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Geochemical reactions add complexity to the characterization and prediction of fracture hydraulic properties because they depend on factors that are highly heterogeneous, such as mineral composition. However, systematic analyses of fracture evolution in mineralogically heterogeneous systems are still limited. In this study, we investigated fracture evolution in multimineral systems using a reduced dimension reactive transport model. The model was developed and tested based on experimental studies and addresses the complex morphological and geochemical changes that arise from the presence of multiple minerals of different reactivities. Numerical experiments were performed using randomly generated initial fracture geometries based on representative geostatistics, different categories of mineral composition, and a range of flow rates that are relevant to geologic carbon storage systems. The simulation results showed distinct dissolution regimes at different flow rates, each of which produced characteristic d...

The geological calcium cycle is linked to the geological carbon cycle through the weathering and burial of carbonate rocks. As a result, calcium (Ca) isotope ratios (44Ca/40Ca, expressed as δ44/40Ca) can help to constrain ancient carbon cycle dynamics if Ca cycle behavior can be reconstructed. However, the δ44/40Ca of carbonate rocks is influenced not only by the δ44/40Ca of seawater but also by diagenetic processes and fractionation associated with carbonate precipitation. In this study, we investigate the dominant controls on carbonate δ44/40Ca in Upper Permian to Middle Triassic limestones (ca. 253 to 244 Ma) from south China and Turkey. This time interval is ideal for assessing controls on Ca isotope ratios in carbonate rocks because fluctuations in seawater δ44/40Ca may be expected based on several large carbon isotope (δ13C) excursions ranging from − 2 to + 8‰. Parallel negative δ13C and δ44/40Ca excursions were previously identified across the end-Permian extinction horizon. Here, we find a second negative excursion in δ44/40Ca of ~ 0.2‰ within Lower Triassic strata in both south China and Turkey; however, this excursion is not synchronous between regions and thus cannot be interpreted to reflect secular change in the δ44/40Ca of global seawater. Additionally, δ44/40Ca values from Turkey are consistently 0.3‰ lower than contemporaneous samples from south China, providing further support for local or regional influences. By measuring δ44/40Ca and Sr concentrations ([Sr]) in two stratigraphic sections located at opposite margins of the Paleo-Tethys Ocean, we can determine whether the data represent global conditions (e.g., secular variations in the δ44/40Ca of seawater) versus local controls (e.g., original mineralogy or diagenetic alteration). The [Sr] and δ44/40Ca data from this study are best described statistically by a log-linear correlation that also exists in many previously published datasets of various geological ages. Using a model of early marine diagenetic water-rock interaction, we illustrate that this general correlation can be explained by the chemical evolution of bulk carbonate sediment samples with different initial mineralogical compositions that subsequently underwent recrystallization. Although early diagenetic resetting and carbonate mineralogy strongly influence the carbonate δ44/40Ca values, the relationship between [Sr] and δ44/40Ca holds potential for reconstructing first-order secular changes in seawater δ44/40Ca composition.

ConspectusGeologic 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 miner...

© 2017 American Chemical Society. A novel reactive transport model has been developed to examine the processes that affect fracture evolution in a carbonate-rich shale. An in situ synchrotron X-ray microtomography experiment, flowing CO2saturated water through a single fracture mini-core of Niobrara Shale provided the experimental observations for the development and testing of the model. The phenomena observed included the development of a porous altered layer, flow channeling, and increasingly limited calcite dissolution. The experimental observations cannot be explained by models that consider only mineral dissolution and development of an altered layer. The difference between the fracture volume change recorded by the microtomography images and what would be expected from mineral dissolution alone suggest that there is erosion of the altered layer as it develops. The numerical model includes this additional mechanism, with the erosion rate based on the thickness of the altered layer, and successfully captures the evolution of the geochemical reactions and morphology of the fracture. The findings imply that the abundance (with a threshold of approximately 35%) and reactivity of the rapidly reacting mineral control the development and erodibility of the altered layer on the fracture surfaces, and therefore fracture opening.

The rates of mineral dissolution reactions in porous media are difficult to predict, in part because of a lack of understanding of mineral reactive surface area in natural porous media. Common estimates of mineral reactive surface area used in reactive transport models for porous media are typically ad hoc and often based on average grain size, increased to account for surface roughness or decreased by several orders of magnitude to account for reduced surface reactivity of field as opposed to laboratory samples. In this study, accessible mineral surface areas are determined for a sample from the reservoir formation at the Nagaoka pilot CO2 injection site (Japan) using a multi-scale image analysis based on synchrotron X-ray microCT, SEM QEMSCAN, XRD, SANS, and FIB-SEM. This analysis not only accounts for accessibility of mineral surfaces to macro-pores, but also accessibility through connected micro-pores in smectite, the most abundant clay mineral in this sample. While the imaging analysis reveals that most of the micro- and macro-pores are well connected, some pore regions are unconnected and thus inaccessible to fluid flow and diffusion. To evaluate whether mineral accessible surface area accurately reflects reactive surface area a flow-through core experiment is performed and modeled at the continuum scale. The core experiment is performed under conditions replicating the pilot site and the evolution of effluent solutes in the aqueous phase is tracked. Various reactive surface area models are evaluated for their ability to capture the observed effluent chemistry, beginning with parameter values determined as a best fit to a disaggregated sediment experiment (Beckingham et al., 2016) described previously. Simulations that assume that all mineral surfaces are accessible (as in the disaggregated sediment experiment) over-predict the observed mineral reaction rates, suggesting that a reduction of RSA by a factor of 10–20 is required to match the core flood experimental data. While the fit of the effluent chemistry (and inferred mineral dissolution rates) greatly improve when the pore-accessible mineral surface areas are used, it was also necessary to include highly reactive glass phases to match the experimental observations, in agreement with conclusions from the disaggregated sediment experiment. It is hypothesized here that the 10–20 reduction in reactive surface areas based on the limited pore accessibility of reactive phases in core flood experiment may be reasonable for poorly sorted and cemented sediments like those at the Nagaoka site, although this reflects pore rather than larger scale heterogeneity.

The strontium/calcium (Sr/Ca) ratio in paleoseawater is important for evaluating the global fluxes of continental weathering products and carbonate deposition in the oceans. Existing reconstructions of the paleoseawater Sr/Ca ratio using different methods give conflicting results. We use a modeling approach to estimate paleo-Sr/Ca for the past 50 million years that uses pore fluid chemistry and bulk sediment measurements of carbonate ooze and chalk from the Ontong Java Plateau as input. The effects of diagenesis in modifying the Sr/Ca ratio recorded in bulk carbonate sediments are estimated using a reactive transport model, and those effects are accounted for in determining the initial Sr/Ca ratio of the biogenic carbonate sediments. The Sr/Ca of the paleo-oceans is calculated based on an effective partition coefficient ( K Sr bio = 0.198 ) inferred from Sr/Ca in modern sediments. The model simulates deposition of sediments on the seafloor, reactions between pore fluid and solid (dissolution and precipitation of calcite), and diffusion within the pore fluid. Measured pore fluid Sr, Ca and sulfate concentrations provide input for the Sr model. This approach, applied to four Ocean Drilling Program (ODP) sites (803, 805, 806, 807) that have long Cenozoic records of carbonate deposition, indicates that the Sr/Ca ratio of seawater has increased slowly over the past 50 million years from a value of about 8 mmol/mol to the modern value of 9.4, with fluctuations of about ±1 over 10 Myr periods. This result is consistent with previous estimates based on foraminifera and coral aragonite, but differs from recent estimates obtained with other approaches. The near-constant seawater Sr/Ca over the past 50 million years is consistent with likely weathering sources to the oceans. The fluctuations suggest that there were modest shifts in the aragonite/calcite ratio of marine carbonate.

The end-Triassic mass extinction coincided with a negative δ13C excursion, consistent with release of 13C-depleted CO2 from the Central Atlantic Magmatic Province. However, the amount of carbon released and its effects on ocean chemistry are poorly constrained. The coupled nature of the carbon and calcium cycles allows calcium isotopes to be used for constraining carbon cycle dynamics and vice versa. We present a high-resolution calcium isotope (δ44/40Ca) record from 100 m of marine limestone spanning the Triassic/Jurassic boundary in two stratigraphic sections from northern Italy. Immediately above the extinction horizon and the associated negative excursion in δ13C, δ44/40Ca decreases by ∼0.8‰ in 20 m of section and then recovers to preexcursion values. Coupled numerical models of the geological carbon and calcium cycles demonstrate that this δ44/40Ca excursion is too large to be explained by changes to seawater δ44/40Ca alone, regardless of CO2 injection volume and duration. Less than 20% of the δ44/40Ca excursion can be attributed to acidification. The remaining 80% likely reflects a higher proportion of aragonite in the original sediment, based largely on high concentrations of Sr in the samples. Our study demonstrates that coupled models of the carbon and calcium cycles have the potential to help distinguish contributions of primary seawater isotopic changes from local or diagenetic effects on the δ44/40Ca of carbonate sediments. Differentiating between these effects is critical for constraining the impact of ocean acidification during the end-Triassic mass extinction, as well as for interpreting other environmental events in the geologic past.

Our limited understanding of mineral reactive surface area contributes to significant uncertainties in quantitative simulations of reactive chemical transport in subsurface processes. Continuum formulations for reactive transport typically use a number of different approximations for reactive surface area, including geometric, specific, and effective surface area. In this study, reactive surface area estimates are developed and evaluated for their ability to predict dissolution rates in a well-stirred flow-through reactor experiment using disaggregated samples from the Nagaoka pilot CO2 injection site (Japan). The disaggregated samples are reacted with CO2 acidified synthetic brine under conditions approximating the field conditions and the evolution of solute concentrations in the reactor effluent is tracked over time. The experiments, carried out in fluid-dominated conditions at a pH of 3.2 for 650 h, resulted in substantial dissolution of the sample and release of a disproportionately large fraction of the divalent cations. Traditional reactive surface area estimation methods, including an adjusted geometric surface area and a BET-based surface area, are compared to a newly developed image-based method. Continuum reactive transport modeling is used to determine which of the reactive surface area models provides the best match with the effluent chemistry from the well-stirred reactor. The modeling incorporates laboratory derived mineral dissolution rates reported in the literature and the initial modal mineralogy of the Nagaoka sediment was determined from scanning electron microscopy (SEM) characterization. The closest match with the observed steady-state effluent concentrations was obtained using specific surface area estimates from the image-based approach supplemented by literature-derived BET measurements. To capture the evolving effluent chemistry, particularly over the first 300 h of the experiment, it was also necessary to account for the grain size distribution in the sediment and the presence of a highly reactive volcanic glass phase that shows preferential cation leaching.

Understanding fracture alteration resulting from geochemical reactions is critical in predicting fluid migration in the subsurface and is relevant to multiple environmental challenges. Here, we present a novel 2.5D continuum reactive transport model that captures and predicts the spatial pattern of fracture aperture change and the development of an altered layer in the near-fracture region. The model considers permeability heterogeneity in the fracture plane and updates fracture apertures and flow fields based on local reactions. It tracks the reaction front of each mineral phase and calculates the thickness of the altered layer. Given this treatment, the model is able to account for the diffusion limitation on reaction rates associated with the altered layer. The model results are in good agreement with an experimental study in which a CO2-acidified brine was injected into a fracture in the Duperow Dolomite, causing dissolution of calcite and dolomite that result in the formation of a preferential flow channel and an altered layer. With an effective diffusion coefficient consistent with the experimentally observed porosity of the altered layer, the model captures the progressive decrease in the dissolution rate of the fast-reacting mineral in the altered layer.

© 2017 Elsevier Ltd Calcite precipitation plays a significant role in processes such as geological carbon sequestration and toxic metal sequestration and, yet, the rates and mechanisms of calcite growth under close to equilibrium conditions are far from well understood. In this study, a quartz crystal microbalance with dissipation (QCM-D) was used for the first time to measure macroscopic calcite growth rates. Calcite seed crystals were first nucleated and grown on sensors, then growth rates of calcite seed crystals were measured in real-time under close to equilibrium conditions (saturation index, SI = log ({Ca2+}/{CO32−}/Ksp) = 0.01–0.7, where {i} represent ion activities and Ksp= 10−8.48is the calcite thermodynamic solubility constant). At the end of the experiments, total masses of calcite crystals on sensors measured by QCM-D and inductively coupled plasma mass spectrometry (ICP-MS) were consistent, validating the QCM-D measurements. Calcite growth rates measured by QCM-D were compared with reported macroscopic growth rates measured with auto-titration, ICP-MS, and microbalance. Calcite growth rates measured by QCM-D were also compared with microscopic growth rates measured by atomic force microscopy (AFM) and with rates predicted by two process-based crystal growth models. The discrepancies in growth rates among AFM measurements and model predictions appear to mainly arise from differences in step densities, and the step velocities were consistent among the AFM measurements as well as with both model predictions. Using the predicted steady-state step velocity and the measured step densities, both models predict well the growth rates measured using QCM-D and AFM. This study provides valuable insights into the effects of reactive site densities on calcite growth rate, which may help design future growth models to predict transient-state step densities.

Volcanogenic sandstones are typically rich in volcanic rock fragments that can provide reactive minerals for CO 2 mineralization in a scenario of CO 2 sequestration. To quantitatively evaluate the extent and time scale of CO 2 mineralization in potential reservoir formations, we characterized example high‐porosity volcanic sand from the San Joaquin Valley of southern Central California. Samples were collected from the volcanic‐rich members of the Etchegoin Formation in the San Joaquin Basin near Coalinga, California. Thin sections made from these samples were examined under petrographic microscope to identify mineral compositions, and then scanning electron microscopy (SEM) and energy dispersive x‐ray spectroscopy (EDX) were used to gather quantitative information on mineral abundances, distribution, and reactive surface areas. Porosity and permeability were also measured using core plugs made from outcrop samples. Results show that the Etchegoin volcanic sandstone has a high percentage (10–15%) of reactive minerals (pyroxenes, Fe‐Ti spinel and clays), and high reactive surface areas at about 1 m-super-2/kg. Reactive transport modeling is conducted and shows that these reactive minerals could mineralize 92% of injected and capillary‐trapped CO 2 within 1000 years of injection. Possible effects of heterogeneity on CO 2 injection and mineralization are also studied using the reactive transport code TOUGHREACT. Vertical heterogeneity of mineralogy and hydrology increases both CO 2 injectivity and mineralization. Available volcanogenic sandstones worldwide like the Etchegoin sandstone are summarized from the literature, with formations from the western USA that have CO 2 sequestration potential emphasized.© 2015 Society of Chemical Industry and John Wiley & Sons, Ltd

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.

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.

The oxygen isotope composition of carbonate minerals varies with temperature as well as other environmental variables. For carbonates that precipitate slowly, under conditions that approach thermodynamic equilibrium, the temperature-dependence of 18 O uptake is the dominant signal and the measured 18 O content can be used as a paleotemperature proxy. In the more common case where carbonate minerals grow in a regime where they are not in isotopic equilibrium with their host solution, their oxygen isotope compositions are a convolution of multiple environmental variables. Here we present results from calcite growth experiments demonstrating the occurrence of large ( > 2 ‰ ) non-equilibrium oxygen isotope effects under conditions relevant to biogenic calcite growth and many natural inorganic systems. We show that these non-equilibrium effects vary systematically with pH and crystal growth rate. An isotopic ion-by-ion crystal growth model quantifies the competing roles of temperature, pH, and growth rate, and provides a general description of calcite–water oxygen isotope fractionation under non-equilibrium conditions. The crystal growth model results show that (1) there are both equilibrium and kinetic contributions to calcite oxygen isotopes at biogenic growth rates, (2) calcite does not directly inherit the oxygen isotope composition of DIC even at fast growth rates, (3) there is a kinetically controlled variation of about 1‰ per pH unit between pH = 7.7 and 9.3 at constant growth rate for inorganic calcite as well as biogenic calcite, and (4) extreme light isotope enrichments in calcite in alkaline environments are likely due to disequilibrium among DIC species in aqueous solution. The model can be extended to 13 C uptake into carbonates as well as clumped isotopes but additional data are needed to constrain the kinetic fractionation factors for carbon isotopes. The experimental and model results constitute an important step in separating the relative influence of inorganic and biologic processes on isotopic fractionation and may aid the development of new paleoproxies based on non-equilibrium effects.

A negative δ C 13 excursion in carbonate sediments near the Guadalupian/Lopingian (Middle/Late Permian) boundary has been interpreted to have resulted from a large carbon cycle disturbance during the end-Guadalupian extinction event (ca. 260 Ma). However, the carbon isotope data alone are insufficient to uniquely determine the type and magnitude of perturbation to the global carbon cycle. Calcium isotopes can be used to further constrain the cause of a carbon isotope excursion because the carbon and calcium cycles are coupled via CaCO3 burial. In this study, we present coupled carbon and calcium isotope records from three Guadalupian–Lopingian (G/L) sections in China (Penglaitan and Chaotian) and Turkey (Koserelik Tepe). The δ C 13 and δ Ca 44 / 40 records differ among our studied sections and do not co-vary in the same manner. No section shows δ C 13 and δ Ca 44 / 40 changes consistent with massive, rapid volcanic CO2 emissions or methane clathrate destabilization. Additionally, many sections with large ( > 3 ‰ ) changes in δ C 13 exhibit δ O 18 evidence for diagenetic alteration. Only one section exhibits a large excursion in the δ Ca 44 / 40 of limestone but the absence of a similar excursion in the δ Ca 44 / 40 of conodont apatite suggests that the limestone excursion reflects a mineralogical control rather than a perturbation to the global calcium cycle. Hence, we interpret the large isotopic changes observed in some sections to have resulted from local burial conditions or diagenetic effects, rather than from a large carbon and calcium cycle disturbance. Perturbations to the global carbon and calcium cycles across the G/L transition were much less intense than the disturbances that occurred across the subsequent Permian–Triassic boundary. This finding is consistent with the much smaller magnitude of the end-Guadalupian extinction relative to the end-Permian.

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 CO2. 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 CO2, and the concentration and isotopic composition of Ca suggest progressive fluid degassing (loss of CO2), 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. Published by Elsevier Ltd.

We proposed to use volcanogenic sandstones for CO2 sequestration. Such sandstones with a relatively high percentage of volcanic rock fragments (VRF) could be a promising target for CO2 sequestration in that they have a sufficient percentage of reactive minerals to allow substantial mineralization of injected scCO2, which provides the most secure form of CO2 storage, but can also be porous and permeable enough to allow injection at acceptable rates. The limitation in using volcanogenic sandstones as CO2 reservoir rocks is that porosity and permeability tend to decrease with increase of volcanic rock fragments (VRF) and with the length and complexity of the diagenetic history. Decreased porosity limits the rate at which CO2 can be injected. We evaluated these tradeoffs to assess the feasibility of using volcanogenic sandstone to achieve highly secure CO2 storage. Using relationships between VRF percent, porosity and permeability from available geological data, the reactive transport code TOUGHREACT was used to estimate the rate and extent of CO2 mineralization over 1000 years, and the trade-off between higher reactivity and lower porosity and permeability. For the parameter set that we believe is defensible, the optimal VRF percent for the largest amount of mineralized CO2 is around 10-20%. The results show that as much as 80% CO2 mineralization could occur in 1000 years and still allow sufficient injectivity so that ca. 1 megaton of CO2 can be injected per year per well. The key to estimating how much CO2 can be injected and mineralized is the relationship between permeability (or injectivity), reactive mineral content, mineral dissolution rates and reactive surface areas. We have sampled examples of volcanogenic sandstones from the Miocene Etchegoin Formation, central California to examine these parameters. Characterizations of these samples by SEM, XRF and XRD show that they are very rich in reactive minerals with around 32% plagioclase, 10% orthopyroxene, 2% clinopyroxene, and 1% ilmenite. Porosities range from 10% to 20%, and permeabilities range from 10 mD to 1000 mD. Batch experiments are also conducted to measure dissolution rates of one of the common minerals in volcanic sandstones, i.e. chlorite. Results show that the released Mg from chlorite in such sandstones could provide enough cations to potentially mineralize about half the stored CO2 in the pore space within 1000 years. The last chapter presents an extension of the TOUGHREACT code to include carbon 13 isotope into reactive transport modeling. 13 C isotope proves to be a great tracer for monitering subsurface flow of CO2.

It is the purpose of this study to demonstrate that the molecular scale reaction mechanisms describing calcite precipitation and calcium isotope fractionations under highly controlled laboratory conditions also reproduce field scale measurements of δ44Ca in groundwater systems. We present data collected from an aquifer during active carbonate mineral precipitation and develop a reactive transport model capturing the observed chemical and isotopic variations. Carbonate mineral precipitation and associated fluid δ44Ca data were measured in multiple clogged well bores during organic carbon amended biogenic reduction of a uranium contaminated aquifer in western Colorado, USA. Secondary mineral formation induced by carbonate alkalinity generated during the biostimulation process lead to substantial permeability reduction in multiple electron-donor injection wells at the field site. These conditions resulted in removal of aqueous calcium from a background concentration of 6 mM to

Paleotemperature reconstructions rely on knowledge of the equilibrium separation of oxygen isotopes between aqueous solution and calcium carbonate. Although oxygen isotope separation is expected on theoretical grounds, the temperature-dependence remains uncertain because other factors, such as slow exchange of isotopes between dissolved CO2-species and water, can obscure the temperature signal. This is problematic for crystal growth experiments on laboratory timescales and for interpreting the oxygen isotope composition of crystals formed in natural settings. We present results from experiments in which inorganic calcite is precipitated in the presence of 0.25μM dissolved bovine carbonic anhydrase (CA). The presence of dissolved CA accelerates oxygen isotope equilibration between the dissolved carbon species CO2, H2CO3, HCO3−, CO32− and water, thereby eliminating this source of isotopic disequilibrium during calcite growth. The experimental results allow us to isolate, for the first time, kinetic oxygen isotope effects occurring at the calcite–water interface. We present a framework of ion-by-ion growth of calcite that reconciles our new measurements with measurements of natural cave calcites that are the best candidate for having precipitated under near-equilibrium conditions. Our findings suggest that isotopic equilibrium between calcite and water is unlikely to have been established in laboratory experiments or in many natural settings. The use of CA in carbonate precipitation experiments offers new opportunities to refine oxygen isotope-based geothermometers and to interrogate environmental variables other than temperature that influence calcite growth rates.

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 e of ...

Obtaining quantitative information about the timescales associated with sediment transport, storage, and deposition in continental settings is important but challenging. The uranium-series comminution age method potentially provides a universal approach for direct dating of Quaternary detrital sediments, and can also provide estimates of the sediment transport and storage timescales. (The word "comminution" means "to reduce to powder," reflecting the start of the comminution age clock as reduction of lithic parent material below a critical grain size threshold of ~50μm.) To test the comminution age method as a means to date continental sediments, we applied the method to drill-core samples of the glacially-derived Kings River Fan alluvial deposits in central California. Sediments from the 45m core have independently-estimated depositional ages of up to ~800ka, based on paleomagnetism and correlations to nearby dated sediments. We characterized sequentially-leached core samples (both bulk sediment and grain size separates) for U, Nd, and Sr isotopes, grain size, surface texture, and mineralogy. In accordance with the comminution age model, where 234U is partially lost from small sediment grains due to alpha recoil, we found that ( 234U/ 238U) activity ratios generally decrease with age, depth, and specific surface area, with depletions of up to 9% relative to radioactive equilibrium. The resulting calculated comminution ages are reasonable, although they do not exactly match age estimates from previous studies and also depend on assumptions about 234U loss rates. The results indicate that the method may be a significant addition to the sparse set of available tools for dating detrital continental sediments, following further refinement. Improving the accuracy of the method requires more advanced models or measurements for both the recoil loss factor f α and weathering effects. We discuss several independent methods for obtaining f α on individual samples that may be useful for future studies. © 2010 Elsevier B.V.

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.

Microscopic mechanisms operating at the mineral–aqueous interface control rates of growth and dissolution, isotope fractionation and trace element partitioning during crystal growth. Despite the importance of characterizing surface kinetic controls on isotopic partitioning, no self-consistent microscopic theory has yet been presented which can simultaneously model both mineral growth rate and isotopic composition. Using a kinetic theory for AB or di-ionic crystal growth, we derive a model to predict precipitation rate and isotope fractionation as a function of growth solution oversaturation and solution stoichiometry and apply the theory to calcium isotope fractionation during calcite precipitation. Our model assimilates the current understanding of surface controlled isotope fractionation with kinetic theories of ion-by-ion mineral growth to predict isotopic partitioning during the growth of ionic crystals. This approach accounts for the effect of solution composition on microscopic mineral surface structure and composition, providing numerous testable hypotheses for growth of sparingly soluble AB crystals such as calcite, namely: (1) Both oversaturation and solution stoichiometry control growth rate and partitioning of isotopes during precipitation; (2) for growth driven primarily by step propagation, distinct expressions describe dislocation- and 2D nucleation-driven growth rates, while the expression for isotope fractionation is the same for both mechanisms; (3) mineral precipitation occurring via the formation of an amorphous precursor will generate isotope effects that are not compatible with ion-by-ion growth theory and may therefore be excluded from comparison; and, (4) the absolute kinetic limit of isotope fractionation may not be accessible at high oversaturation due to the formation of amorphous precursors. Using calcite as a model system, we derive expressions for growth rate and isotopic fractionation as a function of oversaturation and Ca 2 + : CO 3 2 − in solution. Increasing oversaturation increases mineral growth rate and drives isotope partitioning towards the kinetic limit, while increasing the concentration of Ca 2 + relative to CO 3 2 − at a given oversaturation tends to drive crystal growth towards isotopic equilibrium. These competing effects attenuate the magnitude of isotope fractionations observable in terrestrial environments.

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (δ44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of δ44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, δ44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the δ44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.

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.

Surface kinetic model for isotopic and trace element fractionation during precipitation of calcite from aqueous solutions Donald J. DePaolo Earth Sciences Division Lawrence Berkeley Nat ional La boratory Berkeley, C A 94720 Departme nt of Earth and Planetar y Science U niversity of Californi a Berkeley, C A 94720 October 2010

Zoisite-fluid trace element partition coefficients have been determined and are used to model fluids generated during the breakdown of hydrous phases in a subducting slab. Partition coefficients were determined for Rb, Ba, Th, U, Nb, Ta, Pb, Sr, and nine rare earth elements (REE) at 750–900 °C and 2.0 GPa. Our results show that Sr and Pb are extremely compatible in zoisite relative to other high-pressure phases (DSrN100, DPbN10). The zoisite-fluid partition coefficients are combined with previously determined partition coefficients for eclogite-facies minerals (garnet, cpx, rutile, phengite) to generate reaction-specific partition coefficients as well as bulk eclogite-fluid partition coefficients. Batch equilibrium models are then used to approximate the conditions of fluid formation in the slab. Two kinds of fluids are modeled — 1) fluids resulting from specific zoisite breakdown reactions, and 2) combined fluids from a variety of continuous and discontinuous reactions that have had the opportunity to equilibrate with a residual zoisite-bearing eclogite assemblage. We find that fluids generated during individual reactions have much more extreme trace element enrichments than those that have equilibrated with the eclogitic slab as a whole. In particular, fluids generated during zoisitebreakdown reactions tend to be strongly enriched in Pb and Sr. Fluids of extreme composition from individual dehydration reactions maybepreservedasfluidinclusionsandveins inexhumedeclogites.Fluidsthathaveequilibratedwithzoisite-bearingeclogitehavea more moderate trace element enrichment pattern that is more consistent with the fluid component sampled by island arc basalts (IAB) in the zone of melting beneath the volcanic front. We propose that fluids generated in the slab, which may initially have extreme patterns of trace element enrichment and fractionation, and mayshow extreme variation on asmall spatial scale, are ultimately at least partially equilibrated with the bulkeclogite. Subsequent mixing with partial melts of the sediment layer and exchange with the mantle wedge en route to the melting region serve to further homogenize the fluids. Therefore, we expect that “metamorphic” subduction zone fluids recorded by inclusions and veins in eclogite will differ quite markedly in composition from “metasomatic” subduction zone fluids that contribute to the formation of island arc basalts, even though their origin may be the same. © 2007 Elsevier B.V. All rights reserved.

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.

Both chemical weathering rates and fluid flow are difficult to measure in natural systems. However, these parameters are critical for understanding the hydrochemical evolution of aquifers, predicting the fate and transport of contaminants, and for water resources/water quality considerations. 87 Sr/ 86 Sr and ( 234 U/ 238 U) activity ratios are sensitive indicators of water–rock interaction, and thus provide a means of quantifying both flow and reactivity. The 87 Sr/ 86 Sr values in ground waters are controlled by the ratio of the dissolution rate to the flow rate. Similarly, the ( 234 U/ 238 U) ratio of natural ground waters is a balance between the flow rate and the dissolution of solids, and α-recoil loss of 234 U from the solids. By coupling these two isotope systems it is possible to constrain both the long-term (ca. 100’s to 1000’s of years) flow rate and bulk dissolution rate along the flow path. Previous estimates of the ratio of the dissolution rate to the infiltration flux from Sr isotopes ( 87 Sr/ 86 Sr) are combined with a model for ( 234 U/ 238 U) to constrain the infiltration flux and dissolution rate for a 70-m deep vadose zone core from Hanford, Washington. The coupled model for both ( 234 U/ 238 U) ratios and the 87 Sr/ 86 Sr data suggests an infiltration flux of 5 ± 2 mm/yr, and bulk silicate dissolution rates between 10 −15.7 and 10 −16.5 mol/m 2 /s. The process of α-recoil enrichment, while primarily responsible for the observed variation in ( 234 U/ 238 U) of natural systems, is difficult to quantify. However, the rate of this process in natural systems affects the interpretation of most U-series data. Models for quantifying the α-recoil loss fraction based on geometric predictions, surface area constraints, and chemical methods are also presented. The agreement between the chemical and theoretical methods, such as direct measurement of ( 234 U/ 238 U) of the small grain size fraction and geometric calculations for that size fraction, is quite good.

The 87Sr/86Sr ratios and Sr concentrations in sediment and pore fluids are used to evaluate the rates of calcite recrystallization at ODP Site 807A on the Ontong Java Plateau, an 800-meter thick section of carbonate ooze and chalk. A numerical model is used to evaluate the pore fluid chemistry and Sr isotopes in an accumulating section. The deduced calcite recrystallization rate is 2% per million years (%/Myr) near the top of the section and decreases systematically in older parts of the section such that the rate is close to 0.1/age (in years). The deduced recrystallization rates have important implications for the interpretation of Ca and Mg concentration profiles in the pore fluids. The effect of calcite recrystallization on pore fluid chemistry is described by the reaction length, L, which varies by element, and depends on the concentration in pore fluid and solid. When L is small compared to the thickness of the sedimentary section, the pore fluid concentration is controlled by equilibrium or steady-state exchange with the solid phase, except within a distance L of the sediment–water interface. When L is large relative to the thickness of sediment, the pore fluid concentration is mostly controlled by the boundary conditions and diffusion. The values of L for Ca, Sr, and Mg are of order 15, 150, and 1500 meters, respectively. LSr is derived from isotopic data and modeling, and allows us to infer the values of LCa and LMg. The small value for LCa indicates that pore fluid Ca concentrations, which gradually increase down section, must be equilibrium values that are maintained by solution-precipitation exchange with calcite and do not reflect Ca sources within or below the sediment column. The pore fluid Ca measurements and measured alkalinity allow us to calculate the in situ pH in the pore fluids, which decreases from 7.6 near the sediment–water interface to 7.1 ± 0.1 at 400–800 mbsf. While the calculated pH values are in agreement with some of the values measured during ODP Leg 130, most of the measurements are artifacts. The large value for LMg indicates that the pore fluid Mg concentrations at 807A are not controlled by calcite-fluid equilibrium but instead are determined by the changing Mg concentration of seawater during deposition, modified by aqueous diffusion in the pore fluids. We use the pore fluid Mg concentration profile at Site 807A to retrieve a global record for seawater Mg over the past 35 Myr, which shows that seawater Mg has increased rapidly over the past 10 Myr, rather than gradually over the past 60 Myr. This observation suggests that the Cenozoic rise in seawater Mg is controlled by continental weathering inputs rather than by exchange with oceanic crust. The relationship determined between reaction rate and age in silicates and carbonates is strikingly similar, which suggests that reaction affinity is not the primary determinant of silicate dissolution rates in nature.

A mathematical model is presented that describes the effects of pore fluid aqueous diffusion and reaction rate on the isotopic exchange between fluids and rocks in reactive geo-hydrological systems where flow is primarily through fractures. The model describes a simple system with parallel equidistant fractures, and chemical transport in the matrix slabs between fractures by aqueous diffusion through a stagnant pore fluid. The solid matrix exchanges isotopes with pore fluid by solution–precipitation at a rate characterized by a time constant, R (yr −1 ), which is an adjustable parameter. The effects of reaction on the isotopes of a particular element in the fracture fluid are shown to depend on the ratio of the diffusive reaction length for that element ( L ) to the fracture spacing ( b ). The reaction length depends on the solid–fluid exchange rate within the matrix, the partitioning of the element between the matrix pore fluid and the matrix solid phase, the porosity and density of the matrix, and the aqueous diffusivity. For L / b L / b relative to a standard porous flow (single porosity) model. For L / b > 1, the parallel fracture model is no different from a porous flow model. If isotopic data are available for two or more elements with different L values, it may be possible to use the model with appropriate isotopic measurements to estimate the spacing of the primary fluid-carrying fractures in natural fluid–rock systems. Examples are given using Sr and O isotopic data from mid-ocean ridge (MOR) hydrothermal vent fluids and Sr isotopes in groundwater aquifers hosted by fractured basalt. The available data for MOR systems are consistent with average fracture spacing of 1–4 m. The groundwater data suggest larger effective fracture spacing, in the range 50–500 m. In general, for fractured rock systems, the effects of fracture–matrix diffusive exchange must be considered when comparing isotopic exchange effects for different elements, as well as for estimating water age using radioactive and cosmogenic isotopes.

Pore water chemistry and 234U/238U activity ratios from fine-grained sediment cored by the Ocean Drilling Project at Site 984 in the North Atlantic were used as constraints in modeling in situ rates of plagioclase dissolution with the multicomponent reactive transport code Crunch. The reactive transport model includes a solid-solution formulation to enable the use of the 234U/238U activity ratios in the solid and fluid as a tracer of mineral dissolution. The isotopic profiles are combined with profiles of the major element chemistry (especially alkalinity and calcium) to determine whether the apparent discrepancy between laboratory and field dissolution rates still exists when a mechanistic reactive transport model is used to interpret rates in a natural system. A suite of reactions, including sulfate reduction and methane production, anaerobic methane oxidation, CaCO3 precipitation, dissolution of plagioclase, and precipitation of secondary clay minerals, along with diffusive transport and fluid and solid burial, control the pore fluid chemistry in Site 984 sediments. The surface area of plagioclase in intimate contact with the pore fluid is estimated to be 6.9 m2/g based on both grain geometry and on the depletion of 234U/238U in the sediment via α-recoil loss. Various rate laws for plagioclase dissolution are considered in the modeling, including those based on (1) a linear transition state theory (TST) model, (2) a nonlinear dependence on the undersaturation of the pore water with respect to plagioclase, and (3) the effect of inhibition by dissolved aluminum. The major element and isotopic methods predict similar dissolution rate constants if additional lowering of the pore water 234U/238U activity ratio is attributed to isotopic exchange via recrystallization of marine calcite, which makes up about 10–20% of the Site 984 sediment. The calculated dissolution rate for plagioclase corresponds to a rate constant that is about 102 to 105 times smaller than the laboratory-measured value, with the value depending primarily on the deviation from equilibrium. The reactive transport simulations demonstrate that the degree of undersaturation of the pore fluid with respect to plagioclase depends strongly on the rate of authigenic clay precipitation and the solubility of the clay minerals. The observed discrepancy is greatest for the linear TST model (105), less substantial with the Al-inhibition formulation (103), and decreases further if the clay minerals precipitate more slowly or as highly soluble precursor minerals (102). However, even several orders of magnitude variation in either the clay solubility or clay precipitation rates cannot completely account for the entire discrepancy while still matching pore water aluminum and silica data, indicating that the mineral dissolution rate conundrum must be attributed in large part to the gradual loss of reactive sites on silicate surfaces with time. The results imply that methods of mineral surface characterization that provide direct measurements of the bulk surface reactivity are necessary to accurately predict natural dissolution rates.

Bulk dissolution rates for sediment from ODP Site 984A in the North Atlantic are determined using the 234U/238U activity ratios of pore water, bulk sediment, and leachates. Site 984A is one of only several sites where closely spaced pore water samples were obtained from the upper 60 meters of the core; the sedimentation rate is high (11–15 cm/ka), hence the sediments in the upper 60 meters are less than 500 ka old. The sediment is clayey silt and composed mostly of detritus derived from Iceland with a significant component of biogenic carbonate (up to 30%). The pore water 234U/238U activity ratios are higher than seawater values, in the range of 1.2 to 1.6, while the bulk sediment 234U/238U activity ratios are close to 1.0. The 234U/238U of the pore water reflects a balance between the mineral dissolution rate and the supply rate of excess 234U to the pore fluid by α-recoil injection of 234Th. The fraction of 238U decays that result in α-recoil injection of 234U to pore fluid is estimated to be 0.10 to 0.20 based on the 234U/238U of insoluble residue fractions. The calculated bulk dissolution rates, in units of g/g/yr are in the range of 4 × 10−7 to 2 × 10−6 yr−1. There is significant down-hole variability in pore water 234U/238U activity ratios (and hence dissolution rates) on a scale of ca. 10 m. The inferred bulk dissolution rate constants are 100 to 104 times slower than laboratory-determined rates, 100 times faster than rates inferred for older sediments based on Sr isotopes, and similar to weathering rates determined for terrestrial soils of similar age. The results of this study suggest that U isotopes can be used to measure in situ dissolution rates in fine-grained clastic materials. The rate estimates for sediments from ODP Site 984 confirm the strong dependence of reactivity on the age of the solid material: the bulk dissolution rate (Rd) of soils and deep-sea sediments can be approximately described by the expression Rd ≈ 0.1 Age−1 for ages spanning 1000 to 5 × 108 yr. The age of the material, which encompasses the grain size, surface area, and other chemical factors that contribute to the rate of dissolution, appears to be a much stronger determinant of dissolution rate than any single physical or chemical property of the system.

Available constraints on metamorphic reaction rates derived from the study of natural systems are similar to, or slightly lower than, the bulk strain rates measured in the same rocks. Here, we explore whether this apparent relationship is merely coincidence or due to a more fundamental mechanistic link between reaction and strain. Grain boundary migration accommodated dislocation creep (GBMDC) or grain boundary diffusion creep (GBDC) (i.e. pressure solution), both of which involve dissolution-precipitation as we define it, will occur simultaneously with mineral reactions involving dissolution-precipitation in the presence of a non-zero deviatoric stress. The exact relationships between reaction and strain are different depending on whether GBMDC or GBDC is controlling strain, but the mechanistic link exists in both cases. We present theoretical arguments which show that bulk strain by GBMDC or GBDC, which may additionally be accommodated by processes not involving dissolution-precipitation, such as dislocation glide and climb or grain boundary sliding, should in most cases be somewhat faster than the bulk reaction rates as observed. With few exceptions, for natural metamorphic systems undergoing plastic deformation, strain rates provide an upper limit for bulk reaction rates occurring simultaneously in the same rocks. The data suggest that mineral reaction rates may typically be within one order of magnitude of the strain rate.

The U–Th/He system can potentially be used for dating volcanic rocks with ages as young as a few thousand years and as old as several million years, thus providing a valuable supplement to radiocarbon and K–Ar dating. Garnet phenocrysts from the 79 AD eruption of Mt. Vesuvius were dated to evaluate the accuracy with which the necessary measurements and corrections can be made. The determined age, corrected for diffusive loss of He, alpha ejection, and initial U-series disequilibrium, is 1885±188 yr which compares well with the known age of 1923 yr. U and Th concentrations were measured by isotope dilution on different aliquots than were used for He concentration measurements. Step-wise degassing yielded an Arrhenius relationship for He diffusion in garnet with an activation energy of 91.31±5.76 kJ/mol and ln D0/a2=−2.00±0.56. The uniformity of U and Th concentrations in garnet was checked by ion microprobe analysis. The 234U/238U and 230Th/238U activity ratios were measured by MC-ICPMS. The results suggest that with proper analysis and corrections, the U–Th/He method can be used to date young volcanic minerals with useful precision and accuracy, and may therefore be valuable for dating volcanic rocks that have low K or are otherwise difficult to date accurately with Ar–Ar or radiocarbon.

Experimental diffusion couples were used to study chemical diffusion between molten rhyolite and basalt with special emphasis on the associated fractionation of calcium and lithium isotopes. Diffusion couples were made by juxtaposing firmly packed powders of a natural basalt (SUNY MORB) and a natural rhyolite (Lake County Obsidian) and then annealing them in a piston cylinder apparatus for times ranging from 0.1 to 15.7 h, temperatures of 1350–1450°C, and pressures of 1.2–1.3 GPa. Profiles of the major elements and many trace elements were measured on the recovered quenched glasses. The diffusivities of all elements except lithium were found to be remarkably similar, while the diffusivity of lithium was two to three orders of magnitude larger than that of any of the other elements measured. Chemical diffusion of calcium from molten basalt into rhyolite was driven by a concentration ratio of ∼18 and produced a fractionation of 44Ca from 40Ca of about 6 ‰. Because of the relatively low concentration of lithium in the natural starting materials a small amount of spodumene (LiAlSi2O6) was added to the basalt in order to increase the concentration difference between basalt and rhyolite, which was expected to increase the magnitude of diffusive isotopic fractionation of lithium. The concentration ratio between Li-doped basalt and natural rhyolite was ∼15 and the resulting diffusion of lithium into the rhyolite fractionated 7Li from 6Li by about 40‰. We anticipate that several other major rock-forming elements such as magnesium, iron and potassium will also exhibit similarly larger isotopic fractionation whenever they diffuse between natural melts with sufficiently large differences in the abundance of these elements.

Interpretation of U-series disequilibria in midocean ridge basalts is highly dependent on the bulk partition coefficients for U and Th and therefore the mineralogy of the mantle source. Distinguishing between the effect of melting processes and variable source compositions on measured disequilibria (238U-230Th-226Ra and 235U-231Pa) requires measurement of the radiogenic isotopes Hf, Nd, Sr, and Pb. Here, we report measurements of 238U-230Th-226Ra and 235U-231Pa disequilibria; Hf, Nd, Sr, and Pb isotopic; and major and trace element compositions for a suite of 20 young midocean ridge basalts from the East Pacific Rise axis between 9°28′ and 9°52′N. All of the samples were collected within the axial summit trough using the submersible Alvin. The geological setting and observational data collected during sampling operations indicate that all the rocks are likely to have been erupted from 1991 to 1992 or within a few decades of that time. In these samples, 230Th excesses and 226Ra excesses are variable and inversely correlated. Because the eruption ages of the samples are much less than the half-life of 226Ra, this inverse correlation between 230Th and 226Ra excesses can be considered a primary feature of these lavas. For the lava suite analyzed in this study, 226Ra and 230Th excesses also vary with lava composition: 226Ra excesses are negatively correlated with Na8 and La/Yb and positively correlated with Mg#. Conversely, 230Th excesses are positively correlated with Na8 and La/Yb and negatively correlated with Mg#. Th/U, 230Th/232Th, and 230Th excesses are also variable and correlated to one another. 231Pa excesses are large but relatively constant and independent of Mg#, La/Yb, Th/U, and Na8. The isotope ratios 143Nd/144Nd, 176Hf/177Hf, 87Sr/86Sr, and 208Pb/206Pb are constant within analytical uncertainty, indicating that they were derived from a common source. The source is homogeneous with respect to parent/daughter ratios Lu/Hf, Sm/Nd, Rb/Sr, and Th/U; therefore, the measured variations of Th/U, 230Th, and 226Ra excesses and major and trace element compositions in these samples are best explained by polybaric melting of a homogeneous source, not by mixing of compositionally distinct sources.

Bulk metamorphic reaction rates have been measured using Sr isotopes as tracers of reactive transport processes at a field site near Simplon Pass, Switzerland, employing the technique described in Part I of this study (Baxter and DePaolo, 2002a). The reaction rate, R, inferred, similar to the value first reported in Baxter and DePaolo (2000), is 1.4 + 1 . 1 - 0 . 4 x 10 - 7 yr - 1 (or R = 7.0 + 5 . 5 - 2 . 0 x 10 - 9 g/cm 2 /yr normalized to the geometric surface area of plagioclase) which is several orders of magnitude slower than extrapolations of laboratory data. This rate suggests that attainment of local equilibrium may require 10's of millions of years, and consequently equilibrium may not be closely approached in dynamic metamorphic systems if significant changes in P-T-X occur over shorter timescales. These data suggest that there is a problem in current extrapolations or applicability of laboratory kinetic data to natural high-temperature systems. Possible reasons for this discrepancy include differences in reactive surface area, reactant supply limited by slow diffusion of major elements, or an armoring effect by which access to grain interiors is limited. On the basis of microchemical patterns in plagioclase, we identify grain boundary migration (GBM) as the rate limiting process for accessing grain interiors, and thus for bulk reaction. Calculation of reaction quotients for six balanced mineral reactions suggests local disequilibrium for garnet with respect to its Ca content. The characteristic equilibrium lengthscales (Le) for Sr and Ca are both about 1 meter. Equilibrium based geochemical tools such as isochron geochronology or geothermobarometry are compromised within a distance Le of the lithologic contact. Bulk Sr diffusivity measured at the field site changes from 10 - 9 to 10 - 7 m /yr, suggesting that the characteristics of the intergranular transporting medium (ITM) changed significantly during the early retrograde history of the field site.

Knowledge of metamorphic reaction rates is crucial to accurately interpret rock and mineral chemistry. The local equilibrium assumption, used in geochronology, geothermobarometry, and material flux estimates, requires that local reaction rates among system phases are fast relative to local rates of P-T-X change. Natural metamorphic reaction rates are essentially unknown and difficulties and disagreements exist regarding extrapolations of existing laboratory data to natural conditions. Growing recognition of natural effects that could be attributed to slower reaction rates justifies the need for a field-based quantification of reaction rates to assess the accuracy of lab-based predictions. We describe in detail the theory and methodology of a technique for extracting bulk reaction rates directly from isotopic data derived from natural samples (Baxter and DePaolo, 2000). Reaction rates measured using this technique may be judiciously applied to isotopic exchange or net reaction kinetics in other natural systems. The technique requires collection of whole rock and garnet 87Sr/86Sr data along a sampling traverse normal to a lithologic contact where there was, prior to metamorphism, a sharp isotopic discontinuity. Garnet data provide information on syn-metamorphic conditions and the time interval for the exchange process. Forward modeling of the reactive transport process using numerical methods and the equations for diffusive reactive transport allow determination of the reaction rate and bulk Sr diffusivity that provides the best fit to the data. Measurement of reaction rates is best constrained if an isotopic step is preserved at the contact, the size of which is directly proportional to the bulk reaction rate. This contribution is intended to serve as a template for future use and development of this technique to acquire natural reaction rate data from metamorphic systems.

Forty-four biotite samples collected about a lithologic contact between pelite and amphibolite were analyzed for 40Ar/39Ar and demonstrate the importance of bulk Ar diffusivity and system geometry—factors not usually considered in the interpretation and collection of 40Ar/39Ar age data. The resulting 40Ar/39Ar apparent ages range from 11.30 ± 0.05 Ma to 17.90 ± 0.10 Ma. The ages (and excess argon contents) are spatially and lithologically correlated. The pelite samples all yield ages clustering around ∼12 Ma, the age expected for cooling through biotite closure (∼360°C) in this region of the Alps. Ages in the amphibolite biotites are older, showing a smooth trend between 15 Ma at the contact with the pelite to 18 Ma, 34 cm from the contact. This data shows that characterization of the Ar closure age for biotite in a given system should not rest on a single sample, as otherwise irresolvable differences in age between samples within the same outcrop can exist. A generalized mechanistic model for excess argon is presented. The presence (or absence) of excess Ar depends on an intrinsic system parameter, τT, the transmissive timescale, which is the characteristic time for 40Ar to escape through the local intergranular transporting medium (ITM) to some sink for argon. To prevent buildup of geochronologically significant excess 40Ar, τT must be very short relative to the true closure age of the mineral. A FORTRAN code including radiogenic Ar production, diffusive loss of Ar from biotite, and bulk Ar diffusion through the ITM has been developed. Application of numerical modeling suggests that the time-averaged effective bulk diffusivity, DeffAr, in the biotite-amphibolite rock during early retrograde cooling is 2.2 ± 1.0 × 10−8 m2/yr (assuming steady state conditions) - the first such measurement available. Numerical modeling also provides information about the transmissivity and geologic history specific to the field site, including a drop in DeffAr at 15.5 ± 1.0 Ma. The timing of this drop is related to coincident rheological changes and the onset of rapid exhumation of the nappe stack.

The 40Ar/39Ar dating method depends on accurate intercalibration between samples, neutron fluence monitors, and primary 40Ar/40K (or other external) standards. The 40Ar/39Ar age equation may be expressed in terms of intercalibration factors that are simple functions of the relative ages of standards, or equivalently are equal to the ratio of radiogenic to nucleogenic K-derived argon (40Ar/39ArK) values for one standard or unknown relative to another. Intercalibration factors for McClure Mountain hornblende (MMhb-1), GHC-305 biotite, GA-1550 biotite, Taylor Creek sanidine (TCs) and Alder Creek sanidine (ACs), relative to Fish Canyon sanidine (FCs), were derived from 797 analyses involving 11 separate irradiations with well-constrained neutronfluence variations. Values of the intercalibration factors are RFCsMMhb-1 = 21.4876 ± 0.0079; RFCsGA-1550 = 3.5957 ± 0.0038; RFCsTCs = 1.0112 ± 0.0010; RFCsACs = 0.04229 ± 0.00006, based on the mean and standard error of the mean resulting from four or more spatially distinct co-irradiations of FCs with the other standars. Analysis of 35 grains of GHC-305 irradiated in a single irradiation yields RFCsGHC-305 = 3.8367 ± 0.0143. Results at these levels of precision essentially eliminate intercalibration as a significant source of error in 40Ar/39Ar dating. Data for GA-1550 (76 analyses, 5 fluence values), TCs (54 analyses, 4 fluence values), FCs (380 analyses, 40 fluence values) and ACs (86 analyses, 11 fluence values) yield MSWD values showing that the between-grain dispersion of 40Ar∗/39ArK values is consistent with analytical errors alone, whereas MMhb-1 (167 analyses, 4 irradiations) and GHC-305 (34 analyses, 1 fluence value) are heterogeneous and therefore unsuitable as standards for small sample analysis. New K measurements by isotope dilution for two primary standards, GA-1550 biotite (8 analyses averaging 7.626 ± 0.016 wt%) and intralaboratory standard GHC-305 (10 analyses averaging 7.570 ± 0.011 wt%), yield values slightly lower and more consistent than previous data obtained by flame photometry, with resulting 40Ar/40K ages of 98.79 ± 0.96 Ma and 105.6 ± 0.3 Ma for GA-1550 and GHC-305, respectively. Combining these data with the intercalibration approach described herein and using GA-1550 as the primary standard (1.343 × 10−9 mol/g of 40Ar∗; [McDougall, I., Roksandic, Z., 1974. Total fusion 40Ar/39Ar ages using HIFAR reactor. J. Geol. Soc. Aust. 21, 81–89.]) yields ages of 523.1 ± 4.6 Ma for MMhb-1, 105.2 ± 1.1 Ma for GHC-305, 98.79 ± 0.96 Ma for GA-1550, 28.34 ± 0.28 Ma for TCs, 28.02 ± 0.28 for FCs, and 1.194 ± 0.012 Ma for ACs (errors are full external errors, including uncertainty in decay constants). Neglecting error in the decay constants, these ages and uncertainties are: 523.1 ± 2.6 Ma for MMhb-1, 105.2 ± 0.7 Ma for GHC-305, 98.79 ± 0.54 for GA-1550, 28.34 ± 0.16 Ma for TCs, 28.02 ± 0.16 Ma for FCs, and 1.194 ± 0.007 Ma for ACs. Using GHC-305 as the primary standard (1.428 ± 0.004 × 10−9 mol/g of 40Ar∗), ages are 525.1 ± 2.3 Ma for MMhb-1, 105.6 ± 0.3 Ma for GHC-305, 99.17 ± 0.48 Ma for GA-1550, 28.46 ± 0.15 Ma for TCs, 28.15 ± 0.14 Ma for FCs, and 1.199 ± 0.007 Ma for ACs, neglecting decay constant uncertainties. The approach described herein facilitates error propagation that allows for straightforward inclusion of uncertainties in the ages of primary standards and decay constants, without which comparison of 40Ar/39Ar dates with data from independent geochronometers is invalid. Re-examination of 40K decay constants would be fruitful for improved accuracy.

Sr isotope ratios were measured in groundwater, whole rock digestions, and cation exchange extracts from a clay-rich groundwater system at Ernest O. Lawrence Berkeley National Laboratory and were used to constrain flow velocities and search for preferential flow paths. In the Orinda formation siltstone, 87Sr/86Sr increases strongly over tens of meters along presumed flow paths, indicating slow groundwater flow. Dissolved Sr is close to isotopic equilibrium with the exchangeable Sr in the clays, and the observed 87Sr/86Sr increase is interpreted as a cation exchange front moving slowly through the unit combined with dissolution of minerals with relatively high 87Sr/86Sr ratios. The data are inverted using a one-dimensional transport-dissolution-exchange model; the results indicate long-term average flow velocities of less than 0.2 m/yr which are consistent with 14C measurements. The data suggest a lack of strong preferential flow paths through this unit.

A transport-reaction model calculates isotope ratios (e.g., 87Sr/86Sr) in groundwater systems where isotope ratios in the fluid are affected by two distinct types of water-rock interaction: rapid exchange reactions and slower dissolution reactions. Rapid exchange reactions buffer the groundwater isotope ratios, and a two-stage evolution is observed. After a perturbation in the system an exchange front, which can be described by a retardation equation, propagates through the system at a velocity equal to the groundwater velocity divided by a retardation factor. If steady boundary conditions are maintained, the exchange front is advected out of the system and a quasi-steady state develops in which dissolution reactions influence the isotope ratios but the exchange reactions have no effect. Because clay minerals which readily exchange ions or water molecules with groundwater are found in most hydrologic systems, exchange reactions may significantly affect interpretation of isotopic data.

A model is presented that describes diffusive isotopic redistribution in layered fluid-rock systems where the solid and fluid interact by solution-precipitation. The models lead to guidelines for sampling in metamorphic and diagenetically modified rocks that could substantially increase the probability of recovering desired geochronological and geochemical information. The defining parameters of a fluid-rock system are the reaction rate, R, and the effective diffusivity (Deff) of the chemical element in question, the latter a function of ionic diffusivity in the fluid, porosity, and the solid/fluid distribution coefficient. Reactive fluid-rock systems can be uniquely characterized in terms of a wavelength L = 2π(Deff/R)1/2, below which the local equilibrium approximation breaks down. The estimated values of L vary over several orders of magnitude depending on the element of interest and the conditions. For Sr in amphibolite facies metamorphic rocks, for example, LSr is about 1–10 cm, whereas for lower greenschist or zeolite facies rocks LSr, may be 50 m. For oxygen in sedimentary rocks undergoing diagenesis, Lo is greater than 1000 m. The premetamorphic isotopic structure of layered rocks can be conceptualized in terms of a Fourier series representation of isotope ratio vs. distance normal to layering. The effect of metamorphism is to alter the amplitude-wavelength spectrum of the isotopic ratio variations in the solid. Although, in the model transport in the fluid is solely by diffusion, the attenuation of the isotopic variations does not behave like diffusion at all wavelengths. In particular, at wavelengths smaller than L, the rate of isotopic homogenization is limited by the reaction rate rather than the wavelength. The large variability of L in rock systems produces corresponding variability in the effects of isotopic redistribution. The implications of the models are discussed for whole rock and mineral isochrons, porphyroblast-matrix geochronology, and the retrieval of initial isotopic ratios from metamorphic rocks.

We expand a model for isotope ratios in groundwater-rock systems to consider the ratio of 14C to dissolved inorganic carbon, or “percent modern carbon.” The model couples one-dimensional advection and dispersion with water-rock interaction and radioactive decay. We use a Fickian formulation to model longitudinal macrodispersion and present a formula for the groundwater velocity error introduced when dispersion is ignored, as a function of dispersivity and decrease in percent modern carbon. For example, if the longitudinal dispersivity were one tenth the length of observation and percent modern carbon decreased tenfold along a flow path, the error would be 23%. We also present a method for inversion of 87Sr/86Sr and 14C data to obtain carbonate dissolution rates and dissolution-corrected water velocities and apply this technique using published data from the Lincolnshire aquifer, England. The results are similar to those obtained using the δ13C method.

A stratigraphically controlled sequence of Sr, Nd, Pb, and He isotope ratio measurements on tholeiitic basalt cored by the Hawaii Scientific Drilling Project is analyzed to constrain the dispersivity and chromatographic efficiency of the melt-producing zone under Hawaii. The data are interpreted using a simplified model for the transport of isotopic signals through the melt zone as magma separates from the upwelling solid by buoyancy-driven porous flow. A constant lava accumulation rate is assumed for the 620-m-thick section of analyzed basalt; a total duration of lava accumulation of 120 kyr is based on Ar-Ar dating. The amplitude-“period” spectrum of the isotopic variations in the lava sequence is determined by Fourier analysis and compared with a predicted amplitude-period spectrum for the mantle magma sources, based on an assumed amplitude-wavelength spectrum for the mantle and a plume upwelling velocity of 20 cm/yr. The isotopic variations in the mantle appear to be substantially attenuated in the lava record. If the attenuation is due to hydrodynamic dispersion in the melting zone, then the melt zone dispersivity is estimated to be in the range 100–1000 m, depending mainly on the value assumed for the melt-matrix velocity contrast. Dispersivity is a crude measure of effective grain size in the melt zone; the large values, although strictly only upper limits, suggest that permeability in the melt zone is inhomogeneous and some amount of channel development is present. The ratios 3He/4He and 206Pb/204Pb in the Mauna Kea section describe convoluted loops when plotted against one another, consistent with significant chromatographic separation of He and Pb in the melt zone. The evidence for chromatography of isotopic signals is consistent with the porous flow model predictions and indicates that the melt is maintained moderately close to chemical equilibrium with the solid as it separates. The modeling suggests that generally, chromatography in the melting zone causes isotope ratio-ratio relationships observed in the lava record to be severely out-of-phase with those present in the mantle source if the period of the variability is of order 105 years; for periods greater than 106 years the ratios are close to being “in phase,” whereas for periods less than 104 years the lava record is hopelessly scrambled.

We introduce a method to analyze element ratios and isotope ratios in mineral overgrowths. This general technique can quantify environmental controls on proxy behavior for a range of cultured biominerals and can also measure compositional effects during seeded mineral growth. Using a media enriched in multiple stable isotopes, the method requires neither the mass nor the composition of the initial seed or skeleton to be known and involves only bulk isotope measurements. By harnessing the stability and sensitivity of bulk analysis the new approach promises high precision measurements for a range of elements and isotopes. This list includes trace species and select non-traditional stable isotopes, systems where sensitivity and external reproducibility currently limit alternative approaches like secondary ion mass spectrometry (SIMS) and laser ablation mass spectrometry. Since the method separates isotopically labeled growth from unlabeled material, well-choreographed spikes can resolve the compositional effects of different events through time. Among other applications, this feature could be used to separate the impact of day and night on biomineral composition in organisms with photosymbionts.

A model enabling extraction of hydrologic information from spatial and temporal patterns in measurements of isotope ratios in water-rock systems is presented. The model describes the evolution of isotope ratios in response to solute transport and water-rock interaction. In advective systems, a single dimensionless parameter (a Damkohler number, ND) dominates in determining the distance over which isotopic equilibrium between the water and rock is approached. Some isotope ratios act as conservative tracers (ND ≪ 1), while others reflect only interaction with the local host rock (ND ≫ 1). If ND is close to one (i.e., the distance for equilibration is close to the length scale of observation), isotope ratio measurements can be used to determine ND, which in turn may yield information concerning reaction rates, or spatial variations in water velocity. Zones of high velocity (e.g., as a result of greater fracture density), or less reactive zones, may be identified through observation of their lower ND values. The model is applied to paleohydrologic interpretations of Sr isotope data from calcite fracture fillings in drill cores from Yucca Mountain, Nevada (Marshall et al., 1992). The results agree with other studies suggesting “fast path” transport in the unsaturated zone. Also, we find that the data do not give a conclusive indication of paleowater table elevation because of the effects of water-rock interaction.

SILICA-rich lavas, erupted at island-arc or continental volcanoes, are often produced by a complex process involving the assimilation of crust into a crystallizing, mantle-derived basaltic magma1. The different strontium, neodymium and oxygen isotopic compositions of mantle-derived magmas and continental crust provide a powerful method for tracing the different contributions to continental silicic magmas, and for understanding the parameters controlling the composition and volume of erupted magma1–4. In the large rhyolite eruptive centres of the western United States, the largest-volume, explosive rhyolite eruptions have more mantle-like Nd isotope ratios than other silicic lavas from the same centre2–4, a relationship that has been interpreted as reflecting increased influx of mantle-derived basaltic magma to a crustal magma chamber before large-volume eruptions1. Here we report isotope data for lavas from Unzen volcano, which suggest a similar relationship: the Nd isotope composition is more mantle-like in three larger-volume dacite eruptions (>0.1 km3) than in one small-volume (0.02 km3) eruption. We accordingly suggest that, in small-volume systems like Unzen, where the timescales for magma-chamber evolution are of the order of decades, isotope data such as those presented here might be used in volcanic hazard evaluation.

The initial Sr isotopic compositions of glass and mineral separates from the 0.74 Ma Bishop Tuff ashflow in eastern California were determined to investigate the time scales of magmatic processes in a large silicic system. It was found that there is substantial isotopic heterogeneity, both between eruptive units and between glass and phenocryst phases of individual units. The frist-erupted, lower temperature units generally have higher initial 87Sr/86Sr than later crupted, higher temperature units. Within each unit, feldspar phenocrysts have the lowest 87Sr/86Sr, associated glass has higher 87Sr/86Sr, and biotite phenocrysts have the highest 87Sr/86Sr. These isotopic differences were produced by processes in the magma chamber and not by post-eruptive alteration. Two samples were similar Fe−Ti oxide temperatures but from widely separated localities have nearly identifical Sr isotopic characteristics, indicating the existence of compositionally uniform layers of substantial volume within the chamber. Trace element data indicate that the feldspars crystallized from a liquid represented by the associated glass, and that the feldspar-glass pairs are not accidental. The rhyolitic liquids of the Bishoptuff magma chamber apparently experienced increasing 87Sr/86Sr at a rate too fast for feldspar phenocrysts to remain in isotopic equilibrium. The increasing 87Sr/86Sr is caused primarily by radioactive decay of 87Rb in the high-Rb/Sr liquids and not primarily by assimilation of radiogenic wall-rock material. A self-consistent model can be constructed to account for all of the isotopic data except for those on biotite phenocrysts. The time scale for evolution of the system is bounded on the high side at about 500 ky by observations made on precaldera lavas, and on the low side at approximately 300 ky by the time necessary to establish homogeneous layers in an actively differentiating chamber. The deduced time scale is consistent with model Rb−Sr ages, which date the differentiation of low temperature liquids from higher temperature liquids, and is compatible with the observed isotopic disequilibrium between feldspars and glass because of the low diffusivity of Sr in fieldspars ( 3x105 years. The silicic-magma production rate within the Bishop Tuff magma chamber is estimated to be 10-3km3/y. The growth rate of alkali feldspar is estimated to be about 10-14 cm/s based on the Sr isotopic difference between sanidine and glass of the lower Bishop Tuff. The biotite population is inferred to be partially (>50 ppm) xenocrystic, the xenocrysts being introduced to the chamber less than one year prior to eruption.