Ca isotopes record rapid crystal growth in volcanic and subvolcanic systems.

Kinetic calcium isotope effects can be used as growth-rate proxies for volcanic and subvolcanic minerals. Here, we analyze Ca isotopic compositions in experimental and natural samples and confirm that large kinetic effects (>2‰) can occur during magmatic plagioclase crystallization. Experiments confirm theoretical predictions that disequilibrium isotope effects depend mainly on the rates for crystal growth relative to liquid phase Ca diffusivity (R/D). Plagioclase phenocrysts from the 1915 Mount Lassen rhyodacite eruption, the ∼650-y-old Deadman Creek Dome eruption, and several mafic subvolcanic orbicules and plagioclase comb layers from Northern California have disequilibrium Ca isotopic compositions that suggest rapid crystal growth rates (>1 cm/y to 15 cm/y). The Ca isotope results, combined with complementary crystal-size distribution analyses, suggest that magmatic rejuvenation (and eruption) events, as reflected in crystal growth times, can be as short as ∼10-3 y. Although mafic systems are predicted to have shorter magmatic rejuvenation periods, we find similarly short timescales in both mafic and silicic systems. These results are consistent with a growing body of evidence suggesting that dominantly crystalline volcanic magma reservoirs can be rapidly reactivated by the injection of fresh magma prior to eruption. By focusing on a common mineral such as plagioclase, this approach can be applied across all major magmatic compositions, suggesting that Ca isotopes can be used as a tool for investigating the dynamics and timing of volcanic eruptions.

Uranium isotope fractionation by abiotic reductive precipitation.

Significant uranium (U) isotope fractionation has been observed during abiotic reduction of aqueous U, counter to the expectation that uranium isotopes are only fractionated by bioassociated enzymatic reduction. In our experiments, aqueous U is removed from solution by reductive precipitation onto the surfaces of synthetic iron monosulfide. The magnitude of uranium isotopic fractionation increases with decreasing aqueous U removal rate and with increasing amounts of neutrally charged aqueous Ca-U-CO3 species. Our discovery means that abiotic U isotope fractionation likely occurs in any reducing environment with aqueous Ca ≥ 1 mM, and that the magnitude of isotopic fractionation changes in response to changes in aqueous major ion concentrations that affect U speciation. Our results have implications for the study of anoxia in the ancient oceans and other environments.

Supercritical CO2 uptake by nonswelling phyllosilicates.

Interactions between supercritical (sc) CO2 and minerals are important when CO2 is injected into geologic formations for storage and as working fluids for enhanced oil recovery, hydraulic fracturing, and geothermal energy extraction. It has previously been shown that at the elevated pressures and temperatures of the deep subsurface, scCO2 alters smectites (typical swelling phyllosilicates). However, less is known about the effects of scCO2 on nonswelling phyllosilicates (illite and muscovite), despite the fact that the latter are the dominant clay minerals in deep subsurface shales and mudstones. Our studies conducted by using single crystals, combining reaction (incubation with scCO2), visualization [atomic force microscopy (AFM)], and quantifications (AFM, X-ray photoelectron spectroscopy, X-ray diffraction, and off-gassing measurements) revealed unexpectedly high CO2 uptake that far exceeded its macroscopic surface area. Results from different methods collectively suggest that CO2 partially entered the muscovite interlayers, although the pathways remain to be determined. We hypothesize that preferential dissolution at weaker surface defects and frayed edges allows CO2 to enter the interlayers under elevated pressure and temperature, rather than by diffusing solely from edges deeply into interlayers. This unexpected uptake of CO2, can increase CO2 storage capacity by up to ∼30% relative to the capacity associated with residual trapping in a 0.2-porosity sandstone reservoir containing up to 18 mass % of illite/muscovite. This excess CO2 uptake constitutes a previously unrecognized potential trapping mechanism.

Effect of paleoseawater composition on hydrothermal exchange in midocean ridges.

Variations in the Mg, Ca, Sr, and SO4 concentrations of paleoseawater can affect the chemical exchange between seawater and oceanic basalt in hydrothermal systems at midocean ridges (MOR). We present a model for evaluating the nature and magnitude of these previously unappreciated effects, using available estimates of paleoseawater composition over Phanerozoic time as inputs and 87Sr/86Sr of ophiolite epidosites and epidote-quartz veins as constraints. The results suggest that modern hydrothermal fluids are not typical due to low Ca and Sr relative to Mg and SO4 in modern seawater. At other times during the last 500 million years, particularly during the Cretaceous and Ordovician, hydrothermal fluids had more seawater-derived Sr and Ca, a prediction that is supported by Sr isotope data. The predicted 87Sr/86Sr of vent fluids varies cyclically in concert with ocean chemistry, with some values much higher than the modern value of ∼0.7037. The seawater chemistry effects can be expressed in terms of the transfer efficiency of basaltic Ca and Sr to seawater in hydrothermal systems, which varies by a factor of ∼1.6 over the Phanerozoic, with minima when seawater Mg and SO4 are low. This effect provides a modest negative feedback on seawater composition and 87Sr/86Sr changes. For the mid-Cretaceous, the low 87Sr/86Sr of seawater requires either exceptionally large amounts of low-temperature exchange with oceanic crust or that the weathering flux of continentally derived Sr was especially small. The model also has implications for MOR hydrothermal systems in the Precambrian, when low-seawater SO4 could help explain low seawater 87Sr/86Sr.

Rates of CO2 Mineralization in Geological Carbon Storage.

Geologic carbon storage (GCS) involves capture and purification of CO2 at industrial emission sources, compression into a supercritical state, and subsequent injection into geologic formations. This process reverses the flow of carbon to the atmosphere with the intention of returning the carbon to long-term geologic storage. Models suggest that most of the injected CO2 will be "trapped" in the subsurface by physical means, but the most risk-free and permanent form of carbon storage is as carbonate minerals (Ca,Mg,Fe)CO3. The transformation of CO2 to carbonate minerals requires supply of the necessary divalent cations by dissolution of silicate minerals. Available data suggest that rates of transformation are highly uncertain and difficult to predict by standard approaches. Here we show that the chemical kinetic observations and experimental results, when they can be reduced to a single cation-release time scale that describes the fractional rate at which cations are released to solution by mineral dissolution, show sufficiently systematic behavior as a function of pH, fluid flow rate, and time that the rates of mineralization can be estimated with reasonable certainty. The rate of mineralization depends on both the abundance (determined by the reservoir rock mineralogy) and the rate at which cations are released from silicate minerals by dissolution into pore fluid that has been acidified with dissolved CO2. Laboratory-measured rates and field observations give values spanning 8 to 10 orders of magnitude, but when they are evaluated in the context of a reservoir-scale reactive transport simulation, this range becomes much smaller. The reservoir scale simulations provide limits on the applicable conditions under which silicate mineral dissolution and subsequent carbonate mineral precipitation are likely to occur (pH 4.5 to 6, fluid flow velocity less than 5 m/year, and 50-100 years or more after the start of injection). These constraints lead to estimates of 200 to 2000 years for conversion of 60-90% of injected CO2 when the reservoir rock has a sufficient volume fraction of divalent cation-bearing silicate minerals and confirms that when reservoir rock mineralogy is not favorable the fraction of CO2 converted to carbonate minerals is minimal over 104 years. A sufficient amount of reactive minerals is typically about 20% by volume. Our approach may allow for rapid evaluation of mineralization potential of subsurface storage reservoirs and illustrates how reservoir scale modeling can be integrated with other observations to address key issues relating to engineering of geologic systems.

Isotopic Evidence for Reductive Immobilization of Uranium Across a Roll-Front Mineral Deposit.

We use uranium (U) isotope ratios to detect and quantify the extent of natural U reduction in groundwater across a roll front redox gradient. Our study was conducted at the Smith Ranch-Highland in situ recovery (ISR) U mine in eastern Wyoming, USA, where economic U deposits occur in the Paleocene Fort Union formation. To evaluate the fate of aqueous U in and adjacent to the ore body, we investigated the chemical composition and isotope ratios of groundwater samples from the roll-front type ore body and surrounding monitoring wells of a previously mined area. The (238)U/(235)U of groundwater varies by approximately 3‰ and is correlated with U concentrations. Fluid samples down-gradient of the ore zone are the most depleted in (238)U and have the lowest U concentrations. Activity ratios of (234)U/(238)U are ∼5.5 up-gradient of the ore zone, ∼1.0 in the ore zone, and between 2.3 and 3.7 in the down-gradient monitoring wells. High-precision measurements of (234)U/(238)U and (238)U/(235)U allow for development of a conceptual model that evaluates both the migration of U from the ore body and the extent of natural attenuation due to reduction. We find that the premining migration of U down-gradient of the delineated ore body is minimal along eight transects due to reduction in or adjacent to the ore body, whereas two other transects show little or no sign of reduction in the down-gradient region. These results suggest that characterization of U isotopic ratios at the mine planning stage, in conjunction with routine geochemical analyses, can be used to identify where more or less postmining remediation will be necessary.

Se Isotopes as Groundwater Redox Indicators: Detecting Natural Attenuation of Se at an in Situ Recovery U Mine.

One of the major ecological concerns associated with the in situ recovery (ISR) of uranium (U) is the environmental release of soluble, toxic selenium (Se) oxyanions generated by mining. Post-mining natural attenuation by the residual reductants in the ore body and reduced down-gradient sediments should mitigate the risk of Se contamination in groundwater. In this work, we investigate the Se concentrations and Se isotope systematics of groundwater and of U ore bearing sediments from an ISR site at Rosita, TX, USA. Our results show that selenate (Se(VI)) is the dominant Se species in Rosita groundwater, and while several up-gradient wells have elevated Se(VI), the majority of the ore zone and down-gradient wells have little or no Se oxyanions. In addition, the δ82SeVI of Rosita groundwater is generally elevated relative to the U ore up to +6.14‰, with the most enriched values observed in the ore-zone wells. Increasing δ82Se with decreasing Se(VI) conforms to a Rayleigh type distillation model with an ε of -2.25‰ ± 0.61‰, suggesting natural Se(VI) reduction occurring along the hydraulic gradient at the Rosita ISR site. Furthermore, our results show that Se isotopes are excellent sensors for detecting and monitoring post-mining natural attenuation of Se oxyanions at ISR sites.

The Nanoscale Basis of CO2 Trapping for Geologic Storage.

Carbon capture and storage (CCS) is likely to be a critical technology to achieve large reductions in global carbon emissions over the next century. Research on the subsurface storage of CO2 is aimed at reducing uncertainties in the efficacy of CO2 storage in sedimentary rock formations. Three key parameters that have a nanoscale basis and that contribute uncertainty to predictions of CO2 trapping are the vertical permeability kv of seals, the residual CO2 saturation Sg,r in reservoir rocks, and the reactive surface area ar of silicate minerals. This review summarizes recent progress and identifies outstanding research needs in these areas. Available data suggest that the permeability of shale and mudstone seals is heavily dependent on clay fraction and can be extremely low even in the presence of fractures. Investigations of residual CO2 trapping indicate that CO2-induced alteration in the wettability of mineral surfaces may significantly influence Sg,r. Ultimately, the rate and extent of CO2 conversion to mineral phases are uncertain due to a poor understanding of the kinetics of slow reactions between minerals and fluids. Rapidly improving characterization techniques using X-rays and neutrons, and computing capability for simulating chemical interactions, provide promise for important advances.

Isotopic and Geochemical Tracers for U(VI) Reduction and U Mobility at an in Situ Recovery U Mine.

In situ recovery (ISR) uranium (U) mining mobilizes U in its oxidized hexavalent form (U(VI)) by oxidative dissolution of U from the roll-front U deposits. Postmining natural attenuation of residual U(VI) at ISR mines is a potential remediation strategy. Detection and monitoring of naturally occurring reducing subsurface environments are important for successful implementation of this remediation scheme. We used the isotopic tracers (238)U/(235)U (δ(238)U), (234)U/(238)U activity ratio, and (34)S/(32)S (δ(34)S), and geochemical measurements of U ore and groundwater collected from 32 wells located within, upgradient, and downgradient of a roll-front U deposit to detect U(VI) reduction and U mobility at an ISR mining site at Rosita, TX, USA. The δ(238)U in Rosita groundwater varies from +0.61‰ to -2.49‰, with a trend toward lower δ(238)U in downgradient wells. The concurrent decrease in U(VI) concentration and δ(238)U with an ε of 0.48‰ ± 0.08‰ is indicative of naturally occurring reducing environments conducive to U(VI) reduction. Additionally, characteristic (234)U/(238)U activity ratio and δ(34)S values may also be used to trace the mobility of the ore zone groundwater after mining has ended. These results support the use of U isotope-based detection of natural attenuation of U(VI) at Rosita and other similar ISR mining sites.

Ion desolvation as a mechanism for kinetic isotope fractionation in aqueous systems.

Molecular dynamics simulations show that the desolvation rates of isotopes of Li(+), K(+), Rb(+), Ca(2+), Sr(2+), and Ba(2+) may have a relatively strong dependence on the metal cation mass. This inference is based on the observation that the exchange rate constant, k(wex), for water molecules in the first hydration shell follows an inverse power-law mass dependence (k(wex) ∝ m(-γ)), where the coefficient γ is 0.05 ± 0.01 on average for all cations studied. Simulated water-exchange rates increase with temperature and decrease with increasing isotopic mass for each element. The magnitude of the water-exchange rate is different for simulations run using different water models [i.e., extended simple point charge (SPC/E) vs. four-site transferrable intermolecular potential (TIP4P)]; however, the value of the mass exponent γ is the same. Reaction rate theory calculations predict mass exponents consistent with those determined via molecular dynamics simulations. The simulation-derived mass dependences imply that solids precipitating from aqueous solution under kinetically controlled conditions should be enriched in the light isotopes of the metal cations relative to the solutions, consistent with measured isotopic signatures in natural materials and laboratory experiments. Desolvation effects are large enough that they may be a primary determinant of the observed isotopic fractionation during precipitation.

Technical Note: Calcium and carbon stable isotope ratios as paleodietary indicators.

Calcium stable isotope ratios are hypothesized to vary as a function of trophic level. This premise raises the possibility of using calcium stable isotope ratios to study the dietary behaviors of fossil taxa and to test competing hypotheses on the adaptive origins of euprimates. To explore this concept, we measured the stable isotope composition of contemporary mammals in northern Borneo and northwestern Costa Rica, two communities with functional or phylogenetic relevance to primate origins. We found that bone collagen δ(13) C and δ(15) N values could differentiate trophic levels in each assemblage, a result that justifies the use of these systems to test the predicted inverse relationship between bioapatite δ(13) C and δ(44) Ca values. As expected, taxonomic carnivores (felids) showed a combination of high δ(13) C and low δ(44) Ca values; however, the δ(44) Ca values of other faunivores were indistinguishable from those of primary consumers. We suggest that the trophic insensitivity of most bioapatite δ(44) Ca values is attributable to the negligible calcium content of arthropod prey. Although the present results are inconclusive, the tandem analysis of δ(44) Ca and δ(13) C values in fossils continues to hold promise for informing paleodietary studies and we highlight this potential by drawing attention to the stable isotope composition of the Early Eocene primate Cantius.

Calcium isotope constraints on the end-Permian mass extinction.

The end-Permian mass extinction horizon is marked by an abrupt shift in style of carbonate sedimentation and a negative excursion in the carbon isotope (delta(13)C) composition of carbonate minerals. Several extinction scenarios consistent with these observations have been put forward. Secular variation in the calcium isotope (delta(44/40)Ca) composition of marine sediments provides a tool for distinguishing among these possibilities and thereby constraining the causes of mass extinction. Here we report delta(44/40)Ca across the Permian-Triassic boundary from marine limestone in south China. The delta(44/40)Ca exhibits a transient negative excursion of approximately 0.3 per thousand over a few hundred thousand years or less, which we interpret to reflect a change in the global delta(44/40)Ca composition of seawater. CO(2)-driven ocean acidification best explains the coincidence of the delta(44/40)Ca excursion with negative excursions in the delta(13)C of carbonates and organic matter and the preferential extinction of heavily calcified marine animals. Calcium isotope constraints on carbon cycle calculations suggest that the average delta(13)C of CO(2) released was heavier than -28 per thousand and more likely near -15 per thousand; these values indicate a source containing substantial amounts of mantle- or carbonate-derived carbon. Collectively, the results point toward Siberian Trap volcanism as the trigger of mass extinction.

Timing the onset of sulfate reduction over multiple subsurface acetate amendments by measurement and modeling of sulfur isotope fractionation.

Stable isotope fractionations of sulfur are reported for three consecutive years of acetate-enabled uranium bioremediation at the US Department of Energy's Rifle Integrated Field Research Challenge (IFRC) site. The data show a previously undocumented decrease in the time between acetate addition and the onset of sulfate reducing conditions over subsequent amendments, from 20 days in the 2007 experiment to 4 days in the 2009 experiment. Increased sulfide concentrations were observed at the same time as δ(34)S of sulfate enrichment in the first year, but in subsequent years elevated sulfide was detected up to 15 days after increased δ(34)S of sulfate. A biogeochemical reactive transport model is developed which explicitly incorporates the stable isotopes of sulfur to simulate fractionation during the 2007 and 2008 amendments. A model based on an initially low, uniformly distributed population of sulfate reducing bacteria that grow and become spatially variable with time reproduces measured trends in solute concentration and δ(34)S, capturing the change in onset of sulfate reduction in subsequent years. Our results demonstrate a previously unrecognized hysteretic effect in the spatial distribution of biomass growth during stimulated subsurface bioremediation.

Isotopic tracking of Hanford 300 area derived uranium in the Columbia River.

Our objectives in this study are to quantify the discharge rate of uranium (U) to the Columbia River from the Hanford Site's 300 Area and to follow that U downriver to constrain its fate. Uranium from the Hanford Site has variable isotopic composition due to nuclear industrial processes carried out at the site. This characteristic makes it possible to use high-precision isotopic measurements of U in environmental samples to identify even trace levels of contaminant U, determine its sources, and estimate discharge rates. Our data on river water samples indicate that as much as 3.2 kg/day can enter the Columbia River from the 300 Area, which is only a small fraction of the total load of dissolved natural background U carried by the Columbia River. This very low level of Hanford-derived U can be discerned, despite dilution to <1% of natural background U, 400 km downstream from the Hanford Site. These results indicate that isotopic methods can allow the amounts of U from the 300 Area of the Hanford Site entering the Columbia River to be measured accurately to ascertain whether they are an environmental concern or insignificant relative to natural uranium background in the Columbia River.

Pb isotopes as an indicator of the Asian contribution to particulate air pollution in urban California.

During the last two decades, expanding industrial activity in east Asia has led to increased production of airborne pollutants that can be transported to North America. Previous efforts to detect this trans-Pacific pollution have relied upon remote sensing and remote sample locations. We tested whether Pb isotope ratios in airborne particles can be used to directly evaluate the Asian contribution to airborne particles of anthropogenic origin in western North America, using a time series of samples from a pair of sites upwind and downwind of the San Francisco Bay Area. Our results for airborne Pb at these sites indicate a median value of 29% Asian origin, based on mixing relations between distinct regional sample groups. This trans-Pacific Pb is present in small quantities but serves as a tracer for airborne particles within the growing Asian industrial plume. We then applied this analysis to archived samples from urban sites in central California. Taken together, our results suggest that the analysis of Pb isotopes can reveal the distribution of airborne particles affected by Asian industrial pollution at urban sites in northern California. Under suitable circumstances, this analysis can improve understanding of the global transport of pollution, independent of transport models.

Isotopic Fractionation of Potassium by Diffusion in Methanol.

We present the results of experiments involving the isotopic fractionation by diffusion of K+ cations in methanol at 298 K along with supporting molecular dynamic simulations. The experiments, using glass Rayleigh fractionators filled with a methanol solution of KCl, constrain the ratio of the individual diffusivities of 41K and 39K (D 41K/D 39K) in methanol, and so the isotopic fractionation of K+ due to diffusion in methanol, to 0.9995 ± 0.0001. This isotopic fractionation is 25% of the fractionation resulting from K+ diffusion in water. This is consistent with published molecular dynamics simulations indicating greater hydrodynamic coupling between K+ ions and solvating methanol molecules compared to K+ ions and solvating water molecules.

Oxygen isotope variations at the margin of a CAI records circulation within the solar nebula.

Micrometer-scale analyses of a calcium-, aluminum-rich inclusion (CAI) and the characteristic mineral bands mantling the CAI reveal that the outer parts of this primitive object have a large range of oxygen isotope compositions. The variations are systematic; the relative abundance of (16)O first decreases toward the CAI margin, approaching a planetary-like isotopic composition, then shifts to extremely (16)O-rich compositions through the surrounding rim. The variability implies that CAIs probably formed from several oxygen reservoirs. The observations support early and short-lived fluctuations of the environment in which CAIs formed, either because of transport of the CAIs themselves to distinct regions of the solar nebula or because of varying gas composition near the proto-Sun.

Formation of Box Canyon, Idaho, by megaflood: implications for seepage erosion on Earth and Mars.

Amphitheater-headed canyons have been used as diagnostic indicators of erosion by groundwater seepage, which has important implications for landscape evolution on Earth and astrobiology on Mars. Of perhaps any canyon studied, Box Canyon, Idaho, most strongly meets the proposed morphologic criteria for groundwater sapping because it is incised into a basaltic plain with no drainage network upstream, and approximately 10 cubic meters per second of seepage emanates from its vertical headwall. However, sediment transport constraints, 4He and 14C dates, plunge pools, and scoured rock indicate that a megaflood (greater than 220 cubic meters per second) carved the canyon about 45,000 years ago. These results add to a growing recognition of Quaternary catastrophic flooding in the American northwest, and may imply that similar features on Mars also formed by floods rather than seepage erosion.

Tracking sources of unsaturated zone and groundwater nitrate contamination using nitrogen and oxygen stable isotopes at the Hanford site, Washington.

The nitrogen and oxygen isotopic compositions of nitrate in pore water extracts from unsaturated zone (UZ) core samples and groundwater samples indicate at least four potential sources of nitrate in groundwaters at the U.S. DOE Hanford Site in south-central Washington. Natural sources of nitrate identified include microbially produced nitrate from the soil column (delta15N of 4 - 8 per thousand, delta18O of -9 to 2 per thousand) and nitrate in buried caliche layers (delta15N of 0-8 per thousand, delta 18O of -6to 42 per thousand). Isotopically distinctindustrial sources of nitrate include nitric acid in low-level disposal waters (delta15N approximately per thousand, delta 18O approximately 23%o) per thousandnd co-contaminant nitrate in high-level radioactive waste from plutonium processing (6'5delta1of 8-33 % o, per thousand18delta oO -9 to 7%0). per thousandThe isotopic compositions of nitrate from 97 groundwater wells with concentrations up to 1290 mg/L NO3- have been analyzed. Stable isotope analyses from this study site, which has natural and industrial nitrate sources, provide a tool to distinguish nitrate sources in an unconfined aquiferwhere concentrations alone do not. These data indicate that the most common sources of high nitrate concentrations in groundwater at Hanford are nitric acid and natural nitrate flushed out of the UZ during disposal of low-level wastewater. Nitrate associated with high-level radioactive UZ contamination does not appear to be a major source of groundwater nitrate at this time.

Identifying the sources of subsurface contamination at the Hanford Site in Washington using high-precision uranium isotopic measurements.

In the mid-1990s, a groundwater plume of uranium (U) was detected in monitoring wells in the B-BX-BY Waste Management Area at the Hanford Site in Washington. This area has been used since the late 1940s to store high-level radioactive waste and other products of U fuel-rod processing. Using multiple-collector ICP source magnetic sector mass spectrometry, high-precision uranium isotopic analyses were conducted of samples of vadose zone contamination and of groundwater. The isotope ratios 236U/238U, 234U/238U, and 238U/235U are used to distinguish contaminant sources. On the basis of the isotopic data, the source of the groundwater contamination appears to be related to a 1951 overflow event at tank BX-102 that spilled high-level U waste into the vadose zone. The U isotopic variation of the groundwater plume is a result of mixing between contaminant U from this spill and natural background U. Vadose zone U contamination at tank B-110 likely predates the recorded tank leak and can be ruled out as a significant source of groundwater contamination, based on the U isotopic composition. The locus of vadose zone contamination is displaced from the initial locus of groundwater contamination, indicating that lateral migration in the vadose zone was at least 8 times greater than vertical migration. The time evolution of the groundwater plume suggests an average U migration rate of approximately 0.7-0.8 m/day showing slight retardation relative to a groundwater flow of approximately 1 m/day.