Search

The Cedars ultramafic block hosts alkaline springs (pH > 11) in which calcium carbonate forms upon uptake of atmospheric CO2 and at times via mixing with surface water. These processes lead to distinct carbonate morphologies with “floes” forming at the atmosphere-water interface, “snow” of fine particles accumulating at the bottom of pools and terraced constructions of travertine. Floe material is mainly composed of aragonite needles despite CaCO3 precipitation occurring in waters with low Mg/Ca ( The calcium carbonates exhibit an extreme range and approximately 1:1 covariation in δ13C (−9 to −28‰ VPDB) and δ18O (0 to −20‰ VPDB) that is characteristic of travertine formed in high pH waters. The large isotopic fractionations have previously been attributed to kinetic isotope effects accompanying CO2 hydroxylation but the controls on the δ13C-δ18O endmembers and slope have not been fully resolved, limiting the use of travertine as a paleoenvironmental archive. The limited areal extent of the springs (∼0.5 km2) and the limited range of water sources and temperatures, combined with our sampling strategy, allow us to place tight constraints on the processes involved in generating the systematic C and O isotope variations. We develop an isotopic reaction–diffusion model and an isotopic box model for a CO2-fed solution that tracks the isotopic composition of each dissolved inorganic carbon (DIC) species and CaCO3. The box model includes four sources or sinks of DIC (atmospheric CO2, high pH spring water, fresh creek water, and CaCO3 precipitation). Model parameters are informed by new floe Δ44Ca data (−0.75 ± 0.07‰), direct mineral growth rate measurements (4.8 to 8 × 10−7 mol/m2/s) and by previously published elemental and isotopic data of local water and DIC sources. Model results suggest two processes control the extremes of the array: (1) the isotopically light end member is controlled by the isotopic composition of atmospheric CO2 and the kinetic isotope fractionation factor (KFF (‰) = (α − 1) × 1000) accompanying CO2 hydroxylation, estimated here to be −17.1 ± 0.8‰ (vs. CO2(aq)) for carbon and −7.1 ± 1.1‰ (vs. ‘CO2(aq) + H2O’) for oxygen at 17.4 ± 1.0 °C. Combining our results with revised CO2 hydroxylation KFF values based on previous work suggests consistent KFF values of −17.0 ± 0.3‰ (vs. CO2(aq)) for carbon and −6.8 ± 0.8‰ for oxygen (vs. ‘CO2(aq) + H2O’) over the 17–28 °C temperature range. (2) The isotopically heavy endmember of calcium carbonates at The Cedars reflects the composition of isotopically equilibrated DIC from creek or surface water (mostly HC O 3 - , pH = 7.8–8.7) that occasionally mixes with the high-pH spring water. The bulk carbonate δ13C and δ18O values of modern and ancient travertines therefore reflect the proportion of calcium carbonate formed by processes (1) and (2), with process (2) dominating the carbonate precipitation budget at The Cedars. These results show that recent advances in understanding kinetic isotope effects allow us to model complicated but common natural processes, and suggest ancient travertine may be used to retrieve past meteoric water δ18O and atmospheric δ13C values. There is evidence that older travertine at The Cedars recorded atmospheric δ13C that predates large-scale combustion of fossil fuels.

The solution stoichiometry dependence of calcium isotope fractionation during calcite precipitation was investigated as a direct test of the conceptual model of calcium isotope discrimination driven by Ca exchange at surface sites during growth. Classical ion-by-ion models of calcite growth predict a strong solution stoichiometry influence on Δ44/40Cacalcite-fluid: In low Ca2+:CO32– solutions, Δ44/40Ca is predicted to approach a kinetic limit (∼−2 to −4‰), while in high Ca2+:CO32– solutions, exchange at dominantly Ca-occupied kink sites drives Δ44/40Ca towards the equilibrium fractionation (near 0‰). To test this prediction, a series of seeded and unseeded constant composition calcite growth experiments were performed in which all aspects of solution chemistry were held constant and the Ca2+:CO32– activity ratio was varied. Experiments were performed at pH 8.5, ionic strength 0.1 M (adjusted with KCl), and calcite saturation index (SI = log10({Ca2+}{CO32–}/Ksp)) of either 0.5 or 0.8. Calcium isotope fractionation is found to be weakly stoichiometry dependent. The expected trend of larger magnitude fractionations at lower Ca2+:CO32– is observed, but the magnitude of change in Δ44/40Ca over the solution stoichiometries studied (Ca2+:CO32– = 1–250) is only ∼ 0.4‰. Similar trends in Δ44/40Ca with Ca2+:CO32– are observed at SI = 0.5 and 0.8, with smaller magnitude fractionations at lower supersaturation. This yields an inverse correlation between Δ44/40Ca and growth rate, confirming the Δ44/40Ca-rate relationship for inorganic calcite growth observed by Tang et al. (2008) . The ion-by-ion model framework captures measured Δ44/40Ca only when a surface complexation model is incorporated, highlighting the role of surface speciation in dictating Ca attachment/detachment dynamics. The model captures observed trends with Ca2+:CO32– using best-fit kinetic and equilibrium fractionations consistent with end-members observed in natural systems (αkinetic ∼ 0.9978, αeq ∼ 0.9998). This result implies a total possible range in Δ44/40Ca of 2‰ and suggests that for most carbonate precipitating environments, solution supersaturation will be a stronger determinant of Δ44/40Ca than stoichiometry. The demonstrated importance of surface speciation, however, implies a strong pH influence on Δ44/40Ca, independent of its influence on carbonate ion activity, that requires further investigation. The results of this study provide strong evidence supporting the model of kink-exchange driven Ca isotope fractionation and suggest that calcite grows by a dominantly classical mechanism over the solution conditions investigated. Model predictions regarding the relationship between Δ44/40Ca and growth inhibition in the presence of impurity ions lay the foundation for the use of Ca isotopes as molecular tracers of carbonate crystal growth pathways.

The equilibrium partition coefficient of strontium ( K Sr eq ) between aqueous solutions and calcite is still poorly known, even though it is a valuable parameter for studies involving the use of calcite trace element geochemistry for reconstructing paleoenvironments and fluid chemistry. In this paper we use pore fluid data from deep sea carbonate sediments to constrain K Sr eq at low temperature (5–17 °C) and show that the derived values are consistent with laboratory calcite precipitation experiments at 25 °C when the latter are corrected for kinetic effects. Using these low-temperature values, and experimental data available at higher temperature based on replacement reactions, we show that all of the data can be accounted for by a single formulation based on the thermodynamics of the relevant components of seawater-like fluids and the SrCO3–CaCO3 solid solution. The value of pore fluid data is that the fluids and carbonate sediment have been in contact for millions of years so local equilibrium is approached, the overall system can be treated with one-dimensional models, and the temperature is constrained. These natural systems provide an opportunity to investigate low-temperature equilibrium in the carbonate system that is difficult to probe in the laboratory because of sluggish exchange kinetics. We estimate values of K Sr eq using measured Sr and Ca concentrations in pore fluid and sediment solid calcite and a numerical model of sediment deposition, reaction and transport. The model is used to fit the Sr, Ca, and sulfate concentrations observed in pore fluids of several calcite-dominated sites that we believe are optimal for understanding Sr partitioning. Combining the pore fluid results with experimental measurements at higher temperature results in the following expression which applies for the temperature range 0–200 °C: K S r eq T = 0.025 exp Δ G r , 0 R 1 298.15 - 1 T where ΔGr,0 is the free energy change associated with the exchange reaction and temperature is in Kelvin. The uncertainty is approximately ±20%. Recently summarized thermodynamic data yield ΔGr,0 = 1.2 kcal/mol (5.0 kJ/mol) which fits well the lower limit of the high temperature data. The corresponding activity coefficient for the SrCO3 component in the calcite crystal structure is 5.4 for the lower value of ΔGr,0, and 3.17 for the higher value. The derived low-temperature values of K Sr eq of 0.020 to 0.025 (for 0 °C to 25 °C) have implications for models of marine carbonate diagenesis, and the interpretation of vein carbonate Sr/Ca in oceanic crust. Published data showing much higher KSr values in Mg-bearing solutions are not representative of equilibrium values for either Mg or Sr.

We present results from 25 hydrothermal quartz growth experiments, all conducted at 800 °C and 1 kbar but with varying starting materials and run times, to address discrepancies between calibrations of the titanium-in-quartz (TitaniQ) thermobarometer. In our experiments, a gold capsule is loaded with silica glass, water, and either rutile or anatase as the TiO2 source. In most experiments, there is also a large quartz seed crystal contained in an open inner capsule. The use of rutile versus anatase has a significant influence on the (re)crystallization pathways of the SiO2 and TiO2 components. When rutile is used, quartz overgrowths have abundant open cavities and complex zonations. The rutile does not completely dissolve because rutile is the stable TiO2 polymorph, and yet, new rutile forms at the quartz seed-overgrowth interface and on the outer surface of quartz crystals. This suggests crystallization of quartz near Ωrut ∼ 1, but wide-ranging Ti concentrations and zonations in quartz are indicative of kinetic effects. When powdered anatase is used, the quartz overgrowths look markedly different, lacking the open cavities and instead exhibiting step edges and terraces. The Ti concentrations in quartz from these experiments are also wide-ranging but reach larger values. Our results span the range of previous calibrations and indicate that Ti concentrations in quartz are sensitive to the TiO2/SiO2 ratio of the fluid as opposed to the absolute concentration (or activity) of dissolved TiO2. We present a kinetic model for quartz and rutile growth from a fluid where the input parameters are the initial degrees of supersaturation with respect to quartz and rutile, the total reactive surface area, and rate constants that link the degree of supersaturation to net precipitation rates. The model can explain many of the salient features of our experimental results, as well as those from previous studies, but requires that the rate constant multiplied by the reactive surface area for rutile is less than that of quartz, and that rutile solubility depends on the SiO2 concentration of the fluid, as documented in the recent literature. Complete quartz-rutile equilibrium may not have been established in any of the experimental studies, but low-pressure experiments with slowly grown quartz seem to be more reliable than extrapolations from high-pressure experiments for thermobarometry of shallow natural systems.

At equilibrium, the D/H isotope fractionation factor between H2 and H2O (αH2O-H2(eq)) is a sensitive indicator of temperature, and has been used as a geothermometer for natural springs and gas discharges. However, δDH2 measured in spring waters may underestimate subsurface temperatures of origin due to partial isotopic re-equilibration during ascent and cooling. We present new experimental data on the kinetics of D–H exchange for H2 dissolved in liquid water at temperatures below 100 °C. Comparing these results with published exchange rates obtained from gas phase experiments (100–400 °C), we derive a consistent activation energy of 52 kJ/mol, and the following rate expressions; ln k = 9.186 - 6298 / T and k 1 = 9764.61 [ H 2 O ] e - 6298 / T where T is absolute temperature (K), k is the universal rate constant ([L/mol]/hr), and k1 is a pseudo-first-order constant (hr−1) applicable to water-dominated terrestrial systems by constraining [H2O] as the density of H2O (in mol/L) at the P-T of interest. The density-dependent rate constant accounts for the kinetic disparity of D–H exchange with H2 when dissolved in liquid H2O relative to a gas/steam phase, exemplifed by 1/k1 at 100 °C of ∼2 days in liquid, versus ∼7 yrs in saturated steam. This difference may explain the high variability of δDH2 observed in fumarolic gases. Fluids convecting in the crust frequently reach T > 225 °C, where isotopic equilibrium is rapidly attained (

The roughness of solid surfaces influences mineral dissolution rates by affecting flow and transport in the near-surface regions and by increasing the surface area available for reaction. The impact of surface area is commonly accounted for by using the surface roughness factor (SRF), which is the ratio between the total surface area and the nominal or geometric surface area. The coupled impacts of hydrodynamics and transport, however, are rarely considered. In this study, we performed pore-scale reactive transport simulations in a series of synthetic 2D rough fractures to investigate the compound effects of surface roughness on the reaction rates in fractures. Simulation results show that while reaction rates increase with SRF, the increase is not linearly proportional to that of the surface area. Rather, local concentration gradients resulting from flow and transport processes limit the increase in the rate. In addition, surface roughness gives rise to concentration gradients that do not otherwise develop in the flat-surface geometries typically considered in modeling studies. To describe the impacts of the surface area increase on reaction rate at different roughness and flow velocities, three distinct regimes were identified. A unified mathematical relationship was also developed that allows the reaction rate in a rough fracture to be approximated by the well-mixed reactor reaction rate and a correction factor. The correction factor follows a power-law function of SRF, with the multiplying factor and exponent expressed as exponential functions of the Peclet and Damkohler number. This mathematical formulation provides a valuable upscaling approach for effective integration of sub-grid scale surface roughness in larger scale continuum models.

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.

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.

We describe a lattice Boltzmann (LB) method for simulating water isotope fractionation during diffusion-limited ice crystal growth by vapor deposition from water-oversaturated air. These conditions apply to the growth of snow crystals in clouds where the vapor composition is controlled by the presence of both ice crystals and water droplets. Modeling of water condensation with the LB method has the advantage of allowing concentration fields to evolve based on local conditions so that the controls on grain shapes of the condensed phase can be studied simultaneously with the controls on isotopic composition and growth rate. Water isotope fractionation during snow crystal growth involves kinetic effects due to diffusion of water vapor in air, which requires careful consideration of the boundary conditions at the ice-vapor interface. The boundary condition is relatively simple for water isotopes because the molecular exchange rate for water at the interface is large compared to the crystal growth rate. Our results for the bulk crystal isotopic composition are consistent with simpler models using analytical solutions for radial geometry. However, the model results are sufficiently different for oxygen isotopes that they could affect the interpretation of D-excess values of snow and ice. The extent of vapor oversaturation plays a major role in determining the water isotope fractionation as well as the degree of dendritic growth. Departures from isotopic equilibrium increase at colder temperatures as diffusivity decreases. Dendritic crystals are isotopically heterogeneous. Isotopic variations within individual snow crystals could yield information on the microphysics of ice condensation as well as on the accommodation or sticking coefficient of water associated with vapor deposition. Our results are ultimately a first step in implementing LB models for kinetically controlled condensation or precipitation reactions, but needs to be extended also to cases where the molecular exchange rate is comparable to the crystal growth rate. This approach could also be applicable to aerosol chemical evolution.

This study demonstrates a mechanistic incorporation of the stable isotopes of sulfur within the CrunchFlow reactive transport code to model the range of microbially-mediated redox processes affecting kinetic isotope fractionation. Previous numerical models of microbially mediated sulfate reduction using Monod-type rate expressions have lacked rigorous coupling of individual sulfur isotopologue rates, with the result that they cannot accurately simulate sulfur isotope fractionation over a wide range of substrate concentrations using a constant fractionation factor. Here, we derive a modified version of the dual-Monod or Michaelis–Menten formulation ( Maggi and Riley, 2009 , Maggi and Riley, 2010 ) that successfully captures the behavior of the 32S and 34S isotopes over a broad range from high sulfate and organic carbon availability to substrate limitation using a constant fractionation factor. The new model developments are used to simulate a large-scale column study designed to replicate field scale conditions of an organic carbon (acetate) amended biostimulation experiment at the Old Rifle site in western Colorado. Results demonstrate an initial period of iron reduction that transitions to sulfate reduction, in agreement with field-scale behavior observed at the Old Rifle site. At the height of sulfate reduction, effluent sulfate concentrations decreased to 0.5 mM from an influent value of 8.8 mM over the 100 cm flow path, and thus were enriched in sulfate δ34S from 6.3‰ to 39.5‰. The reactive transport model accurately reproduced the measured enrichment in δ34S of both the reactant (sulfate) and product (sulfide) species of the reduction reaction using a single fractionation factor of 0.987 obtained independently from field-scale measurements. The model also accurately simulated the accumulation and δ34S signature of solid phase elemental sulfur over the duration of the experiment, providing a new tool to predict the isotopic signatures associated with reduced mineral pools. To our knowledge, this is the first rigorous treatment of sulfur isotope fractionation subject to Monod kinetics in a mechanistic reactive transport model that considers the isotopic spatial distribution of both dissolved and solid phase sulfur species during microbially-mediated sulfate reduction.

Here we report a combined analysis of carbon mass balance based on isotopic labeling and microbiological characterization during organic carbon stimulated bioreduction of a subsurface sediment in a large laboratory column experimental system. This combination of approaches allows quantification of both the cycling of carbon through multiple redox pathways and the associated spatial and temporal evolution of bacterial communities in response to this nutrient source. Carbon isotope mass balance facilitated by the use of 13C-labeled acetate as the electron donor showed evidence for a net loss of sediment organic carbon over the course of the amendment experiment. Furthermore, these data clearly demonstrated a source of isotopically labeled inorganic carbon that was not attributable to primary metabolism by acetate-oxidizing microorganisms. Fluid samples collected weekly over the duration of the 43-day amendment at

Oxygen isotope analyses (δ18O) of 16 quartz–epidote pairs from late Cambrian (Betts Cove and Mings Bight, Newfoundland), Ordovician (Thetford Mines, Quebec, Canada) and Cretaceous (Troodos, Cyprus) ophiolites are used to calculate the δ18O of the hydrothermal fluids from which they crystallized. We combine these with 3 quartz-fluid inclusion measurements and 3 quartz–magnetite measurements from the Cambrian ophiolites to explore how the range in the δ18O of submarine hydrothermal vent fluid has varied between the late Cambrian, Cretaceous and today. The range of calculated δ18O values of vent fluid (−4 to +7.4) is larger than that of modern seafloor hydrothermal vent fluid (0 to +4). We employ two numerical models to ascertain whether this range is most consistent with changes in paleo-seawater δ18O or with changes in the reactive flow path in ancient hydrothermal systems. A static calculation of the vent fluid oxygen isotope composition as a function of the water–rock ratio suggests that in an ocean with a lower δ18O than today, the range of vent fluid δ18O should be larger. Our data, however, show little evidence that the δ18O of the ocean was much lower than the global ice-free value of −1.2. A dual porosity model for reactive flow through fractured and porous media is used to model the relative evolution of the 87Sr/86Sr and δ18O of vent fluid in contact with rock. Our 87Sr/86Sr and δ18O for Cretaceous epidotes suggest the strontium concentration of the Cretaceous oceans may have been much higher than at present. The 87Sr/86Sr and δ18O data from Cambrian epidotes are strikingly different from the younger samples, and are difficult to model unless fluid-rock interaction in the Cambrian hydrothermal systems was substantially different. It is also possible that some of the quartz–epidote veins have been reset by obduction-related metamorphism. Our data suggest that the high calcium-to-sulfate ratio in early (and Cretaceous) seawater may have affected the degree of strontium isotope exchange, causing hydrothermal fluids to have 87Sr/86Sr closer to that of seawater than in modern systems.

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.

Precipitation of calcium carbonate minerals from aqueous solutions causes surface-controlled kinetic stable Ca isotope fractionation. The magnitude of fractionation depends on the relative rates of ion attachment to and detachment from the mineral surface, which in turn is predicted to depend on both the saturation state and the solution stoichiometry or the Ca 2 + : CO 3 2 - activity ratio. Experimental studies have not directly investigated the effects of varying solution stoichiometry on calcium isotope partitioning during calcite or aragonite growth, but natural alkaline lake systems such as Mono Lake, California provide a test bed for the hypothesized stoichiometry dependence. Mono Lake has a Ca 2 + : CO 3 2 - activity ratio of about 0.0001, seven orders of magnitude lower than ocean water and typical terrestrial freshwater. We present chemical and isotopic measurements of streams, springs, lake water, and precipitated carbonates from the Mono Basin that yield evidence of stoichiometry-dependent Ca isotope fractionation during calcite, aragonite and Mg-calcite precipitation from the alkaline lake water. To estimate the Ca isotope fractionation factors, it is necessary to characterize the lake Ca balance and constrain the variability of lake water chemistry both spatially and temporally. Streams and springs supply Ca to the lake, and a substantial fraction of this supply is precipitated along the lake shore to form tufa towers. Lake water is significantly supersaturated with respect to carbonate minerals, so CaCO3 also precipitates directly from the water column to form carbonate-rich bottom sediments. Growth rate inhibition by orthophosphate likely preserves the high degree of supersaturation in the lake. Strontium isotope ratios are used to estimate the proportions of fresh and alkaline lake water from which each solid carbonate sample precipitated. Carbonate minerals that precipitate directly from lake water (low Ca 2 + : CO 3 2 - ) experience relatively large Ca isotope fractionation during growth. Tufa and shoreline carbonates that precipitate from lake water with a significant fraction of spring water (higher Ca 2 + : CO 3 2 - ) are considerably less fractionated, as predicted from theory. The behavior of the Mono Lake Ca isotope system is similar in some ways to that of the global oceans, in that the average δ44/40Ca of lake water is positive (estimated average of +1) and both riverine inputs and precipitated carbonates are isotopically light (δ44/40Ca between −0.5 and 0). We present a calcium isotope budget of the lake to constrain the long-term average lake water Ca isotope composition. Archived water samples indicate that the lake δ44/40Ca varied by over 2‰ between 1995 and 2010. The most extreme excursions are toward higher δ44/40Ca, and are probably caused by carbonate precipitation events induced by breakdown of chemostratification. This variability indicates that the lake is out of steady state with respect to calcium isotopes, and that unlike the ocean, calcium isotopes in Mono Basin carbonate sediments likely do not record the balance between weathering and carbonate mineralization fluxes to and from the lake.

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

The concentrations of Sr, Mg and other elements in calcite are widely used to infer the conditions of mineral growth. However, such inferences are dependent on the mechanisms that govern the incorporation of minor constituents into the calcite lattice during growth. A particularly confusing observation is that both Sr and Mg are readily incorporated into growing calcite crystals at low concentrations but inhibit calcite growth at higher concentrations. Here we show that the growth rate dependence of Sr and Mg incorporation into calcite, as well the inhibitory effects on calcite growth of both incorporating and non-incorporating ions, can be predicted with an ion-by-ion crystal growth model where ion attachment is confined to kink sites on the crystal surface. The exchange of ions between active growth (kink) sites on the mineral surface and aqueous solution governs both the efficiency of incorporation of minor constituents and the kinetics of mineral precipitation. Ions such as Sr and Mg in calcite, that are not stoichiometric constituents, may attach to kink sites and impede crystal growth by either blocking propagation of the kink (kink blocking), or if incorporated into the growing mineral, straining the local crystal lattice, and hence increasing the mineral solubility (incorporation inhibition). Here we investigate the effects of including these growth inhibition mechanisms into a microscopic model for crystal growth based on kink creation, propagation and collision (CPC) theory. This model predicts that kink blocking by either incorporated or non-incorporated ions causes an exponential decrease in mineral growth rate with increasing impurity concentration, while incorporation inhibition results in more complicated functional forms of the growth rate effect depending on the thermodynamics of the solid solution. Applying this model to existing data on the partitioning of strontium and magnesium into calcite and the simultaneous effects on growth kinetics and mineral composition, we find that strontium uptake inhibits growth by enhancing mineral solubility while magnesium inhibits growth primarily by kink blocking. Our model should be widely applicable to understanding the impurity content of a large range of sparingly soluble minerals that form by precipitation from aqueous solutions.

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.

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

Late Quaternary, post-shield lavas from the Mauna Kea and Kohala volcanoes on the Big Island of Hawaii have been dated using the {sup 40}Ar/{sup 39}Ar and U-Th/He methods. The objective of the study is to compare the recently demonstrated U-Th/He age method, which uses basaltic olivine phenocrysts, with {sup 40}Ar/{sup 39}Ar ages measured on groundmass from the same samples. As a corollary, the age data also increase the precision of the chronology of volcanism on the Big Island. For the U-Th/He ages, U, Th and He concentrations and isotopes were measured to account for U-series disequilibrium and initial He. Single analyses U-Th/He ages for Hamakua lavas from Mauna Kea are 87 {+-} 40 ka to 119 {+-} 23 ka (2{sigma} uncertainties), which are in general equal to or younger than {sup 40}Ar/{sup 39}Ar ages. Basalt from the Polulu sequence on Kohala gives a U-Th/He age of 354 {+-} 54 ka and a {sup 40}Ar/{sup 39}Ar age of 450 {+-} 40 ka. All of the U-Th/He ages, and all but one spurious {sup 40}Ar/{sup 39}Ar ages conform to the previously proposed stratigraphy and published {sup 14}C and K-Ar ages. The ages also compare favorably to U-Th whole rock-olivine ages calculated from {sup 238}U - {sup 230}Th disequilibria. The U-Th/He and {sup 40}Ar/{sup 39}Ar results agree best where there is a relatively large amount of radiogenic {sup 40}Ar (>10%), and where the {sup 40}Ar/{sup 36}Ar intercept calculated from the Ar isochron diagram is close to the atmospheric value. In two cases, it is not clear why U-Th/He and {sup 40}Ar/{sup 39}Ar ages do not agree within uncertainty. U-Th/He and {sup 40}Ar/{sup 39}Ar results diverge the most on a low-K transitional tholeiitic basalt with abundant olivine. For the most alkalic basalts with negligible olivine phenocrysts, U-Th/He ages were unattainable while {sup 40}Ar/{sup 39}Ar results provide good precision even on ages as low as 19 {+-} 4 ka. Hence, the strengths and weaknesses of the U-Th/He and {sup 40}Ar/{sup 39}Ar methods are complimentary for basalts with ages of order 100-500 ka.

Liquid phase diffusion experiments were carried out to determine whether diffusive isotopic fractionation of a major chemical element (Ca) varies with chemical composition in high-temperature molten silicates. The objective was to determine how differences in silicate liquid structure, such as the ratio of bridging to non-bridging oxygen atoms, as well as bulk transport properties such as viscosity, relate to isotope discrimination during diffusion. This information, in turn, may relate to the lifetimes and sizes of multi-atom structures in the liquid. Diffusion couples consisting of juxtaposed natural mafic and felsic liquids were held at T = 1450 C and P = 1.0 GPa for durations of 12–24 h in a standard piston–cylinder assembly. Experiments were done using different mafic endmember compositions (two tholeiitic basalts and a ugandite) and a single rhyolite composition. Major-element diffusion profiles and Ca isotope profiles were measured on the recovered quenched glasses. The starting materials were isotopically indistinguishable, but 44 Ca/ 40 Ca variations of ca. 5& arose due to a mass dependence of the Ca diffusion coefficients. Results indicate that the mass dependence of Ca diffusion coefficients varies with the magnitude and direction of aluminum gradients and the viscosity of the liquid. Some Ca fractionations result mainly from Al gradients. A simplified multicomponent diffusion model was used to model the experimental results. The model allows for diffusion of Ca in response to gradients in the concentrations of both CaO as well as Al2O3, and the model results are consistent with the inferred existence of at least two distinct species of Ca. The magnitude of isotopic discrimination during diffusion also appears to be stronger on the rhyolite versus the basalt/ugandite side of diffusion couples. The results can largely be accounted for by an adaptation of the model of Dingwell (1990), whereby in high silica liquids, Ca diffuses largely by site hopping through a quasi-stationary aluminosilicate matrix, producing strong isotopic effects because the Ca diffusion is not strongly correlated with the movement of the framework atoms. In low-silica liquids, Ca diffusion is correlated with the movement of the other components and there is less mass discrimination. Combining our Ca results with Ca, Mg, and Li data from previous studies, we show that this model can explain most of the cation- and composition-dependence of diffusive isotopic fractionations observed thus far. A key parameter controlling isotopic discrimination is the ratio of the elemental (Ca, Mg, Li) diffusivity to the Eyring (or Si) diffusivity. However, all experiments done so far also exhibit isotopic features that are not yet fully explained; some of these may relate to small temperature gradients in the capsules, or to more complex coupling effects that are not captured in simplified diffusion models. Published by Elsevier Ltd.

The lunar meteorite Northwest Africa (NWA) 032 is a low-Ti basalt that has incompatible-element abundances and Th/Sm ratios characteristic of the involvement of late stage magma ocean crystallization products (urKREEP) in its petrogenesis. This sample is very fine-grained and contains terrestrial weather products. A progressive leaching procedure was therefore developed and applied to magnetic separates and whole rock fractions to obtain Rb–Sr and Sm–Nd ages. Although many of the leachates, as well as the unleached mineral and whole rock fractions contain terrestrial alteration products, selected residue fractions yield concordant Rb–Sr and Sm–Nd ages. Rubidium–Sr isotopic analyses yield an age of 2947 ± 16 Ma with an initial 87 Sr/ 86 Sr of 0.700057 ± 17. These characteristics indicate NWA 032 is derived from a source region with an 87 Rb/ 86 Sr ratio of 0.044 ± 0.001. This value is higher than all but those determined for KREEP basalts, and suggests that NWA 032 is derived from a source region that has higher incompatible-element abundances than other low-Ti basalts. Samarium–neodymium isotopic analysis yield a concordant age of 2931 ± 92 Ma and an initial e Nd of +9.71 ± 0.74 corresponding to a source region with 147 Sm/ 144 Nd ratio of 0.246 ± 0.004. The initial Nd isotopic composition stands in contrast to the initial Sr isotopic composition by requiring NWA 032 to be derived from a source with lower incompatible-element abundances than most low-Ti basalts. The source of NWA 032 is therefore unlike those of other lunar basalts. Modeling of magma ocean cumulate formation demonstrates that unlike other low-Ti basalt source regions the NWA 032 source is a mixture of olivine, pigeonite, and clinopyroxene bearing cumulates and only a small amount of urKREEP. Furthermore, unlike other mare basalt sources, the NWA 032 source does not contain appreciable quantities of plagioclase. Partial melting models demonstrate that the incompatible-element characteristics of the NWA 032 result from formation by smaller degrees of partial melting than other mare basalts. Thus, the incompatible-element geochemical signature that is observed in NWA 032 appears to reflect the combined effects of generation from an unusual plagioclase-free incompatible-element-depleted source region by very small degrees of partial melting. This study demonstrates that both the presence of urKREEP in the source region and small degrees of partial melting generate magmas with similar, but not identical, incompatible-element characteristics. In addition, it underscores the fact that there is significantly more geochemical diversity on the Moon than is represented by samples collected by the American and Soviet lunar missions.

We measured Ca stable isotope ratios (δ 44/40 Ca) in an ancient (2 My), hyperarid soil where the primary source of mobile Ca is atmospheric deposition. Most of the Ca in the upper meter of this soil (3.5 kmol m −2 ) is present as sulfates (2.5 kmol m −2 ), and to a lesser extent carbonates (0.4 kmol m −2 ). In aqueous extracts of variably hydrated calcium sulfate minerals, δ 44/40 Ca E values (vs. bulk Earth) increase with depth (1.4 m) from a minimum of −1.91‰ to a maximum of +0.59‰. The trend in carbonate-δ 44/40 Ca in the top six horizons resembles that of sulfate-δ 44/40 Ca, but with values 0.1–0.6‰ higher. The range of observed Ca isotope values in this soil is about half that of δ 44/40 Ca values observed on Earth. Linear correlation among δ 44/40 Ca, δ 34 S and δ 18 O values indicates either (a) a simultaneous change in atmospheric input values for all three elements over time, or (b) isotopic fractionation of all three elements during downward transport. We present evidence that the latter is the primary cause of the isotopic variation that we observe. Sulfate-δ 34 S values are positively correlated with sulfate-δ 18 O values ( R 2 = 0.78) and negatively correlated with sulfate δ 44/40 Ca E values ( R 2 = 0.70). If constant fractionation and conservation of mass with downward transport are assumed, these relationships indicate a δ 44/40 Ca fractionation factor of −0.4‰ in CaSO 4 . The overall depth trend in Ca isotopes is reproduced by a model of isotopic fractionation during downward Ca transport that considers small and infrequent but regularly recurring rainfall events. Near surface low Ca isotope values are reproduced by a Rayleigh model derived from measured Ca concentrations and the Ca fractionation factor predicted by the relationship with S isotopes. This indicates that the primary mechanism of stable isotope fractionation in CaSO 4 is incremental and effectively irreversible removal of an isotopically enriched dissolved phase by downward transport during small rainfall events.

The calcium isotopic compositions (δ44Ca) of 30 high-purity nannofossil ooze and chalk and 7 pore fluid samples from ODP Site 807A (Ontong Java Plateau) are used in conjunction with numerical models to determine the equilibrium calcium isotope fractionation factor (αs−f) between calcite and dissolved Ca2+ and the rates of post-depositional recrystallization in deep sea carbonate ooze. The value of αs−f at equilibrium in the marine sedimentary section is 1.0000 ± 0.0001, which is significantly different from the value (0.9987 ± 0.0002) found in laboratory experiments of calcite precipitation and in the formation of biogenic calcite in the surface ocean. We hypothesize that this fractionation factor is relevant to calcite precipitation in any system at equilibrium and that this equilibrium fractionation factor has implications for the mechanisms responsible for Ca isotope fractionation during calcite precipitation. We describe a steady state model that offers a unified framework for explaining Ca isotope fractionation across the observed precipitation rate range of ∼14 orders of magnitude. The model attributes Ca isotope fractionation to the relative balance between the attachment and detachment fluxes at the calcite crystal surface. This model represents our hypothesis for the mechanism responsible for isotope fractionation during calcite precipitation. The Ca isotope data provide evidence that the bulk rate of calcite recrystallization in freshly-deposited carbonate ooze is 30–40%/Myr, and decreases with age to about 2%/Myr in 2–3 million year old sediment. The recrystallization rates determined from Ca isotopes for Pleistocene sediments are higher than those previously inferred from pore fluid Sr concentration and are consistent with rates derived for Late Pleistocene siliciclastic sediments using uranium isotopes. Combining our results for the equilibrium fractionation factor and recrystallization rates, we evaluate the effect of diagenesis on the Ca isotopic composition of marine carbonates at Site 807A. Since calcite precipitation rates in the sedimentary column are many orders of magnitude slower than laboratory experiments and the pore fluids are only slightly oversaturated with respect to calcite, the isotopic composition of diagenetic calcite is likely to reflect equilibrium precipitation. Accordingly, diagenesis produces a maximum shift in δ44Ca of +0.15‰ for Site 807A sediments but will have a larger impact where sedimentation rates are low, seawater circulates through the sediment pile, or there are prolonged depositional hiatuses.

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.

The Pb isotopic compositions of phenocrystic phases in young basaltic lavas have been investigated using the Getty-DePaolo method (Getty S. J. and DePaolo D. J. [1995] Quaternary geochronology by the U-Th-Pb method. Geochim. Cosmochim. Acta 59, 3267 3272), which allows for the resolution of small isotopic differences. Phenocryst, matrix, and whole rock analyses were made on samples from the 17 Myr-old Imnaha basalts of the Columbia River Group, a zero-age MORB from the Mid-Atlantic Ridge, and a ca. 260 kyr-old tholeiite from Mount Etna. Plagioclase feldspar phenocrysts have low-(U, Th)/Pb, and in each sample the plagioclase has significantly lower 206Pb/207Pb and 208Pb/207Pb values than whole rock, matrix, and magnetite-rich separates. The Pb isotopic contrast between plagioclase and matrix/whole rock is found in three samples with varying grain sizes (0.5 2 cm for the Imnaha basalt and MORB and

The abundances of 18 O and deuterium in the present and past hydrologic cycle have proven to be an important tool in Earth systems science. In contrast, the abundance of 17 O in precipitation has thus far been assumed to carry no additional information to that of 18 O. Here, we demonstrate, using known constraints on oxygen isotope abundances from the O 2 cycle and existing data about the natural abundance of 17 O in water, that the relationship between the discrimination against 17 O and 18 O in water may vary. This relationship, presented here as θ = ln ( 17 α)/ln ( 18 α), is found to be 0.511 ± 0.005 for kinetic transport effects and 0.526 ± 0.001 for equilibrium effects, with very low temperature sensitivity. As a result, the 17 Δ of precipitation is controlled primarily by kinetic effects during evaporation of the initial vapor and, in contrast to the deuterium excess, is independent of the temperature at the evaporation (and condensation) site. This makes 17 Δ a unique tracer that complements 18 O and deuterium, and may allow for a decoupling of changes in the temperature of the ocean, that serves as the vapor source, from changes in the relative humidity above it. In addition, the 17 Δ of ice caps is influenced by the kinetic effects in ice formation, and therefore measurement of ice 17 Δ can be used as an additional constraint for better understanding and parameterization of these effects.

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.

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.

Measurements of 238U-230Th-226Ra and 235U-231Pa disequilibria in a suite of tholeiitic-to-basanitic lavas provide estimates of porosity, solid mantle upwelling rate and melt transport times beneath Hawaii. The observation that (230Th/238U) > 1 indicates that garnet is required as a residual phase in the magma sources for all of the lavas. Both chromatographic porous flow and dynamic melting of a garnet peridotite source can adequately explain the combined U-Th-Ra and U-Pa data for these Hawaiian basalts. For chromatographic porous flow, the calculated maximum porosity in the melting zone ranges from 0.3–3% for tholeiites and 0.1–1% for alkali basalts and basanites, and solid mantle upwelling rates range from 40 to 100 cm yr−1 for tholeiites and from 1 to 3 cm yr−1 for basanites. For dynamic melting, the escape or threshold porosity is 0.5–2% for tholeiites and 0.1–0.8% for alkali basalts and basanites, and solid mantle upwelling rates range from 10 to 30 cm yr−1 for tholeiites and from 0.1 to 1 cm yr−1 for basanites. Assuming a constant melt productivity, calculated total melt fractions range from 15% for the tholeiitic basalts to 3% for alkali basalts and basanites.

The isotopic compositions of He, Sr, and Nd were measured in Tertiary-age basalts from the Basin and Range province of the western USA to evaluate models for the He isotopic character of subcontinental mantle lithosphere (SCML) and assess the role of recycled SCML in models of mantle evolution. Previous isotopic and trace element measurements suggested that most of these basalts were formed by melting of SCML. 3 He/ 4 He ratios, measured by in-vacuo crushing of olivine phenocrysts, vary from 2.9 to 7.8 times the atmospheric value (2.9 to 7.8 Ra) consistently below the MORB value of 8.7 ± 0.5 Ra. The lowest R/Ra values, associated with low e Nd , high 87 Sr/ 86 Sr, and high La/Nb, are attributable to lithospheric mantle, and indicate that SCML is not dominated by MORB-type He, nor by high R/Ra, plume-type He. Consideration of geographic variability indicates there are two, and possibly three, distinct regions of SCML with differing He isotopic characteristics. SCML beneath the eastern Sierra Nevada is inferred to have 3 He/ 4 He of ∼5.5 Ra and a He/Nd ratio slightly less than MORB-type mantle; SCML beneath the central Basin and Range has 3 He/ 4 He of ∼4 Ra and a higher He/Nd ratio than MORB-type mantle. The SCML under southwestern Utah shows less systematic correlation of He isotopes with other geochemical parameters, but also has a lower bound R/Ra value of about 4 Ra. The inferred SCML helium ratios are consistent with retention of radiogenic 4 He over 800 Ma for the eastern Sierra Nevada and 1700 Ma for the other two regions. The results are not consistent with models of He infiltration from the underlying asthenosphere and suggest the lithosphere of the Basin and Range region was not delaminated during the early Tertiary. The He, Sr, Nd, and Pb isotopic compositions inferred for the SCML of the southwestern USA are a reasonably good match to the characteristics of the EMII component of mantle heterogeneity identified in oceanic island basalts. High R/Ra mantle reservoirs identified in these basalts are not likely to represent recycled SCML.

It has been proposed that trace-element concentration ratios of basalts can be used like isotopic ratios to map the trace-element characteristics of mantle magma sources. We evaluate the assumptions and requirements of this approach and show that the magma source trace-element values inferred from data on basalts are dependent on the petrogenetic model assumed for the basalt. An approach to the analysis of incompatible element concentration ratio data is illustrated that uses the basalt data to obtain internally consistent fractionation models that take into account partial melting effects. The approach is applied to data on Ce/Pb and Nb/U in ocean island basalts (OIBs). Analysis of the basalt data in the literature provides evidence of substantial Ce/Pb fractionation during petrogenesis and a lesser amount of Nb/U fractionation. The estimated source compositions for OIBs in general are found to be consistent with their formation by admixture of (recycled) continental crustal material to the mantle, contrary to conclusions drawn previously from a less detailed analysis of the same data. We find that there are also correlations between trace-element composition and isotopic ratios that are consistent with continental crustal admixing. Other models for the magma source evolution may also be consistent with the data, but proper analysis requires specification of the petrogenetic parameters and consideration of the trace-element properties of the magma sources rather than the lavas. Large uncertainties in petrogenetic models translate to large uncertainties in source composition and weak constraints on the origins of the magma sources. Our analysis leads to estimates of the bulk partition coefficient for Pb (DPb); during mantle partial melting of spinel lherzolite source (DCe = 0.015), we calculate a DPb value of 0.035 ± 0.009 (1σ) and a value of 0.028 ± 0.009 (1σ) for partial melting of a garnet lherzolite source (DCe = 0.009). These values indicate that Pb is more compatible during mid-ocean ridge basalt (MORB) and OIB petrogenesis than previously thought from experimental studies of silicate crystal/melt distribution coefficients, suggesting possibly, that sulfide, present as either a residual mantle phase or as a shallow fractionating phase, strongly influences the partitioning of Pb.

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 describe a method of uranium-thorium-lead (UThPb) isotopic age dating for Quaternary rocks. The approach uses an instrumental mass discrimination correction for lead isotope ratios, which allows small enrichments of radiogenic 206Ph and 208Ph to be detected at the level of 0.001%. Igneous rocks hosting minerals with a range in 238 U 204 Pb values of 100 can be dated with uncertainties of approximately ±15–20 kyr. A Quaternary rhyolite dated at 1.19 Ma by KAr yields a 238U206Ph age of 1.03 ± 0.10 Ma. A Holocene dacite (9.5 ka) has uniform 206 Pb 207 Pb to within 0.0015% in groundmass phases, but 1 mm plagioclase phenocrysts have lower 206 Pb 207 Pb by 0.105 ± 0.002% indicating contamination of the magma after plagioclase crystallization. High precision 206 Pb 207 Ph ratios may be a useful new tool for petrogenetic studies.

A numerical model which describes oxygen isotope exchange during burial and recrystallization of deep-sea carbonate is used to obtain information on how sea surface temperatures have varied in the past by correcting measured δ18O values of bulk carbonate for diagenetic overprinting. Comparison of bulk carbonate and planktonic foraminiferal δ18O records from ODP site 677A indicates that the oxygen isotopic composition of bulk carbonate does reflect changes in sea surface temperature and δ18O. At ODP Site 690, we calculate that diagenetic effects are small, and that both bulk carbonate and planktonic foraminiferal δ18O records accurately reflect Paleogene warming of high latitude surface oceans, biased from diagenesis by no more than 1°C. The same is likely to be true for other high latitude sites where sedimentation rates are low. At DSDP sites 516 and 525, the effects of diagenesis are more significant. Measured δ18O values of Eocene bulk carbonates are more than 2% lower at deeply buried site 516 than at site 525, consistent with the model prediction that the effects of diagenesis should be proportional to sedimentation rate. Model-corrections reconcile the differences in the data between the two sites; the resulting paleotemperature reconstruction indicates a 4°C cooling of mid-latitude surface oceans since the Eocene. At low latitudes, the contrast in temperature between the ocean surface and bottom makes the carbonate δ180 values particularly sensitive to diagenetic effects; most of the observed variations in measured δ18O values are accounted for by diagenetic effects rather than by sea surface temperature variations. We show that the data are consistent with constant equatorial sea surface temperatures through most of the Cenozoic, with the possible exception of the early Eocene, when slightly higher temperatures are indicated. We suggest that the lower equatorial sea surface temperatures for the Eocene and Oligocene reported in other oxygen isotope studies are artifacts of diagenetic recrystallization, and that it is impossible to reconstruct accurately equatorial sea surface temperatures without explicitly accounting for diagenetic overprinting.

The Hawaii Scientific Drilling Project (HSDP) sampled a 3 km section of basalt lava from the Mauna Kea volcano, covering ages of 200–600 ka. When combined with surface and dredge samples, there is a 600 ky record of the lava output from Mauna Kea as well as a 200 ky record from Mauna Loa. The isotopic stratigraphy of the core samples (Gcubed Theme) reflects the geochemical structure of the Hawaiian plume, given a model for the sampling of the plume by melting and melt transport (Bryce et al., 2005). The data show that there is radial geochemical zoning of the plume in terms of He, Pb, Nd, Sr and Hf isotopes. Data from other volcanoes indicate there is also heterogeneity along the axis of the plume, as well as asymmetry (Loa-Kea dichotomy). To first order, the radial geochemical structure of the plume represents the vertical structure at the thermal boundary layer from which the plume originates. Numerical models of plumes show that this vertical structure, which corresponds to potential temperature, is likely to be preserved during passage of the plume through the mantle. In the case of Hawaii, all of the lavas are derived from melting of mantle that originates from within 20–50 km of the base of the mantle, so the inferred radial geochemical structure maps to stratigraphy at the base of the mantle. HSDP data indicate that the high He/He anomaly (R/ Ra > 16) is restricted to the innermost core of the plume and is much larger in amplitude and smaller in diameter than the Nd, Sr or Hf anomalies. The He-3 anomaly must have an origin different from that of other isotopes; the anomalous mantle is restricted to the lowermost 10–20 km of the plume source. This observation accords with along-ridge variations of Nd, Sr, and He near Iceland. The HSDP data are consistent with two models for the configuration of the plume source. If the plume originates from the top of a dense layer separating the main mantle from the outer core, then the high-He signal must be attributed to the dense layer and distinguishes it from the main lower mantle. The dense layer is not significantly different from the rest of the lower mantle in terms of Nd, Sr, or Hf isotopes. If the plume originates directly from the CMB, then probably the He signal comes from the core. Models for core formation can accommodate this possibility. The dense layer may have distinctive He because it receives He from the outer core, or because it has retained primordial He. Hawaii and Iceland data imply that the lower mantle also has large regions with elevated He/He, but these typically have R/Ra 6 16.

The K-Ca radioactive parent-daughter system provides a tool for tracing the origins of igneous rocks. It is complementary to other isotopic systems because as stoichiometric constituents of major minerals, the concentrations of K and Ca, and the K/Ca ratio in rocks, are simply related to mineralogy. In this paper we report the first high-precision calcium isotopic analyses of continental granitic rocks, island arc rocks, and mid-ocean ridge basalts. These data show that mid-ocean ridge basalts have the low 40 Ca 42 Ca ratios expected for the Earth's mantle, but that island arc rocks have slightly higher 40 Ca 42 Ca ratios indicative of crustal calcium in their magma sources. Many granitic rocks have high initial 40 Ca 42 Ca ratios, and in conjunction with independent evidence for the age of the crustal sources, these ratios provide constraints on the K/Ca ratios, and in turn on the silica contents and residual mineralogy, of the deep crustal magma sources.

High precision mass spectrometric determination of calcium isotope ratios allows the 40K → 40Ca radioactive decay to be used for dating a much broader range of geologic materials than is suggested by previous work. 40Ca42Ca is used to monitor enrichments in 40Ca and can be measured to ±0.01% (2σ) using an exponential mass discrimination correction (Russell et al., 1978) and large ion currents. The earth's mantle has such a low KCa (∼0.01) that it has retained “primordial” 40Ca42Ca = 151.016 ± 0.011 (normalized to 42Ca44Ca = 0.31221), as determined by measurements on two meteorites, pyroxene from an ultramafic nodule, metabasalt, and carbonatite. 40Ca42Ca ratios can be conveniently expressed relative to this value as ϵCa in units of 10−4. To test the method for age dating, a mineral isochron has been obtained on a sample of Pikes Peak granite, which has been shown to have concordant KAr, RbSr, and UPb ages. Plagioclase, K-feldspar, biotite, and whole rock yield an age of 1041 ± 32 m.y. (2σ) in agreement with previous age determinations (λK = 0.5543 b.y.−1, λβ−λK = 0.8952, 40K = 0.01167%). The initial 40Ca42Ca of 151.024 ± 0.016 (ϵCa = +0.5 ± 1.0), indicates that assimilation of high K/Ca crust was insufficient to affect calcium isotopes. Measurements on two-mica granite from eastern Nevada indicate that the magma sources had K/Ca ≈ 1, similar to intermediate-composition crustal rocks. These results show that the KCa system can be used as a precise geochromometer for common felsic igneous and metamorphic rocks, and may prove applicable to sedimentary rocks containing authigenic K minerals. The relatively short half-life of 40K, the non-volatile daughter, and the fact that potassium and calcium are stoichiometric constituents of many minerals, make the KCa system complementary to other dating methods, and potentially applicable to a variety of geologic problems.

An internal isochron determined for a gabbro from the Stillwater complex by the Sm-Nd method yields a precise age of 2701 ± 8 Myr and initial ^(143)Nd/^(144)Nd = 0.508248 ± 12. The initial is close to the CHUR evolution curve but clearly displaced below it by ϵ_(Nd) = −2.8 ± 0.2. A spectrum of total rocks in the Stillwater complex ranging from anorthosite to pyroxenite were found to lie on the same isochron to within experimental error indicating the same age and initial. These data demonstrate that some ancient mantle-derived rocks have initial ^(143)Nd/^(144)Nd which deviate substantially from the CHUR evolution curve at the time of their formation. This implies that there was early layering in the mantle with substantial REE fractionation (~6–12% Nd/Sm enrichment) or that the Stillwater complex was highly contaminated with REE from much older continental crust during emplacement. The results show the necessity of high-precision ages and initial ^(143)Nd/^(144)Nd values in order to properly describe REE fractionation in the mantle. While the Sm-Nd age results show no indication of any irregularities, we have confirmed that the Rb-Sr data for the Stillwater are highly disturbed. This comparison indicates that the Sm-Nd parent-daughter system may be much less susceptible to element redistribution during metamorphism, therefore permitting wide application of this technique to rocks of complex histories.