory is pursuing laboratory and field experiments in the development of the Hot Dry Rock concept of geothermal energy. The field program consists of experiments in a hydraulically fractured region of low permeability in which hot rock is intercepted by two wellbores. These experiments are designed to test reservoir engineering parameters such as: heat extraction rates, water loss rates, flow characteristics including impedance and buoyancy, seismic activity and fluid chemistry. Laboratory experiments have been designed to provide information on the mineral reactivity which may be encountered in the field program. Two experimental circulation systems have beenmore » built to study the rates of dissolution and alteration in dynamic flow. Solubility studies have been done in agitated systems. To date, pure minerals, samples of the granodiorite from the actual reservoir and Tijeras Canyon granite have been reacted with distilled water and various solutions of NaCl, NaOH, and Na/sub 2/CO/sub 3/. The results of these experimental systems are compared to observations made in field experiments done in a hot dry rock reservoir at a depth of approximately 3 km with initial rock temperatures of 150 to 200/sup 0/C.« less

Lithogeochemical character of near-surface bedrock in the New England coastal basins

USGS Publications Warehouse

Robinson, Gilpin R.; Ayotte, Joseph D.; Montgomery, Denise L.; DeSimone, Leslie A.

2002-01-01

This geographic information system (GIS) data layer shows the generalized lithologic and geochemical, termed lithogeochemical, character of near-surface bedrock in the New England Coastal Basin (NECB) study area of the U.S. Geological Survey's National Water Quality Assessment (NAWQA) Program. The area encompasses 23,000 square miles in western and central Maine, eastern Massachusetts, most of Rhode Island, eastern New Hampshire and a small part of eastern Connecticut. The NECB study area includes the Kennebec, Androscoggin, Saco, Merrimack, Charles, and Blackstone River Basins, as well as all of Cape Cod. Bedrock units in the NECB study area are classified into lithogeochemical units based on the relative reactivity of their constituent minerals to dissolution and the presence of carbonate or sulfide minerals. The 38 lithogeochemical units are generalized into 7 major groups: (1) carbonate-bearing metasedimentary rocks; (2) primarily noncalcareous, clastic sedimentary rocks with restricted deposition in discrete fault-bounded sedimentary basins of Mississipian or younger age; (3) primarily noncalcareous, clastic sedimentary rocks at or above biotite-grade of regional metamorphism; (4) mafic igneous rocks and their metamorphic equivalents; (5) ultramafic rocks; (6) felsic igneous rocks and their metamorphic equivalents; and (7) unconsolidated and poorly consolidated sediments.

Garnet and clinopyroxene pseudomorphs: example of local mass balance in the Caledonides of western Norway.

NASA Astrophysics Data System (ADS)

Centrella, Stephen; Austrheim, Håkon; Putnis, Andrew

2015-04-01

The Precambrian granulite facies rocks of Lindås Nappe, Bergen Arcs, Caledonides of W.Norway are partially hydrated at amphibolites and eclogite facies conditions. The Lindås Nappe outcrop over an area of ca 1000 km2 where relict granulite facies lenses make up only ca 10%. At Hillandsvatnet, garnetite displays sharp hydration fronts across which the granulite facies assemblage composed of garnet (70%) and clinopyroxene (30%) is replaced by an amphibolite facies mineralogy defined by chlorite, epidote and amphibole. This setting allows us to assess the mechanism of fluid transport through an initially low permeability rock and how this induces changes of texture and element transport. The replacement of garnet and clinopyroxene is pseudomorphic so that the grain shapes of the garnet and clinopyroxene are preserved even if when they are completely replaced. This requires that the reactive fluids must pass through the solid crystal grains and this can be achieved by an interface coupled dissolution-precipitation mechanism. Porosity generation is a key feature of this mechanism (Putnis and Austrheim 2012). The porosity is not only a consequence of reduction in solid molar volume but depends on the relative solubilities of parent and product phases in the reactive fluid. Putnis et al. 2007 and Xia et al. 2009 have shown that even in pseudomorphic reactions where the molar volume increases, porosity may still be generated by the reaction. This is fundamental in understanding the element mobility and the mass transfer in a low permeability rock even more when the bulk rock composition of these two rocks stay unchanged; except a gain in water during amphibolitisation. The textural evolution during the replacement of garnet by pargasite, epidote and chlorite and pyroxene by hornblende and quartz in our rock sample conforms to that expected by a coupled dissolution-precipitation mechanism. SEM and Microprobe analysis coupled with the software XMapTools V 1.06.1 .(Lanari et al., 2014) were used to quantify the local mass transfer required during the replacement processes and to identify the importance of fluid in metamorphic reactions. Lanari, P., Vidal, O., Andrade, V. de, Dubacq, B., Lewin, E., Grosch, E.G., and Schwartz, S., 2014, XMapTools: A MATLAB©-based program for electron microprobe X-ray image processing and geothermobarometry. In: Computers & Geosciences, v. 62, p. 227-240. Putnis A, Austrheim H (2012) Mechanisms of metasomatism and metamorphism on the local mineral scale: The role of dissolution-reprecipitation during mineral re-equilibration. In: Metasomatism and the chemical transformation of rock; the role of fluids in terrestrial and extraterrestrial processes, Springer pp 141-170. Putnis A, Putnis CV (2007) The mechanism of reequilibration of solids in the presence of a fluid phase. J Solid State Chem 180: 1783-1786. Xia F, Brugger J, Chen G, Ngothai Y, O'Neill B, Putnis A, Pring A (2009) Mechanism and kinetics of pseudomorphic mineral replacement reactions: a case study of the replacement of pentlandite by violarite, Geochim Cosmochim Acta 73: 1945-1969. ase fill in your abstract text.

Jarosite dissolution rates in perchlorate brine

NASA Astrophysics Data System (ADS)

Legett, Carey; Pritchett, Brittany N.; Elwood Madden, Andrew S.; Phillips-Lander, Charity M.; Elwood Madden, Megan E.

2018-02-01

Perchlorate salts and the ferric sulfate mineral jarosite have been detected at multiple locations on Mars by both landed instruments and orbiting spectrometers. Many perchlorate brines have eutectic temperatures <250 K, and may exist as metastable or stable liquids for extended time periods, even under current Mars surface conditions. Therefore, jarosite-bearing rocks and sediments may have been altered by perchlorate brines. Here we measured jarosite dissolution rates in 2 M sodium perchlorate brine as well as dilute water at 298 K to determine the effects of perchlorate anions on jarosite dissolution rates and potential reaction products. We developed a simple method for determining aqueous iron concentrations in high salinity perchlorate solutions using ultraviolet-visible spectrophotometry that eliminates the risk of rapid oxidation reactions during analyses. Jarosite dissolution rates in 2 M perchlorate brine determined by iron release rate (2.87 × 10-12 ±0.85 × 10-12 mol m-2 s-1) were slightly slower than the jarosite dissolution rate measured in ultrapure (18.2 MΩ cm-1) water (5.06 × 10-12 mol m-2 s-1) using identical methods. No additional secondary phases were observed in XRD analyses of the reaction products. The observed decrease in dissolution rate may be due to lower activity of water (ɑH2O = 0.9) in the 2 M NaClO4 brine compared with ultrapure water (ɑH2O = 1). This suggests that the perchlorate anion does not facilitate iron release, unlike chloride anions which accelerated Fe release rates in previously reported jarosite and hematite dissolution experiments. Since dissolution rates are slower in perchlorate-rich solutions, jarosite is expected to persist longer in perchlorate brines than in dilute waters or chloride-rich brines. Therefore, if perchlorate brines dominate aqueous fluids on the surface of Mars, jarosite may remain preserved over extended periods of time, despite active aqueous processes.

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

Copuroglu, Oguzhan, E-mail: O.Copuroglu@CiTG.TUDelft.NL; Andic-Cakir, Ozge; Broekmans, Maarten A.T.M.

In this paper, the alkali-silica reaction performance of a basalt rock from western Anatolia, Turkey is reported. It is observed that the rock causes severe gel formation in the concrete microbar test. It appears that the main source of expansion is the reactive glassy phase of the basalt matrix having approximately 70% of SiO{sub 2}. The study presents the microstructural characteristics of unreacted and reacted basalt aggregate by optical and electron microscopy and discusses the possible reaction mechanism. Microstructural analysis revealed that the dissolution of silica is overwhelming in the matrix of the basalt and it eventually generates four consequences:more » (1) Formation of alkali-silica reaction gel at the aggregate perimeter, (2) increased porosity and permeability of the basalt matrix, (3) reduction of mechanical properties of the aggregate and (4) additional gel formation within the aggregate. It is concluded that the basalt rock is highly prone to alkali-silica reaction. As an aggregate, this rock is not suitable for concrete production.« less

Magmatic Enclaves in Granitic Rocks: Paragons or Parasites?

NASA Astrophysics Data System (ADS)

Clemens, John; Stevens, Gary; Elburg, Marlina

2017-04-01

Granitic rocks form the fundamental building blocks of Earth's continents and provide us with a wide range of resources, so their formation is worth trying to understand. Fine-grained, igneous-textured microgranular enclaves of tonalitic to monzogranitic composition (ME) are common in granitic rocks and their origins have been hotly debated, with some workers suggesting that ME are not igneous. These ME have been studied intensively enough that we are now certain that they are of igneous origin - globules of mingled and quenched magma. Although a mantle connection is evident in many cases, their ultimate origin (including where in the lithosphere they originate) is still debated. This contribution explores the systematics of chemical variation in ME and their host granites, with the aim of uncovering any systematics in their behaviour and modelling the processes that have led to the variations that we measure, comparing host-rock series to their respective ME series. As always, the hope is that the study of ME may lead to improved understanding and modelling of the processes that are responsible for the formation of the host granitic magmas. Using variations between the molecular quantities Ti and M (Fe+Mn+Mg), we demonstrate that the petrogenetic processes that operated within a diverse group of S- and I-type granitic host magmas and their ME suites are dissimilar. Variations within the granitic series result from a variety of what might be called 'orderly' processes, resulting in linear or curvilinear trends in chemical variation diagrams. In contrast, processes that affected the ME series commonly resulted in scattered, chaotic variations. Even in cases in which an ME series displays more orderly variation, it can be shown that the hypothesis of simple mixing between a parent enclave magma and its host granitic magma, to produce the overall variations, cannot be supported. ME magmas had vastly smaller volumes compared with their host granitic magmas. Thus, they have commonly undergone hybridisation through mixing with deep crustal melts and both chemical and mechanical interactions with wall rocks and their host granitic magmas. As a result of this complex and chaotic set of processes, it remains extremely difficult to unravel the precise mechanisms that produced a given suite of ME magmas. Due to the similarities between the studied granites and their ME with occurrences worldwide, we suggest that our findings are likely to be generally applicable.

Use of petrophysical data for siting of deep geological repository of radioactive waste

NASA Astrophysics Data System (ADS)

Petrenko, Liliana; Shestopalov, Vyacheslav

2017-11-01

The paper is devoted to analyzing the petrophysical properties and petrographical characteristics of Volyn region with the view to choosing the least permeable and so the most suitable geological formation for the radioactive waste disposal. On a basis of the petrophysical estimations of the granitoids properties the argumentation of permeability has been developed for the petrotypes of Volyn region. Also method of classification of the petrotypes with their relative rate of suitability for radioactive waste disposal was developed. As a result of studying the perspectives were shown of the zhytomyr and korosten types of the granitoids as host rock for the radioactive waste disposal. According to the results of investigations performed by Swedish researchers a comparative analysis of rocks based on the age of formation, composition, structural features and some petrophysical properties of granitoids as host rocks for repository of radioactive waste was performed. Detail comparison the data of the granitoids of the Forsmark site in Sweden and the data of the granitoids of the Volyn megablock can be one of the next steps in researching the host rocks for the development of the RW disposal system in Ukraine.

Characterizing Excavation Damaged Zone and Stability of Pressurized Lined Rock Caverns for Underground Compressed Air Energy Storage

NASA Astrophysics Data System (ADS)

Kim, Hyung-Mok; Rutqvist, Jonny; Jeong, Ju-Hwan; Choi, Byung-Hee; Ryu, Dong-Woo; Song, Won-Kyong

2013-09-01

In this paper, we investigate the influence of the excavation damaged zone (EDZ) on the geomechanical performance of compressed air energy storage (CAES) in lined rock caverns. We conducted a detailed characterization of the EDZ in rock caverns that have been excavated for a Korean pilot test program on CAES in (concrete) lined rock caverns at shallow depth. The EDZ was characterized by measurements of P- and S-wave velocities and permeability across the EDZ and into undisturbed host rock. Moreover, we constructed an in situ concrete lining model and conducted permeability measurements in boreholes penetrating the concrete, through the EDZ and into the undisturbed host rock. Using the site-specific conditions and the results of the EDZ characterization, we carried out a model simulation to investigate the influence of the EDZ on the CAES performance, in particular related to geomechanical responses and stability. We used a modeling approach including coupled thermodynamic multiphase flow and geomechanics, which was proven to be useful in previous generic CAES studies. Our modeling results showed that the potential for inducing tensile fractures and air leakage through the concrete lining could be substantially reduced if the EDZ around the cavern could be minimized. Moreover, the results showed that the most favorable design for reducing the potential for tensile failure in the lining would be a relatively compliant concrete lining with a tight inner seal, and a relatively stiff (uncompliant) host rock with a minimized EDZ. Because EDZ compliance depends on its compressibility (or modulus) and thickness, care should be taken during drill and blast operations to minimize the damage to the cavern walls.

Porosity and Permeability Evolution in Cemented Rock Cores under Reactive Flowing Conditions: Comparative Analysis between Limestone and Sandstone Host Rocks

NASA Astrophysics Data System (ADS)

Cao, P.; Karpyn, Z.; Li, L.

2013-12-01

CO2-brine has the potential to alter wellbore cement in depleted oil and gas reservoirs under geological CO2 sequestration conditions. A better understanding of CO2-brine-cement-rock interaction is needed to evaluate the seal integrity of candidate sequestration formation in the long run. This work investigates possible alteration of wellbore cement when bonded by different host formation rock upon exposure to CO2-saturated brine. Composite cement-sandstone and cement-limestone core samples were created to perform reactive coreflood experiments. After an eight-day dynamic flow-through period, both cores had a similar extent of porosity increase, while the cement-limestone core experienced a ten-fold higher increase in permeability. With the aid of X-ray Micro-CT imaging and Scanning Electron Microscopy, it is observed that cement underwent greater degradation at the cement-sandstone interface. Degradation of cement-limestone core mainly took place on the host rock matrix. Worm holes were developed and a solution channel was formed in the limestone, creating a dominant flow path that altered both flow and reaction behavior. Limestone buffered the injected acidic brine preventing further deterioration of cement near the core outlet. Changes in fluid chemistry of limestone and sandstone coreflood effluents are compared. Results from this work are aimed at assisting the development and validation of robust reactive transport models through direct measurement of cemented rock core porosity and permeability evolution as well as the effluent aqueous chemistry change. This will subsequently improve predictive capabilities of reactive transport models associated with CO2 sequestration in geologic environments. Permeability Evolution of Cement-Rock Core Sample during Dynamic Flow of CO2-Brine

The Alteration History of Clovis Class Rocks in Gusev Crater as Determined by Ti-Normalzed Mass Balance Analysis

NASA Technical Reports Server (NTRS)

Sutter, Brat; Ming, Douglas W.; Niles, P. B.; Golden, D. C.

2012-01-01

The West Spur Clovis class rocks in Gusev Crater are some of the most altered rocks in Gusev Crater and likely contain a mixed sulfate and phyllosilicate mineralogy [1,2]. The high S and Cl content of the Clovis rocks suggests that acidic vapors or fluids of H2SO4 and HCl reacted with the Clovis parent rock to form Ca, Mg,- sulfates, iron-oxyhydroxides and secondary aluminosilicates (approx.60 wt.%) of a poorly crystalline nature (e.g., allophane) [1]. Up to 14-17 wt.% phyllosilicates (e.g., kaolinite, chlorite, serpentine) are hypothesized to exist in the Clovis materials suggesting that Clovis parent materials while possibly exposed to acidic pHs were likely neutralized by basalt dissolution which resulted in mildly acidic pHs (4-6) [1, 2]. This work proposes that subsequent to the alteration of the Clovis rocks, alteration fluids became concentrated in ions resulting in the addition of silicate and salts. The objective of this work is to utilize Ti-normalized mass balance analysis to evaluate (1) mineral gains and losses and (2) elemental gains and losses in the Clovis rocks. Results of this work will be used evaluate the nature of geochemical conditions that affect phyllosilicate and sulfate formation at Gusev crater.

Genesis of sediment-hosted stratiform copper cobalt deposits, central African Copperbelt

NASA Astrophysics Data System (ADS)

Cailteux, J. L. H.; Kampunzu, A. B.; Lerouge, C.; Kaputo, A. K.; Milesi, J. P.

2005-07-01

The Neoproterozoic central African Copperbelt is one of the greatest sediment-hosted stratiform Cu-Co provinces in the world, totalling 140 Mt copper and 6 Mt cobalt and including several world-class deposits (⩾10 Mt copper). The origin of Cu-Co mineralisation in this province remains speculative, with the debate centred around syngenetic-diagenetic and hydrothermal-diagenetic hypotheses. The regional distribution of metals indicates that most of the cobalt-rich copper deposits are hosted in dolomites and dolomitic shales forming allochthonous units exposed in Congo and known as Congolese facies of the Katangan sedimentary succession (average Co:Cu = 1:13). The highest Co:Cu ratio (up to 3:1) occurs in ore deposits located along the southern structural block of the Lufilian Arc. The predominantly siliciclastic Zambian facies, exposed in Zambia and in SE Congo, forms para-autochthonous sedimentary units hosting ore deposits characterized by lower a Co:Cu ratio (average 1:57). Transitional lithofacies in Zambia (e.g. Baluba, Mindola) and in Congo (e.g. Lubembe) indicate a gradual transition in the Katangan basin during the deposition of laterally correlative clastic and carbonate sedimentary rocks exposed in Zambia and in Congo, and are marked by Co:Cu ratios in the range 1:15. The main Cu-Co orebodies occur at the base of the Mines/Musoshi Subgroup, which is characterized by evaporitic intertidal-supratidal sedimentary rocks. All additional lenticular orebodies known in the upper part of the Mines/Musoshi Subgroup are hosted in similar sedimentary rocks, suggesting highly favourable conditions for the ore genesis in particular sedimentary environments. Pre-lithification sedimentary structures affecting disseminated sulphides indicate that metals were deposited before compaction and consolidation of the host sediment. The ore parageneses indicate several generations of sulphides marking syngenetic, early diagenetic and late diagenetic processes. Sulphur isotopic data on sulphides suggest the derivation of sulphur essentially from the bacterial reduction of seawater sulphates. The mineralizing brines were generated from sea water in sabkhas or hypersaline lagoons during the deposition of the host rocks. Changes of Eh-pH and salinity probably were critical for concentrating copper-cobalt and nickel mineralisation. Compressional tectonic and related metamorphic processes and supergene enrichment have played variable roles in the remobilisation and upgrading of the primary mineralisation. There is no evidence to support models assuming that metals originated from: (1) Katangan igneous rocks and related hydrothermal processes or; (2) leaching of red beds underlying the orebodies. The metal sources are pre-Katangan continental rocks, especially the Palaeoproterozoic low-grade porphyry copper deposits known in the Bangweulu block and subsidiary Cu-Co-Ni deposits/occurrences in the Archaean rocks of the Zimbabwe craton. These two sources contain low grade ore deposits portraying the peculiar metal association (Cu, Co, Ni, U, Cr, Au, Ag, PGE) recorded in the Katangan sediment-hosted ore deposits. Metals were transported into the basin dissolved in water. The stratiform deposits of Congo and Zambia display features indicating that syngenetic and early diagenetic processes controlled the formation of the Neoproterozoic Copperbelt of central Africa.

Melt- rock reaction at oceanic peridotite-gabbro transition, through combined EBSD and in-situ mineral geochemistry on the Erro Tobbio peridotitic body (Ligurian ophiolites, Italy).

NASA Astrophysics Data System (ADS)

Basch, Valentin; Rampone, Elisabetta; Ildefonse, Benoit; Godard, Marguerite; Crispini, Laura

2017-04-01

Several lines of evidence have stressed that melt-rock reactions acting at the oceanic mantle-crust boundary play an important role in the chemical evolution of MORBs and the formation of the primitive (olivine-rich) lower oceanic crust. To address this issue, we performed detailed structural analyses and in-situ mineral geochemistry on the Erro-Tobbio (ET) ultramafic unit (Ligurian Alps, Italy), where impregnated mantle peridotites are primarily associated to a hectometre-size mafic body composed of troctolite to plagioclase-bearing wehrlite. The troctolitic body exhibits high complexity, with a host troctolite (Troctolite A) crosscut by troctolitic decametre-size pseudo-tabular bodies (Troctolite B). These different generations of troctolites show distinct modal compositions and textures. The host troctolite A displays a dominant millimetre-size corroded granular texture of olivine associated with dunite pods and a layering defined by poikilitic plagioclase enrichment. The contact between the mafic body and the host mantle peridotites is irregular, and defined by troctolite to wehrlite apophyses. The troctolite A shows microstructures and Crystallographic Preferred Orientation (CPO) indicative of a formation after impregnation of a mantle dunite by an olivine-undersaturated melt. This impregnation leads to olivine dissolution, associated with poikilitic plagioclase and clinopyroxene crystallization. This is indicated by a progressive randoming of the Axial-[100] CPO with olivine disaggregation and increasing melt input in the troctolite. The crosscutting troctolite B exhibits significant olivine textural variation, from fine-grained granular to deformed coarse-grained skeletal olivine. Olivine in the troctolite B shows CPO indicative of crystallization after magmatic flow, intrusive into the host troctolite A. Both troctolite types display large major and trace element variations in minerals, e.g. variation of Anorthite content (An = 54-67) in plagioclase at rather constant Forsterite content in olivine, and significant Zr, Ti, HREE heterogeneity in olivine, systematically correlated with the textural variability (e.g. corroded deformed vs. undeformed granular olivine). These features indicate that reactive crystallization had an important role in the origin of the ET troctolites. We infer that the textural heterogeneity of olivine in the troctolite B is related to variations in the degree of undercooling and cooling rate of the melt (Faure et al, 2003). The skeletal olivine crystallization could correspond to the influx of a more primitive melt into a colder host troctolite, followed by evolution of the melt leading to formation of fine-grained euhedral crystals. Overall, the results of this study suggest a poly-phase formation of this hectometre-scale gabbroic body, involving impregnation of a mantle-derived dunitic body followed by intrusion of undercooled primitive melts. Faure, F., Trolliard, G., Nicollet, C. & Montel, J.M. (2003), A developmental model of olivine morphology as a function of the cooling rate and the degree of undercooling. Contrib. Miner. Petrol. 145:251-263.

Characterization of a fluvial aquifer at a range of depths and scales: the Triassic St Bees Sandstone Formation, Cumbria, UK

NASA Astrophysics Data System (ADS)

Medici, Giacomo; West, L. J.; Mountney, N. P.

2018-03-01

Fluvial sedimentary successions represent porous media that host groundwater and geothermal resources. Additionally, they overlie crystalline rocks hosting nuclear waste repositories in rift settings. The permeability characteristics of an arenaceous fluvial succession, the Triassic St Bees Sandstone Formation in England (UK), are described, from core-plug to well-test scale up to 1 km depth. Within such lithified successions, dissolution associated with the circulation of meteoric water results in increased permeability ( K 10-1-100 m/day) to depths of at least 150 m below ground level (BGL) in aquifer systems that are subject to rapid groundwater circulation. Thus, contaminant transport is likely to occur at relatively high rates. In a deeper investigation (> 150 m depth), where the aquifer has not been subjected to rapid groundwater circulation, well-test-scale hydraulic conductivity is lower, decreasing from K 10-2 m/day at 150-400 m BGL to 10-3 m/day down-dip at 1 km BGL, where the pore fluid is hypersaline. Here, pore-scale permeability becomes progressively dominant with increasing lithostatic load. Notably, this work investigates a sandstone aquifer of fluvial origin at investigation depths consistent with highly enthalpy geothermal reservoirs ( 0.7-1.1 km). At such depths, intergranular flow dominates in unfaulted areas with only minor contribution by bedding plane fractures. However, extensional faults represent preferential flow pathways, due to presence of high connective open fractures. Therefore, such faults may (1) drive nuclear waste contaminants towards the highly permeable shallow (< 150 m BGL) zone of the aquifer, and (2) influence fluid recovery in geothermal fields.

Deformation of host rocks and flow of magma during growth of minette dikes and breccia-bearing intrusions near Ship Rock, New Mexico

USGS Publications Warehouse

Delaney, Paul T.; Pollard, David D.

1981-01-01

We have studied a small group of minette dikes and plugs that crop out within a flat-lying sequence of siltstone and shale near Ship Rock, a prominent volcanic throat of tuff breccia in northwestern New Mexico. Seven dikes form a radial pattern about Ship Rock we describe in detail the northeastern dike, which has an outcrop length of about 2,900 m, an average thickness of 2.3 m, and a maximum thickness of 7.2 m. The dike is composed of 35 discrete segments arranged in echelon; orientation. of dike segments ranges systematically from N. 52? E. to N. 66? E. A prominent joint set strikes parallel to the segments and is localized within several tens of meters of the dike. Regional joint patterns display no obvious relation to dike orientation. Small offsets of segment contacts, as well as wedge-shaped bodies of crumpled host rock within segments mark the sites of coalescence of smaller segments during dike growth. Bulges in the dike contact, which represent a nondilational component of growth, indicate that wall rocks were brecciated and eroded during the flow of magma. Breccias make up about 9 percent of the 7,176-m 2 area of the dike, are concentrated in its southwest half, and are commonly associated with its thickest parts. We also describe three subcircular plugs; each plug is smaller than 30 m in diameter, is laterally associated with a dike, and contains abundant breccias. Field evidence indicates that these plugs grew from the dikes by brecciation and erosion of wallrocks and that the bulges in the contact of the northeastern dike represent an initial stage of this process. From continuum-mechanical models of host-rock deformation, we conclude that dike propagation was the dominant mechanism for creating conduits for magma ascent where the host rock was brittle and elastic. At a given driving pressure, dikes dilate to accept greater volumes of magma than plugs, and for a given dilation, less work is done on the host rocks. In addition, the pressure required for dike growth decreases with dike length. From numerical solutions for dilation of cracks oriented like segments of the northeastern dike, we find that we can best model the form of the dike by treating it as composed of 10 cracks rather than 35. We attribute this result to coalescence of adjacent segments below the present outcrop and to inelastic deformation at segment ends. Using a driving pressure of 2 MPa (20 bars), we estimate a shear modulus of about 10^3 MPa for the host rocks, in agreement with laboratory tests on soft shale. A propagation criterion based on stress intensity at the segment ends indicates a fracture toughness of the host rocks of about 100 MPa-m^? , a hundredfold greater than values reported from laboratory tests. Segmentation of fractures is common in many materials and has been observed during fissure eruptions at Kilauea Volcano in Hawaii. At the northeastern dike, we attribute segmentation to local rotation of the direction of least principal compressive stress. From continuum-mechanical models of magma and heat flow in idealized conduits, we conclude that magma flows far more rapidly and with less relative heat loss in plugs than in dikes. Although dikes are the preferred form for emplacement, plugs are the preferred form for the flow of magma. We present a numerical solution for volumetric flow rate and wall heat flux for the northeastern dike and find that although the flow rate is extremely sensitive to conduit geometry, the rate of heat loss to wall rocks is not. During emplacement of the northeastern dike, local flow rate increased where wall rocks were eroded and reached a maximum of about 45 times the mean initial rate, whereas the maximum rate of heat loss to wallrocks increased to only 1.6 times the mean initial rate. An inferred progression from continuous magma flow along a dike to flow from a plug agrees well with observations of volcanic eruptions that begin from fissures and later are localized at discrete vents. We

Porosity developed during mineral replacement reactions: implications for fluid flux in the Earth

NASA Astrophysics Data System (ADS)

Putnis, Christine V.; Trindade Pedrosa, Elisabete; Hövelmann, Jörn; Renard, François; Ruiz-Agudo, Encarnacion

2017-04-01

Aqueous fluids, that are ubiquitous in the crust of the Earth, will move through possible pathways in rocks. Rocks characteristically have low permeability but fractures can provide fast fluid channels. Mineral grain boundaries also present easy fluid pathways. However, porosity within minerals forms when a mineral is out of equilibrium with an aqueous fluid and reactions take place in an attempt to reach a new equilibrium. Commonly, dissolution at a mineral-fluid interface initiates one or several coupled reactions involving dissolution and precipitation (Putnis C.V. and Ruiz-Agudo E., 2013; Ruiz-Agudo et al., 2014). In pseudomorphic volume-deficit reactions, a new phase forms while porosity is created, and thereby reactive fluid flow through the originally solid mineral is enhanced. These coupled dissolution-replacement reactions therefore will constrain the flux of material carried by the fluid. These reactions are common during such processes as metamorphism, metasomatism, and weathering. When rock-forming minerals such as feldspars, olivine, pyroxenes and carbonates are in contact with aqueous fluids (typically NaCl-rich) porosity is formed during the interfacial replacement reactions. Elements present in the parent mineral are released to the fluid and therefore mobilized for transport elsewhere. Porosity formation has been shown in a number of systems, such as during the albitisation of feldspars (Hövelmann et al., 2009) and the replacement of carbonates by apatite phases (Pedrosa et al., 2016). Some of these examples will be presented as well as examples from atomic force microscopy (AFM) experiments used to image these reactions at a nanoscale, especially at the calcite-fluid interface, when new phases can be directly observed forming. This mechanism has also been shown as a means of carbon and phosphorus sequestration and for the removal of toxic elements from superficial waters, such as Se and As. References Ruiz-Agudo E., Putnis C.V., Putnis A. (2014) Coupled dissolution and precipitation at mineral-fluid interfaces. Chem. Geol., 383, 132-146. Putnis C.V. and Ruiz-Agudo E. (2013) The mineral-water interface: where minerals react with the environment. Elements, 9, 177-182. Hövelmann J., Putnis A., Geisler T., Schmidt B.C., Golla-Schindler U. (2009) The replacement of plagioclase feldspars by albite: observations from hydrothermal experiments. Contrib. Min. and Pet. 159, 43-59. Pedrosa E.T., Putnis C.V., Putnis A. (2016) The pseudomorphic replacement of marble by apatite: the role of fluid composition. Chem. Geol., 425, 1-11.

Rates of CO2 Mineralization in Geological Carbon Storage.

PubMed

Zhang, Shuo; DePaolo, Donald J

2017-09-19

Geologic carbon storage (GCS) involves capture and purification of CO 2 at industrial emission sources, compression into a supercritical state, and subsequent injection into geologic formations. This process reverses the flow of carbon to the atmosphere with the intention of returning the carbon to long-term geologic storage. Models suggest that most of the injected CO 2 will be "trapped" in the subsurface by physical means, but the most risk-free and permanent form of carbon storage is as carbonate minerals (Ca,Mg,Fe)CO 3 . The transformation of CO 2 to carbonate minerals requires supply of the necessary divalent cations by dissolution of silicate minerals. Available data suggest that rates of transformation are highly uncertain and difficult to predict by standard approaches. Here we show that the chemical kinetic observations and experimental results, when they can be reduced to a single cation-release time scale that describes the fractional rate at which cations are released to solution by mineral dissolution, show sufficiently systematic behavior as a function of pH, fluid flow rate, and time that the rates of mineralization can be estimated with reasonable certainty. The rate of mineralization depends on both the abundance (determined by the reservoir rock mineralogy) and the rate at which cations are released from silicate minerals by dissolution into pore fluid that has been acidified with dissolved CO 2 . Laboratory-measured rates and field observations give values spanning 8 to 10 orders of magnitude, but when they are evaluated in the context of a reservoir-scale reactive transport simulation, this range becomes much smaller. The reservoir scale simulations provide limits on the applicable conditions under which silicate mineral dissolution and subsequent carbonate mineral precipitation are likely to occur (pH 4.5 to 6, fluid flow velocity less than 5 m/year, and 50-100 years or more after the start of injection). These constraints lead to estimates of 200 to 2000 years for conversion of 60-90% of injected CO 2 when the reservoir rock has a sufficient volume fraction of divalent cation-bearing silicate minerals and confirms that when reservoir rock mineralogy is not favorable the fraction of CO 2 converted to carbonate minerals is minimal over 10 4 years. A sufficient amount of reactive minerals is typically about 20% by volume. Our approach may allow for rapid evaluation of mineralization potential of subsurface storage reservoirs and illustrates how reservoir scale modeling can be integrated with other observations to address key issues relating to engineering of geologic systems.

EPITHERMAL GOLD-SILVER MINERALIZATION RELATED TO VOLCANIC SUBSIDENCE IN THE CUSTER GRABEN, CUSTER COUNTY, IDAHO.

USGS Publications Warehouse

Johnson, Kathleen M.; McIntyre, David H.

1984-01-01

The Custer graben is a 13 by 32 km northeast-trending volcano-tectonic graben in the Challis volcanic field of central Idaho. Andesites, rhyolites, and associated pyroclastic rocks host vein and disseminated gold-silver deposits that are localized along discrete northeast- and northwest-trending fracture zones. Ore minerals in vein deposits are electrum, native gold and silver, chalcopyrite, and various sulfosalts in a gangue of pyrite and fine-grained quartz. At the Sunbeam Mine, near the center of the graben, vein and disseminated gold-silver mineralization occurred in hydrothermally altered rhyolite and pyroclastic rocks. The host rock has been pervasively silicified, and the feldspars altered to clay minerals. Analyses of surface and drill-core samples show that altered rocks are variably enriched in gold, silver, molybdenum, arsenic, zirconium, and selenium. Intense silicification is shown by SiO//2 values at high as 93%.

Effect of the size of nanoparticles on their dissolution within metal-glass nanocomposites under sustained irradiation

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

Vu, T. H. Y., E-mail: thi-hai-yen.vu@polytechnique.edu; Ramjauny, Y.; Rizza, G.

2016-01-21

We investigate the dissolution law of metallic nanoparticles (NPs) under sustained irradiation. The system is composed of isolated spherical gold NPs (4–100 nm) embedded in an amorphous silica host matrix. Samples are irradiated at room temperature in the nuclear stopping power regime with 4 MeV Au ions for fluences up to 8 × 10{sup 16 }cm{sup −2}. Experimentally, the dependence of the dissolution kinetics on the irradiation fluence is linear for large NPs (45–100 nm) and exponential for small NPs (4–25 nm). A lattice-based kinetic Monte Carlo (KMC) code, which includes atomic diffusion and ballistic displacement events, is used to simulate the dynamical competition between irradiation effectsmore » and thermal healing. The KMC simulations allow for a qualitative description of the NP dissolution in two main stages, in good agreement with the experiment. Moreover, the perfect correlation obtained between the evolution of the simulated flux of ejected atoms and the dissolution rate in two stages implies that there exists an effect of the size of NPs on their dissolution and a critical size for the transition between the two stages. The Frost-Russell model providing an analytical solution for the dissolution rate, accounts well for the first dissolution stage but fails in reproducing the data for the second stage. An improved model obtained by including a size-dependent recoil generation rate permits fully describing the dissolution for any NP size. This proves, in particular, that the size effect on the generation rate is the principal reason for the existence of two regimes. Finally, our results also demonstrate that it is justified to use a unidirectional approximation to describe the dissolution of the NP under irradiation, because the solute concentration is particularly low in metal-glass nanocomposites.« less

Geochemistry of arsenic in low sulfide-high carbonate coal waste rock, Elk Valley, British Columbia, Canada.

PubMed

Biswas, Ashis; Hendry, M Jim; Essilfie-Dughan, Joseph

2017-02-01

This study investigated the geochemistry of arsenic (As) in low sulfide-high carbonate coal waste rock of the Elk Valley, British Columbia, Canada. Its abundance and mineralogical associations in waste rock of different placement periods were determined in addition to its mobilization into porewater and rock-drain effluent. The mean (5.34mg/kg; 95% confidence interval: 4.95-5.73mg/kg) As concentration in the waste rock was typical of sedimentary rock. Electron microprobe and As K-edge X-ray absorption near-edge spectroscopic analyses showed the As is predominantly associated with primary pyrites in both source and freshly blasted waste rock. However, in aged waste rock the As is associated with both primary pyrites and secondary Fe oxyhydroxides. Oxidation of pyrite in waste rock dumps was reflected by the presence of high concentrations of SO 4 2- in porewater and oxidation rims of Fe oxyhydroxides around pyrite grains. Acid released from pyrite oxidation to Fe oxyhydroxides is neutralized by carbonate mineral dissolution that buffers the pH in the waste rock to circumneutral values. Adsorption of As onto secondary Fe oxyhydroxides provides an internal geochemical control on As release during pyrite oxidation and porewater flushing from the dump, resulting in the low As concentrations observed in porewater (median: 9.91μg/L) and rock-drain effluent (median: 0.31μg/L). Secondary Fe oxyhydroxides act as a long-term sink for As under present day hydrologic settings in waste rock dumps in the Elk Valley. Copyright © 2016 Elsevier B.V. All rights reserved.

A deposit model for magmatic iron-titanium-oxide deposits related to Proterozoic massif anorthosite plutonic suites

USGS Publications Warehouse

Woodruff, Laurel G.; Nicholson, Suzanne W.; Fey, David L.

2013-01-01

This descriptive model for magmatic iron-titanium-oxide (Fe-Ti-oxide) deposits hosted by Proterozoic age massif-type anorthosite and related rock types presents their geological, mineralogical, geochemical, and geoenvironmental attributes. Although these Proterozoic rocks are found worldwide, the majority of known deposits are found within exposed rocks of the Grenville Province, stretching from southwestern United States through eastern Canada; its extension into Norway is termed the Rogaland Anorthosite Province. This type of Fe-Ti-oxide deposit dominated by ilmenite rarely contains more than 300 million tons of ore, with between 10- to 45-percent titanium dioxide (TiO2), 32- to 45-percent iron oxide (FeO), and less than 0.2-percent vanadium (V). The origin of these typically discordant ore deposits remains as enigmatic as the magmatic evolution of their host rocks. The deposits clearly have a magmatic origin, hosted by an age-constrained unique suite of rocks that likely are the consequence of a particular combination of tectonic circumstances, rather than any a priori temporal control. Principal ore minerals are ilmenite and hemo-ilmenite (ilmenite with extensive hematite exsolution lamellae); occurrences of titanomagnetite, magnetite, and apatite that are related to this deposit type are currently of less economic importance. Ore-mineral paragenesis is somewhat obscured by complicated solid solution and oxidation behavior within the Fe-Ti-oxide system. Anorthosite suites hosting these deposits require an extensive history of voluminous plagioclase crystallization to develop plagioclase-melt diapirs with entrained Fe-Ti-rich melt rising from the base of the lithosphere to mid- and upper-crustal levels. Timing and style of oxide mineralization are related to magmatic and dynamic evolution of these diapiric systems and to development and movement of oxide cumulates and related melts. Active mines have developed large open pits with extensive waste-rock piles, but because of the nature of the ore and waste rock, the major environmental impacts documented at the mine sites are reported to be waste disposal issues and somewhat degraded water quality.

An Experimental Study on Characterization of Physical Properties of Ultramafic Rocks and Controls on Evolution of Fracture Permeability During Serpentinization at Hydrothermal Conditions

NASA Astrophysics Data System (ADS)

Farough, Aida

Serpentinization is a complex set of hydration reactions, where olivine and pyroxene are replaced by serpentine, magnetite, brucite, talc and carbonate minerals. Serpentinization reactions alter chemical, mechanical, magnetic, seismic, and hydraulic properties of the crust. To understand the complicated nature of serpentinization and the linkages between physical and chemical changes during the reactions, I performed flow-through laboratory experiments on cylindrically cored samples of ultramafic rocks. Each core had a well-mated through-going tensile fracture, to investigate evolution of fracture permeability during serpentinization. The samples were tested in a triaxial loading machine at an effective pressure of 30 MPa, and temperature of 260"aC, simulating a depth of 2 km under hydrostatic conditions. Fracture permeability decreased by one to two orders of magnitude during the 200 to 340 hour experiments. Electron microprobe and SEM data indicated the formation of needle-shaped crystals of serpentine composition along the walls of the fracture, and chemical analyses of sampled pore fluids were consistent with dissolution of ferromagnesian minerals. The rate of transformation of olivine to serpentine in a tensile fracture is calculated using the data on evolution of fracture permeability assuming the fracture permeability could be represented by parallel plates. Assuming the dissolution and precipitation reactions occur simultaneously; the rate of transformation at the beginning of the experiments was 10-8-10-9 (mol/m2s) and decreased monotonically by about an order of magnitude towards the end of the experiment. Results show that dissolution and precipitation is the main mechanism contributing to the reduction in fracture aperture. The experimental results suggest that the fracture network in long-lived hydrothermal circulation systems may be sealed rapidly as a result of mineral precipitation, and generation of new permeability resulting from a combination of tectonic and crystallization-induced stresses may be required to maintain fluid circulation. Another set of flow through experiments were performed on intact samples of ultramafic rocks at room temperature and effective pressures of 10, 20 and 30 MPa to estimate the pressure dependency of intact permeability. Porosity and density measurements were also performed with the purpose of characterizing these properties of ultramafic rocks. The pressure dependency of the coefficient of matrix permeability of the ultramafic rock samples fell in the range of 0.05-0.14 MPa -1. Using porosity and permeability measurements, the ratio of interconnected porosity to total porosity was estimated to be small and the permeability of the samples was dominantly controlled by microcracks. Using the density and porosity measurements, the degree of alteration of samples was estimated. Samples with high density and pressure dependent permeability had a smaller degree of alteration than those with lower density and pressure dependency.

Geologic map of the Storm King Mountain quadrangle, Garfield County, Colorado

USGS Publications Warehouse

Bryant, Bruce; Shroba, Ralph R.; Harding, Anne E.; Murray, Kyle E.

2002-01-01

New 1:24,000-scale geologic mapping in the Storm King Mountain 7.5' quadrangle, in support of the USGS Western Colorado I-70 Corridor Cooperative Geologic Mapping Project, provides new data on the structure on the south margin of the White River uplift and the Grand Hogback and on the nature, history, and distribution of surficial geologic units. Rocks ranging from Holocene to Proterozoic in age are shown on the map. The Canyon Creek Conglomerate, a unit presently known to only occur in this quadrangle, is interpreted to have been deposited in a very steep sided local basin formed by dissolution of Pennsylvanian evaporite late in Tertiary time. At the top of the Late Cretaceous Williams Fork Formation is a unit of sandstone, siltstone, and claystone from which Late Cretaceous palynomorphs were obtained in one locality. This interval has been mapped previously as Ohio Creek Conglomerate, but it does not fit the current interpretation of the origin of the Ohio Creek. Rocks previously mapped as Frontier Sandstone and Mowry Shale are here mapped as the lower member of the Mancos Shale and contain beds equivalent to the Juana Lopez Member of the Mancos Shale in northwestern New Mexico. The Pennsylvanian Eagle Valley Formation in this quadrangle grades into Eagle Valley Evaporite as mapped by Kirkham and others (1997) in the Glenwood Springs area. The Storm King Mountain quadrangle spans the south margin of the White River uplift and crosses the Grand Hogback monocline into the Piceance basin. Nearly flat lying Mississippian through Cambrian sedimentary rocks capping the White River uplift are bent into gentle south dips and broken by faults at the edge of the uplift. South of these faults the beds dip moderately to steeply to the south and are locally overturned. These dips are interrupted by a structural terrace on which are superposed numerous gentle minor folds and faults. This terrace has an east-west extent similar to that of the Canyon Creek Conglomerate to the north. We interpret that the terrace formed by movement of Eagle Evaporite from below in response to dissolution and diapirism in the area underlain by the conglomerate. A low-angle normal fault dipping gently north near the north margin of the quadrangle may have formed also in response to diapirism and dissolution in the area of the Canyon Creek Conglomerate. Along the east edge of the quadrangle Miocene basalt flows are offset by faults along bedding planes in underlying south-dipping Cretaceous rocks, probably because of diapiric movement of evaporite into the Cattle Creek anticline (Kirkham and Widmann, 1997). Steep topography and weak rocks combine to produce a variety of geologic hazards in the quadrangle.

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

Nelson-Moore, J.L.; Collins, D.B.; Hornbaker, A.L.

This two-part report provides an essentially complete listing of radioactive occurrences in Colorado, with a comprehensive bibliography and bibliographic cross-indexes. Part 1 lists approximately 3000 known radioactive occurrences with their locations and brief accounts of the geology, mineralogy, radioactivity, host rock, production data, and source of data for each. The occurrences are classified by host rock and plotted on U.S. Geological Survey 1/sup 0/ x 2/sup 0/ topographic quadrangle maps with a special 1 : 100,000-scale base map for the Uravan mineral belt. Part 2 contains the bibliography of approximately 2500 citations on radioactive mineral occurrences in the state, withmore » cross-indexes by county, host rock, and the special categories of ''Front Range,'' ''Colorado Plateau,'' and ''thorium.'' The term ''occurrence'' as used in this report is defined as any site where the concentration of uranium or thorium is at least 0.01% or where the range of radioactivity is greater than twice the background radioactivity. All citations and occurrence data are stored on computer diskettes for easy retrieval, correction, and updating.« less

Vein deposits hosted by plutonic rocks in the Croesus Stock and Hailey gold belt mineralized areas, Blaine County, Idaho

USGS Publications Warehouse

Worl, Ronald G.; Lewis, Reed S.

2001-01-01

Mineral deposits in the Croesus and Hailey gold belt mineralized areas in Blaine County, south-central Idaho, are preciousand base-metal quartz veins that are part of a family of vein deposits spatially and temporally associated with the Idaho batholith. Historic production from these veins has been mainly gold and silver. Host rocks are older border phase plutons of the Idaho batholith that are characterized by more potassium and less sodium as compared to rocks from the main body of the batholith to the west. Host structures are reverse faults that have moderate to shallow dips to the northeast and high-angle normal faults that also strike northwest. The veins are characterized by several generations of quartz and generally sparse sulfide minerals; gold is associated with late-stage comb quartz. The precious-metal ore bodies are in a series of shoots, each of which is as much as 8 ft in width, 400 ft in breadth, and 1,000 ft in pitch length.

Coupled Thermo-Hydro-Chemical (THC) Modeling of Hypogene Karst Evolution in a Prototype Mountain Hydrologic System

NASA Astrophysics Data System (ADS)

Chaudhuri, A.; Rajaram, H.; Viswanathan, H. S.; Zyvoloski, G.

2011-12-01

Hypogene karst systems are believed to develop when water flowing upward against the geothermal gradient dissolves limestone as it cools. We present a comprehensive THC model incorporating time-evolving fluid flow, heat transfer, buoyancy effects, multi-component reactive transport and aperture/permeability change to investigate the origin of hypogene karst systems. Our model incorporates the temperature and pressure dependence of the solubility and dissolution kinetics of calcite. It also allows for rigorous representation of temperature-dependent fluid density and its influence on buoyancy forces at various stages of karstification. The model is applied to investigate karstification over geological time scales in a prototype mountain hydrologic system. In this system, a high water table maintained by mountain recharge, drives flow downward through the country rock and upward via a high-permeability fault/fracture. The pressure boundary conditions are maintained constant in time. The fluid flux through the fracture remains nearly constant even though the fracture aperture and permeability increase by dissolution, largely because the permeability of the country rock is not altered significantly due to slower dissolution rates. However, karstification by fracture dissolution is not impeded even though the fluid flux stays nearly constant. Forced and buoyant convection effects arise due to the increased permeability of the evolving fracture system. Since in reality the aperture varies significantly within the fracture plane, the initial fracture aperture is modeled as a heterogeneous random field. In such a heterogeneous aperture field, the water initially flows at a significant rate mainly through preferential flow paths connecting the relatively large aperture zones. Dissolution is more prominent at early time along these flow paths, and the aperture grows faster within these paths. With time, the aperture within small sub-regions of these preferential flow paths grows to a point where the permeability is large enough for the onset of buoyant convection. As a result, a multitude of buoyant convection cells form that take on a two-dimensional (2D) maze-like appearance, which could represent a 2D analog of the three-dimensional (3D) mazework pattern widely thought to be characteristic of hypogene cave systems. Although computational limitations limited us to 2D, we suggest that similar process interactions in a 3D network of fractures and faults could produce a 3D mazework.

Spatial variability of damage around faults in the Joe Lott Tuff Member of the Mount Belknap Volcanics, southwestern Utah

NASA Astrophysics Data System (ADS)

Okubo, C. H.

2012-12-01

In order to yield new insight into the process of faulting in fine-grained, poorly indurated volcanic ash, the distribution of strain around faults in the Miocene-aged Joe Lott Tuff Member of the Mount Belknap Volcanics, Utah, is investigated. Several distinct styles of inelastic strain are identified. Deformation bands are observed in tuff that is porous and granular in nature, or is inferred to have been so at the time of deformation. Where silicic alteration is pervasive, fractures are the dominant form of localized strain. Non-localized strain within the host rock is manifest as pore space compaction, including crushing of pumice clasts. Distinct differences in fault zone architecture are observed at different magnitudes of normal fault displacement, in the mode II orientation. A fault with cm-scale displacements is manifest as a single well-defined surface. Off-fault damage occurs as pore space compaction near the fault tips and formation of deformation band damage zones that are roughly symmetric about the fault. At a fault with larger meter-scale displacements, a fault core is present. A recognizable fault-related deformation band damage zone is not observed here, even though large areas of the host rock remain porous and granular and deformation bands had formed prior to faulting. The host rock is instead fractured in areas of pervasive alteration and shows possible textural evidence of fault pulverization. The zones of localized and distributed strain have notably different spatial extents around the causative fault. The region of distributed deformation, as indicated by changes in gas permeability of the macroscopically intact rock, extends up to four times farther from the fault than the highest densities of localized deformation (i.e., fractures and deformation bands). This study identifies a set of fault-related processes that are pertinent to understanding the evolution of fault systems in poorly indurated tuff. Not surprisingly, the type of structural discontinuity that forms in the fault environment is found to be a function of the porosity and granularity of the host rock. Non-localized deformation in the form of pore space compaction of the host rock is found to be prominent around the fault tips at First Spring Hollow. Interestingly, the spatial distribution of host rock compaction and the occurrences of dilational deformation bands around this fault do not correlate with the classic pattern of compression and dilation generally anticipated for slipped normal faults when viewed in mode II. Therefore, while broad generalities regarding the types of discontinuities that form around faults in tuff can be drawn based on current principles, additional work is needed to better understand the genesis of the observed spatial distributions of strain.

The geology of asbestos in the United States and its practical applications

USGS Publications Warehouse

Van Gosen, B. S.

2007-01-01

Recently, naturally occurring asbestos (NOA) has drawn the attention of numerous health and regulatory agencies and citizen groups. NOA can be released airborne by (1) the disturbance of asbestos-bearing bedrocks through human activities or natural weathering, and (2) the mining and milling of some mineral deposits in which asbestos occurs as an accessory mineral(s). Because asbestos forms in specific rock types and geologic conditions, this information can be used to focus on areas with the potential to contain asbestos, rather than devoting effort to areas with minimal NOA potential. All asbestos minerals contain magnesium, silica, and water as essential constituents, and some also contain major iron and/or calcium. Predictably, the geologic environments that host asbestos are enriched in these components. Most asbestos deposits form by metasomatic replacement of magnesium-rich rocks. Asbestos-forming environments typically display shear or evidence for a significant influx of silica-rich hydrothermal fluids. Asbestos-forming processes can be driven by regional metamorphism, contact metamorphism, or magmatic hydrothermal systems. Thus, asbestos deposits of all sizes and styles are typically hosted by magnesium-rich rocks (often also iron-rich) that were altered by a metamorphic or magmatic process. Rock types known to host asbestos include serpentinites, altered ultramafic and some mafic rocks, dolomitic marbles and metamorphosed dolostones, metamorphosed iron formations, and alkalic intrusions and carbonatites. Other rock types appear unlikely to contain asbestos. These geologic insights can be used by the mining industry, regulators, land managers, and others to focus attention on the critical locales most likely to contain asbestos.

The fate of carbon and CO2 - fluid-rock interaction during subduction metamorphism of serpentinites

NASA Astrophysics Data System (ADS)

Menzel, Manuel D.; Garrido, Carlos J.; López Sánchez-Vizcaíno, Vicente; Marchesi, Claudio; Hidas, Károly

2016-04-01

Given to its large relevance for present and past climate studies, the deep carbon cycle received increasing attention recently. However, there are still many open questions concerning total mass fluxes and transport processes between the different carbon reservoirs in the Earth's interior. One key issue is the carbon transfer from the subducting slab into fluids and rocks in the slab and mantle wedge. This transfer is controlled by the amount and speciation of stable carbon-bearing phases, which have a strong impact on the pH, redox conditions and trace-element budget of slab fluids. As recent experiments and thermodynamic modeling have shown, water released from dehydrating serpentinites has a great potential to produce CO2-enriched slab fluids by dissolution of carbonate minerals. To constrain the fate of carbon and CO2-fluid-rock interactions during subduction metamorphism of serpentinites, we have studied carbonate-bearing serpentinites recording different prograde evolutions from antigorite schists to Chl-harzburgites in high-P massifs of the Nevado-Filabride Complex (Betic Cordillera, S. Spain). Our results indicate that dissolution of dolomite in marbles in contact with dehydrating serpentinites is spatially limited during prograde metamorphism of carbonate-bearing serpentinites, but it can lead to the formation of silicate-rich zones in marbles close to the contacts. In lower grade serpentinite massifs (1.0-1.5 GPa / 550 °C), the presence of marble lenses in contact with antigorite schists appears to promote local dehydration of serpentinite coupled with carbonation of antigorite, forming Cpx-Tr-Chl-bearing high grade ophicarbonate zones. At the Cerro del Almirez ultramafic massif, where a dehydration front from antigorite-serpentinite to prograde Chl-harzburgite is preserved (1.9 GPa / 680 °C), a significant amount of carbon is retained in prograde Chl-harzburgites and Tr-Dol-marble lenses. This observation is at odds with thermodynamic models that predict efficient carbonate dissolution during dehydration of carbonate-bearing antigorite serpentinite, and indicates that in natural systems substantial amounts of carbon can be recycled into the deep mantle via subduction of carbonate-bearing serpentinite.

Modeling a CO2 mineralization experiment of fractured peridotite from the Semail ophiolite/ Oman

NASA Astrophysics Data System (ADS)

Muller, Nadja; Zhang, Guoxiang; van Noort, Reinier; Spiers, Chris; Ten Grotenhuis, Saskia; Hoedeman, Gerco

2010-05-01

Most geologic CO2 sequestration technologies focus on sedimentary rocks, where the carbon dioxide is stored in a fluid phase. A possible alternative is to trap it as a mineral in the subsurface (in-situ) in basaltic or even (ultra)mafic rocks. Carbon dioxide in aqueous solution reacts with Mg-, Ca-, and Fe-bearing silicate minerals, precipitates as (MgCa,Fe)CO3 (carbonate), and can thus be permanently sequestered. The cation donors are silicate minerals such as olivine and pyroxene which are abundant in (ultra)mafic rocks, such as peridotite. Investigations are underway to evaluate the sequestration potential of the Semail Ophiolite in Oman, utilizing the large volumes of partially serpentinized peridotite that are present. Key factors are the rate of mineralization due to dissolution of the peridotite and precipitation of carbonate, the extent of the natural and hydraulic fracture network and the accessibility of the rock to reactive fluids. To quantify the influence of dissolution rates on the overall CO2 mineralization process, small, fractured peridotite samples were exposed to supercritical CO2 and water in laboratory experiments. The samples are cored from a large rock sample in the dimension of small cylinders with 1 cm in height and diameter, with a mass of ~2g. Several experimental conditions were tested with different equipment, from large volume autoclave to small volume cold seal vessel. The 650 ml autoclave contained 400-500g of water and a sample under 10 MPa of partial CO2 pressure up to 150. The small capsules in the cold seal vessel held 1-1.5g of water and the sample under CO2 partial pressure from 15MPa to 70 MPa and temperature from 60 to 200°C. The samples remained for two weeks in the reaction vessels. In addition, bench acid bath experiments in 150 ml vials were performed open to the atmosphere at 50-80°C and pH of ~3. The main observation was that the peridotite dissolved two orders of magnitude slower in the high pressure and temperature cell of the cold seal vessel than comparative experiments in large volume autoclaves and bench acid bath vials under lower and atmospheric pressure conditions. We attributed this observation to the limited water availability in the cold seal vessel, limiting the aqueous reaction of bi-carbonate formation and magnesite precipitation. To test this hypothesis, one of the cold seal vessel experiments at 20 MPa and 100°C was simulated with a reactive transport model, using TOUGHREACT. To simulate the actual experimental conditions, the model used a grid on mm and 100's of μm scale and a fractured peridotite medium with serpentine filling the fractures. The simulation produced dissolution comparable to the experiment and showed an effective shut down of the bi-carbonation reaction within one day after the start of the experiment. If the conditions of limited water supply seen in our experiments are applicable in a field setting, we could expect dissolution may be limited by the buffering of the pH and shut down of the bi-carbonate formation. Under field conditions water and CO2 will only flow in hydraulic induced fractures and the natural fracture network that is filled with serpentine and some carbonate. The simulation result and potential implication for the field application will require further experimental investigation in the lab or field in the future.

Genetic Aspects of Gold Mineralization at Some Occurrences in the Eastern Desert of Egypt

NASA Astrophysics Data System (ADS)

Abd El Monsef, M.; Slobodník, M.; Salem, I. A.

2012-04-01

The Eastern Desert of Egypt is well known as a gold-mining area since ancient times, there're more than 95 gold deposits and occurrences spread the whole area covered by the basement rocks of Precambrian age. The basement rocks of the Eastern Desert of Egypt constitute the Nubian Shield that has formed a continuous part of the Arabian-Nubian Shield before the opening of Red Sea (Oligocene-Early Miocene). Commonly, the system of gold-bearing quartz veins in the Eastern Desert is clearly structural controlled related to brittle-ductile shear zones that mostly developed during late deformational stages of the evolution history for basement rocks in the Eastern Desert. This running study principally aims to contribute the mineral resource potential of the gold deposits in Egypt, so particularly Fatira, Gidami and Atalla occurrences have been involved into a comprehensive study based on field, structural, mineralogical, geochemical and genetic investigations. It is intended to better understanding for the characteristics, distribution controls, conditions and age of mineralization in relation to the age of the hosting rocks intrusion to find if there're genetic links between the gold mineralization and the evolution of the host intrusive complex. Several authors suggested that the gold mineralization was related to the intrusion of the (postorogenic) Younger granites. Other authors interpret these deposits as products of hydrothermal activity induced either by metamorphism or cooling effects of early Paleozoic magmatism or as combined metamorphic/magmatic episodes. The prime focus will be directed to the ore itself and the associated hydrothermal alteration zones based on detailed maps and well-distributed samples network and geochemical anomalies distribution. The laboratory studies included microscopic examination (reflecting and transmitting microscopy) to allow for determination of the hosting rocks types and mineralogical changes related to the gold mineralization in each area and revealing the ore mineralogy and the ore textures, geochemical analyses (including rare earth elements) are to be used in order to determine the tectonic setting and magmatic evolution of the host intrusions, scanning electron microscope, microprobe analysis, stable isotopes and fluid inclusions will serve as a new part of this study in detection of the origin and the physico-chemical conditions (P-T condition) for the gold precipitation, Age dating of the host intrusion and mineralization will be based on K-Ar for dating potassium-bearing minerals in fresh host rocks and hydrothermal mineral phases.

Manufactured caverns in carbonate rock

DOEpatents

Bruce, David A.; Falta, Ronald W.; Castle, James W.; Murdoch, Lawrence C.

2007-01-02

Disclosed is a process for manufacturing underground caverns suitable in one embodiment for storage of large volumes of gaseous or liquid materials. The method is an acid dissolution process that can be utilized to form caverns in carbonate rock formations. The caverns can be used to store large quantities of materials near transportation facilities or destination markets. The caverns can be used for storage of materials including fossil fuels, such as natural gas, refined products formed from fossil fuels, or waste materials, such as hazardous waste materials. The caverns can also be utilized for applications involving human access such as recreation or research. The method can also be utilized to form calcium chloride as a by-product of the cavern formation process.

Dissolution enhancement of a model poorly water-soluble drug, atorvastatin, with ordered mesoporous silica: comparison of MSF with SBA-15 as drug carriers.

PubMed

Maleki, Aziz; Hamidi, Mehrdad

2016-01-01

The purpose of this study was to develop mesoporous silica materials incorporated with poorly water-soluble drug atorvastatin calcium (AC) in order to improve drug dissolution, and intended to be orally administrated. A comparison between 2D-hexagonal silica nanostructured SBA-15 and mesocellular siliceous foam (MSF) with continuous 3D pore system on drug release rate was investigated. AC-loaded mesoporous silicas were characterized thorough N2 adsorption-desorption analysis, Fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC) and dynamic light scattering (DLS). Results demonstrated a successful incorporation of AC into the silica-based hosts. The results taken from the drug release tests were also analyzed using different parameters, namely similarity factor (f2), difference factor (f1), dissolution efficiency (DE%), mean dissolution rate (MDR) and dissolution time (tm%). It confirmed a significant enhancement in the release profile of atorvastatin calcium with SBA-15, and MSF as drug carrier. Moreover, in comparison with SBA-15, MSF showed faster release rate of AC in enzyme-free simulated gastric fluid (pH 1.2). We believed that our findings can help the use of mesoporous silica materials in improving bioavailability of poorly water-soluble drugs.

Used Fuel Disposal in Crystalline Rocks. FY15 Progress Report

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

Wang, Yifeng

2015-08-20

The objective of the Crystalline Disposal R&D Work Package is to advance our understanding of long-term disposal of used fuel in crystalline rocks and to develop necessary experimental and computational capabilities to evaluate various disposal concepts in such media. Chapter headings are as follows: Fuel matrix degradation model and its integration with performance assessments, Investigation of thermal effects on the chemical behavior of clays, Investigation of uranium diffusion and retardation in bentonite, Long-term diffusion of U(VI) in bentonite: dependence on density, Sorption and desorption of plutonium by bentonite, Dissolution of plutonium intrinsic colloids in the presence of clay and asmore » a function of temperature, Laboratory investigation of colloid-facilitated transport of cesium by bentonite colloids in a crystalline rock system, Development and demonstration of discrete fracture network model, Fracture continuum model and its comparison with discrete fracture network model.« less

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

Lisabeth, Harrison; Zhu, Wenlu; Xing, Tiange

Olivine and pyroxene bearing rocks in the oceanic crust react with hydrothermal fluids producing changes in the physical characteristics and behaviors of the altered rocks. Notably, these reactions tend to increase solid volume, reducing pore volume, permeability and available reactive surface area; yet, entirely hydrated and/or carbonated rocks are commonly observed in the field. We investigate the evolution of porosity and permeability of fractured dunites reacted with CO 2-rich solutions in laboratory experiments. The alteration of crack surfaces changes the mechanical and transport properties of the bulk samples. Analysis of three-dimensional microstructural data shows that although precipitation of secondary mineralsmore » causes the total porosity of the sample to decrease, an interconnected network of porosity is maintained through channelized dissolution and coupled carbonate precipitation. Lastly, the observed microstructure appears to be the result of chemo-mechanical coupling, which may provide a mechanism of porosity maintenance without the need to invoke reaction-driven cracking.« less

Modeling transport kinetics in clinoptilolite-phosphate rock systems

NASA Technical Reports Server (NTRS)

Allen, E. R.; Ming, D. W.; Hossner, L. R.; Henninger, D. L.

1995-01-01

Nutrient release in clinoptilolite-phosphate rock (Cp-PR) systems occurs through dissolution and cation-exchange reactions. Investigating the kinetics of these reactions expands our understanding of nutrient release processes. Research was conducted to model transport kinetics of nutrient release in Cp-PR systems. The objectives were to identify empirical models that best describe NH4, K, and P release and define diffusion-controlling processes. Materials included a Texas clinoptilolite (Cp) and North Carolina phosphate rock (PR). A continuous-flow thin-disk technique was used. Models evaluated included zero order, first order, second order, parabolic diffusion, simplified Elovich, Elovich, and power function. The power-function, Elovich, and parabolic-diffusion models adequately described NH4, K, and P release. The power-function model was preferred because of its simplicity. Models indicated nutrient release was diffusion controlled. Primary transport processes controlling nutrient release for the time span observed were probably the result of a combination of several interacting transport mechanisms.

Fine-grained rutile in the Gulf of Maine: Diagenetic origin, source rocks, and sedimentary environment of deposition

USGS Publications Warehouse

Valentine, P.C.; Commeau, J.A.

1990-01-01

The Gulf of Maine, an embayment of the New England margin, is floored by shallow, glacially scoured basins that are partly filled with late Pleistocene and Holocene silt and clay containing 0.7 to 1.0 wt percent TiO2 chiefly in the form of silt-size rutile. Much of the rutile in the Gulf of Maine mud probably formed diagenetically in poorly cemented Carboniferous and Triassic coarse-grained sedimentary rocks of Nova Scotia and New Brunswick after the dissolution of titanium-rich detrital minerals (ilmenite, ilmenomagnetite). The diagenesis of rutile in coarse sedimentary rocks (especially arkose and graywacke) followed by erosion, segregation, and deposition (and including recycling of fine-grained rutile from shales) can serve as a model for predicting and prospecting for unconsolidated deposits of fine-grained TiO2. -from Authors

Cognate clinopyroxene from Paleogene mantle xenolith-bearing basanite lavas (East Serbia, SE Europe): the role of dissolution of mantle orthopyroxene

NASA Astrophysics Data System (ADS)

Cvetković, Vladica; Erić, Suzana; Radivojević, Maša; Šarić, Kristina

2012-11-01

The study focuses on clinopyroxene from mantle xenolith-bearing East Serbian basanites and suggests that dissolution of mantle orthopyroxene played an important role in at least some stages of the crystallization of these alkaline magmas. Five compositional types of clinopyroxene are distinguished, some of them having different textural forms: megacrysts (Type-A), green/colourless-cored phenocrysts (Type-B), overgrowths and sieve-textured cores (Type-C), rims and matrix clinopyroxene (Type-D), and clinopyroxene from the reaction rims around orthopyroxene xenocrysts (Type-E). Type-A is high-Al diopside that probably crystallized at near-liquidus conditions either directly from the host basanite or from compositionally similar magmas in previous magmatic episodes. Type-B cores show high VIAl/IVAl≥1 and low Mg# of mostly <75 and are interpreted as typical xenocrysts. Type-C, D and E are interpreted as typical cognate clinopyroxene. Type-D has Mg#<78, Al2O3 = 6-13 wt.%, TiO2 = 1.5-4.5 wt.%, and Na2O = 0.4-0.8 wt.% and compositionally similar clinopyroxene is calculated by MELTS as a phase in equilibrium with the last 30 % of melt starting from the average host lava composition. Type-C has Mg# = 72-89, Al2O3 = 4.5-9.5 wt.%, TiO2 = 1-2.5 wt.%, Na2O = 0.35-1 wt.% and Cr2O3 = 0.1-1.5 wt.%. This clinopyroxene has some compositional similarities to Type-E occurring exclusively around mantle orthopyroxene. Cr/Al vs Al/Ti and Cr/Al vs Na/Ti plots revealed that Type-C clinopyroxene can crystallize from a mixture of the host basanite magma and 2-20 wt.% mantle orthopyroxene. Sieve-textured Type-C crystals show characteristics of experimentally produced skeletal clinopyroxene formed by orthopyroxene dissolution suggesting that crystallization of Type-C was both texturally and compositionally controlled by orthopyroxene breakdown. According to FeO/MgOcpx/melt modelling the first clinopyroxene precipitating from the host basanite was Type-A (T ~ 1250 °C, p ~ 1.5 GPa). Dissolution of orthopyroxene produced decreasing FeO/MgOmelt and crystallization of Type-E and sieve-textured Type-C clinopyroxene (0.3-0.8 GPa and 1200-1050 °C). The melt composition gradually shifted towards higher FeO/MgOmelt ratios precipitating more evolved Type-C and Type-D approaching near-solidus conditions (<0.3 GPa; ~950 °C).

Impact of fluid-rock chemical interactions on tracer transport in fractured rocks.

PubMed

Mukhopadhyay, Sumit; Liu, H-H; Spycher, N; Kennedy, B M

2013-11-01

In this paper, we investigate the impact of chemical interactions, in the form of mineral precipitation and dissolution reactions, on tracer transport in fractured rocks. When a tracer is introduced in fractured rocks, it moves through the fracture primarily by advection and it also enters the stagnant water of the surrounding rock matrix through diffusion. Inside the porous rock matrix, the tracer chemically interacts with the solid materials of the rock, where it can precipitate depending on the local equilibrium conditions. Alternatively, it can be dissolved from the solid phase of the rock matrix into the matrix pore water, diffuse into the flowing fluids of the fracture and is advected out of it. We show that such chemical interactions between the fluid and solid phases have significant impact on tracer transport in fractured rocks. We invoke the dual-porosity conceptualization to represent the fractured rocks and develop a semi-analytical solution to describe the transient transport of tracers in interacting fluid-rock systems. To test the accuracy and stability of the semi-analytical solution, we compare it with simulation results obtained with the TOUGHREACT simulator. We observe that, in a chemically interacting system, the tracer breakthrough curve exhibits a pseudo-steady state, where the tracer concentration remains more or less constant over a finite period of time. Such a pseudo-steady condition is not observed in a non-reactive fluid-rock system. We show that the duration of the pseudo-state depends on the physical and chemical parameters of the system, and can be exploited to extract information about the fractured rock system, such as the fracture spacing and fracture-matrix interface area. © 2013.

Origin of middle rare earth element enrichments in acid waters of a Canadian high Arctic lake.

NASA Astrophysics Data System (ADS)

Johannesson, Kevin H.; Zhou, Xiaoping

1999-01-01

-Middle rare earth element (MREE) enriched rock-normalized rare earth element (REE) patterns of a dilute acidic lake (Colour Lake) in the Canadian High Arctic, were investigated by quantifying whole-rock REE concentrations of rock samples collected from the catchment basin, as well as determining the acid leachable REE fraction of these rocks. An aliquot of each rock sample was leached with 1 N HNO 3 to examine the readily leachable REE fraction of each rock, and an additional aliquot was leached with a 0.04 M NH 2OH · HCl in 25% (v/v) CH 3COOH solution, designed specifically to reduce Fe-Mn oxides/oxyhydroxides. Rare earth elements associated with the leachates that reacted with clastic sedimentary rock samples containing petrographically identifiable Fe-Mn oxide/oxyhydroxide cements and/or minerals/amorphous phases, exhibited whole-rock-normalized REE patterns similar to the lake waters, whereas whole-rock-normalized leachates from mafic igneous rocks and other clastic sedimentary rocks from the catchment basin differed substantially from the lake waters. The whole-rock, leachates, and lake water REE data support acid leaching or dissolution of MREE enriched Fe-Mn oxides/oxyhydroxides contained and identified within some of the catchment basin sedimentary rocks as the likely source of the unique lake water REE patterns. Solution complexation modelling of the REEs in the inflow streams and lake waters indicate that free metal ions (e.g., Ln 3+, where Ln = any REE) and sulfate complexes (LnSO 4+) are the dominant forms of dissolved REEs. Consequently, solution complexation reactions involving the REEs during weathering, transport to the lake, or within the lake, cannot be invoked to explain the MREE enrichments observed in the lake waters.

Characterization of seismic properties across scales: from the laboratory- to the field scale

NASA Astrophysics Data System (ADS)

Grab, Melchior; Quintal, Beatriz; Caspari, Eva; Maurer, Hansruedi; Greenhalgh, Stewart

2016-04-01

When exploring geothermal systems, the main interest is on factors controlling the efficiency of the heat exchanger. This includes the energy state of the pore fluids and the presence of permeable structures building part of the fluid transport system. Seismic methods are amongst the most common exploration techniques to image the deep subsurface in order to evaluate such a geothermal heat exchanger. They make use of the fact that a seismic wave caries information on the properties of the rocks in the subsurface through which it passes. This enables the derivation of the stiffness and the density of the host rock from the seismic velocities. Moreover, it is well-known that the seismic waveforms are modulated while propagating trough the subsurface by visco-elastic effects due to wave induced fluid flow, hence, delivering information about the fluids in the rock's pore space. To constrain the interpretation of seismic data, that is, to link seismic properties with the fluid state and host rock permeability, it is common practice to measure the rock properties of small rock specimens in the laboratory under in-situ conditions. However, in magmatic geothermal systems or in systems situated in the crystalline basement, the host rock is often highly impermeable and fluid transport predominately takes place in fracture networks, consisting of fractures larger than the rock samples investigated in the laboratory. Therefore, laboratory experiments only provide the properties of relatively intact rock and an up-scaling procedure is required to characterize the seismic properties of large rock volumes containing fractures and fracture networks and to study the effects of fluids in such fractured rock. We present a technique to parameterize fractured rock volumes as typically encountered in Icelandic magmatic geothermal systems, by combining laboratory experiments with effective medium calculations. The resulting models can be used to calculate the frequency-dependent bulk modulus K(ω) and shear modulus G(ω), from which the P- and S-wave velocities V P(ω) and V S(ω) and the quality factors QP(ω) and QS(ω) of fluid saturated fractured rock volumes can be estimated. These volumes are much larger and contain more complex structures than the rock samples investigated in the laboratory. Thus, the derived quantities describe the elastic and anelastic (energy loss due to wave induced fluid flow) short-term deformation induced by seismic waves at scales that are relevant for field-scale seismic exploration projects.

Bioremediation in Fractured Rock: 2. Mobilization of Chloroethene Compounds from the Rock Matrix.

PubMed

Shapiro, Allen M; Tiedeman, Claire R; Imbrigiotta, Thomas E; Goode, Daniel J; Hsieh, Paul A; Lacombe, Pierre J; DeFlaun, Mary F; Drew, Scott R; Curtis, Gary P

2018-03-01

A mass balance is formulated to evaluate the mobilization of chlorinated ethene compounds (CE) from the rock matrix of a fractured mudstone aquifer under pre- and postbioremediation conditions. The analysis relies on a sparse number of monitoring locations and is constrained by a detailed description of the groundwater flow regime. Groundwater flow modeling developed under the site characterization identified groundwater fluxes to formulate the CE mass balance in the rock volume exposed to the injected remediation amendments. Differences in the CE fluxes into and out of the rock volume identify the total CE mobilized from diffusion, desorption, and nonaqueous phase liquid dissolution under pre- and postinjection conditions. The initial CE mass in the rock matrix prior to remediation is estimated using analyses of CE in rock core. The CE mass mobilized per year under preinjection conditions is small relative to the total CE mass in the rock, indicating that current pump-and-treat and natural attenuation conditions are likely to require hundreds of years to achieve groundwater concentrations that meet regulatory guidelines. The postinjection CE mobilization rate increased by approximately an order of magnitude over the 5 years of monitoring after the amendment injection. This rate is likely to decrease and additional remediation applications over several decades would still be needed to reduce CE mass in the rock matrix to levels where groundwater concentrations in fractures achieve regulatory standards. © 2017, National Ground Water Association.

Improving Crotalidae polyvalent immune Fab reconstitution times.

PubMed

Quan, Asia N; Quan, Dan; Curry, Steven C

2010-06-01

Crotalidae polyvalent immune Fab (CroFab) is used to treat rattlesnake envenomations in the United States. Time to infusion may be a critical factor in the treatment of these bites. Per manufacturer's instructions, 10 mL of sterile water for injection (SWI) and hand swirling are recommended for reconstitution. We wondered whether completely filling vials with 25 mL of SWI would result in shorter reconstitution times than using 10-mL volumes and how hand mixing compared to mechanical agitation of vials or leaving vials undisturbed. Six sets of 5 vials were filled with either 10 mL or 25 mL. Three mixing techniques were used as follows: undisturbed; agitation with a mechanical agitator; and continuous hand rolling and inverting of vials. Dissolution was determined by observation and time to complete dissolution for each vial. Nonparametric 2-tailed P values were calculated. Filling vials completely with 25 mL resulted in quicker dissolution than using 10-mL volumes, regardless of mixing method (2-tailed P = .024). Mixing by hand was shorter than other methods (P < .001). Reconstitution with 25 mL and hand mixing resulted in the shortest dissolution times (median, 1.1 minutes; range, 0.9-1.3 minutes). This appeared clinically important because dissolution times using 10 mL and mechanical rocking of vials (median, 26.4 minutes) or leaving vials undisturbed (median, 33.6 minutes) was several-fold longer. Hand mixing after filling vials completely with 25 mL results in shorter dissolution times than using 10 mL or other methods of mixing and is recommended, especially when preparing initial doses of CroFab. Copyright (c) 2010 Elsevier Inc. All rights reserved.

Numerical modeling of mineral dissolution - precipitation kinetics integrating interfacial processes

NASA Astrophysics Data System (ADS)

Azaroual, M. M.

2016-12-01

The mechanisms of mineral dissolution/precipitation are complex and interdependent. Within a same rock, the geochemical modelling may have to manage kinetic reactions with high ratios between the most reactive minerals (i.e., carbonates, sulfate salts, etc.) and less reactive minerals (i.e., silica, alumino-silicates, etc.). These ratios (higher than 10+6) induce numerical instabilities for calculating mass and energy transfers between minerals and aqueous phases at the appropriate scales of time and space. The current scientific debate includes: i) changes (or not) of the mineral reactive surface with the progress of the dissolution/precipitation reactions; ii) energy jumps (discontinuity) in the thermodynamic affinity function of some dissolution/precipitation reactions and iii) integration of processes at the "mineral - aqueous solution" interfaces for alumino-silicates, silica and carbonates. In recent works dealing with the specific case of amorphous silica, measurements were performed on nano-metric cross-sections indicating the presence of surface layer between the bulk solution and the mineral. This thin layer is composed by amorphous silica and hydrated silica "permeable" to the transfer of water and ionic chemical constituents. The boundary/interface between the initial mineral and the silica layer is characterized by a high concentration jump of chemical products at the nanoscale and some specific interfacial dissolution/precipitation processes.In this study, the results of numerical simulations dealing with different mechanisms of silicate and carbonate dissolution/precipitation reactions and integrating interfacial processes will be discussed. The application of this approach to silica precipitation is based on laboratory experiments and it highlights the significant role of the "titration" surface induced by surface complexation reactions in the determination of the kinetics of precipitation.

Alternate Fuel Cycle Technologies/Thorium Fuel Cycle Technology Programs. Quarterly report for period 1 April--30 June 1978

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

Vondra, B.L.

1978-08-01

Voloxidation and dissolution studies: rotary-kiln heat-transfer tests are under way using a small rotary kiln along with the development of a mathematical model to determine kiln-heat-flux profiles necessary to maintain a desired temperature gradient. The erosion/corrosion test for evaluating materials of construction is operational. Fuel from a BWR (Big Rock Point) yielded more fine solid residue on dissolution than in previous tests with PWR fuel. Two additional parametric voloxidation tests with H.B. Robinson fuel compared air vs pure oxygen atmospheres at 550{sup 0}C; overall tritium release and subsequent fuel dissolution were equivalent. Thorium dissolution studies: the dissolution rate of thoriamore » in fluoride-catalyzed 8 to 14 M HNO{sub 3} (100{sup 0}C) was max between 0.04 to 0.06 M HF; at higher fluoride concentrations, ThF{sub 4}.5H{sub 2}O precipitated. The rate of zircaloy dissolution continued to increase with increasing fluoride concentration. Stainless-steel-clad (Th,U)0{sub 2} fuel rods irradiated in the NRX reactor were sheared, voloxidized, and dissolved. {le}10% of the tritium was released during voloxidation in air at 600{sup 0}C. Carbon-14 removal from off-gas and fixation: carbon dioxide removal with Linde 13X molecular sieves to less than 100 ppB was experimentally verified using 300 ppM CO in air. Decontamination factors from 3000 to 7500 were obtained for CO{sub 2} removal in the gas-slurry stirred-tank reactor with CA(OH){sub 2}.or Ba(0H){sub 2}/sup .8H2O./. With Ba(OH){sub 2}.H{sub 2}0{sup 2} in a fixed-bed column, decontamination factors of about 30,000 were obtained.« less

Dolomite dissolution rates and possible Holocene dedolomitization of water-bearing units in the Edwards aquifer, south-central Texas

USGS Publications Warehouse

Deike, R.G.

1990-01-01

Rates of dolomite dissolution can be used to test the concept, based on geomorphologic evidence, that a major part of the Edwards aquifer could have formed within the Holocene, a timeframe of approximately 10,000 years. During formation of the aquifer in the Edwards limestone (Cretaceous, Albian) of the Balcones fault zone, dolomite dissolution and porosity development were synchronous and the result of mixing-zone dedolomitization. Initiation of the mixing zone in the early Holocene (???11,000 years before present) is suggested by the maximum age of formation of major discharge sites that allowed the influx of meteoric water into brine-filled, dolomitic preaquifer units. Dedolomitization, the dissolution of dolomite and net precipitation of calcite, has left aquifer units that are calcitic, and 40 vol.% interconnected pore space. The mass of dolomite missing is obtained by comparison of stratigraphically equivalent altered and unaltered units. One dissolution rate (1.76 ?? 10-4 mmol dolomite kgH2O-1yr-1) is determined from this mass, 104yr reaction time, and a log-linear function describing the increase in mass discharge (three orders of magnitude) during aquifer formation. The second estimated dissolution rate is obtained from the mass transfer of dolomite to solution calculated from the increase in magnesium in pore fluids selected from the modern aquifer to represent a typical flowpath during aquifer formation. A reaction time of 104yr for this mass transfer yields a rate of 0.56 ?? 10-4 mmol dolomite kgH2O-1yr-1. Both of these rates are comparable to modern rates of dolomite dissolution (0.3 to 4.5 ?? 10-4 mmol dolomite kgH2O-1yr-1) calculated from measured reaction times in the Tertiary Floridan aquifer system in Florida and the Madison aquifer in the Mississippian Madison Limestone of the Northern Great Plains. Similarity of these rates to the estimated paleo-rates of dolomite dissolution supports a 104 yr reaction timeframe. The Holocene reaction time also can be compared to a series of reaction times calculated by assuming that the mass of dolomite missing from the Edwards was removed at rates observed in the Floridan and Madison aquifers. These reaction times (for complete removal of dolomite) range from 2700 to 58,500 yr and span the Pleistocene-Holocene boundary. Finally, an estimated dolomite reaction rate during dedolomitization of the Edwards aquifer based on surface area of exposed dolomite [mmol cm-2s-1 (millimoles per square centimeter per second)] may be approximated from reaction times. This rate is directly a function of the mass of dolomite removed and the surface area exposed per pore volume passing through the rock. The surface area is available from the observed dolomite rhomb size in unaltered rock. The rate of pore fluid movement is obtained from the averaged annual discharge. Rates during formation of the Edwards aquifer calculated from all reaction times range from 10-13 to 10-14 mmol dolomite cm-2s-1. These rates are faster than rates (10-18 mmol cm-2s-1), measured in the pure laboratory system, CaMg(CO3)2CO2H2O, but slower than rates determined in an alpine stream study (10-10 to 10-11 mmol cm-2s-1) where cold glacial melt water flows over dolostone. Dolomite dissolution rates from both the Edwards and other aquifers support the concept that a major part of the Edwards aquifer could have formed within the Holocene. ?? 1990.

Factors controlling the regional distribution of vanadium in ground water

USGS Publications Warehouse

Wright, Michael T.; Belitz, Kenneth

2010-01-01

Although the ingestion of vanadium (V) in drinking water may have possible adverse health effects, there have been relatively few studies of V in groundwater. Given the importance of groundwater as a source of drinking water in many areas of the world, this study examines the potential sources and geochemical processes that control the distribution of V in groundwater on a regional scale. Potential sources of V to groundwater include dissolution of V rich rocks, and waste streams from industrial processes. Geochemical processes such as adsorption/desorption, precipitation/dissolution, and chemical transformations control V concentrations in groundwater. Based on thermodynamic data and laboratory studies, V concentrations are expected to be highest in samples collected from oxic and alkaline groundwater. However, the extent to which thermodynamic data and laboratory results apply to the actual distribution of V in groundwater is not well understood. More than 8400 groundwater samples collected in California were used in this study. Of these samples, high (> or = 50 μg/L) and moderate (25 to 49 μg/L) V concentrations were most frequently detected in regions where both source rock and favorable geochemical conditions occurred. The distribution of V concentrations in groundwater samples suggests that significant sources of V are mafic and andesitic rock. Anthropogenic activities do not appear to be a significant contributor of V to groundwater in this study. High V concentrations in groundwater samples analyzed in this study were almost always associated with oxic and alkaline groundwater conditions, which is consistent with predictions based on thermodynamic data.

10 CFR 960.4-2-2 - Geochemistry.

Code of Federal Regulations, 2013 CFR

2013-01-01

.... Considering the likely chemical interactions among radionuclides, the host rock, and the ground water, the... the rock matrix, or sorption of radionuclides; inhibit the formation of particulates, colloids... transport of radionuclides by particulates, colloids, or complexes. (3) Mineral assemblages that, when...

10 CFR 960.4-2-2 - Geochemistry.

Code of Federal Regulations, 2014 CFR

2014-01-01

.... Considering the likely chemical interactions among radionuclides, the host rock, and the ground water, the... the rock matrix, or sorption of radionuclides; inhibit the formation of particulates, colloids... transport of radionuclides by particulates, colloids, or complexes. (3) Mineral assemblages that, when...

Water chemistry at Snowshoe Mountain, Colorado: mixed processes in a common bedrock

USGS Publications Warehouse

Hoch, A.R.; Reddy, M.M.

2001-01-01

At Snowshoe Mountain the primary bedrock is quite homogeneous, but weathering processes vary as waters moves through the soils, vadose zone and phreatic zone of the subsurface. In the thin soil, physical degradation of tuff facilitates preferential dissolution of potassium ion from glass within the rock matrix, while other silicate minerals remain unaltered. In the vadose zone, in the upper few meters of fractured bedrock, dilute water infiltrates during spring snowmelt and summer storms, leading to preferential dissolution of augite exposed on fracture surfaces. Deeper yet, in the phreatic zone of the fractured bedrock, Pleistocene calcite fracture fillings dissolve, and dioctahedral and trioctahedral clays form as penetrative weathering alters feldspar and pyroxene. Alkalinity is generated and silica concentrations are buffered by mineral alteration reactions.

The Unicorn Cave, Southern Harz Mountains, Germany: From known passages to unknown extensions with the help of geophysical surveys

NASA Astrophysics Data System (ADS)

Kaufmann, Georg; Nielbock, Ralf; Romanov, Douchko

2015-12-01

In soluble rocks (limestone, dolomite, anhydrite, gypsum, …), fissures and bedding partings can be enlarged with time by both physical and chemical dissolution of the host rock. With time, larger cavities evolve, and a network of cave passages can evolve. If the enlarged cave voids are not too deep under the surface, geophysical measurements can be used to detect, identify and trace these karst structures, e.g.: (i) gravity revealing air- and sediment-filled cave voids through negative Bouguer anomalies, (ii) electrical resistivity imaging (ERI) mapping different infillings of cavities either as high resistivities from air-filled voids or dry soft sediments, or low resistivities from saturated sediments, and (iii) groundwater flow through electrical potential differences (SP) arising from dislocated ionic charges from the walls of the underground flow paths. We have used gravity, ERI, and SP methods both in and above the Unicorn Cave located in the southern Harz Mountains in Germany. The Unicorn Cave is a show cave developed in the Werra dolomite formation of the Permian Zechstein sequence, characterised by large trunk passages interrupted by larger rooms. The overburden of the cave is only around 15 m, and passages are filled with sediments reaching infill thicknesses up to 40 m. We present results from our geophysical surveys above the known cave and its northern and southern extension, and from the cave interior. We identify the cave geometry and its infill from gravity and ERI measurements, predict previously unknown parts of the cave, and subsequently confirm the existence of these new passages through drilling. From the wealth of geophysical data acquired we derive a three-dimensional structural model of the Unicorn Cave and its surrounding, especially the cave infill.

Investigation of the geochemical evolution of groundwater under agricultural land: A case study in northeastern Mexico

NASA Astrophysics Data System (ADS)

Ledesma-Ruiz, Rogelio; Pastén-Zapata, Ernesto; Parra, Roberto; Harter, Thomas; Mahlknecht, Jürgen

2015-02-01

Zona Citrícola is an important area for Mexico due to its citriculture activity. Situated in a sub-humid to humid climate adjacent to the Sierra Madre Oriental, this valley hosts an aquifer system that represents sequences of shales, marls, conglomerates, and alluvial deposits. Groundwater flows from mountainous recharge areas to the basin-fill deposits and provides base flows to supply drinking water to the adjacent metropolitan area of Monterrey. Recent studies examining the groundwater quality of the study area urge the mitigation of groundwater pollution. The objective of this study was to characterize the physical and chemical properties of the groundwater and to assess the processes controlling the groundwater's chemistry. Correlation was used to identify associations among various geochemical constituents. Factor analysis was applied to identify the water's chemical characteristics that were responsible for generating most of the variability within the dataset. Hierarchical cluster analysis was employed in combination with a post-hoc analysis of variance to partition the water samples into hydrochemical water groups: recharge waters (Ca-HCO3), transition zone waters (Ca-HCO3-SO4 to Ca-SO4-HCO3) and discharge waters (Ca-SO4). Inverse geochemical models of these groups were developed and constrained using PHREEQC to elucidate the chemical reactions controlling the water's chemistry between an initial (recharge) and final water. The primary reactions contributing to salinity were the following: (1) water-rock interactions, including the weathering of evaporitic rocks and dedolomitization; (2) dissolution of soil gas carbon dioxide; and (3) input from animal/human wastewater and manure in combination with by denitrification processes. Contributions from silicate weathering to salinity ranged from less important to insignificant. The findings suggest that it may not be cost-effective to regulate manure application to mitigate groundwater pollution.

Reaction softening by dissolution–precipitation creep in a retrograde greenschist facies ductile shear zone, New Hampshire, USA

USGS Publications Warehouse

McAleer, Ryan J.; Bish, David L.; Kunk, Michael J.; Sicard, Karri R.; Valley, Peter M.; Walsh, Gregory J.; Wathen, Bryan A.; Wintsch, R.P.

2016-01-01

We describe strain localization by a mixed process of reaction and microstructural softening in a lower greenschist facies ductile fault zone that transposes and replaces middle to upper amphibolite facies fabrics and mineral assemblages in the host schist of the Littleton Formation near Claremont, New Hampshire. Here, Na-poor muscovite and chlorite progressively replace first staurolite, then garnet, and finally biotite porphyroblasts as the core of the fault zone is approached. Across the transect, higher grade fabric-forming Na-rich muscovite is also progressively replaced by fabric-forming Na-poor muscovite. The mineralogy of the new phyllonitic fault-rock produced is dominated by Na-poor muscovite and chlorite together with late albite porphyroblasts. The replacement of the amphibolite facies porphyroblasts by muscovite and chlorite is pseudomorphic in some samples and shows that the chemical metastability of the porphyroblasts is sufficient to drive replacement. In contrast, element mapping shows that fabric-forming Na-rich muscovite is selectively replaced at high-strain microstructural sites, indicating that strain energy played an important role in activating the dissolution of the compositionally metastable muscovite. The replacement of strong, high-grade porphyroblasts by weaker Na-poor muscovite and chlorite constitutes reaction softening. The crystallization of parallel and contiguous mica in the retrograde foliation at the expense of the earlier and locally crenulated Na-rich muscovite-defined foliation destroys not only the metastable high-grade mineralogy, but also its stronger geometry. This process constitutes both reaction and microstructural softening. The deformation mechanism here was thus one of dissolution–precipitation creep, activated at considerably lower stresses than might be predicted in quartzofeldspathic rocks at the same lower greenschist facies conditions.

4D synchrotron X-ray imaging to understand porosity development in shales during exposure to hydraulic fracturing fluid

NASA Astrophysics Data System (ADS)

Kiss, A. M.; Bargar, J.; Kohli, A. H.; Harrison, A. L.; Jew, A. D.; Lim, J. H.; Liu, Y.; Maher, K.; Zoback, M. D.; Brown, G. E.

2016-12-01

Unconventional (shale) reservoirs have emerged as the most important source of petroleum resources in the United States and represent a two-fold decrease in greenhouse gas emissions compared to coal. Despite recent progress, hydraulic fracturing operations present substantial technical, economic, and environmental challenges, including inefficient recovery, wastewater production and disposal, contaminant and greenhouse gas pollution, and induced seismicity. A relatively unexplored facet of hydraulic fracturing operations is the fluid-rock interface, where hydraulic fracturing fluid (HFF) contacts shale along faults and fractures. Widely used, water-based fracturing fluids contain oxidants and acid, which react strongly with shale minerals. Consequently, fluid injection and soaking induces a host of fluid-rock interactions, most notably the dissolution of carbonates and sulfides, producing enhanced or "secondary" porosity networks, as well as mineral precipitation. The competition between these mechanisms determines how HFF affects reactive surface area and permeability of the shale matrix. The resultant microstructural and chemical changes may also create capillary barriers that can trap hydrocarbons and water. A mechanistic understanding of the microstructure and chemistry of the shale-HFF interface is needed to design new methodologies and fracturing fluids. Shales were imaged using synchrotron micro-X-ray computed tomography before, during, and after exposure to HFF to characterize changes to the initial 3D structure. CT reconstructions reveal how the secondary porosity networks advance into the shale matrix. Shale samples span a range of lithologies from siliceous to calcareous to organic-rich. By testing shales of different lithologies, we have obtained insights into the mineralogic controls on secondary pore network development and the morphologies at the shale-HFF interface and the ultimate composition of produced water from different facies. These results show that mineral texture is a major control over secondary porosity network morphology.

Geochemistry of surface and subsurface waters in quartz-sandstones: significance for the geomorphic evolution of tepui table mountains (Gran Sabana, Venezuela)

NASA Astrophysics Data System (ADS)

Mecchia, Marco; Sauro, Francesco; Piccini, Leonardo; De Waele, Jo; Sanna, Laura; Tisato, Nicola; Lira, Jesus; Vergara, Freddy

2014-04-01

In situ measurements of discharge, pH, electric conductivity (EC), temperature, and SiO2 content have been carried out during five expeditions in the last 20 years on the summit plateaus, inside caves and along the rivers of the surrounding lowlands of three tepui massifs in Venezuela (Auyan, Roraima, and Chimanta). Additionally, detailed chemical analyses were performed on waters sampled in a newly discovered extensive quartz-sandstone cave system on the Auyan Tepui. Rock samples of the quartz-sandstone bedrock from different locations have been analysed to obtain their chemical composition with a wavelength dispersive X-ray fluorescence spectrometer. These data show that the majority of silica present in surface and subsurface water comes from dissolution of quartz and only in minor amount from hydrolysis of other silicate minerals. Probably the presence of a hardened crust of iron hydroxides limits the dissolution of silica on the top surface of tepuis. Dissolution in the subsurface, instead, is more significant and causes, in the long term, the “arenisation” of the quartz-sandstone and its subsequent removal by mechanical erosion. On the other hand, waters flowing on the arkosic rock outcropping on the lowland below the tepuis obtain their high dissolved silica content mainly from hydrolysis of silicates. The morphological evolution of these table mountains appears thus to be controlled mainly by the underground weathering of the quartz-sandstone, with the opening of deep fractures (grietas) and the collapse of large underground horizontal cave systems. Scarp retreat, instead, seems to be related to the higher weathering rate of the more arkosic formations underlying the quartz-sandstones.

Shallow properties of faults in carbonate rocks - The Jandaíra Formation, Potiguar Basin, Brazil

NASA Astrophysics Data System (ADS)

Bezerra, F. H.; Bertotti, G.; Rabelo, J.; Silva, A. T.; Carneiro, M. A.; Cazarin, C. L.; Silva, C. C.; Vieira, M. M.; Bisdom, K.; Moraes, A.

2014-12-01

We studied the development of shallow faults in the Jandaíra Formation, a Turonian-Campanian carbonate platform in the Potiguar Basin, northeastern Brazil. Our main goal was to characterize fault geometry and properties such as porosity and permeability, and associate these results with fluid flow in shallow conditions. We used an integrated multidisciplinary approach, which combined Quickbird satellite and an unmanned aerial vehicle (UAV, drone) imagery, structural and sedimentary-facies mapping, and petrographic and petrophysical analyses. The Jandaíra Formation presents a variety of carbonate facies, which include mudstones to bioclastic, peloidal, intraclastic, and oolitic grainstones. We modeled our remote sensing and structural data using a finite element analysis system for 2D deformation modeling. We applied the magnitudes and directions of the present-day stress field to simulate depths as deep as 500 m. These stress data were derived from borehole breakout data and drilling-induced tensile fractures observed in resistivity image logs. Our results indicate the occurrence of dilation processes along three sets of joints that were reactivated as faults in the upper crust: N-S, NE-, and E-W-striking faults. These faults provided preferential leaching pathways to fresh water percolation, contributing to localized dissolution and increased secondary porosity and permeability. The results also indicate that the tectonic stresses are concentrated in preferred structural zones such as fault intersection and termination, which are sites of increased fracturing and dissolution. Dissolution by fluids increased permeability in carbonate rocks from primary values of 0.0-0.94 mD to as much as 1370.11 mD. This process is mostly Cenozoic.

Gas-water-rock interactions in Frio Formation following CO2 injection: Implications for the storage of greenhouse gases in sedimentary basins

USGS Publications Warehouse

Kharaka, Yousif K.; Cole, David R.; Hovorka, Susan D.; Gunter, W.D.; Knauss, Kevin G.; Freifeild, Barry M.

2006-01-01

To investigate the potential for the geologic storage of CO2 in saline sedimentary aquifers, 1600 t of CO2 were injected at 1500 m depth into a 24-m-thick sandstone section of the Frio Formation, a regional brine and oil reservoir in the U.S. Gulf Coast. Fluid samples obtained from the injection and observation wells before CO2 injection showed a Na-Ca-Cl–type brine with 93,000 mg/L total dissolved solids (TDS) at near saturation with CH4 at reservoir conditions. Following CO2 breakthrough, samples showed sharp drops in pH (6.5–5.7), pronounced increases in alkalinity (100–3000 mg/L as HCO3) and Fe (30–1100 mg/L), and significant shifts in the isotopic compositions of H2O, dissolved inorganic carbon (DIC), and CH4. Geochemical modeling indicates that brine pH would have dropped lower but for the buffering by dissolution of carbonate and iron oxyhydroxides. This rapid dissolution of carbonate and other minerals could ultimately create pathways in the rock seals or well cements for CO2 and brine leakage. Dissolution of minerals, especially iron oxyhydroxides, could mobilize toxic trace metals and, where residual oil or suitable organics are present, the injected CO2 could also mobilize toxic organic compounds. Environmental impacts could be major if large brine volumes with mobilized toxic metals and organics migrated into potable groundwater. The δ18O values for brine and CO2 samples indicate that supercritical CO2 comprises ∼50% of pore-fluid volume ∼6 mo after the end of injection. Postinjection sampling, coupled with geochemical modeling, indicates that the brine gradually will return to its preinjection composition.

Magnetic properties of frictional volcanic materials

NASA Astrophysics Data System (ADS)

Kendrick, Jackie E.; Lavallée, Yan; Biggin, Andrew; Ferk, Annika; Leonhardt, Roman

2015-04-01

During dome-building volcanic eruptions, highly viscous magma extends through the upper conduit in a solid-like state. The outer margins of the magma column accommodate the majority of the strain, while the bulk of the magma is able to extrude, largely undeformed, to produce magma spines. Spine extrusion is often characterised by the emission of repetitive seismicity, produced in the upper <1 km by magma failure and slip at the conduit margins. The rheology of the magma controls the depth at which fracture can occur, while the frictional properties of the magma are important in controlling subsequent marginal slip processes. Upon extrusion, spines are coated by a carapace of volcanic fault rocks which provide insights into the deeper conduit processes. Frictional samples from magma spines at Mount St. Helens (USA), Soufriere Hills (Montserrat) and Mount Unzen (Japan) have been examined using structural, thermal and magnetic analyses to reveal a history of comminution, frictional heating, melting and cooling to form volcanic pseudotachylyte. Pseudotachylyte has rarely been noted in volcanic materials, and the recent observation of its syn-eruptive formation in dome-building volcanoes was unprecedented. The uniquely high thermal conditions of volcanic environments means that frictional melt remains at elevated temperatures for longer than usual, causing slow crystallisation, preventing the development of some signature "quench" characteristics. As such, rock-magnetic tests have proven to be some of the most useful tools in distinguishing pseudotachylytes from their andesite/ dacite hosts. In volcanic pseudotachylyte the mass normalised natural remanent magnetisation (NRM) when further normalised with the concentration dependent saturation remanence (Mrs) was found to be higher than the host rock. Remanence carriers are defined as low coercive materials across all samples, and while the remanence of the host rock displays similarities to an anhysteretic remanent magnetisation (ARM), as expected for a thermal origin, the remanence of volcanic pseudotachylyte has been found to be comparable to an isothermal remanent magnetisation (IRM). Thus, the pseudotachylyte has experienced a strong magnetic field that overwrote the previous thermoremanent magnetisation of the magma, such as the strong local electric current that occurs in faults (e.g. Ferré et al., 2005). Additionally, the pseudotachylyte seems more often to comprise of uniaxial non-interacting single-domain particles compared to pseudo-single in the host, and to have a single Curie temperature whereas the host more commonly exhibits multiple phases. Differences in rock-magnetic parameters between the pseudotachylyte and host are significant, but not as high as those observed in granites by Nakamura et al. (2002) or Ferré et al. (2005), probably because granitic host rocks do not already carry a strong and stable remanence as do these extrusive volcanic rocks. The application of rock-magnetic tests in volcanology will undoubtedly continue to be a "go-to" tool for identification of pseudotachylytes, which are increasingly being recognised to play an important role in dome-building eruptions. Refs: Ferré, E.C., Zechmeister, M.S., Geissman, J.W., MathanaSekaran, N. and Kocak, K., 2005. The origin of high magnetic remanence in fault pseudotachylites: Theoretical considerations and implication for coseismic electrical currents. Tectonophysics, 402(1-4): 125-139. Nakamura, N., Hirose, T. and Borradaile, G.J., 2002. Laboratory verification of submicron magnetite production in pseudotachylytes: relevance for paleointensity studies. . Earth and Planetary Science Letters, 201(1): 13-18.

Incremental growth of an upper crustal, A-type pluton, Argentina: Evidence of a re-used magma pathway

NASA Astrophysics Data System (ADS)

Alasino, Pablo H.; Larrovere, Mariano A.; Rocher, Sebastián; Dahlquist, Juan A.; Basei, Miguel A. S.; Memeti, Valbone; Paterson, Scott; Galindo, Carmen; Macchioli Grande, Marcos; da Costa Campos Neto, Mario

2017-07-01

Carboniferous igneous activity in the Sierra de Velasco (NW Argentina) led to the emplacement of several magmas bodies at shallow levels (< 2 kbar). One of these, the San Blas intrusive complex formed over millions of years (≤ 2-3 m.y.) through three periods of magma additions that are characterized by variations in magma sources and emplacement style. The main units, mostly felsic granitoids, have U-Pb zircon crystallization ages within the error range. From older to younger (based on cross-cutting relationships) intrusive units are: (1) the Asha unit (340 ± 7 Ma): a tabular to funnel-shaped intrusion emplaced during a regional strain field dominated by WSW-ENE shortening with contacts discordant to regional host-rock structures; (2) the San Blas unit (344 ± 2 Ma): an approximate cylindrical-shaped intrusion formed by multiple batches of magmas, with a roughly concentric fabric pattern and displacement of the host rock by ductile flow of about 35% of shortening; and (3) the Hualco unit (346 ± 6 Ma): a small body with a possible mushroom geometry and contacts concordant to regional host-rock structures. The magma pulses making up these units define two groups of A-type granitoids. The first group includes the peraluminous granitic rocks of the Asha unit generated mostly by crustal sources (εNdt = - 5.8 and εHft in zircon = - 2.9 to - 4.5). The second group comprises the metaluminous to peraluminous granitic rocks of the youngest units (San Blas and Hualco), which were formed by a heterogeneous mixture between mantle and crustal sources (εNdt = + 0.6 to - 4.8 and εHft in zircon = + 3 to - 6). Our results provide a comprehensive view of the evolution of an intrusive complex formed from multiple non-consanguineous magma intrusions that utilized the same magmatic plumbing system during downward transfer of host materials. As the plutonic system matures, the ascent of magmas is governed by the visco-elastic flow of host rock that for younger batches include older hot magma mush. The latter results in ductile downward flow of older, during rise of younger magma. Such complexes may reflect the plutonic portion of volcanic centers where chemically distinct magmas are erupted.

Central Antarctic provenance of Permian sandstones in Dronning Maud Land and the Karoo Basin: Integration of U Pb and TDM ages and host-rock affinity from detrital zircons

NASA Astrophysics Data System (ADS)

Veevers, J. J.; Saeed, A.

2007-12-01

In conjugate SE Africa and Antarctica, Early Permian sandstones of the Swartrant Formation of the Ellisras Basin, Vryheid Formation of the Karoo Basin, and Amelang Plateau Formation of Dronning Maud Land (DML) were deposited after Gondwanan glaciation on a westward paleoslope. We analysed detrital zircons for U-Pb ages by a laser ablation microprobe-inductively coupled plasma mass spectrometer (LAM-ICPMS) and attached age significance only to clusters of three or more overlapping analyses. We analysed Hf-isotope compositions by a multi-collector spectrometer (LAM-MC-ICPMS) and trace elements by electron microprobe (EMP) and ICPMS. These analyses indicate the rock type and source (whether crustal or juvenile mantle) of the host magma, and a "crustal" model age ( TDMC). The integrated analysis gives a more distinctive, and more easily interpreted, picture of crustal evolution in the provenance area than age data alone. Zircons from the Ellisras Basin are aged 2700-2540 Ma with minor populations about 2815 Ma and 2040 Ma, which correspond with the ages of the upslope parts of the proximal Kaapvaal Craton and Limpopo Belt. Mafic rock is the dominant host rock, and it reflects the Archean granite-greenstone terrane of the Kaapvaal Craton. The three Karoo Basin samples and the two DML samples have zircons with these common properties: (1) 1160-880 Ma, host magma mafic granitoid (< 65% SiO 2) derived from juvenile depleted mantle sources ( ɛHf positive) at 1.65 Ga and 1.35 Ga, with TDMC of 2.0-0.9 Ga; (2) 760 to 480 Ma, host magma granitoid and low-heavy rare earth element rock (?alkaline rock-carbonatite), derived from mixed crustal and juvenile depleted mantle sources ( ɛHf positive and negative) at 1.50 Ga and 1.35 Ga, with TDMC of 2.0-0.9 Ga. Together with similar detrital zircons in Triassic sandstone of SE Australia, these properties reflect those in upslope central Antarctica, indicating a provenance of ˜ 1000 Ma (Grenville) cratons embedded in 700-500 Ma (Pan-Gondwanaland) fold belts. Detrital zircons in Cambrian sediments of the Ellsworth-Whitmore Mountains block and Cambrian metasediments of the Welch Mountains with comparable properties suggest that the central Antarctic provenance operated also in the ˜ 500 Ma Cambrian.

Local equilibrium of mafic enclaves and granitoids of the Turtle pluton, southeast California: Mineral, chemical, and isotopic evidence

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

Allen, C.M.

Major element and trace element compositions of whole rocks, mineral compositions, and Rb-Sr isotopic compositions of enclave and host granitoid pairs from the Early Cretaceous, calc-alkaline Turtle pluton of southeastern California suggest that the local environmental profoundly affects some enclave types. In the Turtle pluton, where the source of fine-grained, mafic enclaves can be deduced to be magmatic by the presence of partially disaggregated basaltic dikes, mineral chemistry suggests partial or complete local equilibrium among mineral species in the enclave and its host granitoid. Because of local Rb-Sr isotopic equilibration between fine-grained enclaves and host granitoid, one cannot use Srmore » isotopes to distinguish an enclave source independent of its host rocks from an enclave source related to the enclosing pluton. However, preliminary Nd isotopic data suggest an independent, mantle source for enclaves.« less

Nectonema zealandica n. sp. (Nematomorpha: Nectonematoidea) parasitising the purple rock crab Hemigrapsus edwardsi (Brachyura: Decapoda) in New Zealand, with notes on the prevalence of infection and host defence reactions.

PubMed

Poinar, G; Brockerhoff, A M

2001-10-01

A new species of marine hairworm, Nectonema zealandica (Nematomorpha: Nectonematoidea), is described from the purple rock crab Hemigrapsus edwardsi Hilgendorf from the South Island, New Zealand. This is the first record of Nectonema in the South Pacific Ocean and the southernmost locality for the genus. The description is based on juveniles and pre-adults taken from crabs. The new species is characterised by its stomal structure, presence of four cephalic papillae, mesenchyme arranged in eight lobes in pre-adults, insertion of muscle layer increasing body diameter at the septum and translucent anterior chamber. Data on the prevalence of infection over a three-year period, rates of parasitism in relation to host sex and size, and host defence reactions are presented. A list of all reported hosts of nectonematids is included.

The initial stages of NaCl dissolution: Ion or ion pair solvation?

NASA Astrophysics Data System (ADS)

Klimes, Jiri; Michaelides, Angelos

2009-03-01

The interaction of water with rock salt (NaCl) is important in a wide variety of natural processes and human activities. A lot is known about NaCl dissolution at the macroscopic level but we do not yet have a detailed atomic scale picture of how salt crystals dissolve. Here we report an extensive series of density functional theory, forcefield and molecular dynamics studies of water clusters at flat and defective NaCl surfaces and NaCl clusters. The focus is on answering seemingly elementary questions such as how many water molecules are needed before it becomes favorable to extract an ion or a pair of ions from the crystal or the cluster. It turns out, however, that the answers to these questions are not so straightforward: below a certain number of water molecules (˜ 12) solvation of individual ions is less costly and above this number solvation of ion pairs is favored. These results reveal a hitherto unknown complexity in the NaCl dissolution process born out of a subtle interplay between water-water and water-ion interactions.

The hydrogeology of complex lens conditions in Qatar

NASA Astrophysics Data System (ADS)

Lloyd, J. W.; Pike, J. G.; Eccleston, B. L.; Chidley, T. R. E.

1987-01-01

The emirate of Qatar lies on a peninsula extending northward from the mainland of Saudi Arabia into the Arabian Gulf. The peninsula is underlain by sedimentary rocks ranging from late Cretaceous to Holocene age but only two Lower Tertiary units are identified as aquifers. The groundwater distribution in these units is seen to be controlled by facies distributions related to tectonically controlled sedimentation and subsequent dissolution. Dissolution has created permeability, in the Umm er Rhaduma limestones and in the overlying Rus anhydrites. In the latter case the dissolution has lead to extensive surface collapse which has provided a mechanism for recharge from runoff. Despite very low rainfall and high evaporation rates, recharge related to storm runoff has resulted in the establishment of a complex fresh groundwater lens in both aquifer units. The lens is constrained by saline groundwaters which in the lower unit are controlled by heads in eastern Saudi Arabia but in the upper unit by the Arabian Gulf sea level. Groundwater abstraction is shown to be distorting the fresh groundwater lens configuration, and estimates of the resultant flow responses affecting the lens are given.

Estimation of the reactive mineral surface area during CO2-rich fluid-rock interaction: the influence of neogenic phases

NASA Astrophysics Data System (ADS)

Scislewski, A.; Zuddas, P.

2010-12-01

Mineral dissolution and precipitation reactions actively participate to control fluid chemistry during water-rock interaction. It is however, difficult to estimate and well normalize bulk reaction rates if the mineral surface area exposed to the aqueous solution and effectively participating on the reactions is unknown. We evaluated the changing of the reactive mineral surface area during the interaction between CO2-rich fluids and Albitite/Granitoid rocks (similar mineralogy but different abundances), reacting under flow-through conditions. Our methodology, adopting an inverse modeling approach, is based on the estimation of dissolution rate and reactive surface area of the different minerals participating in the reactions by the reconstruction the chemical evolution of the interacting fluids. The irreversible mass-transfer processes is defined by a fractional degree of advancement, while calculations were carried out for Albite, Microcline, Biotite and Calcite assuming that the ion activity of dissolved silica and aluminium ions was limited by the equilibrium with quartz and kaolinite. Irrespective of the mineral abundance in granite and albitite, we found that mineral dissolution rates did not change significantly in the investigated range of time where output solution’s pH remained in the range between 6 and 8, indicating that the observed variation in fluid composition depends not on pH but rather on the variation of the parent mineral’s reactive surface area. We found that the reactive surface area of Albite varied by more than 2 orders of magnitude, while Microcline, Calcite and Biotite surface areas changed by 1-2 orders of magnitude. We propose that parent mineral chemical heterogeneity and, particularly, the stability of secondary mineral phases may explain the observed variation of the reactive surface area of the minerals. Formation of coatings at the dissolving parent mineral surfaces significantly reduced the amount of surface available to react with CO2-rich fluids, decreasing the effective reactive surface area. Predictive models of CO2 sequestration under geological conditions should take into account the inhibiting role of surface coating formation. The CO2 rich fluid-rock interactions may also have significant consequences on metal mobilization. Our results indicated that the formation of stable carbonate complexes enhances the solubility of uranium minerals of both albitite and granite, facilitating the U(IV) oxidation, and limiting the extent of uranium adsorption onto particles in oxidized waters. This clearly produces an increase of the uranium mobility with significant consequences for the environment.

Evaluation of magma mixing in the subvolcanic rocks of Ghansura Felsic Dome of Chotanagpur Granite Gneiss Complex, eastern India

NASA Astrophysics Data System (ADS)

Gogoi, Bibhuti; Saikia, Ashima; Ahmad, Mansoor; Ahmad, Talat

2018-06-01

The subvolcanic rocks exposed in the Ghansura Felsic Dome (GFD) of the Bathani volcano-sedimentary sequence at the northern fringe of the Rajgir fold belt in the Proterozoic Chotanagpur Granite Gneiss Complex preserves evidence of magma mixing and mingling in mafic (dolerite), felsic (microgranite) and intermediate (hybrid) rocks. Structures like crenulated margins of mafic enclaves, felsic microgranular enclaves and ocelli with reaction surfaces in mafic rocks, hybrid zones at mafic-felsic contacts, back-veining and mafic flows in the granitic host imply magma mingling phenomena. Textural features like quartz and titanite ocelli, acicular apatite, rapakivi and anti-rapakivi feldspar intergrowths, oscillatory zoned plagioclase, plagioclase with resorbed core and intact rim, resorbed crystals, mafic clots and mineral transporting veins are interpreted as evidence of magma mixing. Three distinct hybridized rocks have formed due to varied interactions of the intruding mafic magma with the felsic host, which include porphyritic diorite, mingled rocks and intermediate rocks containing felsic ocelli. Geochemical signatures confirm that the hybrid rocks present in the study area are mixing products formed due to the interaction of mafic and felsic magmas. Physical parameters like temperature, viscosity, glass transition temperature and fragility calculated for different rock types have been used to model the relative contributions of mafic and felsic end-member magmas in forming the porphyritic diorite. From textural and geochemical investigations it appears that the GFD was a partly solidified magma chamber when mafic magma intruded it leading to the formation of a variety of hybrid rock types.

Role of Silica Redistribution in the Rate-State Behavior of Megathrusts: Field Observations and Experimental Results

NASA Astrophysics Data System (ADS)

Fisher, D. M.; Den Hartog, S. A. M.

2014-12-01

Observations of ancient fault zones and results of high temperature friction experiments indicate that silica redistribution influences the rate (response to velocity increases) and state (time-dependent healing) behavior of megathrusts. The Kodiak Accretionary Complex in Alaska has four shear zones that record plate boundary deformation: the Ghost Rocks mélange, the Uganik thrust, the Uyak mélange, and the central belt of the Kodiak Formation. All these examples of underplated rocks represent top-toward-the-trench shear zones that extend along the plate margin for 100's of kms. The first three examples were accreted within the seismogenic zone and record a progressive history from stratal disruption and particulate flow to localized shearing on pervasive web-like arrays of scaly microfaults in shales. Microfaults show evidence for silica dissolution and local reprecipitation in dilational stepovers and in intensely veined sandstone blocks. The fourth example (the central belt) was accreted further downdip, and these rocks have pervasive, regularly spaced en echelon quartz vein systems. Microstructures within veins indicate periodic cracking and sealing during progressive simple shear. Silica depletion zones adjacent to veins indicate diffusive transport of silica in response to local chemical potential gradients. A simple 1-D transport-kinetics model indicates that cracks in this case could be filled with quartz in less than a year and in as little as a week. Rock friction experiments on lithologies similar to Kodiak examples depict three distinct regimes of frictional behavior as a function of increasing temperature, with velocity weakening in a T range that can be related to the seismogenic zone. These three regimes are predicted by a model for gouge deformation that includes thermally activated pressure solution during shear of quartz grains embedded in a foliated matrix. The slip instabilities that characterize the seismogenic zone may therefore be related in part to grain scale diffusive mass transfer of silica. The observations of Kodiak Fault zones indicate that silica redistribution also plays an important role in the interseismic period through crack healing and dissolution of silica, both along the plate interface and within the adjacent rocks that store elastic strain.

Lithological Properties of Inception Horizons - The key to understand cave development along bedding planes

NASA Astrophysics Data System (ADS)

Filipponi, M.; Jeannin, P.-Y.

2009-04-01

Recent studies on the complex 3D geometry of large cave systems around the World allowed us to get statistical evidence of the inception horizon hypothesis. It clearly confirmed the idea that the development of karst conduits under phreatic conditions is strongly related to a restricted number of so-called inception horizons. An inception horizon is a part of a rock succession that favours the earliest cave forming processes. However some main question remains: What makes one specific stratigraphical horizon favourable to karstification? What kinds of processes are involved and which of them are the most important? Furthermore is it possible to recognize an inception horizon by some lithological properties? In order to understand the reason(s) why a specific stratigraphical horizon is used for cave development we sampled 18 inception horizons of six cave systems as well as the surrounding rock mass. More than 200 rock micro-cores have been drilled and analysed to determine parameters controlling the speleogenesis. The analysis of these cores gives a first idea of the different key properties of inception horizons. From a theoretical point of view it can be expected that during the process of karst development the significance the property/ies will change, because they have been consumed or the associated speleogenetical processes become subordinated to others. Therefore we suggest using an approached named the "speleogenetic scale of influence". The idea is to consider the increase of porosity produced by the speleogenetic processes associated to one specific property. For example, the scale of influence of a pyrite crystal is determined by the dissolution capacity of the sulphuric acid produced by the weathering process of this crystal (i.e. around 6 time the volume of the crystal). This means that the influence of the pyrite can be assumed to be potentially relevant as long as the size of the pores is smaller than around 6 times the average volume of the pyrite crystals present in a rock; beyond this size the effect of the additional dissolution capacity related to pyrite dissolution is expected to become subordinate to other processes. Contrary other processes can only become dominant once the pores have reached a certain size. For example the total carbonate content has an influence on the dissolution rate of a rock mass only if the pore surface is larger than some square millimetres. Considering the properties of the core samples we collected, the estimation of the influence scale and the incorporation into the general concept of the inception horizon hypothesis, we could recognize that (apart from the special case of gypsum) most properties are only significant during certain periods of speleogenesis: 1) The primary permeability it the controlling factor during the early inception phase (beginning of the karstification). 2) The pyrite content as well as the matrix composition (content and type) are mostly significant during the inception and gestation phases. 3) The total carbonate content is relevant during the cave development phase. However it must be noticed that horizons with unfavourable properties can still be incepted and develop karstification: they just need more time. The evidence that only a few horizons feature a distinct cave development suggests that for most of the horizons the time needed to be incepted exceed the available time given by the hydrologic boundary conditions. This approach makes it possible to identify potential inception horizons from lithological data (e.g. from drilling core). The identification of the position of inception horizons in a rock mass will provide a substantial increase of information for engineering proposes as well as for karst hydrogeological investigations. It is thus now possible to assess, in a probabilistic way, the spatial distribution of karst occurrences inside a karst massif. This implies the identification of potential inception horizons and the reconstruction of the hydrogeolgical history (evolution of the hydogeological boundary conditions along the history of the karst system).

Kinetics of scheelite dissolution in groundwater: defining the release rate of tungsten contamination from a natural source

NASA Astrophysics Data System (ADS)

Montgomery, S. D.; Mckibben, M. A.

2011-12-01

Tungsten, an emerging contaminant, has no EPA standard for its permissible levels in drinking water. At sites in California, Nevada, and Arizona there may be a correlation between elevated levels of tungsten in drinking water and clusters of childhood acute lymphocytic leukemia (ALL). Developing a better understanding of how tungsten is released from rocks into surface and groundwaters is therefore of growing environmental interest. Knowledge of tungstate ore mineral weathering processes, particularly the rates of dissolution of scheelite (CaWO4) in groundwater, could improve models of how tungsten is released and transported in natural waters. Our research is focusing on experimental determination of the rates and products of tungstate mineral dissolution in synthetic groundwater, as a function of temperature, pH and mineral surface area. The initial rate method is being used to develop rate laws. Batch reactor experiments are conducted within constant temperature circulation baths over a pH range of 2-9. Cleaned scheelite powder with grain diameters of 106-150um is placed between two screens in a sample platform and then placed inside a two liter Teflon vessel filled with synthetic groundwater. Ports on the vessel allow sample extraction, temperature and pH measurement, gas inflow, and water circulation. Aliquots of solution are taken periodically for product analysis by ICP -MS. Changes in mineral surface characteristics are monitored using SEM and EDS methods. Results so far reveal that the dissolution of scheelite is incongruent at both neutral and low pH. Solid tungstic acid forms on scheelite mineral surfaces under acidic conditions, implying that this phase controls the dissolution rate in acidic environments. The influence of dissolved CO2 and resultant calcium carbonate precipitation on the dissolution of scheelite at higher pH is also being investigated. The rate law being developed for scheelite dissolution will be useful in reactive-transport computer codes designed to model tungsten contamination in a variety of surface and groundwater settings.

Transport of barium through dolomite rocks under the presence of guar gum and brine salinities of hydraulic fracturing wastewater

NASA Astrophysics Data System (ADS)

Ebrahimi, P.; Vilcaez, J.

2017-12-01

Hydraulic fracturing wastewater (HFW) containing high concentrations of Ba, is commonly disposed into the deep saline aquifers. We investigate the effect of brine salinity, competing cations (Ca and Mg), and guar gum (most common fracturing viscosifier) on the sorption and transport of Ba through dolomite rocks. To this aim, we have conducted batch sorption and core-flooding experiments at both ambient (22°C) and deep subsurface (60°C) temperature conditions. The effect of mineral composition is assessed by comparing batch and core-flooding experimental results obtained with sandstone and dolomite rocks. Batch sorption experiments conducted using powdered dolomite rocks (500-600 µm particle size) revealed that Ba sorption on dolomite greatly decreases with increasing brine salinity (0 - 180,000 mg-NaCl/L), and that at brine salinities of HFW, chloro-complexation reactions between Ba and Cl ions and changes in pH (that results from dolomite dissolution) are the controlling factors of Ba sorption on dolomite. Organo-complexation reactions between Ba and guar gum, and competition of Ba with common cations (Ca and Mg) for hydration sites of dolomite, play a secondary role. This finding is in accordance with core-flooding experimental results, showing that the transport of Ba through synthetic dolomite rocks of high flow properties (25-29.6% porosity, 9.6-13.7 mD permeability), increases with increasing brine salinity (0-180,000 mg-NaCl/L), while the presence of guar gum (50-500 mg/L) does not affect the transport of Ba. On the other hand, core-flooding experiments conducted using natural dolomite core plugs (6.5-8.6% porosity, 0.06-0.3 mD permeability), indicates that guar gum can clog the pore throats of tight dolomite rocks retarding the transport of Ba. Results of our numerical simulation studies indicate that the mechanism of Ba sorption on dolomite can be represented by a sorption model that accounts for both surface complexation reactions on three distinct hydration sites (>CaOHo, >MgOHo, and >CO3Ho), and the kinetic dissolution of dolomite. The presented results are important in understanding the fate of heavy metals present in HFW disposed into deep saline aquifers.

A global sensitivity analysis of two-phase flow between fractured crystalline rock and bentonite with application to spent nuclear fuel disposal

NASA Astrophysics Data System (ADS)

Dessirier, Benoît; Frampton, Andrew; Jarsjö, Jerker

2015-11-01

Geological disposal of spent nuclear fuel in deep crystalline rock is investigated as a possible long term solution in Sweden and Finland. The fuel rods would be cased in copper canisters and deposited in vertical holes in the floor of deep underground tunnels, embedded within an engineered bentonite buffer. Recent experiments at the Äspö Hard Rock Laboratory (Sweden) showed that the high suction of unsaturated bentonite causes a de-saturation of the adjacent rock at the time of installation, which was also independently predicted in model experiments. Remaining air can affect the flow patterns and alter bio-geochemical conditions, influencing for instance the transport of radionuclides in the case of canister failure. However, thus far, observations and model realizations are limited in number and do not capture the conceivable range and combination of parameter values and boundary conditions that are relevant for the thousands of deposition holes envisioned in an operational final repository. In order to decrease this knowledge gap, we introduce here a formalized, systematic and fully integrated approach to study the combined impact of multiple factors on air saturation and dissolution predictions, investigating the impact of variability in parameter values, geometry and boundary conditions on bentonite buffer saturation times and on occurrences of rock de-saturation. Results showed that four parameters consistently appear in the top six influential factors for all considered output (target) variables: the position of the fracture intersecting the deposition hole, the background rock permeability, the suction representing the relative humidity in the open tunnel and the far field pressure value. The combined influence of these compared to the other parameters increases as one targets a larger fraction of the buffer reaching near-saturation. Strong interaction effects were found, which means that some parameter combinations yielded results (e.g., time to saturation) far outside the range of results obtained by the rest of the scenarios. This study also addresses potential air trapping by dissolution of part of the initial air content of the bentonite, showing that neglecting gas flow effects and trapping could lead to significant underestimation of the remaining air content and the duration of the initial aerobic phase of the repository.

A global sensitivity analysis of two-phase flow between fractured crystalline rock and bentonite with application to spent nuclear fuel disposal.

PubMed

Dessirier, Benoît; Frampton, Andrew; Jarsjö, Jerker

2015-11-01

Geological disposal of spent nuclear fuel in deep crystalline rock is investigated as a possible long term solution in Sweden and Finland. The fuel rods would be cased in copper canisters and deposited in vertical holes in the floor of deep underground tunnels, embedded within an engineered bentonite buffer. Recent experiments at the Äspö Hard Rock Laboratory (Sweden) showed that the high suction of unsaturated bentonite causes a de-saturation of the adjacent rock at the time of installation, which was also independently predicted in model experiments. Remaining air can affect the flow patterns and alter bio-geochemical conditions, influencing for instance the transport of radionuclides in the case of canister failure. However, thus far, observations and model realizations are limited in number and do not capture the conceivable range and combination of parameter values and boundary conditions that are relevant for the thousands of deposition holes envisioned in an operational final repository. In order to decrease this knowledge gap, we introduce here a formalized, systematic and fully integrated approach to study the combined impact of multiple factors on air saturation and dissolution predictions, investigating the impact of variability in parameter values, geometry and boundary conditions on bentonite buffer saturation times and on occurrences of rock de-saturation. Results showed that four parameters consistently appear in the top six influential factors for all considered output (target) variables: the position of the fracture intersecting the deposition hole, the background rock permeability, the suction representing the relative humidity in the open tunnel and the far field pressure value. The combined influence of these compared to the other parameters increases as one targets a larger fraction of the buffer reaching near-saturation. Strong interaction effects were found, which means that some parameter combinations yielded results (e.g., time to saturation) far outside the range of results obtained by the rest of the scenarios. This study also addresses potential air trapping by dissolution of part of the initial air content of the bentonite, showing that neglecting gas flow effects and trapping could lead to significant underestimation of the remaining air content and the duration of the initial aerobic phase of the repository. Copyright © 2015. Published by Elsevier B.V.

Arctic lake sediments as records of climate change using rock magnetic properties and paleomagnetic data

NASA Astrophysics Data System (ADS)

Murdock, Kathryn J.

Two lakes were studied in detail for rock magnetic properties: Lake El'gygytgyn, a crater lake formed 3.6Ma in the Far Eastern Russian Arctic, and Heimerdalsvatnet, a Holocene coastal lake located in the Lofotens off the coast of northern Norway. These two lakes have vastly different environmental histories, the former a terrestrial lake formed from a meteor impact and never covered by continental ice sheets whereas the latter went from a coastal marine setting to a completely lacustrine environment due to isostatic rebound and sea level fluctuations. Their differences are considerable, however they provide the opportunity to compare Arctic lake systems to discern similarities and differences in their magnetic properties for application to future climatic investigations. Paleomagnetic measurements and down-core magnetic susceptibility were performed at the GFZ German Research Centre for Geosciences in Potsdam for Lake El'gygytgyn and at the Laboratoire de paleomagnetisme sedimentaire at ISMER for Heimerdalsvatnet. Rock magnetic properties were measured at the University of Massachusetts Amherst, Institute of Rock Magnetism, and/or Trinity College. These measurements included: magnetic susceptibility, hysteresis parameters, Curie temperatures, and low-temperature magnetic behavior. Imaging of magnetite grains was also performed. Magnetic susceptibility measurements in Lake El'gygytgyn suggested a correlation between glacials (interglacials) and low (high) susceptibility. The large range in susceptibility indicated there could be magnetite dissolution. The first study supported this hypothesis with evidence at low temperatures (10-35K) of minerals such as siderite, rhodochrosite, and/or vivianite which could form from iron released during dissolution. Marine Isotope Stage 31 was investigated for rock magnetic properties that could continue to support or oppose findings from the first study. It was determined the presence of siderite only occurred in interglacial periods whereas its absence (and probably presence of vivianite) related to glacial periods, indicating more reduced environments during glacials versus interglacials. Heimerdalsvatnet paleomagnetic data from the marine environment (lower part of the core) revealed scattered directions whereas data from the upper part of the core (lacustrine environment) showed better consistency. Rock magnetic measurements showed some variation downcore, however the measurements are not dependable since the amount of paramagnetic material was overwhelming compared to any ferromagnetic mineral present.

Origins of igneous microgranular enclaves in granites: the example of Central Victoria, Australia

NASA Astrophysics Data System (ADS)

Clemens, J. D.; Elburg, M. A.; Harris, C.

2017-10-01

To investigate their genesis and relations with their host rocks, we study igneous microgranular enclaves (IMEs) in the c. 370 Ma, post-orogenic, high-level, felsic plutons and volcanic rocks of Central Victoria, Australia. The IMEs are thermally quenched magma globules but are not autoliths, and they do not form mixing series with their host magmas. These IMEs generally represent hybrids between mantle-derived magmas and very high- T crust-derived melts, modified by fractionation, ingestion of host-derived crystals and, to a lesser extent, by chemical interactions with their hosts. Isotopic and elemental evidence suggests that their likely mafic progenitors formed by partial melting of subcontinental mantle, but that the IME suites from different felsic host bodies did not share a common initial composition. We infer that melts of heterogeneous mantle underwent high- T hybridisation with melts from a variety of crustal rocks, which led to a high degree of primary variability in the IME magmas. Our model for the formation of the Central Victorian IMEs is likely to be applicable to other occurrences, especially in suites of postorogenic granitic magmas emplaced in the shallow crust. However, there are many different origins for the mingled magma globules that we call IMEs, and different phenomena seem to occur in differing tectonic settings. The complexity of IME formation means that it is difficult to unravel the petrogenesis of these products of chaotic magma processes. Nevertheless, the survival of fine-grained, non-equilibrium mineralogy and texture in the IMEs suggests that their tenure in the host magmas must have been geologically brief.

Volatile Element Fluxes at Copahue Volcano, Argentina

NASA Astrophysics Data System (ADS)

Varekamp, J. C.

2002-05-01

Copahue volcano has a crater lake and acid hot springs that discharge into the Rio Agrio river system. These fluids are very concentrated (up to 6 % sulfate), rich in rock-forming elements (up to 2000 ppm Mg) and small spheres of native sulfur float in the crater lake. The stable isotope composition of the waters (delta 18O =-2.1 to + 3.6 per mille; delta D = -49 to -26 per mille) indicates that the hot spring waters are at their most concentrated about 70% volcanic brine and 30 % glacial meltwater. The crater lake waters have similar mixing proportions but added isotope effects from intense evaporation. Further dilution of the waters in the Rio Agrio gives values closer to local meteoric waters (delta 18O = -11 per mille; delta D = -77 per mille), whereas evaporation in closed ponds led to very heavy water (up to delta 18O = +12 per mille). The delta 34S value of dissolved sulfate is +14.2 per mille, whereas the native sulfur has values of -8.2 to -10.5 per mille. The heavy sulfate probably formed when SO2 disproportionated into bisulfate and native sulfur at about 300 C. We measured the sulfate fluxes in the Rio Agrio, which ranged from 20-40 kilotons S/year. The whole system was releasing sulfur at an equivalent rate of about 250-650 tons SO2/day. From the river flux sulfur values and the stochiometry of the disproportionation reaction we calculated the rate of liquid sulfur storage inside the volcano (6000 m3/year). During the eruptions of 1995/2000, large amounts of that stored liquid sulfur were ejected as pyroclastic sulfur. The calculated rate of rock dissolution (from rock- forming element fluxes in the Rio Agrio) suggests that the void space generated by rock dissolution is largely filled by native sulfur and silica. The S/Cl ratio in the hydrothermal fluids is about 2, whereas glass inclusions have S/Cl = 0.2, indicating the strong preferential degassing of sulfur.

Porosity Gradient Development Around Karst Features due to Tidal Pumping in Eastern Yucatan Peninsula

NASA Astrophysics Data System (ADS)

Maqueda, A.; Renard, P.

2016-12-01

Water exchange between karst features and the porous matrix around them has been observed in karst aquifers by previous research. The exchange is driven by hydraulic head gradients caused by stormwater runoff or sea tides and may cause mineral dissolution. The authors of this work proposed a conceptual model of porosity development under tidal variations of hydraulic head is proposed. Simulations of reactive transport and porosity evolution were conducted to explore the porosity gradient development around a karst feature. Simulations account for petrophysical properties of porous media and groundwater geochemical characteristics. Data used in simulations corresponds to an eogenetic karst aquifer found on the eastern coast of Yucatan Peninsula in Mexico. Simulations include both analytical and numerical solutions of porosity increase caused by mineral dissolution. The estimated rate of porosity development and associated wall retreat (3-30 cm/100 yr) are large enough to develop karst cavities on time periods relevant to karst formation in the study area (10K yr). The analytical solution could be used to assess porosity increase in rock samples and can be also applied to model slow reactions in porous media under flow driven by sinusoidal hydraulic boundary conditions. The results show a possible alternative mechanism of karst cavity development in a high conductive limestone rock matrix aquifer.

Synthetic H sub 2 O-CO sub 2 fluid inclusions in spontaneously nucleated forsterite, enstatite, and diopside hosts: The method and applications

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

Johnson, E.L.; Jenkins, D.M.

1991-04-01

This paper describes an experimental technique for the production of primary synthetic H{sub 2}O-CO{sub 2} and H{sub 2}O-CO{sub 2}-NaCl fluid inclusions in forsterite, orthopyroxene, and clinopyroxene hosts spontaneously nucleated during the incongruent dissolution of tremolite. The host producing reactions involve the complexation and transport of Ca, Mg, and SiO{sub 2} to the growing product phases in which the inclusions are hosted. This technique, therefore, provides the opportunity to study the effects of a complex host-producing reaction on the composition of the fluids trapped as primary inclusions in the growing host phase. In addition to providing a model for the entrapmentmore » of primary fluid inclusions, the reactions provide an excellent model of the onset of granulite facies metamorphism where, in nature, fluid inclusion compositions are commonly in disequilibrium with the mineral assemblages in which they are hosted.« less

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.

Finite-element modeling of magma chamber-host rock interactions prior to caldera collapse

NASA Astrophysics Data System (ADS)

Kabele, Petr; Žák, Jiří; Somr, Michael

2017-06-01

Gravity-driven failure of shallow magma chamber roofs and formation of collapse calderas are commonly accompanied by ejection of large volumes of pyroclastic material to the Earth's atmosphere and thus represent severe volcanic hazards. In this respect, numerical analysis has proven as a key tool in understanding the mechanical conditions of caldera collapse. The main objective of this paper is to find a suitable approach to finite-element simulation of roof fracturing and caldera collapse during inflation and subsequent deflation of shallow magma chambers. Such a model should capture the dominant mechanical phenomena, for example, interaction of the host rock with magma and progressive deformation of the chamber roof. To this end, a comparative study, which involves various representations of magma (inviscid fluid, nearly incompressible elastic, or plastic solid) and constitutive models of the host rock (fracture and plasticity), was carried out. In particular, the quasi-brittle fracture model of host rock reproduced well the formation of tension-induced radial and circumferential fractures during magma injection into the chamber (inflation stage), especially at shallow crustal levels. Conversely, the Mohr-Coulomb shear criterion has shown to be more appropriate for greater depths. Subsequent magma withdrawal from the chamber (deflation stage) results in further damage or even collapse of the chamber roof. While most of the previous studies of caldera collapse rely on the elastic stress analysis, the proposed approach advances modeling of the process by incorporating non-linear failure phenomena and nearly incompressible behaviour of magma. This leads to a perhaps more realistic representation of the fracture processes preceding roof collapse and caldera formation.

Petrographic and geochemical data for Cenozoic volcanic rocks of the Bodie Hills, California and Nevada

USGS Publications Warehouse

du Bray, Edward A.; John, David A.; Box, Stephen E.; Vikre, Peter G.; Fleck, Robert J.; Cousens, Brian L.

2013-04-23

Petrographic and geochemical data for Cenozoic volcanic rocks of the Bodie Hills, California and Nevada // // This report presents petrographic and geochemical data for samples collected during investigations of Tertiary volcanism in the Bodie Hills of California and Nevada. Igneous rocks in the area are principally 15–6 Ma subduction-related volcanic rocks of the Bodie Hills volcanic field but also include 3.9–0.1 Ma rocks of the bimodal, post-subduction Aurora volcanic field. Limited petrographic results for local basement rocks, including Mesozoic granitoid rocks and their metamorphic host rocks, are also included in the compilation. The petrographic data include visual estimates of phenocryst abundances as well as other diagnostic petrographic criteria. The geochemical data include whole-rock major oxide and trace element data, as well as limited whole-rock isotopic data.

Karst in Wadi Bani Khalid, Oman

NASA Astrophysics Data System (ADS)

Abdelaziz, Ramadan

2017-04-01

There are several important in Oman. The main aquifer is surficial aquifer and fractured rocks. In fact, the geology of Oman is complex whichmake the hydraulic continuity of bedrock is limited and formaing localized aquifers. caves in Oman are varying types and length, size and geographic formations. Many caves and valleys founded in Oman. Wadi Bani Khalid hosts complex network of fractured rock. Karst in Wadi Bani Kalid made upof Limestone(Calcium, which is dissolve in water.A rain water pass through the rock it is erode the rock and form caves. The cave located in Miqil. The karst was formed in Calcium Carbonate rocks.

Damage-plasticity model of the host rock in a nuclear waste repository

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

Koudelka, Tomáš; Kruis, Jaroslav, E-mail: kruis@fsv.cvut.cz

The paper describes damage-plasticity model for the modelling of the host rock environment of a nuclear waste repository. Radioactive Waste Repository Authority in Czech Republic assumes the repository to be in a granite rock mass which exhibit anisotropic behaviour where the strength in tension is lower than in compression. In order to describe this phenomenon, the damage-plasticity model is formulated with the help of the Drucker-Prager yield criterion which can be set to capture the compression behaviour while the tensile stress states is described with the help of scalar isotropic damage model. The concept of damage-plasticity model was implemented inmore » the SIFEL finite element code and consequently, the code was used for the simulation of the Äspö Pillar Stability Experiment (APSE) which was performed in order to determine yielding strength under various conditions in similar granite rocks as in Czech Republic. The results from the performed analysis are presented and discussed in the paper.« less

Major magmatic events in Mt Meredith, Prince Charles Mountains: First evidence for early Palaeozoic syntectonic granites

USGS Publications Warehouse

Gongurov, N.A.; Laiba, A.A.; Beliatsky, B.V.

2007-01-01

Precambrian rocks at Mt Meredith underwent granulite-facies metamorphism M1. Zircon isotope dating for two orthogneisses revealed the following age signatures: 1294±3 and 957±4Ma; 1105±5 and 887±2Ma. The oldest ages could reflect the time of orthogneiss protolith crystallization and the latest age determinations date Grenvillian metamorphism. The metamorphic rocks were intruded by two-mica and garnet-biotite granites. The granites and host rocks underwent amphibolite-facies metamorphism M2. Zircon isotope analysis of the two-mica granites showed age estimation within 550-510Ma and zircon dating of the garnet-biotite granites revealed the ages of 1107±5, 953±8, and 551±4Ma. As Pan-African age signatures were obtained from only the granite samples, it is possible to suggest that the granites were formed at the time of 510-550Ma and the zircons with greater age values were captured by granites from the host rocks.

The Role of Tectonic Stress in Triggering Large Silicic Caldera Eruptions

NASA Astrophysics Data System (ADS)

Cabaniss, Haley E.; Gregg, Patricia M.; Grosfils, Eric B.

2018-05-01

We utilize 3-D temperature-dependent viscoelastic finite element models to investigate the mechanical response of the host rock supporting large caldera-size magma reservoirs (volumes >102 km3) to local tectonic stresses. The mechanical stability of the host rock is used to determine the maximum predicted repose intervals and magma flux rates that systems may experience before successive eruption is triggered. Numerical results indicate that regional extension decreases the stability of the roof rock overlying a magma reservoir, thereby promoting early-onset caldera collapse. Alternatively, moderate amounts of compression (≤10 mm/year) on relatively short timescales (<104 years) increases roof rock stability. In addition to quantifying the affect of tectonic stresses on reservoir stability, our models indicate that the process of rejuvenation and mechanical failure is likely to take place over short time periods of hundreds to thousands of years. These findings support the short preeruption melt accumulation timescales indicated by U series disequilibrium studies.

Multiple metasomatic events recorded in Kilbourne Hole peridotite xenoliths: the relative contribution of host basalt interaction vs. silicate metasomatic glass

NASA Astrophysics Data System (ADS)

Hammond, S. J.; Yoshikawa, M.; Harvey, J.; Burton, K. W.

2010-12-01

Stark differences between bulk-rock lithophile trace element budgets and the sum of the contributions from their constituent minerals are common, if not ubiquitous in peridotite xenoliths [1]. In the absence of modal metasomatism this discrepancy is often attributed to the “catch-all”, yet often vague process of cryptic metasomatism. This study presents comprehensive Sr-Nd isotope ratios for variably metasomatized bulk-rock peridotites, host basalts, constituent peridotite mineral phases and interstitial glass from 13 spinel lherzolite and harzburgite xenoliths from the Kilbourne Hole volcanic maar, New Mexico, USA. Similar measurements were also made on hand-picked interstitial glass from one of the most highly metasomatized samples (KH03-16) in an attempt to unravel the effects of multiple metasomatic events. In all Kilbourne Hole peridotites analysed, hand-picked, optically clean clinopyroxenes preserve a more primitive Sr isotope signature than the corresponding bulk-rock; a pattern preserved in all but one sample for Nd isotope measurements. Reaction textures, avoided during hand-picking, around clinopyroxene grains are evident in the most metasomatized samples and accompanied by films of high-SiO2 interstitial glass. The margins of primary minerals appear partially resorbed and trails of glassy melt inclusions similar in appearance to those previously reported from the same locality [2], terminate in these films. Hand-picked glass from KH03-16 reveals the most enriched 87Sr/86Sr of any component recovered from these xenoliths (87Sr/86Sr = 0.708043 ± 0.00009; [Sr] = 81 ppm). Similarly, the 143Nd/144Nd of the glass is amongst the most enriched of the peridotite components (143Nd/144Nd = 0.512893 ± 0.000012; [Nd] = 10 ppm). However, the host basalt (87Sr/86Sr = 0.703953 ± 0.00012; 143Nd/144Nd = 0.512873 ± 0.000013), similar in composition to nearby contemporaneous Potrillo Volcanic Field basalts [3], contains nearly an order of magnitude more Sr and more than three times more Nd ([Sr] = 655 ppm; [Nd] = 34 ppm) than the interstitial glass. While the enriched nature of the host basalt, combined with high [Sr] and [Nd], makes it the most likely candidate for the enrichment of the peridotite bulk rocks, mixing between clinopyroxenes and the host basalt cannot account for the full range of bulk-rock Sr-Nd isotope ratios and nearly half of the xenoliths require an additional component that could involve varying amounts of interstitial glass. Moreover, three bulk-rock samples require a further, as yet unidentified component in order to explain the bulk-rock Sr-Nd isotope composition fully, implying that at least three episodes of metasomatism/refertilization must have occurred prior to the arrival of the xenoliths at the surface in their host lava. References: [1] Bedini & Bodinier (1999) Geochim. Cosmochim. Acta 63, 3883-3900. [2] Schiano & Clocchiatti (1994) Nature 368, 622-624. [3] Thompson et al., (2005) J. Petrol. 46, 1603-1643.

Petrophysical and transport parameters evolution during acid percolation through structurally different limestones

NASA Astrophysics Data System (ADS)

Martinez Perez, Laura; Luquot, Linda

2017-04-01

Processes affecting geological media often show complex and unpredictable behavior due to the presence of heterogeneities. This remains problematic when facing contaminant transport problems, in the CO2 storage industry or dealing with the mechanisms underneath natural processes where chemical reactions can be observed during the percolation of rock non-equilibrated fluid (e.g. karst formation, seawater intrusion). To understand the mechanisms taking place in a porous medium as a result of this water-rock interaction, we need to know the flow parameters that control them, and how they evolve with time as a result of that concurrence. This is fundamental to ensure realistic predictions of the behavior of natural systems in response of reactive transport processes. We investigate the coupled influence of structural and hydrodynamic heterogeneities in limestone rock samples tracking its variations during chemical reactions. To do so we use laboratory petrophysical techniques such as helium porosimetry, gas permeability, centrifugue, electrical resistivity and sonic waves measurements to obtain the parameters that characterize flow within rock matrix (porosity, permeability, retention curve and pore size distribution, electrical conductivity, formation factor, cementation index and tortuosity) before and after percolation experiments. We built an experimental setup that allows injection of acid brine into core samples under well controlled conditions, monitor changes in hydrodynamic properties and obtain the chemical composition of the injected solution at different stages. 3D rock images were also acquired before and after the experiments using a micro-CT to locate the alteration processes and perform an acurate analysis of the structural changes. Two limestones with distinct textural classification and thus contrasting transport properties have been used in the laboratory experiments: a crinoid limestone and an oolithic limestone. Core samples dimensions were 1 inch in diameter and varied from 0.5 to 2 inches in length. Experiments were performed at room temperature, 8 bar of total pressure and 3 bar of PCO2. The acidic fluid has been injected at constant flow rate ranging from 0.4 mL/min to 6.7 mL/min depending of the rock typology and sample length. As expected, limestone dissolution occurred during the different percolation experiments, porosity and permeability augmented and sonic waves speed propagation decreased, showing an increase in the degree of heterogeneity of the rocks. The integration of all these parameters measured at different stages of dissolution provides contrasted and realistic geochemical, hydrodynamic and structural parameters to improve numerical simulations.

Geochemical behavior of ultramafic waste rocks with carbon sequestration potential: a case study of the Dumont Nickel Project, Amos, Québec.

PubMed

Kandji, El Hadji Babacar; Plante, Benoit; Bussière, Bruno; Beaudoin, Georges; Dupont, Pierre-Philippe

2017-04-01

The geochemical behavior of ultramafic waste rocks and the effect of carbon sequestration by these waste rocks on the water drainage quality were investigated using laboratory-scale kinetic column tests on samples from the Dumont Nickel Project (RNC Minerals, QC, Canada). The test results demonstrated that atmospheric CO 2 dissolution induced the weathering of serpentine and brucite within the ultramafic rocks, generating high concentrations of Mg and HCO 3 - with pH values ranging between 9 and 10 in the leachates that promote the precipitation of secondary Mg carbonates. These alkaline pH values appear to have prevented the mobilization of many metals; Fe, Ni, Cu, and Zn were found at negligible concentrations in the leachates. Posttesting characterization using chemical analyses, diffuse reflectance infrared Fourier transform (DRIFT), and scanning electron microscope (SEM) observations confirmed the precipitation of secondary hydrated Mg carbonates as predicted by thermodynamic calculations. The formation of secondary Mg carbonates induced cementation of the waste particles, resulting in the development of a hardpan.

SIMS Investigations on Growth and Sector Zoning in Natural Hydrothermal Quartz: Isotopic and Trace Element Analyses

NASA Astrophysics Data System (ADS)

May, E.; Vennemann, T. W.; Baumgartner, L. P.; Meisser, N.

2014-12-01

Quartz is the most abundant mineral in the Earth's crust and is found in virtually every geological context. Despite its ubiquity and the detailed studies on the conditions of quartz crystallization, some questions concerning its growth and sector zoning with regard to trace element incorporation and oxygen isotope fractionations and the implications thereof for interpretations on the conditions of formation remain (e.g., Jourdan et al., 2009). This study presents new in-situ measurements of trace element and oxygen isotope ratios on natural hydrothermal quartz from an extensional gold-bearing quartz vein in the western Swiss Alps. The temperature of formation of the veins is estimated by quartz-hematite oxygen isotope thermometry to be about 360°C. A detailed SEM-CL study of this sample shows cyclic lamellar growth, alternating with phases of dissolution that are directly followed by macro-mosaic growth of the quartz, before returning to a cyclic lamellar growth again. Trace element concentrations (measured for Na, K, Li, Al, and Ti) notably showed Al/Si variations of three orders of magnitude and coupled Al and Li variations, likely substituting for Si in different growth zones with lower values in macro-mosaic zones precipitating after the period of dissolution. The oxygen isotope composition of the crystal, in contrast, is homogeneous through all growth zones (δ18O values between 15.6‰ and 16.2‰) indicating that the fluid must have been buffered by the host-rock and/or the source of the fluid remained the same despite the period of quartz dissolution. Furthermore, the temperature during crystallization of the quartz crystal has likely also remained similar. The fact that no variations are measured in oxygen isotope compositions but some variations in trace element contents may suggest that changes in pressure were important during the formation of this quartz crystal. Give the pressure effects on the solubility of quartz (Fournier and Potter, 1982), both the cyclic character of quartz growth and perhaps also the changes in Al/Si may be related to pressure variations caused by seismic activity during retrograde Alpine metamorphism. A-L. Jourdan et al. (2009) Mineralogical Magazine, 73, 615-632. R.O. Fournier and R.W. Potter (1982) Geochimica et Cosmochimica Acta, 46, 1969-1973.

Characterization of Geologic Structures and Host Rock Properties Relevant to the Hydrogeology of the Standard Mine in Elk Basin, Gunnison County, Colorado

USGS Publications Warehouse

Caine, Jonathan S.; Manning, Andrew H.; Berger, Byron R.; Kremer, Yannick; Guzman, Mario A.; Eberl, Dennis D.; Schuller, Kathryn

2010-01-01

The Standard Mine Superfund Site is a source of mine drainage and associated heavy metal contamination of surface and groundwaters. The site contains Tertiary polymetallic quartz veins and fault zones that host precious and base metal sulfide mineralization common in Colorado. To assist the U.S. Environmental Protection Agency in its effort to remediate mine-related contamination, we characterized geologic structures, host rocks, and their potential hydraulic properties to better understand the sources of contaminants and the local hydrogeology. Real time kinematic and handheld global positioning systems were used to locate and map precisely the geometry of the surface traces of structures and mine-related features, such as portals. New reconnaissance geologic mapping, field and x-ray diffraction mineralogy, rock sample collection, thin-section analysis, and elemental geochemical analysis were completed to characterize hydrothermal alteration, mineralization, and subsequent leaching of metallic phases. Surface and subsurface observations, fault vein and fracture network characterization, borehole geophysical logging, and mercury injection capillary entry pressure data were used to document potential controls on the hydrologic system.

Witwatersrand gold deposits formed by volcanic rain, anoxic rivers and Archaean life

NASA Astrophysics Data System (ADS)

Heinrich, Christoph A.

2015-03-01

The Witwatersrand Basin in South Africa is one of the best-preserved records of fluvial sedimentation on an Archaean continent. The basin hosts the worlds biggest gold resource in thin pebble beds, but the process for gold enrichment is debated. Mechanical accumulation of gold particles from flowing river water is the prevailing hypothesis, yet there is evidence for hydrothermal mobilization of gold by fluids invading the metasedimentary rocks after their burial. Earth's atmosphere three billion years ago was oxygen free, but already sustained some of the oldest microbial life on land. Here I use thermodynamic modelling and mass-balance calculations to show that these conditions could have led to the chemical transport and precipitation of gold in anoxic surface waters, reconciling the evidence for fluvial deposition with evidence for hydrothermal-like chemical reactions. I suggest that the release of sulphurous gases from large volcanic eruptions created acid rain that enabled the dissolution and transport of gold in surface waters as sulphur complexes. Precipitation of the richest gold deposits could have been triggered by chemical reduction of the dissolved gold onto organic material in shallow lakes and pools. I conclude that the Witwatersrand gold could have formed only during the Archaean, after the emergence of continental life but before the rise of oxygen in the Earth's atmosphere.

Thermohydrologic modeling of the large-block test in partially saturated fractured tuff at Yucca Mountain, Nevada

NASA Astrophysics Data System (ADS)

Lee, K.; Buscheck, T. A.; Glascoe, L. G.; Gansemer, J.; Sun, Y.

2002-12-01

In support of the characterization of Yucca Mountain as a potential site for as a geologic repository for high-level nuclear waste, the US Department of Energy conducted the Large Block Test (LBT) at nearby Fran Ridge. The LBT was conducted in an excavated 3x 3x 4.5m block of partially saturated, fractured nonlithophysal Topopah Spring tuff, which is one of the host-rock units for the potential repository at Yucca Mountain. The LBT was one of a series of field-scale thermohydrologic tests conducted in the repository host-rock units. The LBT was heated by line heaters installed in five boreholes lying in a horizontal plane 2.75 m below the upper surface of the block. The field-scale thermal tests were designed to help investigators better understand the coupled thermohydrologic-mechanical-chemical processes that would occur in the host rock in response to the radioactive heat of decay from emplaced waste packages. The tests also provide data for the calibration and validation of numerical models used to analyze the thermohydrologic response of the near-field host rock and Engineered Barrier System (EBS). Using the NUFT code and the dual-permeability approach to representing fracture-matrix interaction, we simulated the thermohydrologic response of the block to a heating and cooling cycle. The primary goals of the analysis were to study the heat-flow mechanisms and water redistribution patterns in the boiling and sub-boiling zones, and to compare model results with measured temperature and liquid saturation data, and thereby evaluate two rock property data sets available for modeling thermohydrologic behavior in the rock. Model results were also used for model calibration and validation. We obtained a good to excellent match between model and observed temperatures, and found that the distinct dryout and condensation zones modeled above and below the heater level agreed fairly well with the liquid-saturation measurements. We identified the best-fit data set by using a statistical analysis to compare model and field temperatures, and found that heat flow in the block was dominated by conduction.

Simulation of Mechanical Processes in Gas Storage Caverns for Short-Term Energy Storage

NASA Astrophysics Data System (ADS)

Böttcher, Norbert; Nagel, Thomas; Kolditz, Olaf

2015-04-01

In recent years, Germany's energy management has started to be transferred from fossil fuels to renewable and sustainable energy carriers. Renewable energy sources such as solar and wind power are subjected by fluctuations, thus the development and extension of energy storage capacities is a priority in German R&D programs. This work is a part of the ANGUS+ Project, funded by the federal ministry of education and research, which investigates the influence of subsurface energy storage on the underground. The utilization of subsurface salt caverns as a long-term storage reservoir for fossil fuels is a common method, since the construction of caverns in salt rock is inexpensive in comparison to solid rock formations due to solution mining. Another advantage of evaporate as host material is the self-healing behaviour of salt rock, thus the cavity can be assumed to be impermeable. In the framework of short-term energy storage (hours to days), caverns can be used as gas storage reservoirs for natural or artificial fuel gases, such as hydrogen, methane, or compressed air, where the operation pressures inside the caverns will fluctuate more frequently. This work investigates the influence of changing operation pressures at high frequencies on the stability of the host rock of gas storage caverns utilizing numerical models. Therefore, we developed a coupled Thermo-Hydro-Mechanical (THM) model based on the finite element method utilizing the open-source software platform OpenGeoSys. The salt behaviour is described by well-known constitutive material models which are capable of predicting creep, self-healing, and dilatancy processes. Our simulations include the thermodynamic behaviour of gas storage process, temperature development and distribution on the cavern boundary, the deformation of the cavern geometry, and the prediction of the dilatancy zone. Based on the numerical results, optimal operation modes can be found for individual caverns, so the risk of host rock damage can be minimized. Furthermore, the model can be used to design efficient monitoring programs to detect possible variations of the host rock due construction and operation of the storage facility. The developed model will be used by public authorities for land use planning issues.

Geochemical and isotopic study of impact melts and spherules from the Lonar impact crater, India, indicate melting of the Precambrian basement beneath the 'target' Deccan basalts

NASA Astrophysics Data System (ADS)

Chakrabarti, R.; Goderis, S.; Banerjee, A.; Gupta, R. D.; Claeys, P.; Vanhaecke, F. F.

2016-12-01

The 1.88 km diameter Lonar impact Crater, with age estimates ranging from 52 -570 ka, is located in the Buldana district of Maharashtra, India. It is an almost circular depression hosted entirely in the 65Ma old basalt flows of the Deccan Traps and is the best-known terrestrial analogue for impact craters in the Inner Solar System. Isotopic studies indicate that the basalts around Lonar correlate with the Poladpur suite, one of the mid-section volcano-stratigraphic units of the Deccan traps. Recently collected samples of the host basalt and impact melts, were analyzed for major and trace element concentrations using ICPMS, as well as for Nd and Sr isotope ratios using TIMS. Relatively more radiogenic Sr and less radiogenic Nd isotopic composition of the melt rocks compared to earlier measurements of similar rocks from Lonar are consistent with melting of the Precambrian basement beneath the Deccan basalt. Spherules ranging in size from 100 mm to 1 mm, were hand-picked under a binocular microscope from unconsolidated soil samples, collected from the south-eastern rim of the crater. Thirty-five spherule samples, screened for surface alteration using SEM were analyzed for major and trace element concentrations including PGEs using LA-ICPMS. The spherules were further classified into two groups using the Chemical Index of Alteration(CIA). Iridium and Cr concentrations of the spherules are consistent with mixing of a chondritic impactor (with 2-8% contribution) with the target rock(s). On a Nb (fluid immobile) -normalized binary plot of Th versus Cr, the composition of the spherules can be explained by mixing between the host basalt and a chondritic impactor with a definite, but minor contribution of the basement beneath Lonar, the composition of which is approximated using the average composition of the upper continental crust (UCC). Variability in the light-REE fractionation of the spherules (La/Sm(N)) can also be explained by a similar three component mixing. Overall, our geochemical data for both the melt rocks and spherules suggest mixing between the chondritic impactor, the Deccan host basalt and the basement rocks at Lonar.

Fluid-flow, diagenesis and generation of secondary porosity-permeability in the Cretaceous Jandaira Formation, Brazil - an analogue of karstified carbonate reservoirs

NASA Astrophysics Data System (ADS)

Bezerra, F. H.; Cazarin, C. L.; Srivastava, N. K.

2017-12-01

This study investigates the diagenetic processes that generated secondary porosity-permeability in carbonates. Our study area is the Jandaira Formation, a post-rift unit, 50-700 m thick, which occurs over an area of 70 x 260 km in the Potiguar Basin, Equatorial margin of Brazil. The Jandaira Formation formed in the Turonian-Campanian and is the major exposed Cretaceous carbonate platform in the eastern continental margin of South America. Little folding and nearly flat-lying layers characterize this unit. We used a multidisciplinary approach, which included drone imagery, petrographic, petrophysical, petrological, and structural studies. Our results indicate that several levels of dissolution occurred in mudstone, grainstone, and wackestone facies along faults, fractures, and bedding planes. Fracture and faults provided vertical leaching pathways and sedimentary bedding provided horizontal pathways of increased secondary porosity and permeability. Dissolution resulted in a multi-scale karst system that could reach voids 5 m wide and 1 km long. Dissolution mostly affect the dolomitized sedimentary facies in the form of vugular, moldic, interparticular, and intercrystalline porosity. It also generated a new modified facies that we defined as karstified facies. Dissolution increased permeability in carbonate rocks from primary values of 0.0-0.94 mD to as much as 1370.11 mD. Micritization, lixiviation of evaporites, meteoric water infiltration and dolomitization during late diagenesis could have triggered dissolution processes. The Jandaira Formation serves as an analog of fractured and karstified carbonate reservoirs, where faults, joints, and bedding acted as pathways of high permeability.

Nature and origin of mineral coatings on volcanic rocks of the Black Mountain, Stonewall Mountain, and Kane Springs Wash volcanic centers, Southern Nevada

NASA Technical Reports Server (NTRS)

Taranik, James V.; Hsu, Liang C.; Spatz, David

1988-01-01

Comparative lab spectra and Thematic Mapper imagery investigations at 3 Tertiary calderas in southern Nevada indicate that desert varnish is absorbant relative to underlying host rocks below about 0.7 to 1.3 microns, depending on mafic affinity of the sample, but less absorbant than mafic host rocks at higher wavelengths. Desert varnish occurs chiefly as thin impregnating films. Distribution of significant varnish accumulations is sparse and localized, occurring chiefly in surface recesses. These relationships result in the longer wavelength bands and high 5/2 values over felsic units with extensive desert varnish coatings. These lithologic, petrochemical, and desert varnish controlled spectral responses lead to characteristic TM band relationships which tend to correlate with conventionally mappable geologic formations. The concept of a Rock-Varnish Index (RVI) is introduced to help distinguish rocks with a potentially detectable varnish. Felsic rocks have a high RVI, and those with extensive desert varnish behave differently, spectrally, from those without extensive varnish. The spectrally distinctive volcanic formations at Stonewall Mountain provide excellent statistical class segregation on supervised classification images. A binary decision rule flow-diagram is presented to aid TM imagery analysis over volcanic terrane in semi-arid environments.

Carbon Dioxide - rock interaction: from molecular observations to theorised interactions in fluid-rock systems

NASA Astrophysics Data System (ADS)

Calcara, Massimo; Borgia, Andrea

2013-04-01

Current global warming theories have produced some benefits: among them, detailed studies on CO2 and its properties, possible applications and perspectives. Starting from its use as a "green solvent" (for instance in decaffeination process), to enhance system in oil recovery, to capture and storage enough amount of CO2 in geological horizon. So, a great debate is centred around this molecule. One More useful research in natural horizon studies is its theorised use in Enhanced Geothermal Systems with CO2 as the only working fluid. In any case, the CO2 characteristics should be deeply understood, before injecting a molecule prone to change easily its aggregation state at relatively shallow depth. CO2 Rock interaction becomes therefore a focal point in approaching research sectors linked in some manner to natural or induced presence of carbon dioxide in geological horizons. Possible chemical interactions between fluids and solids have always been a central topic in defining evolution of the system as a whole in terms of dissolutions, reactions, secondary mineral formation and, in case of whichever plant, scaling. Questions arise in case of presence of CO2 with host rocks. Chemical and molecular properties are strategic. CO2 Rock interactions are based on eventual solubility capability of pure liquid and supercritical CO2 seeking and eventually quantifying its polar and/or ionic solvent capabilities. Single molecule at STP condition is linear, with central carbon atom and oxygen atoms at opposite site on a straight line with a planar angle. It has a quadrupolar moment due to the electronegativity difference between carbon and oxygen. As soon as CO2 forms bond with water, it deforms even at atmospheric pressure, assuming an induced dipole moment with a value around 0.02 Debye. Hydrated CO2 forms a hydrophilic bond; it deforms with an angle of 178 degrees. Pure CO2 forms self aggregates. In the simplest case a dimer, with two molecules of CO2 exerting mutual attraction and forming at a first impact a structure defined parallel or slipped parallel or a more stable T shaped. As soon as pressure is applied, density changes and appears a stable (induced) dipole moment 0.22 Debye: phase changes and CO2 dipole moment reaches 0.85 Debye dipole moment. Pure CO2, here the only liquid phase, assumes Lewis acid/base properties. Polar solvent properties seem to be real, and some experiments have observed this characteristics. This stated, present work try to show computer aided simulation in chemical and physical evolution of a portion of rock with liquid and supercritical CO2, with and without water, in granite and oceanic basalt formations.

Effects of shallow basaltic intrusion into pyroclastic deposits, Grants Ridge, New Mexico, USA

NASA Astrophysics Data System (ADS)

WoldeGabriel, Giday; Keating, Gordon N.; Valentine, Greg A.

1999-10-01

A localized aureole up to 10 m wide developed around a 150-m-wide, 2.6 Ma basaltic plug at Grants Ridge, New Mexico. The plug intruded into nonwelded, pumice-rich compositionally homogenous tuff and volcaniclastic sediments of similar age (3.3 Ma). Color variation (pinkish to orange), strong local contact welding, brecciation, partial melting, and stoping characterize the host rock within the contact zone. Despite the high-temperature basaltic intrusion, there is no indication of extensive fluid-driven convective heat transfer and pervasive hydrothermal circulation and alteration of the country rock. The proportion of volcanic glass, loss on ignition (LOI), fluorine, iron, and some trace and rare earth element contents in the host rocks are somewhat depleted at the contact of the intrusion. Conversely, the degree of devitrification and the potassium content are higher along the contact. Vapor-phase expulsion of elemental species as complexes of fluoride, chloride, hydroxide, sulfide, and carbon dioxide may have been responsible for the minor depletion of the elements during the devitrification of silicic glass at near-solidus temperature related to the basaltic intrusion. The results of finite-difference numerical modeling of the intrusion as a dry, conduction-dominated system agree well with geochemical and mineralogical data. Contact welding of the host rocks apparently occurred at temperatures >700°C under a density-driven lateral load of approximately 1 MPa, corresponding to the observed depth below the former ground surface of ˜100 m. Other physical changes in the first 10 m of host rock, represented by partial devitrification and color changes, apparently occurred at temperatures of 500-600°C, which probably persisted for up to 55 years after the emplacement of the basaltic plug. Devitrification is generally enhanced by the presence of aqueous fluids; however, the abundance of volcanic glass within a short distance (˜10 m) from the plug is consistent with our inference that the plug intruded into a dry (unsaturated) environment.

Reproducing early Martian atmospheric carbon dioxide partial pressure by modeling the formation of Mg-Fe-Ca carbonate identified in the Comanche rock outcrops on Mars

NASA Astrophysics Data System (ADS)

Berk, Wolfgang; Fu, Yunjiao; Ilger, Jan-Michael

2012-10-01

The well defined composition of the Comanche rock's carbonate (Magnesite0.62Siderite0.25Calcite0.11Rhodochrosite0.02) and its host rock's composition, dominated by Mg-rich olivine, enable us to reproduce the atmospheric CO2partial pressure that may have triggered the formation of these carbonates. Hydrogeochemical one-dimensional transport modeling reveals that similar aqueous rock alteration conditions (including CO2partial pressure) may have led to the formation of Mg-Fe-Ca carbonate identified in the Comanche rock outcrops (Gusev Crater) and also in the ultramafic rocks exposed in the Nili Fossae region. Hydrogeochemical conditions enabling the formation of Mg-rich solid solution carbonate result from equilibrium species distributions involving (1) ultramafic rocks (ca. 32 wt% olivine; Fo0.72Fa0.28), (2) pure water, and (3) CO2partial pressures of ca. 0.5 to 2.0 bar at water-to-rock ratios of ca. 500 molH2O mol-1rock and ca. 5°C (278 K). Our modeled carbonate composition (Magnesite0.64Siderite0.28Calcite0.08) matches the measured composition of carbonates preserved in the Comanche rocks. Considerably different carbonate compositions are achieved at (1) higher temperature (85°C), (2) water-to-rock ratios considerably higher and lower than 500 mol mol-1 and (3) CO2partial pressures differing from 1.0 bar in the model set up. The Comanche rocks, hosting the carbonate, may have been subjected to long-lasting (>104 to 105 years) aqueous alteration processes triggered by atmospheric CO2partial pressures of ca. 1.0 bar at low temperature. Their outcrop may represent a fragment of the upper layers of an altered olivine-rich rock column, which is characterized by newly formed Mg-Fe-Ca solid solution carbonate, and phyllosilicate-rich alteration assemblages within deeper (unexposed) units.

Rare earth element content of cryptocrystalline magnesites of Konya, Turkey

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

Zedef, Veysel, E-mail: vzedef@selcuk.edu.tr; Russell, Michael

We examined the rare earth element content of several cryptocrystalline magnesites as well as hydromagnesite, host rock serpentinites, lake water and hot spring water from Turkey. Southwestern Turkey hosts cryptocrystalline magnesites, sedimentary magnesites with presently forming, biologically mediated hydromagnesites and travertines. Our results show the REE content of the minerals, rocks and waters are well below detection limits. One hydromagnesite sample from Lake Salda has slightly high La (2.38ppb), Ce (3.91 ppb) and Nd (1.68 ppb) when compared to other samples, but these are also still below detection limits of the method we followed.

Microbial- and thiosulfate-mediated dissolution of mercury sulfide minerals and transformation to gaseous mercury

DOE PAGES

Vázquez-Rodríguez, Adiari I.; Hansel, Colleen M.; Zhang, Tong; ...

2015-06-23

Mercury (Hg) is a toxic heavy metal that poses significant environmental and human health risks. Soils and sediments, where Hg can exist as the Hg sulfide mineral metacinnabar (β-HgS), represent major Hg reservoirs in aquatic environments. Metacinnabar has historically been considered a sink for Hg in all but severely acidic environments, and thus disregarded as a potential source of Hg back to aqueous or gaseous pools. In this study, we conducted a combination of field and laboratory incubations to identify the potential for metacinnabar as a source of dissolved Hg within near neutral pH environments and the underpinning (a)biotic mechanismsmore » at play. We show that the abundant and widespread sulfur-oxidizing bacteria of the genus Thiobacillus extensively colonized metacinnabar chips incubated within aerobic, near neutral pH creek sediments. Laboratory incubations of axenic Thiobacillus thioparus cultures led to the release of metacinnabar-hosted Hg(II) and subsequent volatilization to Hg(0). This dissolution and volatilization was greatly enhanced in the presence of thiosulfate, which served a dual role by enhancing HgS dissolution through Hg complexation and providing an additional metabolic substrate for Thiobacillus. These findings reveal a new coupled abiotic-biotic pathway for the transformation of metacinnabar-bound Hg(II) to Hg(0), while expanding the sulfide substrates available for neutrophilic chemosynthetic bacteria to Hg-laden sulfides. Lastly, they also point to mineral-hosted Hg as an underappreciated source of gaseous elemental Hg to the environment.« less

Fungal oxidative dissolution of the Mn(II)-bearing mineral rhodochrosite and the role of metabolites in manganese oxide formation.

PubMed

Tang, Yuanzhi; Zeiner, Carolyn A; Santelli, Cara M; Hansel, Colleen M

2013-04-01

Microbially mediated oxidation of Mn(II) to Mn(III/IV) oxides influences the cycling of metals and remineralization of carbon. Despite the prevalence of Mn(II)-bearing minerals in nature, little is known regarding the ability of microbes to oxidize mineral-hosted Mn(II). Here, we explored oxidation of the Mn(II)-bearing mineral rhodochrosite (MnCO3 ) and characteristics of ensuing Mn oxides by six Mn(II)-oxidizing Ascomycete fungi. All fungal species substantially enhanced rhodochrosite dissolution and surface modification. Mineral-hosted Mn(II) was oxidized resulting in formation of Mn(III/IV) oxides that were all similar to δ-MnO2 but varied in morphology and distribution in relation to cellular structures and the MnCO3 surface. For four fungi, Mn(II) oxidation occurred along hyphae, likely mediated by cell wall-associated proteins. For two species, Mn(II) oxidation occurred via reaction with fungal-derived superoxide produced at hyphal tips. This pathway ultimately resulted in structurally unique Mn oxide clusters formed at substantial distances from any cellular structure. Taken together, findings for these two fungi strongly point to a role for fungal-derived organic molecules in Mn(III) complexation and Mn oxide templation. Overall, this study illustrates the importance of fungi in rhodochrosite dissolution, extends the relevance of biogenic superoxide-based Mn(II) oxidation and highlights the potential role of mycogenic exudates in directing mineral precipitation. © 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.

Microbial- and thiosulfate-mediated dissolution of mercury sulfide minerals and transformation to gaseous mercury

PubMed Central

Vázquez-Rodríguez, Adiari I.; Hansel, Colleen M.; Zhang, Tong; Lamborg, Carl H.; Santelli, Cara M.; Webb, Samuel M.; Brooks, Scott C.

2015-01-01

Mercury (Hg) is a toxic heavy metal that poses significant environmental and human health risks. Soils and sediments, where Hg can exist as the Hg sulfide mineral metacinnabar (β-HgS), represent major Hg reservoirs in aquatic environments. Metacinnabar has historically been considered a sink for Hg in all but severely acidic environments, and thus disregarded as a potential source of Hg back to aqueous or gaseous pools. Here, we conducted a combination of field and laboratory incubations to identify the potential for metacinnabar as a source of dissolved Hg within near neutral pH environments and the underpinning (a)biotic mechanisms at play. We show that the abundant and widespread sulfur-oxidizing bacteria of the genus Thiobacillus extensively colonized metacinnabar chips incubated within aerobic, near neutral pH creek sediments. Laboratory incubations of axenic Thiobacillus thioparus cultures led to the release of metacinnabar-hosted Hg(II) and subsequent volatilization to Hg(0). This dissolution and volatilization was greatly enhanced in the presence of thiosulfate, which served a dual role by enhancing HgS dissolution through Hg complexation and providing an additional metabolic substrate for Thiobacillus. These findings reveal a new coupled abiotic-biotic pathway for the transformation of metacinnabar-bound Hg(II) to Hg(0), while expanding the sulfide substrates available for neutrophilic chemosynthetic bacteria to Hg-laden sulfides. They also point to mineral-hosted Hg as an underappreciated source of gaseous elemental Hg to the environment. PMID:26157421

Evidence for tectonic, lithologic, and thermal controls on fracture system geometries in an andesitic high-temperature geothermal field

NASA Astrophysics Data System (ADS)

Massiot, Cécile; Nicol, Andrew; McNamara, David D.; Townend, John

2017-08-01

Analysis of fracture orientation, spacing, and thickness from acoustic borehole televiewer (BHTV) logs and cores in the andesite-hosted Rotokawa geothermal reservoir (New Zealand) highlights potential controls on the geometry of the fracture system. Cluster analysis of fracture orientations indicates four fracture sets. Probability distributions of fracture spacing and thickness measured on BHTV logs are estimated for each fracture set, using maximum likelihood estimations applied to truncated size distributions to account for sampling bias. Fracture spacing is dominantly lognormal, though two subordinate fracture sets have a power law spacing. This difference in spacing distributions may reflect the influence of the andesitic sequence stratification (lognormal) and tectonic faults (power law). Fracture thicknesses of 9-30 mm observed in BHTV logs, and 1-3 mm in cores, are interpreted to follow a power law. Fractures in thin sections (˜5 μm thick) do not fit this power law distribution, which, together with their orientation, reflect a change of controls on fracture thickness from uniform (such as thermal) controls at thin section scale to anisotropic (tectonic) at core and BHTV scales of observation. However, the ˜5% volumetric percentage of fractures within the rock at all three scales suggests a self-similar behavior in 3-D. Power law thickness distributions potentially associated with power law fluid flow rates, and increased connectivity where fracture sets intersect, may cause the large permeability variations that occur at hundred meter scales in the reservoir. The described fracture geometries can be incorporated into fracture and flow models to explore the roles of fracture connectivity, stress, and mineral precipitation/dissolution on permeability in such andesite-hosted geothermal systems.

More than Meets the Ear: A Factor Analysis of Student Impressions of Television Talk Show Hosts.

ERIC Educational Resources Information Center

Walker, James R.

To identify the descriptors most frequently associated with four popular television talk show hosts and to isolate the fundamental dimensions of the images of those talk show hosts, a study surveyed 209 students from Memphis State University and the University of Arkansas (Little Rock) about their impressions of Johnny Carson, David Letterman,…