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USGS2013

Determination of diffusion coefficients of carbon dioxide in water between 268 and 473 K in a high-pressure capillary optical cell with in situ Raman spectroscopic measurements

Accurate values of diffusion coefficients for carbon dioxide in water and brine at reservoir conditions are essential to our understanding of transport behavior of carbon dioxide in subsurface pore space. However, the experimental data are limited to conditions at low temperatures and pressures. In this study, diffusive transfer of carbon dioxide in water at pressures up to 45 MPa and temperatures from 268 to 473 K was observed within an optical capillary cell via time-dependent Raman spectroscopy. Diffusion coefficients were estimated by the least-squares method for the measured variations in carbon dioxide concentration in the cell at various sample positions and time. At the constant pressure of 20 MPa, the measured diffusion coefficients of carbon dioxide in water increase with increasing temperature from 268 to 473 K. The relationship between diffusion coefficient of carbon dioxide in water [D(CO 2 ) in m 2 /s] and temperature (T in K) was derived with Speedy–Angell power-law approach as: D(CO 2 )=D 0 [T/Ts-1] m where D 0 = 13.942 × 10 −9 m 2 /s, Ts = 227.0 K, and m = 1.7094. At constant temperature, diffusion coefficients of carbon dioxide in water decrease with pressure increase. However, this pressure effect is rather small (within a few percent).

Geochimica et Cosmochimica Acta↗

USGS2013

Evaluation of the rhenium-osmium geochronometer in the Phosphoria petroleum system, Bighorn Basin of Wyoming and Montana, USA

Rhenium-osmium (Re-Os) geochronometry is applied to crude oils derived from the Permian Phosphoria Formation of the Bighorn Basin in Wyoming and Montana to determine whether the radiogenic age reflects the timing of petroleum generation, timing of migration, age of the source rock, or the timing of thermochemical sulfate reduction (TSR). The oils selected for this study are interpreted to be derived from the Meade Peak Phosphatic Shale and Retort Phosphatic Shale Members of the Phosphoria Formation based on oil-oil and oil-source rock correlations utilizing bulk properties, elemental composition, δ 13 C and δ 34 S values, and biomarker distributions. The δ 34 S values of the oils range from -6.2‰ to +5.7‰, with oils heavier than -2‰ interpreted to be indicative of TSR. The Re and Os isotope data of the Phosphoria oils plot in two general trends: (1) the main trend (n = 15 oils) yielding a Triassic age (239 ± 43 Ma) with an initial 187 Os/ 188 Os value of 0.85 ± 0.42 and a mean square weighted deviation (MSWD) of 1596, and (2) the Torchlight trend (n = 4 oils) yielding a Miocene age (9.24 ± 0.39 Ma) with an initial 187Os/188Os value of 1.88 ± 0.01 and a MSWD of 0.05. The scatter (high MSWD) in the main-trend regression is due, in part, to TSR in reservoirs along the eastern margin of the basin. Excluding oils that have experienced TSR, the regression is significantly improved, yielding an age of 211 ± 21 Ma with a MSWD of 148. This revised age is consistent with some studies that have proposed Late Triassic as the beginning of Phosphoria oil generation and migration, and does not seem to reflect the source rock age (Permian) or the timing of re-migration (Late Cretaceous to Eocene) associated with the Laramide orogeny. The low precision of the revised regression (±21 Ma) is not unexpected for this oil family given the long duration of generation from a large geographic area of mature Phosphoria source rock, and the possible range in the initial 187 Os/ 188 Os values of the Meade Peak and Retort source units. Effects of re-migration may have contributed to the scatter, but thermal cracking and biodegradation likely have had minimal or no effect on the main-trend regression. The four Phosphoria-sourced oils from Torchlight and Lamb fields yield a precise Miocene age Re-Os isochron that may reflect the end of TSR in the reservoir due to cooling below a threshold temperature in the last 10 m.y. from uplift and erosion of overlying rocks. The mechanism for the formation of a Re-Os isotopic relationship in a family of crude oils may involve multiple steps in the petroleum generation process. Bitumen generation from the source rock kerogen may provide a reset of the isotopic chronometer, and incremental expulsion of oil over the duration of the oil window may provide some of the variation seen in 187 Re/ 188 Os values from an oil family.

Montana, Wyoming↗

USGS2013

Disproportionation and thermochemical sulfate reduction reactions in S-H 2 0-Ch 4 and S-D 2 O-CH 4 systems from 200 to 340 °C at elevated pressures

Elemental sulfur, as a transient intermediate compound, by-product, or catalyst, plays significant roles in thermochemical sulfate reduction (TSR) reactions. However, the mechanisms of the reactions in S-H 2 O-hydrocarbons systems are not clear. To improve our understanding of reaction mechanisms, we conducted a series of experiments between 200 and 340 °C for S-H 2 O-CH 4 , S-D 2 O-CH 4 , and S-CH 4 -1m ZnBr 2 systems in fused silica capillary capsules (FSCC). After a heating period ranging from 24 to 2160 hours (hrs), the quenched samples were analyzed by Raman spectroscopy. Combined with the in situ Raman spectra collected at high temperatures and pressures in the S-H 2 O and S-H 2 O-CH 4 systems, our results showed that (1) the disproportionation of sulfur in the S-H 2 O-CH 4 system occurred at temperatures above 200 °C and produced H 2 S, SO 4 2- , and possibly trace amount of HSO 4- ; (2) sulfate (and bisulfate), in the presence of sulfur, can be reduced by methane between 250 and 340 °C to produce CO 2 and H 2 S, and these TSR temperatures are much closer to those of the natural system (<200 °C) than those of any previous experiments; (3) the disproportionation and TSR reactions in the S-H 2 O-CH 4 system may take place simultaneously, with TSR being favored at higher temperatures; and (4) in the system S-D 2 O-CH 4 , both TSR and the competitive disproportionation reactions occurred simultaneously at temperatures above 300 °C, but these reactions were very slow at lower temperatures. Our observation of methane reaction at 250 °C in a laboratory time scale suggests that, in a geologic time scale, methane may be destroyed by TSR reactions at temperatures > 200 °C that can be reached by deep drilling for hydrocarbon resources.

Geochimica et Cosmochimica Acta↗

USGS2013

Discerning crystal growth from diffusion profiles in zoned olivine by in situ Mg–Fe isotopic analyses

Mineral zoning is used in diffusion-based geospeedometry to determine magmatic timescales. Progress in this field has been hampered by the challenge to discern mineral zoning produced by diffusion from concentration gradients inherited from crystal growth. A zoned olivine phenocryst from Kilauea Iki lava lake (Hawaii) was selected for this study to evaluate the potential of Mg and Fe isotopes for distinguishing these two processes. Microdrilling of the phenocryst (∼300 μm drill holes) followed by MC-ICPMS analysis of the powders revealed negatively coupled Mg and Fe isotopic fractionations (δ 26 Mg from +0.1‰ to −0.2‰ and δ 56 Fe from −1.2‰ to −0.2‰ from core to rim), which can only be explained by Mg–Fe exchange between melt and olivine. The data can be explained with ratios of diffusivities of Mg and Fe isotopes in olivine scaling as D 2 /D 1 = (m 1 /m 2 )β with β Mg ∼0.16 and β Fe ∼0.27. LA-MC-ICPMS and MC-SIMS Fe isotopic measurements are developed and are demonstrated to yield accurate δ 56 Fe measurements within precisions of ∼0.2‰ (1 SD) at spatial resolutions of ∼50 μm. δ 56 Fe and δ 26 Mg stay constant with Fo# in the rim (late-stage overgrowth), whereas in the core (original phenocryst) δ 56 Fe steeply trends toward lighter compositions and δ 26 Mg trends toward heavier compositions with higher Fo#. A plot of δ 56 Fe vs. Fo# immediately distinguishes growth-controlled from diffusion-controlled zoning in these two regions. The results are consistent with the idea that large isotopic fractionation accompanies chemical diffusion in crystals, whereas fractional crystallization induces little or no isotopic fractionation. The cooling timescale inferred from the chemical-isotope zoning profiles is consistent with the documented cooling history of the lava lake. In the absence of geologic context, in situ stable isotopic measurements may now be used to interpret the nature of mineral zoning. Stable isotope measurements by LA-MC-ICPMS and MC-SIMS can be used as standard petrologic tools to identify samples for diffusion-based geospeedometry.

Geochimica et Cosmochimica Acta↗

USGS2013

DOM composition in an agricultural watershed: assessing patterns and variability in the context of spatial scales

Willow Slough, a seasonally irrigated agricultural watershed in the Sacramento River valley, California, was sampled synoptically in order to investigate the extent to which dissolved organic carbon (DOC) concentrations and compositions from throughout the catchment are represented at the mouth. DOC concentrations ranged from 1.8 to 13.9 mg L −1 , with the lowest values in headwater 1st and 2nd order streams, and the highest values associated with flood irrigation. Carbon-normalized vanillyl phenols varied from 0.05 to 0.67 mg 100 mg OC −1 (0.37 mean), indicative of considerable contributions from vascular plants. DOC concentrations and compositions at the mouth appear to be primarily influenced by land use (agriculture) in the lower reaches, and therefore very little of the headwater chemistry (1st and 2nd order streams) can be discerned from the chemistry at or near the mouth (3rd and 4th order streams), indicating the need for synoptic sampling to capture the breadth of organic carbon cycling within a catchment. Field sampling during irrigation showed the large impact that flood irrigation can have on DOC concentrations and compositions, likely a primary cause of significantly elevated Willow Slough DOC concentrations during the summer irrigation season. Optical proxies exhibited varying degrees of correlation with chemical measurements, with strongest relationships to DOC and dissolved lignin ( r 2 = 0.95 and 0.73, respectively) and weaker relationships to carbon-normalized lignin yields and C:V ( r 2 from 0.31 to 0.42). Demonstrating the importance of matching scale to processes, we found no relationship between dissolved lignin concentrations and total suspended sediments (TSS) across all sites, in contrast to the strong relationship observed in weekly samples at the mouth. As DOC concentrations and compositions at the mouth of Willow Slough are closely tied to anthropogenic activities within the catchment, future changes in land-use driven by climate change, water availability, and economic pressures on crop types will also bring about changes in the overall biogeochemistry.

California↗

USGS2013

Ca, Sr, O and D isotope approach to defining the chemical evolution of hydrothermal fluids: example from Long Valley, CA, USA

We present chemical and isotopic data for fluids, minerals and rocks from the Long Valley meteoric-hydrothermal system. The samples encompass the presumed hydrothermal upwelling zone in the west moat of the caldera, the Casa Diablo geothermal field, and a series of wells defining a nearly linear, ∼16 km long, west-to-east trend along the likely fluid flow path. Fluid samples were analyzed for the isotopes of water, Sr, and Ca, the concentrations of major cations and anions, alkalinity, and total CO 2 . Water isotope data conform to trends documented in earlier studies, interpreted as indicating a single hydrothermal fluid mixing with local groundwater. Sr isotopes show subtle changes along the flow path, which requires rapid fluid flow and minimal reaction between the channelized fluids and the wallrocks. Sr and O isotopes are used to calculate fracture spacing using a dual porosity model. Calculated fracture spacing and temperature data for hydrothermal fluids indicate the system is (approximately) at steady-state. Correlated variations among total CO 2 , and the concentration and isotopic composition of Ca suggest progressive fluid degassing (loss of CO 2 ), which drives calcite precipitation as the fluid flows west-to-east and cools. The shifts in Ca isotopes require that calcite precipitated at temperatures of 150–180 °C is fractionated by ca. −0.3‰ to −0.5‰ relative to aqueous species. Our data are the first evidence that Ca isotopes undergo kinetic fractionation at high temperatures (>100 °C) and can be used to trace calcite precipitation along hydrothermal fluid flow paths.

California↗

USGS2014

Dynamics of submarine groundwater discharge and associated fluxes of dissolved nutrients, carbon, and trace gases to the coastal zone (Okatee River estuary, South Carolina)

Multiple techniques, including thermal infrared aerial remote sensing, geophysical and geological data, geochemical characterization and radium isotopes, were used to evaluate the role of groundwater as a source of dissolved nutrients, carbon, and trace gases to the Okatee River estuary, South Carolina. Thermal infrared aerial remote sensing surveys illustrated the presence of multiple submarine groundwater discharge sites in Okatee headwaters. Significant relationships were observed between groundwater geochemical constituents and 226 Ra activity in groundwater with higher 226 Ra activity correlated to higher concentrations of organics, dissolved inorganic carbon, nutrients, and trace gases to the Okatee system. A system-level radium mass balance confirmed a substantial submarine groundwater discharge contribution of these constituents to the Okatee River. Diffusive benthic flux measurements and potential denitrification rate assays tracked the fate of constituents in creek bank sediments. Diffusive benthic fluxes were substantially lower than calculated radium-based submarine groundwater discharge inputs, showing that advection of groundwater-derived nutrients dominated fluxes in the system. While a considerable potential for denitrification in tidal creek bank sediments was noted, in situ denitrification rates were nitrate-limited, making intertidal sediments an inefficient nitrogen sink in this system. Groundwater geochemical data indicated significant differences in groundwater chemical composition and radium activity ratios between the eastern and western sides of the river; these likely arose from the distinct hydrological regimes observed in each area. Groundwater from the western side of the Okatee headwaters was characterized by higher concentrations of dissolved organic and inorganic carbon, dissolved organic nitrogen, inorganic nutrients and reduced metabolites and trace gases, i.e. methane and nitrous oxide, than groundwater from the eastern side. Differences in microbial sulfate reduction, organic matter supply, and/or groundwater residence time likely contributed to this pattern. The contrasting features of the east and west sub-marsh zones highlight the need for multiple techniques for characterization of submarine groundwater discharge sources and the impact of biogeochemical processes on the delivery of nutrients and carbon to coastal areas via submarine groundwater discharge.

South Carolina↗

USGS2014

Mineralogical, chemical and K-Ar isotopic changes in Kreyenhagen Shale whole rocks and <2 µm clay fractions during natural burial and hydrous-pyrolysis experimental maturation

Progressive maturation of the Eocene Kreyenhagen Shale from the San Joaquin Basin of California was studied by combining mineralogical and chemical analyses with K–Ar dating of whole rocks and <2 μm clay fractions from naturally buried samples and laboratory induced maturation by hydrous pyrolysis of an immature outcrop sample. The K–Ar age decreases from 89.9 ± 3.9 and 72.4 ± 4.2 Ma for the outcrop whole rock and its <2 μm fraction, respectively, to 29.7 ± 1.5 and 21.0 ± 0.7 Ma for the equivalent materials buried to 5167 m. The natural maturation does not produce K–Ar ages in the historical sense, but rather K/Ar ratios of relative K and radiogenic 40 Ar amounts resulting from a combined crystallization of authigenic and alteration of initial detrital K-bearing minerals of the rocks. The Al/K ratio of the naturally matured rocks is essentially constant for the entire depth sequence, indicating that there is no detectable variation in the crystallo-chemical organization of the K-bearing alumino-silicates with depth. No supply of K from outside of the rock volumes occurred, which indicates a closed-system behavior for it. Conversely, the content of the total organic carbon (TOC) content decreases significantly with burial, based on the progressive increasing Al/TOC ratio of the whole rocks. The initial varied mineralogy and chemistry of the rocks and their <2 μm fractions resulting from differences in detrital sources and depositional settings give scattered results that homogenize progressively during burial due to increased authigenesis, and concomitant increased alteration of the detrital material. Hydrous pyrolysis was intended to alleviate the problem of mineral and chemical variations in initially deposited rocks of naturally matured sequences. However, experiments on aliquots from thermally immature Kreyenhagen Shale outcrop sample did not mimic the results from naturally buried samples. Experiments conducted for 72 h at temperatures from 270 to 365 °C did not induce significant changes at temperatures above 310 °C in the mineralogical composition and K–Ar ages of the rock and <2 μm fraction. The K–Ar ages of the <2 μm fraction range from 72.4 ± 4.2 Ma in the outcrop sample to 62.4 ± 3.4 Ma in the sample heated the most at 365 °C for 216 h. This slight decrease in age outlines some loss of radiogenic 40 Ar, together with losses of organic matter as oil, gas, and aqueous organic species. Large amounts of smectite layers in the illite–smectite mixed layers of the pyrolyzed outcrop <2 μm fraction remain during thermal experiments, especially above 310 °C. With no illitization detected above 310 °C, smectite appears to have inhibited rather than promoted generation of expelled oil from decomposition of bitumen. This hindrance is interpreted to result from bitumen impregnating the smectite interlayer sites and rock matrix. Bitumen remains in the <2 μm fraction despite leaching with H 2 O 2 . Its presence in the smectite interlayers is apparent by the inability of the clay fraction to fully expand or collapse once bitumen generation from the thermal decomposition of the kerogen is completed, and by almost invariable K–Ar ages confirming for the lack of any K supply and/or radiogenic 40 Ar removal. This suggests that once bitumen impregnates the porosity of a progressively maturing source rock, the pore system is no longer wetted by water and smectite to illite conversion ceases. Experimental attempts to evaluate the smectite conversion to illite should preferentially use low-TOC rocks to avoid inhibition of the reaction by bitumen impregnation.

California↗

USGS2014

Component geochronology in the polyphase ca. 3920 Ma Acasta Gneiss

The oldest compiled U–Pb zircon ages for the Acasta Gneiss Complex in the Northwest Territories of Canada span about 4050–3850 Ma; yet older ca. 4200 Ma xenocrystic U–Pb zircon ages have also been reported for this terrane. The AGC expresses at least 25 km 2 of outcrop exposure, but only a small subset of this has been documented in the detail required to investigate a complex history and resolve disputes over emplacement ages. To better understand this history, we combined new ion microprobe 235,238 U– 207,206 Pb zircon geochronology with whole-rock and zircon rare earth element compositions ([REE] zirc ), Ti-in-zircon thermometry (Ti xln ) and 147 Sm– 143 Nd geochronology for an individual subdivided &sim;60 cm 2 slab of Acasta banded gneiss comprising five separate lithologic components. Results were compared to other variably deformed granitoid-gneisses and plagioclase-hornblende rocks from elsewhere in the AGC. We show that different gneissic components carry distinct [Th/U] zirc vs. Ti xln and [REE] zirc signatures correlative with different zircon U–Pb age populations and WR compositions, but not with 147 Sm– 143 Nd isotope systematics. Modeled [REE] from lattice-strain theory reconciles only the ca. 3920 Ma zircons with the oldest component that also preserves strong positive Eu &lowast; anomalies. Magmas which gave rise to the somewhat older (inherited) ca. 4020 Ma AGC zircon age population formed at &sim;IW (iron–wüstite) to <FMQ (fayalite–magnetite–quartz) oxygen fugacities. A ca. 3920 Ma emplacement age for the AGC is contemporaneous with bombardment of the inner solar system. Analytical bombardment simulations show that crustal re-working from the impact epoch potentially affected the precursors to the Acasta gneisses.

Geochimica et Cosmochimica Acta↗

USGS2014

Oxygen isotope systematics in the aragonite-CO2-H2O-NaCl system up to 0.7 mol/kg ionic strength at 25 °C

To investigate the oxygen isotope systematics in the aragonite-CO2-H2O-NaCl system, witherite (BaCO3) was precipitated quasi-instantaneously and quantitatively from Na-Cl-Ba-CO2 solutions of seawater-like ionic strength (I = 0.7 mol/kg) at two pH values (~7.9 and ~10.6) at 25 °C. The oxygen isotope composition of the witherite and the dissolved inorganic carbon speciation in the starting solution were used to estimate the oxygen isotope fractionations between HCO3¯ and H2O as well as between CO3 2 and H2O. Given the analytical error on the oxygen isotope composition of the witherite and uncertainties of the parent solution pH and speciation, oxygen isotope fractionation between NaHCO3° and HCO3¯, as well as between NaCO3¯ and CO3 2, is negligible under the experimental conditions investigated. The influence of dissolved NaCl concentration on the oxygen isotope fractionation in the aragonite-CO2-H2O-NaCl system also was investigated at 25 °C. Aragonite was precipitated from Na-Cl-Ca-Mg-(B)-CO2 solutions of seawater-like ionic strength using passive CO2 degassing or constant addition methods. Based upon our new experimental observations and published experimental data from lower ionic strength solutions by Kim et al. (2007b), the equilibrium aragonite-water oxygen isotope fractionation factor is independent of the ionic strength of the parent solution up to 0.7 mol/kg. Hence, our study also suggests that the aragonite precipitation mechanism is not affected by the presence of sodium and chloride ions in the parent solution over the range of concentrations investigated.

Geochimica et Cosmochimica Acta↗

USGS2014

Re-Os geochronology and Os isotope fingerprinting of petroleum sourced from a Type I lacustrine kerogen: insights from the natural Green River petroleum system in the Uinta Basin and hydrous pyrolysis experiments

Rhenium–osmium (Re–Os) geochronology of marine petroleum systems has allowed the determination of the depositional age of source rocks as well as the timing of petroleum generation. In addition, Os isotopes have been applied as a fingerprinting tool to correlate oil to its source unit. To date, only classic marine petroleum systems have been studied. Here we present Re–Os geochronology and Os isotope fingerprinting of different petroleum phases (oils, tar sands and gilsonite) derived from the lacustrine Green River petroleum system in the Uinta Basin, USA. In addition we use an experimental approach, hydrous pyrolysis experiments, to compare to the Re–Os data of naturally generated petroleum in order to further understand the mechanisms of Re and Os transfer to petroleum. The Re–Os geochronology of petroleum from the lacustrine Green River petroleum system (19 ± 14 Ma – all petroleum phases) broadly agrees with previous petroleum generation basin models (∼25 Ma) suggesting that Re–Os geochronology of variable petroleum phases derived from lacustrine Type I kerogen has similar systematics to Type II kerogen (e.g., Selby and Creaser, 2005a, Selby and Creaser, 2005b and Finlay et al., 2010). However, the large uncertainties (over 100% in some cases) produced for the petroleum Re–Os geochronology are a result of multiple generation events occurring through a ∼3000-m thick source unit that creates a mixture of initial Os isotope compositions in the produced petroleum phases. The 187Os/188Os values for the petroleum and source rocks at the time of oil generation vary from 1.4 to 1.9, with the mode at ∼1.6. Oil-to-source correlation using Os isotopes is consistent with previous correlation studies in the Green River petroleum system, and illustrates the potential utility of Os isotopes to characterize the spatial variations within a petroleum system. Hydrous pyrolysis experiments on the Green River Formation source rocks show that Re and Os transfer are mimicking the natural system. This transfer from source to bitumen to oil does not affect source rock Re–Os systematics or Os isotopic compositions. This confirms that Os isotope compositions are transferred intact from source to petroleum during petroleum generation and can be used as a powerful correlation tool. These experiments further confirm that Re–Os systematics in source rocks are not adversely affected by petroleum maturation. Overall this study illustrates that the Re–Os petroleum geochronometer and Os isotope fingerprinting tools can be used on a wide range of petroleum types sourced from variable kerogen types.

Utah↗

USGS2014

Modeling the influence of organic acids on soil weathering

Biological inputs and organic matter cycling have long been regarded as important factors in the physical and chemical development of soils. In particular, the extent to which low molecular weight organic acids, such as oxalate, influence geochemical reactions has been widely studied. Although the effects of organic acids are diverse, there is strong evidence that organic acids accelerate the dissolution of some minerals. However, the influence of organic acids at the field-scale and over the timescales of soil development has not been evaluated in detail. In this study, a reactive-transport model of soil chemical weathering and pedogenic development was used to quantify the extent to which organic acid cycling controls mineral dissolution rates and long-term patterns of chemical weathering. Specifically, oxalic acid was added to simulations of soil development to investigate a well-studied chronosequence of soils near Santa Cruz, CA. The model formulation includes organic acid input, transport, decomposition, organic-metal aqueous complexation and mineral surface complexation in various combinations. Results suggest that although organic acid reactions accelerate mineral dissolution rates near the soil surface, the net response is an overall decrease in chemical weathering. Model results demonstrate the importance of organic acid input concentrations, fluid flow, decomposition and secondary mineral precipitation rates on the evolution of mineral weathering fronts. In particular, model soil profile evolution is sensitive to kaolinite precipitation and oxalate decomposition rates. The soil profile-scale modeling presented here provides insights into the influence of organic carbon cycling on soil weathering and pedogenesis and supports the need for further field-scale measurements of the flux and speciation of reactive organic compounds.

California↗

USGS2014

Compositional and stable carbon isotopic fractionation during non-autocatalytic thermochemical sulfate reduction by gaseous hydrocarbons

The possibility of autocatalysis during thermochemical sulfate reduction (TSR) by gaseous hydrocarbons was investigated by examination of previously reported laboratory and field data. This reaction was found to be a kinetically controlled non-autocatalytic process, and the apparent lack of autocatalysis is thought to be due to the absence of the required intermediate species. Kinetic parameters for chemical and carbon isotopic fractionations of gaseous hydrocarbons affected by TSR were calculated and found to be consistent with experimentally derived values for TSR involving long-chain hydrocarbons. Model predictions based on these kinetic values indicate that TSR by gaseous hydrocarbon requires high-temperature conditions. The oxidation of C 2–5 hydrocarbons by sulfate reduction is accompanied by carbon isotopic fractionation with the residual C 2–5 hydrocarbons becoming more enriched in 13 C. Kinetic parameters were calculated for the stable carbon isotopic fractionation of gaseous hydrocarbons that have experienced TSR. Model predictions based on these kinetics indicate that it may be difficult to distinguish the effects of TSR from those of thermal maturation at lower levels of hydrocarbon oxidation; however, unusually heavy δ 13 C 2+ values (>−10‰) can be diagnostic of high levels of conversion (>50%). Stoichiometric and stable carbon isotopic data show that methane is stable under the investigated reaction conditions and is likely a product of TSR by other gaseous hydrocarbons rather than a significant reactant. These results indicate that the overall TSR reaction mechanism for oxidation of organic substrates containing long-chain hydrocarbons involves three distinct phases as follows: (1) an initial slow and non-autocatalytic stage characterized by the reduction of reactive sulfate by long-chain saturated hydrocarbons; (2) a second autocatalytic reaction phase dominated by reactions involving reduced sulfur species and partially oxidized hydrocarbons; (3) and a final, or late-stage, TSR reaction in which hydrocarbon oxidation continues at a slower rate via the non-autocatalytic reduction of sulfate by gaseous hydrocarbons.

Geochimica et Cosmochimica Acta↗

USGS2014

Sulfur isotope fractionation between fluid and andesitic melt: An experimental study

Glasses produced from decompression experiments conducted by Fiege et al. (2014a) were used to investigate the fractionation of sulfur isotopes between fluid and andesitic melt upon magma degassing. Starting materials were synthetic glasses with a composition close to a Krakatau dacitic andesite. The glasses contained 4.55–7.95 wt% H 2 O, ∼140 to 2700 ppm sulfur (S), and 0–1000 ppm chlorine (Cl). The experiments were carried out in internally heated pressure vessels (IHPV) at 1030 °C and oxygen fugacities ( f O 2 ) ranging from QFM+0.8 log units up to QFM+4.2 log units (QFM: quartz–fayalite–magnetite buffer). The decompression experiments were conducted by releasing pressure ( P ) continuously from ∼400 MPa to final P of 150, 100, 70 and 30 MPa. The decompression rate ( r ) ranged from 0.01 to 0.17 MPa/s. The samples were annealed for 0–72 h (annealing time, t A ) at the final P and quenched rapidly from 1030 °C to room temperature ( T ). The decompression led to the formation of a S-bearing aqueous fluid phase due to the relatively large fluid–melt partitioning coefficients of S. Secondary ion mass spectrometry (SIMS) was used to determine the isotopic composition of the glasses before and after decompression. Mass balance calculations were applied to estimate the gas–melt S isotope fractionation factor α g-m . No detectable effect of r and t A on α g-m was observed. However, SIMS data revealed a remarkable increase of α g-m from ∼0.9985 ± 0.0007 at >QFM+3 to ∼1.0042 ± 0.0042 at ∼QFM+1. Noteworthy, the isotopic fractionation at reducing conditions was about an order of magnitude larger than predicted by previous works. Based on our experimental results and on previous findings for S speciation in fluid and silicate melt a new model predicting the effect of f O 2 on α g-m (or Δ 34 S g–m ) in andesitic systems at 1030 °C is proposed. Our experimental results as well as our modeling are of high importance for the interpretation of S isotope signatures in natural samples (e.g., melt inclusions or volcanic gases).

Geochimica et Cosmochimica Acta↗

USGS2015

Strontium isotopes in otoliths of a non-migratory fish (slimy sculpin): Implications for provenance studies

Heterogeneity in 87Sr/86Sr ratios of river-dissolved strontium (Sr) across geologically diverse environments provides a useful tool for investigating provenance, connectivity and movement patterns of various organisms and materials. Evaluation of site-specific 87Sr/86Sr temporal variability throughout study regions is a prerequisite for provenance research, but the dynamics driving temporal variability are generally system-dependent and not accurately predictable. We used the time-keeping properties of otoliths from non-migratory slimy sculpin (Cottus cognatus) to evaluate multi-scale 87Sr/86Sr temporal variability of river waters throughout the Nushagak River, a large (34,700 km2) remote watershed in Alaska, USA. Slimy sculpin otoliths incorporated site-specific temporal variation at sub-annual resolution and were able to record on the order of 0.0001 changes in the 87Sr/86Sr ratio. 87Sr/86Sr profiles of slimy sculpin collected in tributaries and main-stem channels of the upper watershed indicated that these regions were temporally stable, whereas the Lower Nushagak River exhibited some spatio-teporal variability. This study illustrates how the behavioral ecology of a non-migratory organism can be used to evaluate sub-annual 87Sr/86Sr temporal variability and has broad implications for provenance studies employing this tracer.

Alaska↗

USGS2015

Uranium isotopes and dissolved organic carbon in loess permafrost: Modeling the age of ancient ice

The residence time of ice in permafrost is an indicator of past climate history, and of the resilience and vulnerability of high-latitude ecosystems to global change. Development of geochemical indicators of ground-ice residence times in permafrost will advance understanding of the circumstances and evidence of permafrost formation, preservation, and thaw in response to climate warming and other disturbance. We used uranium isotopes to evaluate the residence time of segregated ground ice from ice-rich loess permafrost cores in central Alaska. Activity ratios of 234 U vs. 238 U ( 234 U/ 238 U) in water from thawed core sections ranged between 1.163 and 1.904 due to contact of ice and associated liquid water with mineral surfaces over time. Measured ( 234 U/ 238 U) values in ground ice showed an overall increase with depth in a series of five neighboring cores up to 21 m deep. This is consistent with increasing residence time of ice with depth as a result of accumulation of loess over time, as well as characteristic ice morphologies, high segregated ice content, and wedge ice, all of which support an interpretation of syngenetic permafrost formation associated with loess deposition. At the same time, stratigraphic evidence indicates some past sediment redistribution and possibly shallow thaw among cores, with local mixing of aged thaw waters. Using measures of surface area and a leaching experiment to determine U distribution, a geometric model of ( 234 U/ 238 U) evolution suggests mean ages of up to &sim;200 ky BP in the deepest core, with estimated uncertainties of up to an order of magnitude. Evidence of secondary coatings on loess grains with elevated ( 234 U/ 238 U) values and U concentrations suggests that refinement of the geometric model to account for weathering processes is needed to reduce uncertainty. We suggest that in this area of deep ice-rich loess permafrost, ice bodies have been preserved from the last glacial period (10–100 ky BP), despite subsequent fluctuations in climate, fire disturbance and vegetation. Radiocarbon ( 14 C) analysis of dissolved organic carbon (DOC) in thaw waters supports ages greater than &sim;40 ky BP below 10 m. DOC concentrations in thaw waters increased with depth to maxima of >1000 ppm, despite little change in ice content or cryostructures. These relations suggest time-dependent production of old DOC that will be released upon permafrost thaw at a rate that is mediated by sediment transport, among other factors.

Alaska↗

USGS2015

Quantification of colloidal and aqueous element transfer in soils: The dual-phase mass balance model

Mass balance models have become standard tools for characterizing element gains and losses and volumetric change during weathering and soil development. However, they rely on the assumption of complete immobility for an index element such as Ti or Zr. Here we describe a dual-phase mass balance model that eliminates the need for an assumption of immobility and in the process quantifies the contribution of aqueous versus colloidal element transfer. In the model, the high field strength elements Ti and Zr are assumed to be mobile only as suspended solids (colloids) and can therefore be used to distinguish elemental redistribution via colloids from redistribution via dissolved aqueous solutes. Calculations are based upon element concentrations in soil, parent material, and colloids dispersed from soil in the laboratory. We illustrate the utility of this model using a catena in South Africa. Traditional mass balance models systematically distort elemental gains and losses and changes in soil volume in this catena due to significant redistribution of Zr-bearing colloids. Applying the dual-phase model accounts for this colloidal redistribution and we find that the process accounts for a substantial portion of the major element (e.g., Al, Fe and Si) loss from eluvial soil. In addition, we find that in illuvial soils along this catena, gains of colloidal material significantly offset aqueous elemental loss. In other settings, processes such as accumulation of exogenous dust can mimic the geochemical effects of colloid redistribution and we suggest strategies for distinguishing between the two. The movement of clays and colloidal material is a major process in weathering and pedogenesis; the mass balance model presented here is a tool for quantifying effects of that process over time scales of soil development.

Geochimica et Cosmochimica Acta↗

USGS2015

Normalization of stable isotope data for carbonate minerals: implementation of IUPAC guideline

Carbonate minerals provide a rich source of geochemical information because their δ 13 C and δ 18 O values provide information about surface and subsurface Earth processes. However, a significant problem is that the same δ 18 O value is not reported for the identical carbonate sample when analyzed in different isotope laboratories in spite of the fact that the International Union of Pure and Applied Chemistry (IUPAC) has provided reporting guidelines for two decades. This issue arises because (1) the δ 18 O measurements are performed on CO 2 evolved by reaction of carbonates with phosphoric acid, (2) the acid-liberated CO 2 is isotopically fractionated (enriched in 18 O) because it contains only two-thirds of the oxygen from the solid carbonate, (3) this oxygen isotopic fractionation factor is a function of mineralogy, temperature, concentration of the phosphoric acid, and δ 18 O value of water in the phosphoric acid, (4) researchers may use any one of an assortment of oxygen isotopic fractionation factors that have been published for various minerals at various reaction temperatures, and (5) it sometimes is not clear how one should calculate δ 18 O VPDB values on a scale normalized such that the δ 18 O value of SLAP reference water is −55.5 &permil; relative to VSMOW reference water. To enable researchers worldwide to publish the same δ 18 O value (within experimental uncertainty) for the same carbonate sample, we have re-evaluated reported acid fractionation factors for calcite at 25, 50, and 75 °C and propose a revised relation for the temperature dependence of oxygen isotopic acid fractionation factor, α CO 2 ( ACID ) -calcite αCO2(ACID)-calcite , of 1000ln α CO 2 ( ACID ) -calcite=3.48(10 3 /T)-1.47 1000lnαCO2(ACID)-calcite=3.48(103/T)-1.47 Turn MathJax on where T is temperature in kelvin. At 25 °C, α CO 2 ( ACID ) -calcite=1.01025 αCO2(ACID)-calcite=1.01025 , the most commonly accepted value for this quantity. We propose a normalization protocol in which (1) the internationally distributed carbonate isotopic reference materials NBS 18 and NBS 19 are interspersed among carbonate samples analyzed by treatment with phosphoric acid, (2) the δ 18 O values of the calcite reference materials and the carbonate samples are calculated, respectively, by using the α CO 2 ( ACID ) -calcite αCO2(ACID)-calcite relation above and oxygen-isotope acid fractionation factors appropriate for the sample mineralogy and reaction temperature, (3) the δ 18 O values of solid carbonate samples are determined on the VPDB scale ( δ 18 O VPDB ) with IUPAC-recommended scale expansion such that the δ 18 O of SLAP reference water is −55.5 &permil; relative to VSMOW reference water by normalizing δ 18 O values of carbonate samples with 2014-IUPAC-recommended δ 18 O values of NBS 18 and NBS 19, and (4) δ 18 O values on the VPDB scale are converted to δ 18 O values on the VSMOW-SLAP scale by using IUPAC recommendations. To ease calculations in the protocol, a software application titled “Carbon and Oxygen Isotopic Normalization Tool for Carbonates” is available that relies upon IUPAC-recommended δ 13 C and δ 18 O values of carbonate isotopic reference materials ( http://isotopes.usgs.gov/research/topics/carbonatesnormalizationtool.html ).

Geochimica et Cosmochimica Acta↗