The Partial Molar Volume and Compressibility of the FeO Component in Model Basalts (Mixed CaAl2Si2O8-CaMgSi2O6-CaFeSi2O6 Liquids) at 0 GPa: evidence of Fe2+ in 6-fold coordination

NASA Astrophysics Data System (ADS)

Guo, X.; Lange, R. A.; Ai, Y.

2010-12-01

FeO is an important component in magmatic liquids and yet its partial molar volume at one bar is not as well known as that for Fe2O3 because of the difficulty of performing double-bob density measurements under reducing conditions. Moreover, there is growing evidence from spectroscopic studies that Fe2+ occurs in 4, 5, and 6-fold coordination in silicate melts, and it is expected that the partial molar volume and compressibility of the FeO component will vary accordingly. We have conducted both density and relaxed sound speed measurements on four liquids in the An-Di-Hd (CaAl2Si2O8-CaMgSi2O6-CaFeSi2O6) system: (1) Di-Hd (50:50), (2) An-Hd (50:50), (3) An-Di-Hd (33:33:33) and (4) Hd (100). Densities were measured between 1573 and 1838 K at one bar with the double-bob Archimedean method using molybdenum bobs and crucibles in a reducing gas (1%CO-99%Ar) environment. The sound speeds were measured under similar conditions with a frequency-sweep acoustic interferometer, and used to calculate isothermal compressibility. All the density data for the three multi-component (model basalt) liquids were combined with density data on SiO2-Al2O3-CaO-MgO-K2O-Na2O liquids (Lange, 1997) in a fit to a linear volume equation; the results lead to a partial molar volume (±1σ) for FeO =11.7 ± 0.3(±1σ) cm3/mol at 1723 K. This value is similar to that for crystalline FeO at 298 K (halite structure; 12.06 cm3/mol), which suggests an average Fe2+ coordination of ~6 in these model basalt compositions. In contrast, the fitted partial molar volume of FeO in pure hedenbergite liquid is 14.6 ± 0.3 at 1723 K, which is consistent with an average Fe2+ coordination of 4.3 derived from EXAFS spectroscopy (Rossano, 2000). Similarly, all the compressibility data for the three multi-component liquids were combined with compressibility data on SiO2-Al2O3-CaO-MgO liquids (Ai and Lange, 2008) in a fit to an ideal mixing model for melt compressibility; the results lead to a partial molar compressibility (±1σ) for FeO = 2.4 (± 0.3) 10-2 GPa-1 at 1723 K. In contrast, the compressibility of FeO in pure hedenbergite liquid is more than twice as large: 6.3 (± 0.2) 10-2 GPa-1. When these results are combined with density and sound speed data on CaO-FeO-SiO2 liquids at one bar (Guo et al., 2009), a systematic and linear variation between the partial molar volume and compressibility of the FeO component is obtained, which appears to track changes in the average Fe2+ coordination in these liquids. Therefore, the three most important conclusions of this study are: (1) ideal mixing of volume and compressibility does not occur for all FeO-bearing magmatic liquids, owing to changes in Fe2+ coordination, (2) the partial molar volume and compressibility of FeO varies linearly and systematically with Fe2+ coordination, and (3) ideal mixing of volume and compressibility does occur among the three mixed An-Di-Hd liquids, presumably because of a common, average Fe2+ coordination of ~6.

Ca-Fe and Alkali-Halide Alteration of an Allende Type B CAI: Aqueous Alteration in Nebular or Asteroidal Settings

NASA Technical Reports Server (NTRS)

Ross, D. K.; Simon, J. I.; Simon, S. B.; Grossman, L.

2012-01-01

Ca-Fe and alkali-halide alteration of CAIs is often attributed to aqueous alteration by fluids circulating on asteroidal parent bodies after the various chondritic components have been assembled, although debate continues about the roles of asteroidal vs. nebular modification processes [1-7]. Here we report de-tailed observations of alteration products in a large Type B2 CAI, TS4 from Allende, one of the oxidized subgroup of CV3s, and propose a speculative model for aqueous alteration of CAIs in a nebular setting. Ca-Fe alteration in this CAI consists predominantly of end-member hedenbergite, end-member andradite, and compositionally variable, magnesian high-Ca pyroxene. These phases are strongly concentrated in an unusual "nodule" enclosed within the interior of the CAI (Fig. 1). The Ca, Fe-rich nodule superficially resembles a clast that pre-dated and was engulfed by the CAI, but closer inspection shows that relic spinel grains are enclosed in the nodule, and corroded CAI primary phases interfinger with the Fe-rich phases at the nodule s margins. This CAI also contains abundant sodalite and nepheline (alkali-halide) alteration that occurs around the rims of the CAI, but also penetrates more deeply into the CAI. The two types of alteration (Ca-Fe and alkali-halide) are adjacent, and very fine-grained Fe-rich phases are associated with sodalite-rich regions. Both types of alteration appear to be replacive; if that is true, it would require substantial introduction of Fe, and transport of elements (Ti, Al and Mg) out of the nodule, and introduction of Na and Cl into alkali-halide rich zones. Parts of the CAI have been extensively metasomatized.

Evidence for the extraterrestrial origin of a natural quasicrystal

PubMed Central

Bindi, Luca; Eiler, John M.; Guan, Yunbin; Hollister, Lincoln S.; MacPherson, Glenn; Steinhardt, Paul J.; Yao, Nan

2012-01-01

We present evidence that a rock sample found in the Koryak Mountains in Russia and containing icosahedrite, an icosahedral quasicrystalline phase with composition Al63Cu24Fe13, is part of a meteorite, likely formed in the early solar system about 4.5 Gya. The quasicrystal grains are intergrown with diopside, forsterite, stishovite, and additional metallic phases [khatyrkite (CuAl2), cupalite (CuAl), and β-phase (AlCuFe)]. This assemblage, in turn, is enclosed in a white rind consisting of diopside, hedenbergite, spinel (MgAl2O4), nepheline, and forsterite. Particularly notable is a grain of stishovite (from the interior), a tetragonal polymorph of silica that only occurs at ultrahigh pressures (≥10 Gpa), that contains an inclusion of quasicrystal. An extraterrestrial origin is inferred from secondary ion mass spectrometry 18O/16O and 17O/16O measurements of the pyroxene and olivine intergrown with the metal that show them to have isotopic compositions unlike any terrestrial minerals and instead overlap those of anhydrous phases in carbonaceous chondrite meteorites. The spinel from the white rind has an isotopic composition suggesting that it was part of a calcium-aluminum-rich inclusion similar to those found in CV3 chondrites. The mechanism that produced this exotic assemblage is not yet understood. The assemblage (metallic copper-aluminum alloy) is extremely reduced, and the close association of aluminum (high temperature refractory lithophile) with copper (low temperature chalcophile) is unexpected. Nevertheless, our evidence indicates that quasicrystals can form naturally under astrophysical conditions and remain stable over cosmic timescales, giving unique insights on their existence in nature and stability. PMID:22215583

Petrology and Geochemistry of D'Orbigny, Geochemistry of Sahara 99555, and the Origin of Angrites

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Killgore, Marvin; Lee, Michael T.

2001-01-01

We have done detailed petrologic study of the angrite, D'Orbigny, and geochemical study of it and Sahara 99555. D'Orbigny is an igneous-textured rock composed of Ca-rich olivine, Al-Ti-diopside-hedenbergite, subcalcic kirschsteinite, two generations of hercynitic spinel and anorthite, with the mesostasis phases ulv6spinel, Ca-phosphate, a silicophosphate phase and Fe-sulfide. We report an unknown Fe-Ca-Al-Ti-silicate phase in the mesostasis not previously found in angrites. One hercynitic spinel is a large, rounded homogeneous grain of a different composition than the euhedral and zoned grains. We believe the former is a xenocryst, the first such described from angrites. The mafic phases are highly zoned; mg# of cores for olivine are approx.64, and for clinopyroxene approx.58, and both are zoned to Mg-free rims. The Ca content of olivine increases with decreasing mg#, until olivine with approx.20 mole% Ca is overgrown by subcalcic kirschsteinite with Ca approx.30-35 mole%. Detailed zoning sequences in olivine-subcalcic kirschsteinite and clinopyroxene show slight compositional reversals. There is no mineralogic control that can explain these reversals, and we believe they were likely caused by local additions of more primitive melt during crystallization of D'Orbigny. D'Orbigny is the most ferroan angrite with a bulk rock mg# of 32. Compositionally, it is virtually identical to Sahara 99555; the first set of compositionally identical angrites. Comparison with the other angrites shows that there is no simple petrogenetic sequence, partial melting with or without fractional crystallization, that can explain the angrite suite. Angra dos Reis remains a very anomalous angrite. Angrites show no evidence for the brecciation, shock, or impact or thermal metamorphism that affected the HED suite and ordinary chondrites. This suggests the angrite parent body may have followed a fundamentally different evolutionary path than did these other parent bodies.

Sr and Nd isotopic compositions, age and petrogenesis of A-type granitoids of the Vernon Supersuite, New Jersey Highlands, USA

USGS Publications Warehouse

Volkert, R.A.; Feigenson, M.D.; Patino, L.C.; Delaney, J.S.; Drake, Avery A.

2000-01-01

Voluminous late Mesoproterozoic monzonite through granite of the Vernon Supersuite underlies an area of approximately 1300 km2 in the Highlands of northern New Jersey. The Vernon Supersuite consists of hastingsite ?? biotite-bearing granitoids of the Byram Intrusive Suite (BIS) and hedenbergite-bearing granitoids of the Lake Hopatcong Intrusive Suite (LHIS). These rocks have similar major and trace element abundances over a range of SiO2 from 58 to 75 wt.%, are metaluminous to weakly peraluminous, and have a distinctive A-type chemistry characterized by high contents of Y, Nb, Zr, LREE, and Ga/Al ratios, and low MgO, CaO, Sr and HREE. Whole-rock Rb-Sr isochrons of BIS granite yield an age of 1116 ?? 41 Ma and initial 87Sr/86Sr ratio of 0.70389, and of LHIS granite an age of 1095 ?? 9 Ma and initial 87Sr/86Sr ratio of 0.70520. Both suites have similar initial 143Nd/144Nd ratios of 0.511267 to 0.511345 (BIS) and 0.511359 to 0.511395 (LHIS). Values of ??(Nd) are moderately high and range from +1.21 to +2.74 in the BIS and +2.24 +2.95 in the LHIS. Petrographic evidence, field relationships, geochemistry, and isotopic data support an interpretation of comagmatism and the derivation of both suites from a mantle-derived or a juvenile lower crustal parent with little crustal assimilation. Both suites crystallized under overlapping conditions controlled by P-T-f(H(2)O). Lake Hopatcong magma crystallized at a liquidus temperature that approached 900??C and a pressure of about 6 kbar, and remained relatively anhydrous throughout its evolution. Initial P-T conditions of the Byram magma were ??? 850??C and about 5.5 kbar. BIS magma was emplaced contemporaneous with, or slightly preceding LHIS magma, and both magmas were emplaced during a compressional tectonic event prior to granulite facies metamorphism that occurred in the Highlands between 1080 and 1030 Ma. (C) 2000 Elsevier Science B.V. All rights reserved.

Isotope geochemistry and fluid inclusion study of skarns from Vesuvius

USGS Publications Warehouse

Gilg, H.A.; Lima, A.; Somma, R.; Belkin, H.E.; de Vivo, B.; Ayuso, R.A.

2001-01-01

We present new mineral chemistry, fluid inclusion, stable carbon and oxygen, as well as Pb, Sr, and Nd isotope data of Ca-Mg-silicate-rich ejecta (skarns) and associated cognate and xenolithic nodules from the Mt. Somma-Vesuvius volcanic complex, Italy. The typically zoned skarn ejecta consist mainly of diopsidic and hedenbergitic, sometimes "fassaitic" clinopyroxene, Mg-rich and Ti-poor phlogopite, F-bearing vesuvianite, wollastonite, gehlenite, meionite, forsterite, clinohumite, anorthite and Mg-poor calcite with accessory apatite, spinell, magnetite, perovskite, baddeleyite, and various REE-, U-, Th-, Zr- and Ti-rich minerals. Four major types of fluid inclusions were observed in wollastonite, vesuvianite, gehlenite, clinopyroxene and calcite: a) primary silicate melt inclusions (THOM = 1000-1050??C), b) CO2 ?? H2S-rich fluid inclusions (THOM = 20-31.3??C into the vapor phase), c) multiphase aqueous brine inclusions (THOM = 720-820??C) with mainly sylvite and halite daughter minerals, and d) complex chloride-carbonate-sulfate-fluoride-silicate-bearing saline-melt inclusions (THOM = 870-890??C). The last inclusion type shows evidence for immiscibility between several fluids (silicate melt - aqueous chloride-rich liquid - carbonate/sulfate melt?) during heating and cooling below 870??C. There is no evidence for fluid circulation below 700??C and participation of externally derived meteoric fluids in skarn formation. Skarns have considerably variable 206Pb/204Pb (19.047-19.202), 207Pb/204Pb (15.655-15.670), and 208Pb/204Pb (38.915-39.069) and relatively low 143Nd/144Nd (0.51211-0.51244) ratios. The carbon and oxygen isotope compositions of skarn calcites (??13CV-PDB = -5.4 to -1.1???; ??18OV-SMOW = 11.7 to 16.4???) indicate formation from a 18O- and 13C-enriched fluid. The isotope composition of skarns and the presence of silicate melt inclusion-bearing wollastonite nodules suggests assimilation of carbonate wall rocks by the alkaline magma at moderate depths (< 5 km) and consequent exsolution of CO2-rich vapor and complex saline melts from the contaminated magma that reacted with the carbonate rocks to form skarns.

Evidence of a Pre-eruptive Fluid Phase for the Millennium Eruption, Paektu Volcano, North Korea

NASA Astrophysics Data System (ADS)

Iacovino, K.; Sisson, T. W.; Lowenstern, J. B.

2014-12-01

We present initial results of a study of comenditic to trachytic melt inclusions from the Millennium Eruption (ME) of Paektu volcano (AD 946; VEI≥7; 25 km3 DRE). Paektu volcano (aka Changbaishan) is a remote and poorly studied intraplate stratovolcano whose 37 km2 caldera is bisected by the political border between North Korea and China, limiting studies of its proximal deposits. ME magmas are predominantly phenocryst-poor (≤3 vol%) comendites plus a volumetrically minor late-stage, more phenocryst-rich (10-20 vol%) trachyte. Sizeable (100-500 µm diameter) glassy but bubble-bearing melt inclusions are widespread in anorthoclase and hedenbergite phenocrysts, as well as in rarer quartz and fayalite phenocrysts. Comparing the relative enrichments of incompatible volatile and non-volatile elements in melt inclusions along a liquid line of descent shows decreasing volatile/Zr ratios suggesting the partitioning of volatiles into a fluid phase. This suggests that current gas-yield estimates (Horn & Schminke, 2000) for the ME, based on the petrologic method (difference in volatiles between melt inclusions and matrix glass), could be severe underestimates. Establishing the composition and quantity of a pre-eruptive fluid phase is the primary goal of this study and has implications for eruption triggering and for modeling the climatic effects of one of the largest eruptions in the last 10,000 years. Including results from Horne and Schminke (2000), melt inclusions from within a single pumice fall unit show a wide range in dissolved volatile contents and magma chemistries. Concentrations of H2O are moderate (2-3.5 wt% via FTIR), with Cl and F ranging from 500-4600 ppm and 1100-4700 ppm (via EPMA). CO2 is below the detection limit of 2 ppm (FTIR with N2 purge) in bubble-bearing melt inclusions, but is detectable (≤56 ppm) in melt inclusions homogenized at 100 MPa and 850-900 °C for ~30 min (conditions also leading to reduction of dissolved H2O to 0.6-2 wt%). Characterization of a co-existing fluid phase in ME magmas is being investigated with further melt inclusion analyses, mineral-melt-fluid equilibrium calculations, and phase equilibrium experiments on fluid-saturated liquid lines of descent and on volatile solubilities of the ME trachyite-comendite suite.

Genesis of the Datuanshan stratabound skarn Cu(-Mo) deposit, Middle-Lower Yangtze Valley, Eastern China: constraints from geology, Re-Os geochronology, mineralogy, and sulfur isotopes

NASA Astrophysics Data System (ADS)

Cao, Yi; Gao, Fuping; Du, Yangsong; Du, Yilun; Pang, Zhenshan

2017-03-01

Stratabound deposits are the most abundant and economically significant ore type in the Middle-Lower Yangtze River Valley, one of the most important metallogenic belts in China. The Datuanshan deposit is one of the largest and most representative stratabound Cu(-Mo) deposits in the Tongling district of the Middle-Lower Yangtze River metallogenic belt. All the orebodies of the Datuanshan deposit occur around Mesozoic quartz monzodiorite and are tabular or semi-tabular bodies along bedding-parallel faults within upper Permian to Lower Triassic strata. However, discordant and crosscutting relationships (e.g., the host rocks crosscut by skarn- and quartz-sulfide veins, with alteration halos around the veins) have also been found, especially along the skarn-host contact and orebody-host contact, indicating that skarnitization and mineralization postdated the deposition of the host sediments. The skarn consists mainly of prograde garnet and pyroxene and retrograde alteration assemblages of amphibole, epidote, and chlorite, as well as quartz and sulfides. Electron microprobe analyses show that the garnets and pyroxenes are grossular-andradite and hedenbergite-diopside series, respectively, and all samples plot in the field of typical skarn copper deposits worldwide. Molybdenite samples from stratiform copper ores yield Re-Os model ages of 138.2-139.9 Ma with a weighted mean age of 139.2 ± 0.9 Ma. This is reasonably consistent with the ages of the stratiform Mo ores (138.0-140.8 Ma) and genetically related quartz monzodiorite (135.2-139.3 Ma) in the Datuanshan deposit, indicating that the stratiform Cu and Mo mineralization was contemporaneous with emplacement of the quartz monzodiorite magmas in the Early Cretaceous. Fifteen δ34S values for sulfides range from -1.8 to +4.7 ‰, with a mean of 0.5 ‰, indicating that the sulfur was derived mainly from a magmatic source. Moreover, the sulfur isotope values of the ores are consistent with those of Mesozoic intermediate-acid intrusions but are different from those of sediments in the Shizishan orefield. Based on these lines of evidence, we conclude that the Datuanshan stratabound Cu(-Mo) deposit is the result of replacement related to Mesozoic magmatic rocks and is not a product of submarine exhalative sedimentary processes.

The Tephra Layer From the Plinian Eruption in ™r‘faj”kull 1362, Southeast Iceland

NASA Astrophysics Data System (ADS)

Selbekk, R. S.

2002-12-01

Pyroclastic fallout from the 1362 eruption of ™r‘faj”kull forms one of the volcanic marker horizons of the North Atlantic. This contribution reports the mineralogical and geochemical characteristics of the ™r‘faj”kull 1362 fallout and its grain-size distribution. A non-rifting 120 km long volcanic lineament some 50 km east of the Eastern Rift-Zone of Iceland is defined by transitional and alkalic volcanic rocks resting unconformably on late Tertiary strata. ™r‘faj”kull which forms the southern termination of this off-rift liniment is an ice-covered stratovolcano (2200 masl) composed mostly of subglacially formed hyaloclastite ranging from basalts to rhyolites. The two historical (1100 yrs) eruptions of ™r‘faj”kull include a small explosive eruption in 1727 and a large devastating Plinian eruption associated with major lahars and a caldera collapse in 1362. Between 1 and 2 km3 dense rock equivalent or 5-10 km3 of rhyolitic pumice was erupted and the fallout was mainly towards ESE. Tentative modelling of the PT-conditions of the magma formation, based on glass/mineral equilibria, indicates that the source was a near-eutectic melt in equilibrium with fayalite, hedenbergite, oligoclase and hematite at some 0.2 GPa pressure. A profile through the fallout was sampled at elevation of about 1100 masl on the SE flank of the volcano. A deposit of 1.8 m thickness was collected in 14 units for examination of composition, mineralogy and grain-size distribution during the eruption. In the profile the fallout is fine grained vesicular glass (1-3% minerals, 3% lithic fragments) with bubble wall thickness in the low micron range. The high and even vesiculation of the glass indicates fast magma ascent and explains the extreme mechanical fragmentation within the eruptive column, yielding between 50 and 80 wt% of less than 0.25 mm grain size. A reconstruction of the Plinian phase, based on grain-size analysis and abundance of lithic fragments, reveals that the eruption proceeded in three successive phases. An initial explosion produced phreatomagmatic debris associated with up to 35% of lithic fragments. In distal facies of the fallout, the initial phase is recognised as pale brownish base of the otherwise white glassy layer. The material ejection proceeded in two largely similar phases. These phases are separated only by a transition in grain size distribution indicating a temporary lowering in the effusion rate.

Geochemical characterization and leaching behavior of slags: by-product materials from an old lead smelter in Chihuahua, Mexico

NASA Astrophysics Data System (ADS)

Espejel-Garcia, D.; Wenglas-Lara, G.; Villalobos-Aragon, A.; Espejel-Garcia, V. V.

2012-12-01

Steel slags are stored in piles or stocks around or near the smelter site. Currently, there is an increasing interest in the use of waste materials, especially in the construction industry, to replace natural aggregates, help the environment and reduce the costs. Slags are being used widely as road ballast, road base or sub-base material, sandblasting agents or cement additives, but normally contain high concentrations of potentially toxic metals. Although these metals are associated with glass, silicate and oxide minerals, with slow solubilities in water, a characterization of the leaching behavior is essential in environmental evaluation for reuse scenarios. The state of Chihuahua is located in northern Mexico, and mining has been an important economic activity since the 18th century. In the early 1900's, a lead smelter operated in Avalos, Chihuahua (in the southern surroundings of Chihuahua city), and left considerable slag piles after their closure in the 1980's. In this study, this material has been geochemically analyzed to identify the metals contained in it, and used in "tank tests" experiments, to assess its leaching behavior. The slags from Chihuahua contain Pb (0.5 - 4 wt.%), Zn (15-35 wt.%) and As (0.6 wt.%) in different minerals such as hardystonite (Ca2ZnSi2O7), melanotekite (Pb2Fe3+3O2Si2O7), kentrolite (Pb2Mn2Si2O9) and sphalerite (ZnS) or trapped in the glass. Major elements are present in phases such as monticellite (CaMgSiO4), kirschsteinite (CaFe2+SiO4), hedenbergite (CaFeSi2O6), babingtonite (Fe2Si3O9), magnetite (Fe3O4), and calcite (CaCO3). The leaching experiments were performed for 6, 24, 168 and 360 hours in mixtures of 30 and 50% of slags with natural road base material using distilled water at a pH 5 and 8 to recreate acidic and alkaline waters. The amounts of leached Pb ranges from 0.1 to 0.5 ppm, Zn from 0.1 to 0.6 ppm, As from 0 to 0.09 ppm, and Ca from 40 to 180 ppm, being the acidic experiments the ones that leached out the highest amounts of metals. Based on the results of analyses and experiments, it is recommended to use the waste material (slags) as aggregates in road construction, but only as minor constituent (<30%) in base materials.

Uranium-lead dating of hydrothermal zircon and monazite from the Sin Quyen Fe-Cu-REE-Au-(U) deposit, northwestern Vietnam

NASA Astrophysics Data System (ADS)

Li, Xiao-Chun; Zhou, Mei-Fu; Chen, Wei Terry; Zhao, Xin-Fu; Tran, MyDung

2018-03-01

The Sin Quyen deposit in northwestern Vietnam contains economic concentrations of Cu, Au and LREE, and sub-economic concentration of U. In this deposit, massive and banded replacement ores are hosted in Neoproterozoic metapelite. The paragenetic sequence includes sodic alteration (stage I), calcic-potassic alteration and associated Fe-REE-(U) mineralization (stage II), Cu-Au mineralization (stage III), and sulfide-(quartz-carbonate) veins (stage IV). The Sin Quyen deposit experienced an extensive post-ore metamorphic overprint, which makes it difficult to precisely determine the mineralization age. In this study, zircon and monazite U-Pb geochronometers and the Rb-Sr isochron method are used to constrain the timing of mineralization. Zircon grains in the ore are closely intergrown or texturally associated with hydrothermal minerals of stage II (e.g., garnet, allanite, and hedenbergite). They may contain primary fluid inclusions and display irregular zoning in cathodoluminescence (CL) images. Zircon grains are rich in U (688 to 2902 ppm) and poor in Th (0.2 to 2.9 ppm). Their δ18OV-SMOW values range from 11.9 to 14.0‰, higher than those of typical magmatic zircon. These textural and compositional features imply that zircon precipitated from 18O- and U-rich hydrothermal fluids, coeval with the minerals of stage II. Monazite occurs in close association with stage II magnetite and allanite and has low contents of Th (<2700 ppm), indicative of a hydrothermal origin. Hydrothermal zircon and monazite have indistinguishable U-Pb ages of 841 ± 12 and 836 ± 18 Ma, respectively, representing the timing of Fe-REE mineralization. There is no direct isotopic constraint on the timing of the Cu-Au mineralization, but geological observations suggest that the Cu-Au and Fe-REE ores most likely formed within a single evolved hydrothermal process. In the plot of 87Rb/86Sr vs. 87Sr/86Sr, the composition of bulk-ore and biotite separates from ore lie along a reference line for 30 Ma, which is consistent with the timing of metamorphism in the region. The mineralization age of the Sin Quyen deposit falls within the overall age range (740 to 860 Ma) of the regional Neoproterozoic igneous rocks. This temporal linkage, in combination with the magmatic-like sulfur isotopes of sulfide minerals (δ34SV-CDT = -0.8 to 3.1), indicates that the mineralization may have a close genetic association with the Neoproterozoic igneous activity.

The Minerals of Candor Chasma

NASA Technical Reports Server (NTRS)

2008-01-01

The Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) took this image of sulfate- and pyroxene-containing deposits in the Candor Chasma region of Mars at 0747 UTC (2:47 a.m. EST) on December 2, 2006, near 6.7 degrees south latitude, 75.8 degrees west longitude. The image was taken in 544 colors covering 0.36-3.92 micrometers, and shows features as small as 40 meters (132 feet) across. The image is about 10 kilometers (6.2 miles) wide at its narrowest point.

Candor Chasma is a deep, elongated, steep-sided depression some 813 kilometers (505 miles) long. It is one of two large chasmata that make up the northern end of the Valles Marineris system.

The top panel in the montage above illustrates the location of CRISM data on a mosaic taken by the Mars Odyssey spacecraft's Thermal Emission Imaging System (THEMIS). CRISM data cover an area centered on the southwestern part of Candor Chasma, where highland crust was depressed by faulting and buried by a kilometers-thick stack of layered deposits.

The bottom two images are views of CRISM data. The lower left image is an infrared false color image, while at lower right is a spectral image that illustrates the distribution of sulfates in the layered deposits, the olivine and pyroxene that make up the faulted highland crust, and high-calcium pyroxene in the highland crust.

The northern part of CRISM's data swath covers interior deposits formed after the canyon floor was faulted and depressed. This lighter region in the infrared image at lower left exhibits the spectral signatures of sulfates (blues) in the CRISM spectral image at lower right. The southern end of CRISM's data reveals volcanic minerals (pyroxene and olivine) that make up the older, underlying highland crust. The strongest signature comes from the common diopside-hedenbergite series of pyroxenes a group of silicate materials rich in iron, magnesium, and calcium.

CRISM is one of six science instruments on NASA's Mars Reconnaissance Orbiter. Led by The Johns Hopkins University Applied Physics Laboratory, Laurel, Md., the CRISM team includes expertise from universities, government agencies and small businesses in the United States and abroad. NASA's Jet Propulsion Laboratory, a division of the California Institute of Technology in Pasadena, manages the Mars Reconnaissance Orbiter and the Mars Science Laboratory for NASA's Science Mission Directorate, Washington. Lockheed Martin Space Systems, Denver, built the orbiter.

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

Sugama, Toshifumi; Pyatina, Tatiana

The study aims at evaluating the bond durability of a carbon microfiber (CMF)-reinforced alkali-activating calcium aluminate cement (CAC)/fly ash F (FAF) blend cementitious material adhering to carbon steel (CS) under stresses induced by a 350°C heat-25°Cwater cooling cycle. This cementitious material/CS joint sample was originally prepared in an autoclave at 300°C under a pressure of 8.3 MPa. For comparison, two reference geothermal well cements, Class G modified with silica (G) and calciumaluminum phosphate (CaP), were employed as well reinforced with CMF. In the CAC/FAF blending cement systems, the CAC-derived cementitious reaction products preferentially adhered to CS surfaces, rather than thatmore » of FAF-related reaction products. CMF played a pivotal role in creating tough interfacial bond structure of cement layer adhering to CS. The bond toughness also was supported by the crystalline cementitious reaction products including sodalite, brownmillerite, and hedenbergite as major phases, and aragonite, boehmite, and garronite as minor ones. The brownmillerite as an interfacial reaction product between cement and CS promoted the chemical bonding of the cement to CS, while the other phases served in providing the attractive bonding of the cement to CS. The post-stress-test joint samples revealed the formation of additional brown-millerite, aragonite, and garronite, in particular brownmillerite as the major one. The combination of chemical bonding and self-advancing adherence behavior of the cement was essential for creating a better interfacial bond structure. A similar interfacial bond structure was observed with CaP. The crystalline phase composition of the autoclaved cement revealed apatite, zeolite, and ferrowyllieite as major reaction products, and aragonite and al-katoite as the minor ones. Ferrowyllieite was identified as cement/CS interfacial reaction product contributing to the chemical bond of cement, while the other phases aided in providing the attractive bond of cement. After a stress test, two phases, ferrowyllieite and aragonite, promoted the self-advancing adherence of cement to CS. However, the effectiveness of these phases in improving adherence performance of cement was less than that of CAC/FAF blend cement, reflecting the fact that the bond durability of CAC/FAF blend cement was far better than that of the CaP. In contrast, the autoclaved silica-modified G cement consisting of xonotlite, and 0.9 nm-to-bermorite and riversideite, with calcite as the crystalline reaction products, had no significant effect on improving the shear bond strength and the bond’s toughness. No interaction product with CS was found in the cement adhering to CS. After a stress test, the calcite phase acted only to promote the self-advancing adherence of cement, but its extent was minimal compared with that of the other cements, thereby resulting in poor bond durability.« less

Mineralogical and geochemical controls on the release of trace elements from slag produced by base- and precious-metal smelting at abandoned mine sites

USGS Publications Warehouse

Piatak, N.M.; Seal, R.R.; Hammarstrom, J.M.

2004-01-01

Slag collected from smelter sites associated with historic base-metal mines contains elevated concentrations of trace elements such as Cu, Zn and Pb. Weathering of slag piles, many of which were deposited along stream banks, potentially may release these trace elements into the environment. Slags were sampled from the Ely and Elizabeth mines in the Vermont copper belt, from the copper Basin mining district at Ducktown, Tennessee and from the Clayton silver mine in the Bayhorse mining district, Idaho, in the USA. Primary phases in the slags include: olivine-group minerals, glass, spinels, sulfide minerals and native metals for Vermont samples; glass, sulfide minerals and native metals for the Ducktown sample; and olivine-group minerals, clinopyroxenes, spinels, sulfide minerals, native metals and other unidentified metallic compounds for Clayton slag. Olivine-group minerals and pyroxenes are dominantly fayalitic and hedenbergitic in composition, respectively and contain up to 1.25 wt.% ZnO. Spinel minerals range between magnetite and hercynite in composition and contain Zn (up to 2.07 wt.% ZnO), Ti (up to 4.25 wt.% TiO2) and Cr (up to 1.39 wt.% Cr2O3). Cobalt, Ni, Cu, As, Ag, Sb and Pb occur in the glass phase, sulfides, metallic phases and unidentified metallic compounds. Bulk slag trace-element chemistry shows that the metals of the Vermont and Tennessee slags are dominated by Cu (1900-13,500 mg/kg) and Zn (2310-10,200 mg/kg), whereas the Clayton slag is dominated by Pb (63,000 mg/kg), Zn (19,700 mg/kg), Cu (7550 mg/kg), As (555 mg/kg), Sn (363 mg/kg) and Ag (200 mg/kg). Laboratory-based leach tests indicate metals can be released under simulated natural conditions. Leachates from most slags were found to contain elevated concentrations of Cu and Zn (up to 1800 and 470 ??g/l, respectively), well in excess of the acute toxicity guidelines for aquatic life. For the Idaho slag, the concentration of Pb in the leachate (11,000 ??g/l) is also in excess of the acute toxicity guideline. Geochemical modeling of the leachate chemistry suggests that leachates from the Vermont, Tennessee and Clayton slags are saturated with amorphous silica and Al hydroxide. Therefore, the dissolution of silicate and oxide phases, the oxidation of sulfide phases, as well as the precipitation of secondary phases may control the composition of leachate from slags. The presence of secondary minerals on slag deposits in the field is evidence that these materials are reactive. The petrographic data and results of leaching tests from this study indicate slag may be a source of potentially toxic metals at abandoned mine sites.

Bond Durability of Carbon-Microfiber-Reinforced Alkali-Activated High-Temperature Cement Adhering to Carbon Steel

DOE PAGES

Sugama, Toshifumi; Pyatina, Tatiana

2017-02-01

The study aims at evaluating the bond durability of a carbon microfiber (CMF)-reinforced alkali-activating calcium aluminate cement (CAC)/fly ash F (FAF) blend cementitious material adhering to carbon steel (CS) under stresses induced by a 350°C heat-25°Cwater cooling cycle. This cementitious material/CS joint sample was originally prepared in an autoclave at 300°C under a pressure of 8.3 MPa. For comparison, two reference geothermal well cements, Class G modified with silica (G) and calciumaluminum phosphate (CaP), were employed as well reinforced with CMF. In the CAC/FAF blending cement systems, the CAC-derived cementitious reaction products preferentially adhered to CS surfaces, rather than thatmore » of FAF-related reaction products. CMF played a pivotal role in creating tough interfacial bond structure of cement layer adhering to CS. The bond toughness also was supported by the crystalline cementitious reaction products including sodalite, brownmillerite, and hedenbergite as major phases, and aragonite, boehmite, and garronite as minor ones. The brownmillerite as an interfacial reaction product between cement and CS promoted the chemical bonding of the cement to CS, while the other phases served in providing the attractive bonding of the cement to CS. The post-stress-test joint samples revealed the formation of additional brown-millerite, aragonite, and garronite, in particular brownmillerite as the major one. The combination of chemical bonding and self-advancing adherence behavior of the cement was essential for creating a better interfacial bond structure. A similar interfacial bond structure was observed with CaP. The crystalline phase composition of the autoclaved cement revealed apatite, zeolite, and ferrowyllieite as major reaction products, and aragonite and al-katoite as the minor ones. Ferrowyllieite was identified as cement/CS interfacial reaction product contributing to the chemical bond of cement, while the other phases aided in providing the attractive bond of cement. After a stress test, two phases, ferrowyllieite and aragonite, promoted the self-advancing adherence of cement to CS. However, the effectiveness of these phases in improving adherence performance of cement was less than that of CAC/FAF blend cement, reflecting the fact that the bond durability of CAC/FAF blend cement was far better than that of the CaP. In contrast, the autoclaved silica-modified G cement consisting of xonotlite, and 0.9 nm-to-bermorite and riversideite, with calcite as the crystalline reaction products, had no significant effect on improving the shear bond strength and the bond’s toughness. No interaction product with CS was found in the cement adhering to CS. After a stress test, the calcite phase acted only to promote the self-advancing adherence of cement, but its extent was minimal compared with that of the other cements, thereby resulting in poor bond durability.« less

Aegirine as a late-stage phase in an alkaline pluton associated with carbonate assimilation

NASA Astrophysics Data System (ADS)

Barnes, C. G.; Prestvik, T.; Hiller, J.

2006-12-01

The Hortavaer Complex in north-central Norway is a well-documented example of formation of an alkaline magmatic suite due to assimilation of carbonate and calc-silicate rocks (Vogt 1916; Gustavson & Prestvik, 1979; Barnes et al., 2003, 2005). The alkaline nature developed primarily as the result of increased stability and fractionation of Ca-pyroxene at the expense of olivine, resulting in enrichment of Na and K compared to Si. Calcic pyroxene is a common mineral in rocks that range from gabbro through diorite and monzonite to syenite, with a compositional range from augite to hedenbergite. In addition to calcic pyroxene, glassy, pale green aegirine occurs in veins near skarn-like assemblages in a zone where dioritic sheets were emplaced into syenite. Other vein minerals are biotite, albite, K-feldspar, calcite, and ilmenite. The aegirine is almost pure NaFeSi2O6 (Ae = 91.1%, Jd = 7.4%, Q = 1.5%; where Ae is the aegirine component, Jd the jadeite component, and Q the "quadrilateral" pyroxene component). Laser-ablation ICP-MS analysis shows that the aegirine crystals are typically lower in trace element concentrations than the calcic cpx. For example, Sr is < 2 ppm in the aegirine but > 20 ppm in cpx from evolved syenites and > 85 ppm in cpx from dioritic samples. Chondrite-normalized rare earth element (REE) patterns show a prominent cup shape and light REE abundances range from ~0.1X > 10X chondrites. Aegirine occurs in many locations in Norway (Neumann 1985), where it is generally related to alkaline rocks. Compared to the Hortavaer locality, aegirine from the type area in the Permian Oslo Region has 77% of the NaFeSi2O6 (Ae) component, whereas acmite has 89% Ae. Larsen and Raade (1997) presented c. 30 XRF and EMP analyses of pyroxenes from syenite pegmatites of the southern part of Oslo Region. There is a wide range in composition, and some have up to 95% of the Ae component. Most of the Na-rich pyroxenes (Ae > 90) are low in the Jd component (1.6 to 4.7%), and Q varies in the 4 to 6% range. Thus, compared to pyroxenes similarly high in Ae (> 90%) from the Oslo Region, the Hortavaer aegirine has more of the Jd component and less of the "quadrilateral" component. This feature is striking because host rocks to the Hortavaer aegirine are exceptionally rich in CaO. We suggest that aegirine from Hortavaer is distinct from aegirine from the Oslo region for at least two reasons. First, the Oslo occurrences are associated with rift-related magmatic rocks in which alkalinity resulted by fractionation of an alkaline parent. In contrast, alkalinity in the Hortavær complex developed due to in situ assimilation of carbonate rocks by a sub-alkaline parent. Assimilation resulted in a fluid-rich environment that provided Na, it enhanced the stability of titanite and suppressed magnetite stability. This sequestered Ti and made ferric iron available for aegirine growth. The higher Al may have resulted from differentiation of Hortavaer magmas in a deep-seated magmatic arc.

The petrology and petrogenesis of the Swaldale region, Motzfeldt Center, South Greenland

NASA Astrophysics Data System (ADS)

Reekie, Callum; Finch, Adrian

2016-04-01

Motzfeldt is one of several high-level alkaline plutonic centers that collectively define the mid-Proterozoic Gardar Province of South Greenland. Despite pyrochlore-hosted Ta-enrichment (± Nb-Zr-REE), the petrology, geochemistry and petrogenesis across the center remain to be fully constrained. We present petrological and geochemical data for the Swaldale region, an arcuate band of nepheline syenite and associated intrusives on Motzfeldt's NW margin. Work for this present study was undertaken in collaboration with the license holder, Regency Mines plc. Swaldale comprises two geochemically distinct magmatic members. The largest, the Motzfeldt Sø Formation (MSF; EuN/Eu*N = 0.35), is a suite of diverse syenite variants that show significant petrological and geochemical heterogeneity. These rocks have a relatively restricted SiO2 range (57.4-62.9 wt.%) with concurrent variation in (Na+K)/Al (0.75-0.95), Mg/(Mg+Fe) (2.18-19.82) and ΣREE (595.0-3095.9 ppm), emphasizing their evolved but not peralkaline nature. Fractionation is mirrored by pyroxene geochemistry with evolution from aegirine-augite, aegirine-hedenbergite, to aegirine. Accessory pyrochlore, titanite, and zircon are rare; however, anomalous facies of zircon-rich (~2 wt.%) syenite are observed. Intercumulus fluorite is a common accessory within MSF rocks. Hydrothermal alteration, marked by hematized alkali-feldspar, is pervasive and ubiquitous. Further peraluminous syenite of the Geologfjeld Formation ((Na+K)/Al = 0.74; EuN/Eu*N = 1.60) marks the truncated remnant of an early syenite stock to the north of the MSF. These rocks contain salite, which, in addition to a lower ΣREE and higher Mg/(Mg+Fe) (18.01), demonstrates the less-fractionated nature of this stock in comparison with the MSF. Sheeted intrusions of peralkaline syenite ((Na+K)/Al = 1.1; Ta = 32.4 ppm) truncate the MSF across central Swaldale. On a mineralogical basis, it is hypothesized that such intrusions reflect outward sheeting of the central Flinks Dal Formation, the last major expression of Motzfeldt magmatism. Further NE-SW dykes of the Igaliku Dyke Swarm and termed 'Big Feldspar Dykes' are present across the region. The MSF has bulk-rock Ta, Nb, and Zr concentrations of 7.2-22.1 ppm, 156.9-402.7 ppm, and 563.0-13790.0 ppm, respectively. We interpret lesser enrichment in HFSE's over both central and NE Motzfeldt as consistent with the inferred enhancement of HFSE complex solubility in F-rich residual melts. Accordingly, the most evolved and enriched melts are expected towards the top of the Motzfeldt Center where concentrations exceeding 250 ppm Ta are observed (McCreath et al., 2013). This inference is additionally supported by observed changes to Nb/Ta ratios throughout the MSF whereby the solubility of Ta complexes in F-rich melt is greater than Nb. Our data are consistent with a model whereby MSF melts of the Swaldale region are intermediaries between parental and the most evolved melts of the MSF. Our data supplement previous investigations to constrain fully the abundance and distribution of Motzfeldt Ta-Nb-Zr-REE-mineralization within the Gardar rift. References: McCreath, J.A., Finch, A.A., Herd, D.A., Armour-Brown, A., 2013, Geochemistry of pyrochlore minerals from the Motzfeldt Center, South Greenland: The mineralogy of a syenite hosted Ta, Nb deposit. American Mineralogist, v. 98, p. 426-438.

Melts in the Deep Earth: Calculating the Densities of CaO-FeO-MgO-Al2O3-SiO2 Liquids

NASA Astrophysics Data System (ADS)

Thomas, C.; Guo, X.; Agee, C. B.; Asimow, P. D.; Lange, R. A.

2012-12-01

We present new equation of state (EOS) measurements for hedenbergite (Hd, CaFeSi2O6) and forsterite (Fo, Mg2SiO4) liquids. These liquid EOS add to the basis set in the CaO-FeO-MgO-Al2O3-SiO2 (CMASF) oxide space at elevated temperatures and pressures; other liquids include: enstatite (En, MgSiO3), anorthite (An, CaAl2Si2O8), diopside (Di, CaMgSi2O6), and fayalite (Fa, Fe2SiO4). The Hd EOS measurement was a multi-technique collaboration using 1-atm double-bob Archimedean, ultrasonic, sink/float, and shock wave techniques. Un-weighted linear fitting of the shock data in shock velocity (US)-particle velocity (up) space defines a pre-heated (1400 °C) Hugoniot US = 2.628(0.024) + 1.54(0.01)up km/s. The slope corresponds to a K' of 5.16(0.04), consistent with piston-cylinder and multi-anvil sink/float experiments. The intercept is fixed at the ultrasonic sound speed (Co) since the unconstrained intercept is within the stated error. This behavior demonstrates consistency across methods and that the liquid is relaxed during shock compression. Shock compression of pre-heated (2000°C) single crystal Fo gives an un-weighted linear Hugoniot of US = 2.674(0.188) + 1.64(0.06)up km/s. The unconstrained Co falls below estimates based on extrapolation in both temperature and composition from two published partial molar sound speed models, 3.195m/s [1] and 3.126 m/s [2]. The shock-derived Co indicates that dC/dT is negative for Fo liquid, contrary to the positive [1] and zero [2] temperature dependences derived over relatively narrow temperature intervals. CMASF liquid isentropes were calculated using five end-members (En, Fo, Fa, An, Di). For modeling crystallization of a fictive magma ocean, we examined two liquids: peridotite [3] (P=.33En+.56Fo+.07Fa+.03An+.007Di) and simplified chondrite [4] (Ch=.62En+.24Fo+.08Fa+.04An+.02Di). Each end-member is defined by a 3rd or 4th order Birch-Murnaghan isentrope, Mie-Grüneisen thermal pressure and a constant heat capacity. The volumes are assumed to ideally mix allowing for interpolation between end-member compositions. Results show the chondrite critical isentrope intersecting its liquidus at the core-mantle boundary with a potential temperature (TP) of 2400 K, whereas the peridotite critical isentrope has a TP of 2800 K and first crystallizes at 85 GPa. An identical calculation fails to recover the Hd isentrope (Hd = Di+0.5Fa-0.5Fo). This failure is likely due to the very different partial molar volumes of FeO in Hd and Fa, which have average Fe2+ coordination states of ~4.5 and ~6, respectively [5]. Consequently the simple ideal model is likely to only support mixing among like-coordinated Fe2+ liquids. We hope to further investigate this hypothesis for linear-mixing by constraining the EOS of An-Hd (50:50), and An-Di-Hd (33:33:33) melts using pre-heated shock wave techniques. [1] Ghiorso & Kress (2004) AJS 304, 679-751.[2] Ai & Lange(2008) JGR 113,B04203.[3] Fiquet et al. (2010) Science 329, 1516-1518.[4]Andrault et al. (2011) EPSL 304, 251-259.[5]Lange et al. (2012) Goldschmidt meeting, abstract.

Indications for a CO2-rich fluid cap in the uppermost part of the Laacher See Magma Chamber

NASA Astrophysics Data System (ADS)

Aßbichler, Donjá; Heuss-Aßbichler, Soraya; Kunzmann, Thomas

2017-04-01

Sanidinites are rare holocrystalline to hypocrystalline magmatic cumulates and are found as volcanic ejecta of potassic explosive volcanoes. They all have trachytic to phonolitic whole rock composition. Main constituent of these rocks is sanidine forming a framework of interlocking crystals creating miarolithic cavities. In this study we were investigating sodalite bearing sanidinites from the tephra deposits of the Laacher See Volcano, Eifel, Germany with the aim to decipher the processes in the uppermost, rigid part of the magma chamber. Macroscopically three different types can be distinguished: (1) dark haüyne-sanidinites, (2) bright haüyne-sanidinites and (3) nosean-sanidinites. Both types of haüyne-sanidinites contain glass, rich in vesicles, forming a film around most of the mineral grains or sometimes filling up the miarolithic cavities. Minor mineral phases are haüyne occurring within these cavities, mainly adjacent to plagioclase as well as clinopyroxene and biotite. Accessories are apatite, magnetite and titanite. In nosean-sanidinites glass is absent or occurs occasionally as a minor phase. Major crystals within the miarolithic cavities are nosean and calcite, while clinopyroxene and biotite are rarely observed. A special feature is the formation of HFSE minerals as euhedral crystals, including zircon, baddeleyite, pyrochlore and REE-apatites. The difference in mineral assemblage is also reflected in the whole rock composition of the investigated samples. Nosean-sanidinites are compared to haüyne-sanidinites (i) enriched in Na, Ca, Mn, S, Cl, Zr, U, Th, Hf, Zn and REE (+LOI) and (ii) depleted in K, Mg, Si, Ti, P, Ba, Sr and V. From dark haüyne-sanidinite over bright haüyne-sanidinite to nosean-sanidinites the mineral composition of the major phases shows following systematic trends: Ca content of sanidine decreases indicating decreasing temperature during crystallization. The minerals of the sodalite group show an increase of Na and CO2 whereas the content of Ca and SO4 decreases. Clinopyroxene observed in the haüyne-sanidinite has diospidic to hedenbergitic composition while in the nosean-sanidinites it is enriched in Mn (ferroan johannsenite with up to 0.55 apfu Mn; 15.5 wt.-% MnO). Several features indicate the presence of an aggressive fluid phase during formation of the nosean-sanidinites: all silicates expose etching structures such as jagged or rounded mineral surfaces, and/or holes and channels within the mineral grains. To a lesser extent these structures are also observed in the silicates of the bright haüyne-sanidinites. In nosean-sanidinites the etching holes are often filled by calcite. Occasionally these fillings are bounded by a calcite filled fluid vain. All these observations indicate the presence of a CO2-rich fluid phase. The sanidinites are suggested to be formed at late magmatic conditions from a phonolitic melt. The systematics in the textures indicates, that the minerals within the miarolithic cavities of the haüyne-sanidinites crystallized from an evolved, volatile rich phonolitic melt. In contrast the crystallization within the miarolithic pore space of the nosean-sanidinites took place in the rigid zone of the uppermost part of the magma chamber where the mineral forming processes are induced by CO2-rich fluid.

Preservation of Fe Isotope Proxies in the Rock Record

NASA Astrophysics Data System (ADS)

Johnson, C.; Beard, B.; Valley, J.; Valaas, E.

2005-12-01

Iron isotope variations provide powerful constraints on redox conditions and pathways involved during biogeochemical cycling of Fe in surface and near-surface environments. The relative isotopic homogeneity of igneous rocks and most bulk weathering products contrasts with the significant isotopic variations (4 per mil in 56Fe/54Fe) that accompany oxidation of Fe(II)aq, precipitation of sulfides, and reduction by bacteria. These isotopic variations often reflect intrinsic (equilibrium) Fe isotope fractionations between minerals and aqueous species whose interactions may be directly or indirectly catalyzed by bacteria. In addition, Fe isotope exchange may be limited between reactive Fe pools in low-temperature aqueous-sediment environments, fundamentally reflecting disequilibrium effects. In the absence of significant sulfide, dissimilatory Fe(III) reduction by bacteria produces relatively low 56Fe/54Fe ratios for Fe(II)aq and associated biogenic minerals such as magnetite and siderite. In contrast, Fe(II)aq that exchanges with Fe sulfides (FeS and pyrite) is relatively enriched in 56Fe/54Fe ratios. In modern and ancient environments, anoxic diagenesis tends to produce products that have low 56Fe/54Fe ratios, whereas oxidation of Fe(II)aq from hydrothermal sources tends to produce ferric Fe products that have high 56Fe/54Fe ratios. Redox cycling by bacteria tends to produce reactive ferric Fe reservoirs that have low 56Fe/54Fe ratios. Application of Fe isotopes as a proxy for redox conditions in the ancient rock record depends upon the preservation potential during metamorphism, given the fact that most Archean sedimentary sequences have been subjected to regional greenschist- to granulite-facies metamorphism. The 1.9 Ga banded iron formations (BIFs) of the Lake Superior region that are intruded by large ~1 Ga intrusions (e.g., Duluth gabbro) provide a test of the preservation potential for primary, low-temperature Fe isotope variations in sedimentary rocks. 56Fe/54Fe ratios for re-crystallized magnetite from BIFs of the Biwabik iron formation that have apparent oxygen-isotope (quartz-magnetite) temperatures between 270 and 800 oC span a significant portion of the range measured in lower-grade BIFs from South Africa and Australia. d56Fe values for Biwabik magnetite vary from -0.2 to +0.7 per mil, whereas magnetite from the Dales Gorge member of the Brockman iron formation and the Kuruman iron formation has d56Fe values that lie between -1.2 and +1.3 per mil. Iron isotope fractionations between magnetite and Fe silicates (greenalite, hedenbergite, and fayalite) in the Biwabik iron formation regularly decrease with increasing oxygen-isotope temperatures, approaching the zero fractionation expected at igneous temperatures; apparent magnetite-Fe silicate fractionations range from +0.2 per mil at 650 oC to +0.5 per mil at 300 oC, lying close to those predicted using the revised beta factors of Polyakov et al. (2005, Goldschmidt). During closed-system Fe isotope exchange during metamorphism, the overall range in d56Fe values for magnetite will remain relatively constant, although it may shift to higher d56Fe values relative to primary (low-temperature) magnetite due to the non-zero magnetite-Fe silicate fractionation factor at moderate temperature ranges. If the mineral parageneis is known, and some assumptions regarding primary mineralogy can be made, these small corrections may be made to successfully infer the original Fe isotope compositions of sedimentary minerals and rocks that have been subjected to metamorphism.

Kontay intrusion (Polar Siberia)- an example of strong magmatic differentiation in the single magmatic body

NASA Astrophysics Data System (ADS)

Zaitsev, Victor

2016-04-01

Kontay intrusion is located in the north-west part of Maimecha-Kotuy province, (part of Siberian Large Igneous Province) in the northern part of the Siberian Platform. Intrusion is fully overlaid and practically not studied before. Geophysical data evident that intrusion has form of laccolite with diameter ˜7.5 km and thickness ˜ 2.5 km [1]. Initially lower part of intrusion was described as "gabbro-anortozite and anortositic gabbro" and higher part - as "leucocratic granophyric anortosites" [2]. Complex mineralo-petrological-geochemical study allow to divide intrusion section on three zones: Lower zone (below 1100 m) - layered sequence of leucocratic and melanocratic of biotite- and ortopyroxene-bearing gabbro, with minor alkaline feldspar, Middle zone (1100-700m) - biotite- and K-feldspar bearing gabbro and monzonotes, interstitial space often contain micrographical structures. Biotite corroded clinopyroxene and form interstitial crystals and Upper zone (700-214 m) - petrographically monotone porthyric quartz-monzonites and granosyenites with rare phenocrysts of plagioclase, magnetite, clinopyroxene and biotite. The main secondary minerals are albite, amphibole (edenite-feroedenite), secondary biotite, chlorite, and F,Al-bearing titanite. Rocks of the all parts fall in the same trends on the binary petrochemical diagrams, they belong to the High-K calc-alkaline seria. They are clearly more alkaline then intrusions of Norilsk district and less alkaline then alkaline-ultramafic intrusions of Maymecha-Kotuy province. Volcanic rocks of Norilsk and Maymecha-Kotuy area was subdivided for four geochemical types, mainly by the Ti-content, Th/U, Gd/Yb and Sm/Yb ratio: Low-Ti-1 (predominated), Low-Ti-2 (well -developed in Norilsk region), Moderate-Ti (developed only in the lower part of volcanic formation in Norilsk region), High-Ti (rare in Norilsk region, but widely spread in Mailecha-Kotuy area) [3]. Kontay intrusion rocks belong to Moderate-Ti group. The closest analog is Ivakinsky-1 subsute. Cumulus minerals composition changed systematically upward. Two populations of clinopyroxene occur, both are diopside-hedenbergite. The pyroxenes of first population contain 1-1.2% TiO22-2.5% Al2O3 0.2-0.3 % MnO, 0.3-0.35% Na2O, Mg/(Mg+Fe)=0.44-0.50 present only in the lower part of intrusion. These pyroxenes was formed from the melt of High-Ti geochemical type; the second population of pyroxene present overall, Mg/(Mg+Fe) decrease from 0.7 to 0.63, concentration of Al2O3 increase from 0.7 to 1.3, TiO2 increase from 0.4 to 0.6, MnO from 0.4 to 0.7 and Na2O decrease from 0.32 to 0.28 wt%. Biotite Mg/(Mg+Fe) increase from 0.60-0.62 up to 0.76-0.78, TiO2 content decrease from 5 -6.2% to 1.9-2.4%, and MnO content increase from 0.1 to 0.3-0.4%. Plagioclase in the lowest part of intrusion contains An60-An45 cores and An32-An26rims, but in the middle and upper zone plagioclase composition of plagioclase changed systematically with an increase in Ca. Based on the petrochemical and mineralogical data, Kontay intrusion is an example of strongly in-situ differentiated layered intrusion, formed in subvolcanic conditions form the subalkaline moderate-Ti melt with admixture of crystals, genetically linked with high-Ti melts. This study was financially supported by the Russian Science Foundation (grant 115-17-30019) [1] Kushnir (2005) Ph.d. thesises, 25.00.10 Ekatirenburg, 154. [2] Lopatin and Kalashnik (2004) Mineral resourses and perspectives of Taimyr district. 154-156 [3] Fedorenko et al. (2000) International Geology Review. 42. 769-804.

Composition of uppermost mantle beneath the Northern Fennoscandia - numerical modeling and petrological interpretation

NASA Astrophysics Data System (ADS)

Virshylo, Ivan; Kozlovskaya, Elena; Prodaivoda, George; Silvennoinen, Hanna

2013-04-01

Studying of the uppermost mantle beneath the northern Fennoscandia is based on the data of the POLENET/LAPNET passive seismic array. Firstly, arrivals of P-waves of teleseismic events were inverted into P-wave velocity model using non-linear tomography (Silvennoinen et al., in preparation). The second stage was numerical petrological interpretation of referred above velocity model. This study presents estimation of mineralogical composition of the uppermost mantle as a result of numerical modeling. There are many studies concerning calculation of seismic velocities for polymineral media under high pressure and temperature conditions (Afonso, Fernàndez, Ranalli, Griffin, & Connolly, 2008; Fullea et al., 2009; Hacker, 2004; Xu, Lithgow-Bertelloni, Stixrude, & Ritsema, 2008). The elastic properties under high pressure and temperature (PT) conditions were modelled using the expanded Hook's law - Duhamel-Neumann equation, which allows computation of thermoelastic strains. Furthermore, we used a matrix model with multi-component inclusions that has no any restrictions on shape, orientation or concentration of inclusions. Stochastic method of conditional moment with computation scheme of Mori-Tanaka (Prodaivoda, Khoroshun, Nazarenko, & Vyzhva, 2000) is applied instead of traditional Voigt-Reuss-Hill and Hashin-Shtrikman equations. We developed software for both forward and inverse problem calculation. Inverse algorithm uses methods of global non-linear optimization. We prefer a "model-based" approach for ill-posed problem, which means that the problem is solved using geological and geophysical constraints for each parameter of a priori and final models. Additionally, we are checking at least several different hypothesis explaining how it is possible to get the solution with good fit to the observed data. If the a priori model is close to the real medium, the nearest solution would be found by the inversion. Otherwise, the global optimization is searching inside the restricted volume in the multi-dimensional parameter space. In order to constrain concentration of minerals we used equilibrium of mineral associations for selected P-T condition obtained by free Gibbs energy minimization (c.f. Stixrude & Lithgow-Bertelloni, 2005). We also considered the mineralogical composition of upper mantle xenoliths, although the representativeness of xenoliths in Precambrian rocks could be treated with care, if one tries to describe the modern mantle. As a first step, we estimated 1D model of mineralogical composition in the depth range of 35-350 km using the IASP91 reference model (Kennett & Engdahl, 1991). Both the P- and S- wave velocities were used for inversion, in order to improve the reliability of the model. More comprehensive result could be obtained if density distribution is involved. In our study we used the 1D PEMC density model (Dziewonski, Hales & Lapwood, 1975) as it is the most adequate for the continental lithosphere. The 1D modeling showed that the garnet lherzolite model (forsterite, fayalite, enstatite, ferrosilite, diopside, jadeite, pyrope) can be considered as a basic one. The end-members of olivine and orthopyroxene solutions were included with the aim of Fe/Mg ratio estimation. Testing with modified models including hedenbergite, harzburgite spinel, etc. showed that these minerals have no significant influence on bulk elastic properties. Selected set of minerals allows modelling the most species of peridote-pyroxenite associations known from xenoliths investigations (Kukkonen, Kuusisto, Lehtonen, & Peltonen, 2008; Lehtonen, O'Brien, Peltonen, Johanson, & Pakkanen, 2004). However, there exist also a number of evidences for mantle eclogite xenoliths from the region under study and its surrounding (Lehtonen et al., 2004; Peltonen, Kinnunen, & Huhma, 2002). That is why we also made modelling for garnet-clinopyroxene model of eclogite. The volumetric mineral compositions obtained were transformed into weight concentration of rock-forming oxides using stoichiometric formulas. The results indicate significant variation of Fe and Mg oxides concentration in the uppermost mantle. The Mg/Fe ratio could be different from the results of previous studies (Griffin et al., 2003; Svetov & Smolkin, 2003), but it is in agreement with the geophysical models considered in our study. At the same time the SiO2 concentration is close to the chemical composition of xenoliths from the Fennoscandia, including Kola Peninsula and Central Finland (Beard, Downes, Mason, & Vetrin, 2007; Kukkonen et al., 2008; Lehtonen et al., 2004). Brief conclusions from our study could be formulated as follows: 1) Modelling confirms potential significant lateral inhomogeneity of mineral composition of the uppermost mantle of northern Fennoscandian Shield. 2) Lherzolitic composition of the mantle lithosphere generally explains seismic velocities obtained by teleseismic tomography in northern Fennoscandian Shield. It could be used as a primary a priori model for interpretation. But potential presence of eclogites cannot be rejected, at least for some parts of studied area. 3) The future study needs to include more precise evaluation of temperature and density in the upper mantle using gravity and heat flow data. Afonso, J. C., Fernàndez, M., Ranalli, G., Griffin, W. L., & Connolly, J. a. D. (2008). Integrated geophysical-petrological modeling of the lithosphere and sublithospheric upper mantle: Methodology and applications. Geochemistry Geophysics Geosystems, 9(5). doi:10.1029/2007GC001834 Beard, a. D., Downes, H., Mason, P. R. D., & Vetrin, V. R. (2007). Depletion and enrichment processes in the lithospheric mantle beneath the Kola Peninsula (Russia): Evidence from spinel lherzolite and wehrlite xenoliths. Lithos, 94(1-4), 1-24. doi:10.1016/j.lithos.2006.02.002 Dziewonski, A.M., A.L. Hales, & E.R. Lapwood. (1975) Parametrically simple earth models consistent with geophysical data Phys. Earth Plan. Int. 10:12. Fullea, J., Afonso, J. C., Connolly, J. A. D., Fernàndez, M., García-Castellanos, D., & Zeyen, H. (2009). LitMod3D: An interactive 3-D software to model the thermal, compositional, density, seismological, and rheological structure of the lithosphere and sublithospheric upper mantle. Geochemistry Geophysics Geosystems, 10(8), 1-21. doi:10.1029/2009GC002391 Griffin, W. ., O'Reilly, S. ., Abe, N., Aulbach, S., Davies, R. ., Pearson, N. ., Doyle, B. ., et al. (2003). The origin and evolution of Archean lithospheric mantle. Precambrian Research, 127(1-3), 19-41. doi:10.1016/S0301-9268(03)00180-3 Hacker, B. R. (2004). Subduction Factory 3: An Excel worksheet and macro for calculating the densities, seismic wave speeds, and H 2 O contents of minerals and rocks at pressure and temperature. Geochemistry Geophysics Geosystems, 5(1), 1-7. doi:10.1029/2003GC000614 Kennett B.L.N. & Engdahl E.R. (1991) Travel times for global earthquake location and phase association. Geophysical Journal International, 105:429-465. Kukkonen, I., Kuusisto, M., Lehtonen, M., & Peltonen, P. (2008). Delamination of eclogitized lower crust: Control on the crust-mantle boundary in the central Fennoscandian shield. Tectonophysics, 457(3-4), 111-127. doi:10.1016/j.tecto.2008.04.029 Lehtonen, M. L., O'Brien, H. E., Peltonen, P., Johanson, B. S., & Pakkanen, L. K. (2004). Layered mantle at the Karelian Craton margin: P - T of mantle xenocrysts and xenoliths from the Kaavi - Kuopio kimberlites , Finland. Lithos, 77, 593-608. doi:10.1016/j.lithos.2004.04.026 Peltonen, P., Kinnunen, K. A., & Huhma, H. (2002). Petrology of two diamondiferous eclogite xenoliths from the Lahtojoki kimberlite pipe , eastern Finland. Lithos, 63, 151-164. Prodaivoda, G. T., Khoroshun, L. P., Nazarenko, L. V, & Vyzhva, S. A. (2000). Mathematical modeling of the azimuthal anisotropy in thermoelasic properties of the oceanic upper mantle. IzvestiyaPhysics of the Solid Earth, 36(5), 394-405. Stixrude, L., & Lithgow-Bertelloni, C. (2005). Thermodynamics of mantle minerals - I. Physical properties. Geophysical Journal International, 162(2), 610-632. Retrieved from http://discovery.ucl.ac.uk/8891/ Svetov, S. A., & Smolkin, V. F. (2003). Model P - T Conditions of High-Magnesia Magma Generation in the Precambrian of the Fennoscandian Shield. Geochemistry International, 41(8), 799-811. Xu, W., Lithgow-Bertelloni, C., Stixrude, L., & Ritsema, J. (2008). The effect of bulk composition and temperature on mantle seismic structure. Earth and Planetary Science Letters, 275(1-2), 70-79. doi:10.1016/j.epsl.2008.08.012