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Valley, John W.

Publications and source records attributed to Valley, John W..

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Comparison of δ 13 C analyses of individual foraminifer ( Orbulina universa ) shells by secondary ion mass spectrometry and gas source mass spectrometry

Rationale: The use of secondary ion mass spectrometry (SIMS) to perform micrometer-scale in situ carbon isotope (δ 13 C) analyses of shells of marine microfossils called planktic foraminifers holds promise to explore calcification and ecological processes. The potential of this technique, however, cannot be realized without comparison to traditional whole-shell δ 13 C values measured by gas source mass spectrometry (GSMS). Methods: Paired SIMS and GSMS δ 13 C values measured from final chamber fragments of the same shell of the planktic foraminifer Orbulina universa are compared. The SIMS–GSMS δ 13 C differences (Δ 13 C SIMS-GSMS ) were determined via paired analysis of hydrogen peroxide-cleaned fragments of modern cultured specimens and of fossil specimens from deep-sea sediments that were either untreated, sonicated, and cleaned with hydrogen peroxide or vacuum roasted. After treatment, fragments were analyzed by a CAMECA IMS 1280 SIMS instrument and either a ThermoScientific MAT-253 or a Fisons Optima isotope ratio mass spectrometer (GSMS). Results: Paired analyses of cleaned fragments of cultured specimens (n = 7) yield no SIMS–GSMS δ 13 C difference. However, paired analyses of untreated (n = 18) and cleaned (n = 12) fragments of fossil shells yield average Δ 13 C SIMS-GSMS values of 0.8‰ and 0.6‰ (±0.2‰, 2 SE), respectively, while vacuum roasting of fossil shell fragments (n = 11) removes the SIMS–GSMS δ 13 C difference. Conclusions: The noted Δ 13 C SIMS-GSMS values are most likely due to matrix effects causing sample–standard mismatch for SIMS analyses but may also be a combination of other factors such as SIMS measurement of chemically bound water. The volume of material analyzed via SIMS is ~10 5 times smaller than that analyzed by GSMS; hence, the extent to which these Δ 13 C SIMS-GSMS values represent differences in analyte or instrument factors remains unclear.

58 GEOSCIENCES↗
DOE OSTI2023

An empirical calibration of the serpentine-water oxygen isotope fractionation at T = 25–100°C

The ability to precisely constrain the physical–chemical conditions of serpentinization, such as temperature and fluid source, is limited by the accuracy of calibrations for oxygen isotope fractionation between serpentine and water – i.e., 1000 lnα( serpentine-water ) – which disagree by up to 20‰ when extrapolated to T<200°C. In this study, we present a new empirical calibration of 1000 lnα( serpentine-water ) aiming to improve applications of oxygen isotope geochemistry to very low-T serpentinization (T<100°C). We used the high-spatial resolution capabilities of Secondary Ion Mass Spectrometry (SIMS) to analyze oxygen isotope ratios in mineral pairs of calcite + serpentine, quartz + serpentine and talc + serpentine co-crystallized at scales≤50μm in six serpentinite samples from the Samail ophiolite (Oman). SIMS analysis shows that the mineral pairs are relatively homogenous in oxygen isotope ratios with variability in δ 18 O values ≤2‰ (2s). Clumped isotope thermometry and petrological constraints indicate crystallization temperatures from 25 to 100°C for the investigated samples. These independent constraints on temperature allowed us to derive 1000 lnα( serpentine-water ) by combining Δ 18 O( quartz-serpentine ), Δ 18 O( talc-serpentine ) and Δ 18 O( calcite-serpentine ) measured by SIMS in the investigated samples with Δ 18 O( quartz-water ), Δ 18 O( talc-water ) and Δ 18 O( calcite-water ) calibrations available in the literature. Our empirical calibration of 1000 lnα( serpentine-water ) = 1.04±0.20 (2SE) × 10 6 /T 2 (T in K), from T = 25 to 100°C, is within uncertainty of former high-temperature empirical calibrations extrapolated to T<100°C and matches experimental calibrations when extrapolated to T=250°C. In conclusion, the new serpentine-water calibration enables more accurate reconstructions of fluid-rock interactions occurring during low-temperature serpentinization processes in various tectonic settings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Oxygen diffusion in garnet: Experimental calibration and implications for timescales of metamorphic processes and retention of primary O isotopic signatures

Knowledge of oxygen diffusion in garnet is crucial for a correct interpretation of oxygen isotope signatures in natural samples. A series of experiments was undertaken to determine the diffusivity of oxygen in garnet, which remains poorly constrained. The first suite included high-pressure (HP), nominally dry experiments performed in piston-cylinder apparatus at: (1) T = 1050–1600 °C and P = 1.5 GPa and (2) T = 1500 °C and P = 2.5 GPa using yttrium aluminum garnet (YAG; Y3Al5O12) cubes. Second, HP H2O-saturated experiments were conducted at T = 900 °C and P = 1.0–1.5 GPa, wherein YAG crystals were packed into a YAG + Corundum powder, along with 18O-enriched H2O. Third, 1 atm experiments with YAG cubes were performed in a gas-mixing furnace at T = 1500–1600 °C under Ar flux. Finally, an experiment at T = 900 °C and P = 1.0 GPa was done using a pyrope cube embedded into pyrope powder and 18O-enriched H2O. Experiments using grossular were not successful. Profiles of 18O/(18O+16O) in the experimental charges were analyzed with three different secondary ion mass spectrometers (SIMS): sensitive high-resolution ion microprobe (SHRIMP II and SI), CAMECA IMS-1280, and NanoSIMS. Considering only the measured length of 18O diffusion profiles, similar results were obtained for YAG and pyrope annealed at 900 °C, suggesting limited effects of chemical composition on oxygen diffusivity. However, in both garnet types, several profiles deviate from the error function geometry, suggesting that the behavior of O in garnet cannot be fully described as simple concentration-independent diffusion, certainly in YAG and likely in natural pyrope as well. The experimental results are better described by invoking O diffusion via two distinct pathways with an inter-site reaction allowing O to move between these pathways. Modeling this process yields two diffusion coefficients (D values) for O, one of which is approximately two orders of magnitude higher than the other. Taken together, Arrhenius relationships are:logDm2s-1=-7.2(±1.3)+(-321(±32)kJmol-12.303RT) for the slow pathway, andlogDm2s-1=-5.4(±0.7)+(-321(±20)kJmol-12.303RT) for the fast pathway. We interpret the two pathways as representing diffusion following vacancy and inter-stitial mechanisms, respectively. Regardless, our new data suggest that the slow mechanism is prevalent in garnet with natural compositions, and thus is likely to control the retentivity of oxygen isotopic signatures in natural samples. The diffusivity of oxygen is similar to Fe-Mn diffusivity in garnet at 1000–1100 °C and Ca diffusivity at 850 °C. However, the activation energy for O diffusion is larger, leading to lower diffusivities at P-T conditions characterizing crustal metamorphism. Therefore, original O isotopic signatures can be retained in garnets showing major element zoning partially re-equilibrated by diffusion, with the uncertainty caveat of extrapolating the experimental data to lower temperature conditions.

Geochemistry & Geophysics↗
DOE OSTI2021

Oxygen isotope evidence for input of magmatic fluids and precipitation of Au-Ag-tellurides in an otherwise ordinary adularia-sericite epithermal system in NE China

Abstract Tellurium-rich (Te) adularia-sericite epithermal Au-Ag deposits are an important current and future source of precious and critical metals. However, the source and evolution of ore-forming fluids in these deposits are masked by traditional bulk analysis of quartz oxygen isotope ratios that homogenize fine-scale textures and growth zones. To advance understanding of the source of Te and precious metals, herein, we use petrographic and cathodoluminescence (CL) images of such textures and growth zones to guide high spatial resolution secondary ion mass spectroscopy (SIMS) oxygen isotope analyses (10 µm spot) and spatially correlated fluid inclusion microthermometric measurements on successive quartz bands in contemporary Te-rich and Te-poor adularia-sericite (-quartz) epithermal Au-Ag vein deposits in northeastern China. The results show that large positive oxygen isotope shifts from –7.1 to +7.7‰ in quartz rims are followed by precipitation of Au-Ag telluride minerals in the Te-rich deposit, whereas small oxygen isotope shifts of only 4‰ (–2.2 to +1.6‰) were detected in quartz associated with Au-Ag minerals in the Te-poor deposits. Moreover, fluid-inclusion homogenization temperatures are higher in comb quartz rims (avg. 266.4 to 277.5 °C) followed by Au-Ag telluride minerals than in previous stages (~250 °C) in the Te-rich deposit. The Te-poor deposit has a consistent temperature (~245 °C) in quartz that pre- and postdates Au-Ag minerals. Together, the coupled increase in oxygen isotope ratios and homogenization temperatures followed by precipitation of Au-Ag tellurides strongly supports that inputs of magmatic fluid containing Au, Ag, and Te into barren meteoric water-dominated flow systems are critical to the formation of Te-rich adularia-sericite epithermal Au-Ag deposits. In contrast, Te-poor adularia-sericite epithermal Au-Ag deposits show little or no oxygen isotope or fluid-inclusion evidence for inputs of magmatic fluid.

Geochemistry & Geophysics↗
DOE OSTI2021

Oxygen isotope ratios in zircon and garnet: A record of assimilation and fractional crystallization in the Dinkey Dome peraluminous granite, Sierra Nevada, California

Abstract The 119 Ma Dinkey Dome pluton in the central Sierra Nevada Batholith is a peraluminous granite and contains magmatic garnet and zircon that are complexly zoned with respect to oxygen isotope ratios. Intracrystalline SIMS analysis tests the relative importance of magmatic differentiation processes vs. partial melting of metasedimentary rocks. Whereas δ18O values of bulk zircon concentrates are uniform across the entire pluton (7.7‰ VSMOW), zircon crystals are zoned in δ18O by up to 1.8‰, and when compared to late garnet, show evidence of changing magma chemistry during multiple interactions of the magma with wall rock during crustal transit. The evolution from an early high-δ18O magma [δ18O(WR) = 9.8‰] toward lower values is shown by high-δ18O zircon cores (7.8‰) and lower δ 18O rims (6.8‰). Garnets from the northwest side of the pluton show a final increase in δ18O with rims reaching 8.1‰. In situ REE measurements show zircon is magmatic and grew before garnets. Additionally, δ18O in garnets from the western side of the pluton are consistently higher (avg = 7.3‰) relative to the west (avg = 5.9‰). These δ18O variations in zircon and garnet record different stages of assimilation and fractional crystallization whereby an initially high-δ18O magma partially melted low-δ18O wallrock and was subsequently contaminated near the current level of emplacement by higher δ18O melts. Collectively, the comparison of δ18O zoning in garnet and zircon shows how a peraluminous pluton can be constructed from multiple batches of variably contaminated melts, especially in early stages of arc magmatism where magmas encounter significant heterogeneity of wall-rock assemblages. Collectively, peraluminous magmas in the Sierran arc are limited to small <100 km2 plutons that are intimately associated with metasedimentary wall rocks and often surrounded by later and larger metaluminous tonalite and granodiorite plutons. The general associations suggest that early-stage arc magmas sample crustal heterogeneities in small melt batches, but that with progressive invigoration of the arc, such compositions are more effectively blended with mantle melts in source regions. Thus, peraluminous magmas provide important details of the nascent Sierran arc and pre-batholithic crustal structure.

Geochemistry & Geophysics↗
DOE OSTI2020

In Situ Oxygen Isotope Determination in Serpentine Minerals by SIMS: Addressing Matrix Effects and Providing New Insights on Serpentinisation at Hole BA1B (Samail ophiolite, Oman)

The ability to constrain the petrogenesis of multiple serpentine generations recorded at the microscale is crucial for estimating the extent and conditions of modern versus fossil serpentinisation in ophiolites. To address matrix bias effects during oxygen isotope analysis by SIMS, we present the first investigation analysing antigorite in the compositional range Mg# = 77.5–99.5 mole %, using a CAMECA IMS–1280 secondary ion mass spectrometer. Spot–to–spot homogeneity is ≤ 0.5‰ (2s) for the new antigorite reference materials. The relative bias between antigorite reference materials with different Mg/Fe ratios is described by a second order polynomial, and a maximum difference in bias of ~ 1.8‰ was measured for Mg# ~ 78 to 100. We observed a bias up to ~ 1.0‰ between lizardite and antigorite attributed to their different crystal structure. Orientation effects up to ~ 1‰ were observed in chrysotile. The new analytical protocol allowed the identification of oxygen isotope zoning up to ~ 7‰ in serpentine minerals from two serpentinites recovered from an area of active serpentinisation in the Samail ophiolite. Furthermore in situ analysis is capable of resolving isotopic heterogeneity that may directly reflect changes in the physical and chemical conditions of multiple serpentinisation events in the Samail ophiolite.

47 OTHER INSTRUMENTATION↗
DOE OSTI2020

Large isotopic variability at the micron-scale in ‘Shuram’ excursion carbonates from South Australia

Ediacaran-aged (635–541 million years ago) marine sediments contain a large negative carbon isotope (δ 13 C) excursion, in which carbonate δ 13 C values reach -12‰ (VPDB). Known as the ‘Shuram’ excursion, many workers have interpreted this δ 13 C record as an unprecedented perturbation to the global carbon cycle, leading to speculation about a causal connection to the broadly contemporaneous rise of animal life. Others have interpreted the δ 13 C signal as a product of diagenesis, thereby minimizing its relevance for understanding the evolution of metazoans. In this work, we present SEM imaging and in-situ δ 13 C and δ 18 C values measured by secondary ion mass spectrometry (SIMS) to assess these competing hypotheses in the Wonoka Formation of South Australia. Our results from the minimum of the excursion show that rounded sedimentary grains of calcite have δ 13 C values between -12.8 to -10.6‰ and δ 18 C values between 17.8 to 15.5‰ (VPDB). Euhedral dolomite that appears to have grown unimpeded in open sedimentary pore spaces also is present. These early-stage dolomites are interpreted as early authigenic in origin and have δ 13 C values that reach +5‰, requiring a formation fluid with a substantially different δ 13 C composition from basin waters or bulk sediment. Together, these results provide little evidence for the hypothesis that a late diagenetic overprint has generated the ‘Shuram’ excursion in the Wonoka. Instead, they suggest the presence of a large carbon isotopic gradient in the surface environment, with shallow waters capable of precipitating carbonates with very low δ 13 C (down to 12‰) and deeper shelf and/or marine pore waters generating carbonates with positive carbon isotope values (up to +5‰). Because negative isotope excursions of similar magnitude are found in widely dispersed Ediacaran basins, it is likely that this gradient was characteristic of shelf environments of this period and that a still-unknown global process led to the ‘Shuram’ excursion in shallow water carbonates.

58 GEOSCIENCES↗
DOE OSTI2020

Using SIMS to decode noisy stratigraphic δ 13 C variations in Ediacaran carbonates

Carbonate carbon isotope (δ 13 C carb ) chemostratigraphy is a valuable tool in Precambrian stratigraphic correlation. The effectiveness of this tool rests on the assumption that δ 13 C carb data record global seawater signals. However, in some cases δ 13 C carb data exhibit rapid and noisy stratigraphic variations that may have been influenced by authigenic or diagenetic carbonate minerals. To assess the contribution of non-primary minerals towards bulk carbonate carbon isotope values, we acquired SIMS (secondary ion mass spectrometry) δ 13 C carb data, electron microscopic data, and CL (cathodoluminescence) microscopic data from two Ediacaran successions—the lower Member II of the Doushantuo Formation in South China and the Mooifontein Member of the Zaris Formation in southern Namibia. The Doushantuo samples came from a stratigraphic interval with noisy meter-scale δ 13 C carb variations of up to 10‰, whereas the Mooifontein Member is characterized by consistent δ13Ccarb values with limited meter-scale variations of less than ~4‰. Our data show that the meter-scale stratigraphic variations in δ 13 C carb are also mirrored in the SIMS data at μm-mm scales in both Doushantuo and Mooifontein samples. In the Doushantuo samples, SIMS δ 13 C carb values of authigenic calcite vary by up to 10‰ over μm-mm scales and can be either higher or lower than those of the co-existing dolomite matrix, which also appears to be affected by authigenic carbonate on the basis of petrographic observation. Bulk-sample δ 13 C carb values measured on powders microdrilled from the same SIMS specimens are within the range of SIMS δ 13 C carb values. Thus, we infer that bulk-sample δ 13 C carb values of Doushantuo samples represent mixtures of different carbonate components. The Doushantuo and Mooifontein SIMS δ 13 C carb data validate the traditional method of using chemostratigraphic consistency to evaluate authigenic/diagenetic alteration, but given that secondary phases may be 13 C-enriched relative to matrix carbonate, caution is warranted when taking maximum values to approximate primary chemostratigraphic trends.

58 GEOSCIENCES↗
DOE OSTI2020

Vertical effective stress and temperature as controls of quartz cementation in sandstones: Evidence from North Sea Fulmar and Gulf of Mexico Wilcox sandstones

Here we present quantitative petrographic data, high spatial resolution oxygen isotope analyses of quartz cement, basin modelling and a kinetic model for quartz precipitation for two Paleocene-Eocene Wilcox Group sandstones from Texas and two Jurassic Fulmar Formation sandstones from the Central North Sea. At each location, one sandstone has been buried to ca. 145 °C and one to ca. 185 °C. A key difference between the Wilcox and Fulmar burial histories is that the Wilcox sandstones are currently at higher vertical effective stresses and, from basin modelling studies, have been subjected to generally higher vertical effective stresses through their burial history. The amounts of quartz cement in the Wilcox sandstones are between 12 and 18%, and between 2 and 6% in the Fulmar sandstones. High-spatial-resolution oxygen isotope data obtained from the quartz cements suggest temperature ranges for quartz precipitation from 60 to 80 °C to values approaching maximum burial temperature. Factors such as grain coatings or the timing of petroleum emplacement cannot explain the differences in the amounts of quartz cement. Petrographic data show that most of the silica for quartz cement can be derived from intergranular pressure dissolution. Although the sample set is small, we interpret the results to suggest that the differences in quartz cementation in Fulmar and Wilcox sandstones can be explained better by differences in their vertical effective stress history than their temperature history; in this case, the supply of silica rather than the precipitation of quartz becomes an important control on the rate and extent of cementation.

58 GEOSCIENCES↗
DOE OSTI2019

A history of pore water oxygen isotope evolution in the Cretaceous Travis Peak Formation in East Texas

Oxygen isotope analyses of diagenetic cements can provide detailed evidence of sedimentary burial processes and conditions, as the δ 18 O values of precipitating minerals reflect contemporaneous local δ 18 O water and temperature conditions. Uncertainties in the timing and rates of pore water δ 18 O evolution in sedimentary basins can complicate interpretation of these records. Fracture-bridging (0.5–1 mm) quartz cements observed in sandstones of the Cretaceous Travis Peak Formation in the East Texas basin show clear growth-zoning by cathodoluminescence and contain detailed fluid inclusion records of temperature that make them excellent candidates for interrogating prolonged histories of basin temperature and the evolution of δ 18 O in basin pore water. New secondary ion mass spectrometer (SIMS) δ 18 O quartz isotopic data from fluid inclusion-rich quartz bridges in Travis Peak sandstones record a steady increase of pore water δ 18 O values from ~5 to 7‰ (VSMOW; Vienna Standard Mean Ocean Water) as the sandstone warms from ~130 to 150 °C. To help evaluate whether this trend could be generated solely from local water-rock interactions in response to burial compaction, a one-dimensional closed system isotopic burial model was created to simulate how δ 18 O water values change in a quartz-dominated sandstone during diagenesis. Using both directly measured and inferred rates of Travis Peak compaction, the magnitude of change in δ 18 O water that we calculate from quartz bridge geochemistry cannot be reasonably modeled solely by local quartz mechanical compaction, pressure solution, and cementation processes, necessitating significant fluxes of silica and high-δ 18 O water from outside of the sandstones prior to maximum burial. In conclusion, this indicates that even units which appear surrounded by significant barriers to fluid flow (i.e., mudrock-bounded channel sandstones) may have been infiltrated and diagenetically modified by large fluxes of fluid on geologic time scales.

58 GEOSCIENCES↗
DOE OSTI2019

Constraining the magnitude of the carbon isotope excursion during the Paleocene-Eocene thermal maximum using larger benthic foraminifera

The Paleocene-Eocene thermal maximum (PETM) was an extraordinary pulse of global warming approximately 56 Ma. This warmingevent is associated with an addition of large amounts of 13C-depleted carbon into the atmosphere-ocean system, but the magnitude of the negative carbon isotope excursion (CIE)signaling the PETMand often used to estimate mass of the released carbonis still debated. Here we gauge the CIE magnitude usingsecondary ion mass spectrometry (SIMS) to perform in situ δ 13 C measurements within individual larger benthic foraminifera preserved in a tropical shallow marine limestone section in south Tibet. This SIMS-based δ 13 C record yields a negative CIE (Δ~7‰) comparable in magnitude to that registered by terrestrial records but larger than the ~4‰CIE returned by surface-dwelling planktonic foraminiferain deep-sea records. We therefore posit that the CIE magnitude was~7‰ in the surface ocean, and that theprevious~4‰ estimates for the CIE areattenuated by incomplete preservation and diagenetic overprinting. The large CIE magnitude in the surface ocean (~7‰) and the evidently smaller CIE magnitude registeredby deep-sea benthic foraminifera(~2-3.5‰) arelikely a function of rateand duration of carbon release as well as ocean stratification during the PETM.

58 GEOSCIENCES↗
DOE OSTI2019

Regionally Correlated Oxygen and Carbon Isotope Zonation in Diagenetic Carbonates of the Bakken Formation

Diagenetic minerals preserve records of burial processes that overprint records of seawater chemistry and impact reservoir porosity. The Mississippian-Devonian aged Bakken Formation in the Williston Basin is a reservoir rock of economic importance whose productivity is affected by diagenetic carbonates, particularly dolomite-ankerite-series carbonates. To investigate how diagenetic carbonate alteration manifests in the Bakken and how that might change across the basin, a combined δ18O and δ13C isotope dataset for diagenetic carbonates was collected by in situ SIMS analysis of 10-μm spots from nine drill holes covering a ~250 km transect of the middle Bakken member. Observed core-to-rim isotopic variability in these small Fe-zoned dolomites and calcites frequently exceeds 10‰ in both δ 18 O and δ 13 C, indicating significant changes in thermal and chemical conditions during cementation. Individual ankeritic growth bands can be correlated across the basin by systematic similarities in minor-element compositions and isotope ratios. In the central part of the basin, δ 18 O and δ 13 C trends at sub-mm-scale decline consistently towards the rims of ankerite-series carbonates, which is interpreted to reflect mineral growth coincident with rising temperatures and an increasing organic contribution to inorganic carbon during burial. The most abrupt shifts in δ 18 O and δ 13 C (changes as large as 12‰ for δ 18 O and 6.5‰ for δ13C within distances < 15 μm) are observed along the basin margin, and are believed to preserve signals of hydrocarbon expulsion and fluid infiltration along basin margins. Based on the data, we conclude that ankerite-series carbonates preserve records of prolonged thermal and chemical processes that operated basinwide. The isotopic trends presented here show diagenetic rock evolution from shallow dolomite formation to deep burial ankerites, as well as the isotopic responses of carbonates to changing fluids and availability of organic δ 13 C. These results provide important constraints on how carbonate isotope records may be altered during burial in organic-rich sedimentary rocks and emphasize the need for caution in using bulk powder samples for geochemical analysis in carbonate systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Oxygen isotopic investigation of silicic magmatism in the Stillwater caldera complex, Nevada: Generation of large-volume, low-δ 18 O rhyolitic tuffs and assessment of their regional context in the Great Basin of the western United States

Successive caldera-forming eruptions from ca. 30 to 25 Ma generated a large nested caldera complex in western Nevada that was subsequently dissected by Basin and Range extension, providing extraordinary cross-sectional views through diverse volcanic and plutonic rocks. A high-resolution oxygen isotopic study was conducted on units that represent all major parts of the Job Canyon, Louderback Mountains, Poco Canyon, and Elevenmile Canyon caldera cycles (29.2–25.1 Ma), and several Cretaceous plutons that flank the Stillwater caldera complex. We provide new oxygen and strontium isotope data for 12 additional caldera centers in the Great Basin, which are synthesized with >150 published oxygen and strontium isotope analyses for regional Mesozoic basement rocks. Stillwater zircons span a large isotopic range (δ 18 O zircon of 3.6‰–8.2‰), and all caldera cycles possess low-δ 18 O zircons. In some cases, they are a small proportion of the total populations, and in others, they dominate, such as in the low-δ 18 O rhyolitic tuffs of Job Canyon and Poco Canyon (δ 18 O zircon = 4.0‰–4.3‰; δ 18 O magma = 5.5‰–6‰). These are the first low-δ 18 O rhyolites documented in middle Cenozoic calderas of the Great Basin, adding to the global occurrence of these important magma types that fingerprint recycling of shallow crust altered by low-δ 18 O meteoric waters. The appearance of low-δ 18 O rhyolites in the Stillwater caldera complex is overprinted on a Great Basin–wide trend of miogeoclinal sediment contribution to silicic magmas that elevates δ 18 O compositions, making identification of 18 O depletions difficult. Though not a nominally low-δ 18 O rhyolite, the tuff of Elevenmile Canyon possesses both low-δ 18 O and high-δ 18 O zircon cores that are overgrown by homogenized zircon rims that approximate the bulk zircon average, pointing to batch assembly of isotopically diverse upper crustal melts to generate one of the most voluminous (2500–5000 km 3 ) tuff eruptions in the Great Basin. Despite overlapping in space and time, each caldera-forming cycle of the Stillwater complex has a unique oxygen isotope record as retained in single zircons. Most plutons that were spatially and temporally coincident with calderas have isotopic compositions that diverge from the caldera-forming tuffs and cannot be their cogenetic remnants.

58 GEOSCIENCES↗
NASA NTRS2011

Spatially Resolved, In Situ Carbon Isotope Analysis of Archean Organic Matter

Spatiotemporal variability in the carbon isotope composition of sedimentary organic matter (OM) preserves information about the evolution of the biosphere and of the exogenic carbon cycle as a whole. Primary compositions, and imprints of the post-depositional processes that obscure them, exist at the scale of individual sedimentary grains (mm to micron). Secondary ion mass spectrometry (SIMS) (1) enables analysis at these scales and in petrographic context, (2) permits morphological and compositional characterization of the analyte and associated minerals prior to isotopic analysis, and (3) reveals patterns of variability homogenized by bulk techniques. Here we present new methods for in situ organic carbon isotope analysis with sub-permil precision and spatial resolution to 1 micron using SIMS, as well as new data acquired from a suite of Archean rocks. Three analytical protocols were developed for the CAMECA ims1280 at WiscSIMS to analyze domains of varying size and carbon concentration. Average reproducibility (at 2SD) using a 6 micron spot size with two Faraday cup detectors was 0.4 %, and 0.8 % for analyses using 1 micron and 3 micron spot sizes with a Faraday cup (for C-12) and an electron multiplier (for C-13). Eight coals, two ambers, a shungite, and a graphite were evaluated for micron-scale isotopic heterogeneity, and LCNN anthracite (delta C-13 = -23.56 +/- 0.1 %, 2SD) was chosen as the working standard. Correlation between instrumental bias and H/C was observed and calibrated for each analytical session using organic materials with H/C between 0.1 and 1.5 (atomic), allowing a correction based upon a C-13H/C-13 measurement included in every analysis. Matrix effects of variable C/SiO2 were evaluated by measuring mm to sub-micron graphite domains in quartzite from Bogala mine, Sri Lanka. Apparent instrumental bias and C-12 count rate are correlated in this case, but this may be related to a crystal orientation effect in graphite. Analyses of amorphous Archean OM suggest that instrumental bias is consistent for 12C count rates as low as 10% relative to anthracite. Samples from the ABDP-9 (n=3; Mount McRae Shale, approximately 2.5 Ga), RHDH2a (n=2; Carrawine Dolomite and Jeerinah Fm, approximately 2.6 Ga), WRL1 (n=3; Wittenoom Fm, Marra Mamba Iron Formation, and Jeerinah Fm, approximately 2.6 Ga), and SV1 (n=1; Tumbiana Fm, approximately 2.7 Ga) drill cores, each previously analyzed for bulk organic carbon isotope composition, yielded 100 new, in situ data from Neoarchean sedimentary OM. In these samples, delta C-13 varies between -53.1 and -28.3 % and offsets between in situ and bulk compositions range from -8.3 to 18.8%. In some cases, isotopic composition and mode of occurrence (e.g. morphology and mineral associations) are statistically correlated, enabling the identification of distinct reservoirs of OM. Our results support previous evidence for gradients of oxidation with depth in Neoarchean environments driven by photosynthesis and methane metabolism. The relevance of these findings to questions of bio- and syngenicity as well as the alteration history of previously reported Archean OM will be discussed.

Williford, Kenneth H.↗
NASA NTRS1988

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

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

Morrison, J.↗