Equilibrium Isotope Fractionation Research Articles

Evidence from Ab Initio and Transport Modeling for Diffusion-Driven Zirconium Isotopic Fractionation in Igneous Rocks

We use density functional theory to calculate the equilibrium isotopic fractionation factors of zirconium (Zr) in a variety of minerals including zircon, baddeleyite, Ca-catapleiite, ilmenite, geik...

Calibration of carbonate-water triple oxygen isotope fractionation: Seeing through diagenesis in ancient carbonates

High precision triple oxygen isotope measurements of carbonates can better constrain temperatures and oxygen isotope compositions of seawater through geologic time than 18O/16O measurements alone, but lack of a definitive calibration has hindered progress. In this study, we fluorinated both carbonate and water samples to measure quantitatively the triple oxygen isotope composition of each phase. We compared the oxygen isotope fractionation between carbonate and water for different carbonate materials: calcite synthesized with and without carbonic anhydrase, abiogenic calcite from Devils Hole, and extant biogenic calcite and aragonite of marine origin. We found similar 1000lnα18Occ-wt values for all materials and combined the results with the high temperature experimental data of O'Neil et al. (1969), resulting in the following fractionation equation (T in Kelvins) 1000lnα18Occ-wt=2.84(±0.02)×106T2-2.96(±0.19). The calcite triple oxygen isotope values yielded a θ-T relationship of θcc-wt = –1.39(±0.01)/T + 0.5305 whereas the aragonite triple oxygen isotope values yielded a θ-T relationship of θara-wt = –1.53(±0.02)/T + 0.5305. The calcite-water triple oxygen isotope equilibrium fractionation equation for natural samples is Δ17′Occ-Δ17′Owt=2.84(±0.02)×106T2-2.96(±0.19)-1.39(±0.01)T+0.5305-λ. The combined 1000lnα18O and 1000lnα17O relationships can be used to assess equilibrium in ancient samples and to evaluate potential secular changes in the δ18O value of seawater. Most of the Phanerozoic samples analyzed in this study, which were determined to be pristine in previous studies, have undergone some level of diagenesis. Two samples appear to preserve their original oxygen isotope compositions and suggest a cool ocean with a δ18O value similar to the modern ocean. Using a fluid-rock interaction model, we can “see through” the diagenetic process and estimate the triple oxygen isotope composition of the carbonate prior to alteration. In doing so, we show that for the time intervals and sample locations measured in this study, Phanerozoic oceans had a comparable range of oxygen isotope compositions and temperatures as modern seawater.

Constraining speleothem oxygen isotope disequilibrium driven by rapid CO2 degassing and calcite precipitation: Insights from monitoring and modeling

Oxygen isotopes are the most commonly applied speleothem proxy for reconstructing Quaternary changes in precipitation and/or temperature. These interpretations are either limited to qualitative wetting and drying trends or rely on theoretical, experimental and/or empirical equilibrium isotope fractionation factors for more quantitative constraints. These various fractionation factors have similar temperature sensitivities, but their absolute values differ, and cave calcite does not appear to generally precipitate in isotopic equilibrium with its drip water. Rapid CO2 degassing paired with calcite precipitation, both occurring under disequilibrium conditions, are a set of mechanisms commonly invoked to explain offsets between observed and equilibrium isotopic fractionation between cave calcites and drip waters. However, the relevance of these disequilibrium mechanisms to speleothem records remains unresolved. Here, we compare measured δ18O values of modern speleothem calcite from a tropical cave in Guam to calcite δ18O values predicted by a modified version of the ISOLUTION proxy system model. This extends the global comparison of cave drip water and modern calcite δ18O values to higher temperatures. We initialize the model using contemporaneous measurements of drip water (δ18O values, [Ca+], and pH), and cave air (CO2, and T) from four drip sites over 3.5 years of monitoring in the cave. Through this comparison, we show that for a slow drip-rate site, ventilation-driven CO2 degassing can explain seasonal variations in calcite oxygen isotope composition. At faster-dripping sites in this cave, the seasonal effect is limited. At these sites, the DIC reservoir is replenished by new drips faster than its isotopic composition can be modified by degassing CO2 and calcite precipitation, whether occurring each is occurring as an equilibrium or kinetic process. For the slow drip rate site, however, this is the first observation of cave air CO2 variations exerting a control on cave calcite oxygen isotope values. The confirmation of ventilation-driven processes controlling oxygen isotope values at a slow-drip site advances the process-based understanding of stalagmite formation that is required to move beyond the wetter-or-drier paradigm and make quantitative interpretations of speleothem oxygen isotope records.

Experimental constraints on magnesium isotope fractionation during abiogenic calcite precipitation at room temperature

Magnesium (Mg) isotopes in carbonate minerals are a useful proxy for paleoclimate studies, but interpretations are often limited by an inadequate understanding of the various factors controlling Mg isotopic fractionation during carbonate formation. Previous work has studied a number of parameters including aqueous chemistry, mineralogy, temperature, and precipitation rate. However, little is known about the impact of solid/solution ratio, calcite growth mechanism, and crystal morphology on isotope fractionation. In this work, two groups of seeded chemo-stat calcite precipitation experiments were conducted at 25 °C to explore the potential impact of crystal growth and morphology on the fractionation of Mg isotopes. Group-1 experiments (G1) contained nine individual runs that were performed under identical physicochemical conditions, except for solid/solution ratio and the length of an experiment. The isotope fractionation between precipitated calcite and aqueous solution is limited, with Δ26Mgcal-sol ranging from −2.58 to −2.40‰ and an average of −2.49 ± 0.12‰ (2SD, n = 9). The Group-2 experiments (G2) contained 3 paired runs with solution Mg/Ca molar ratios of 0.5, 2.0, and 5.0, and yielded Δ26Mgcal-sol values that ranged from −2.69 to −2.36‰ with an average of −2.62 ± 0.25‰ (2SD, n = 6).The average Δ26Mgcal-sol value for both sets of experiments is −2.54 ± 0.22‰ (2SD, n = 15), and it is independent of precipitation rate, solution Mg/Ca molar ratio, solid/solution ratio, amount of overgrowth, and mol% Mg content in overgrowth. The form and texture of the calcite overgrowths in our experiments range from {104} rhombohedra with smooth crystal faces containing few macrosteps to {104} rhombohedra containing extensive evidence for 2-D nucleation on crystal faces, to more steeply sided rhombohedra {0kl}. While significant changes in crystal morphology are related to solid/solution ratio and solution composition in the G1 and G2 experiments, respectively, there was no difference in Mg isotope systematics, suggesting that crystal morphology does not affect the Mg isotopic composition of calcite within the range of features investigated and 2-D nucleation may be less affected by calcite growth kinetics than a spiral growth mechanism. Integrating our results with previous published values, an equilibrium isotopic fractionation factor of −2.47 ± 0.09‰ (weighted average ± weighted 2SD, n = 70) between calcite and aqueous solutions is derived at room temperature.

Uranium Isotope Fractionation (238U/235U) during U(VI) Uptake by Freshwater Plankton.

Uranium contamination in the environment is a serious public health concern. Biotic U(VI) reduction and nonreductive U(VI) uptake by microorganisms (e.g., U(VI) biosorption by cyanobacteria) are effective U remediation techniques. Variations of 238U/235U have been extensively explored to track biotic U(VI) reduction in laboratory experiments and field applications. However, U isotope fractionation during nonreductive U(VI) uptake by microorganisms is poorly constrained. To investigate U isotope fractionation in this process, we cultured freshwater plankton in the presence of U(VI) and measured 238U/235U in the culture media and biomass. We found that nonreductive U(VI) uptake by freshwater plankton fractionated U isotopes in the opposite direction compared to biotic U(VI) reduction. δ238U values in freshwater plankton were consistently ∼0.23 ± 0.06‰ lighter than those in dissolved U in the culture medium at various fractions of U removal (12-30%), consistent with equilibrium isotope fractionation in a closed system. The equilibrium isotope fractionation observed in our experiments possibly results from changes in coordination geometry between dissolved U(VI) in the culture media and adsorbed U(VI) on cell surfaces. Our experimental results highlight the need to consider U isotope fractionation during nonredox U(VI) uptake by microorganisms and organic matter when applying variations of 238U/235U to track biogeochemical processes and evaluate U remediation.

Inelastic neutron scattering: a novel approach towards determination of equilibrium isotopic fractionation factors. Size effects on heat capacity and beta-factor of diamond.

A new experimental method for the determination of equilibrium isotopic properties of substances based on inelastic neutron scattering (INS) is proposed. We present a mathematical formalism, which allows the calculation of the beta-factor of single-element solids based on INS-derived Phonon Density of States (PDOS). PDOS data for nanodiamonds of widely different sizes and of macroscopic diamond were determined from inelastic neutron scattering experiments. This allowed the determination of heat capacities and, for the first time, β-factors of the diamond nanoparticles. We demonstrate a considerable size-dependent increase of the heat capacities and decrease of the beta-factors for nanodiamonds relative to bulk diamond. Contributions of surface impurities/phases and phonon confinement to the size effects are evaluated. Applications in the formation of diamond nanoparticles in nature are briefly discussed.

Calibrating equilibrium Fe isotope fractionation factors between magnetite, garnet, amphibole, and biotite

Equilibrium isotope fractionation factors are the basis for application of stable isotopes in geological studies. Experimental calibration and theoretical calculations have been employed to determine Fe isotope fractionation factors for a variety of minerals, however, these methods have their limitations. An alternative approach to calibrating inter-mineral Fe isotope fractionation factors is to use well-characterized geological samples; this approach has unique advantages over the other methods including attainment of equilibrium at relatively low temperatures. In this study, we investigated the Fe isotope composition of magnetite (Mt), garnet (Grt), amphibole (Amp) and biotite (Bt) from the metamorphosed Yingshan iron formation in South China. Two independent geothermometers, quartz–magnetite oxygen isotope and amphibole–garnet–biotite Fe–Mg exchange geothermometers, give a consistent metamorphic temperature of 538 ± 39 °C. The Fe isotope composition of the different Fe-bearing minerals is highly variable in different ironstone samples, with δ56Fe values (relative to IRMM-014) ranging from −0.23 to +0.37‰ in magnetite, −0.44 to +0.09‰ in amphibole, −0.78 to +0.02‰ in garnet, and −0.61 to +0.04‰ in biotite. Despite that, the offsets of δ56Fe values for mineral pairs are consistent, implying attainment of equilibrium isotope fraction between these minerals. Inter-mineral Fe isotopic fractionations (±2 standard deviation) measured from the multiple mineral pairs are Δ56FeMt–Grt = +0.55 ± 0.08‰, Δ56FeMt–Amp = +0.25 ± 0.06‰, Δ56FeMt–Bt = +0.42 ± 0.11‰, Δ56FeAmp–Grt = +0.34 ± 0.15‰, Δ56FeAmp–Bt = +0.26 ± 0.04‰, and Δ56FeBt–Grt = +0.13 ± 0.08‰. Based on the well-defined metamorphic temperature (538 ± 39 °C) and internally consistent inter-mineral fractionation factors, the temperature-dependent functions for equilibrium Fe isotope fractionation between the following mineral pairs are derived:103lnαMt–Grt = 0.36(±0.05) × 106/T2, 103lnαMt–Bt = 0.28(±0.07) × 106/T2,103lnαMt–Amp = 0.16(±0.04) × 106/T2, 103lnαAmp–Grt = 0.22(±0.10) × 106/T2,103lnαAmp–Bt = 0.17(±0.03) × 106/T2, and 103lnαBt–Grt = 0.09(±0.05) × 106/T2,where Fe3+/ΣFe ratio is 0.05 ± 0.02 in garnet, 0.29 ± 0.04 in biotite, and 0.24 ± 0.06 in amphibole for the above functions. The equilibrium Fe isotope fractionation factors derived in this study enable estimation of the metamorphic temperature of rocks that contain these mineral pairs, and identification of secondary processes that may have induced disequilibrium Fe isotope distribution in rocks, such as retrograde metamorphism and hydrothermal alteration.

Experimental and theoretical modelling of kinetic and equilibrium Ba isotope fractionation during calcite and aragonite precipitation

Barium isotope fractionation during calcite and aragonite inorganic precipitation was studied in mixed flow reactors as a function of precipitation rate at 25 °C and pH = 6.3 ± 0.1. The measured Ba isotope fractionation that occurs between calcite and the forming fluid in the investigated range of calcite growth rates (10-8.0 ≤ Rp(calcite) ≤ 10−7.3 mol/m2/s) is insignificant. Barium isotope fractionation between aragonite and the fluid decreases with increasing precipitation rate from Δ137/134Baaragonite-fluid = +0.25 ± 0.06‰ for Rp(aragonite) ≤ 10−8.7 mol/m2/s to −0.10 ± 0.08‰ for Rp(aragonite) = 10−7.6 mol/m2/s, thus reflecting preferential incorporation of either heavy or light Ba isotopes in aragonite at slow and fast growth rates, respectively. The dependence of Ba isotope fractionation on aragonite growth rate is well described by the surface reaction kinetic model developed by DePaolo (2011) when the values +0.27‰ and −2.0 ± 0.2‰ are used for the equilibrium and kinetic Ba isotope fractionation factor, respectively. The enrichment of aragonite in the heavier Ba isotopes is consistent with the equilibrium fractionation factor of +0.34‰, calculated here between Ba-substituted aragonite and Ba2+ (aq), from first-principles calculations. This positive fractionation is related to a shorter average BaO bond length in the aragonite structure while the coordination number does not change much (i.e. 9). The lack of isotope fractionation between the Ba aquo ions and the 6-coordinated Ba in calcite likely suggests that the coordination reduction required for the incorporation in the lattice of Ba adsorbed at calcite growing sites proceeds without isotope fractionation with the fluid. Otherwise the precipitated calcite should have been enriched in heavy isotopes by ∼0.17‰, as predicted by first-principles calculations. These results are the first experimental measurements of Ba isotope fractionation during inorganic calcite and aragonite mineral formation and set the basis for understanding the mechanisms controlling Ba isotope composition in CaCO3 minerals that is an essential perquisite for application of this isotopic system in natural samples.

Evaluating Computational Chemistry Methods for Isotopic Fractionation between CO2(g) and H2O(g).

Quantum mechanical calculations can be useful in predicting equilibrium isotopic fractionations of geochemical reactions. However, these computational chemistry methods vary widely in their effectiveness in the prediction of various physical observables. Most studies employing the approach known as density functional theory (DFT) to model these observable quantities focus on predictive accuracy for energetics and geometries. In this study, several density functionals are evaluated against experimental bond lengths, harmonic vibrational frequencies, frequency shifts upon isotopic substitution, and 18O/16O isotopic fractionation between CO2(g) and H2O(g). Successful prediction of harmonic vibrational frequencies strongly correlates with successful prediction of isotopic fractionation, despite the possible introduction of errors by the harmonic approximation. Harmonic experimental frequencies, not anharmonic ones, must be used when comparing spectra and when predicting isotope fractionation. The B3LYP and X3LYP functionals perform more accurately in the evaluation of both harmonic vibrational frequencies and isotopic fractionation factors using the 6-311+G(d,p) and 6-311++G(2d,p) basis sets, achieving fractionation factor errors of 0.2-0.6‰ at 25 °C out of a total fractionation of 51‰. Error cancellation between vibrational frequencies and the harmonic approximation is crucial to their success. The above combination of exchange-correlation functionals and basis sets also well predicts the vibrational properties of interacting CO2 and H2O molecules, suggesting that they may be applicable to more complex geochemical reactions involving C and O isotopic fractionations.

Sn isotope fractionation during volatilization of Sn(IV) chloride: Laboratory experiments and quantum mechanical calculations

Volatilization is an important pathway of element transport in nature, and this process may be associated with stable isotope fractionation, which could be used to understand the elemental volatilization mechanisms. In this study, we report that evaporation of Sn(IV) chloride solution under experimental conditions (96 °C, 1 atmospheric pressure) results in significant loss of aqueous Sn(IV) and Sn stable isotope fractionation. The δ122/116Sn of the residue solution can increase by up to 0.50‰ (or a 0.33‰ increase in δ122/118Sn) after repeated evaporation, indicating preferential partitioning of isotopically light Sn species into the vapor phase during evaporation. The observed Sn loss and associated Sn isotope fractionation during the evaporation experiments can be described using a Rayleigh fractionation function, with a best-fitting isotope fractionation factor of −0.36‰ in Δ122/116Snvapor-aq (or −0.24‰ in Δ122/118Snvapor-aq). We also performed quantum mechanical calculations to assess the stability of different potential Sn(IV) species in aqueous and vapor phases, and derived the equilibrium Sn isotope fractionation factors between these Sn(IV) species. The calculation results suggest that the dominant gaseous species of Sn(IV), SnCl4, is isotopically heavier than the aqueous Sn(IV) species by 1.24‰–0.35‰ in δ122/116Sn (or 0.82‰–0.19‰ in δ122/118Sn) under equilibrium at 96 °C, which is opposite to the experimental results. Such contrast in the direction of Sn isotope fractionation implies that kinetic isotope fractionation, rather than thermodynamic equilibrium isotope fractionation, took place for SnCl4 in the evaporation experiments at 96 °C. The observed experimental data can be explained by a kinetic isotope fractionation model involving backward reaction of SnCl4 vaporization at the solution-vapor boundary. This study, in combination with a recent report of positive Δ122/116Snvapor-aq (or Δ122/118Snvapor-aq) factor during evaporation of SnCl4 at 150 °C (Wang et al., 2019a), suggests that Sn(IV) volatilization mechanisms may be different with and without fluid boiling. Combined laboratory experiments and quantum mechanical calculations on the isotopic effects of Sn(IV) chloride solution evaporation provide important constraints for understanding the rapidly accumulating Sn isotopes data from studies on Sn ore-forming processes, bronze metallurgy and archeology, and volatile elements in planetary processes.

Ab Initio Calculation of Equilibrium Isotopic Fractionations of Potassium and Rubidium in Minerals and Water

We used first-principle approaches to calculate the equilibrium isotopic fractionation factors of potassium (K) and rubidium (Rb) in a variety of minerals of geological relevance (orthoclase, albit...

Isotopic compositions of ground ice in near-surface permafrost in relation to vegetation and microtopography at the Taiga-Tundra boundary in the Indigirka River lowlands, northeastern Siberia.

The warming trend in the Arctic region is expected to cause drastic changes including permafrost degradation and vegetation shifts. We investigated the spatial distribution of ice content and stable isotopic compositions of water in near-surface permafrost down to a depth of 1 m in the Indigirka River lowlands of northeastern Siberia to examine how the permafrost conditions control vegetation and microtopography in the Taiga–Tundra boundary ecosystem. The gravimetric water content (GWC) in the frozen soil layer was significantly higher at microtopographically high elevations with growing larch trees (i.e., tree mounds) than at low elevations with wetland vegetation (i.e., wet areas). The observed ground ice (ice-rich layer) with a high GWC in the tree mounds suggests that the relatively elevated microtopography of the land surface, which was formed by frost heave, strongly affects the survival of larch trees. The isotopic composition of the ground ice indicated that equilibrium isotopic fractionation occurred during ice segregation at the tree mounds, which implies that the ice formed with sufficient time for the migration of unfrozen soil water to the freezing front. In contrast, the isotopic data for the wet areas indicated that rapid freezing occurred under relatively non-equilibrium conditions, implying that there was insufficient time for ice segregation to occur. The freezing rate of the tree mounds was slower than that of the wet areas due to the difference of such as soil moisture and snow cover depends on vegetation and microtopography. These results indicate that future changes in snow cover, soil moisture, and organic layer, which control underground thermal conductivity, will have significant impacts on the freezing environment of the ground ice at the Taiga–Tundra boundary in northeastern Siberia. Such changes in the freezing environment will then affect vegetation due to changes in the microtopography of the ground surface.

Accelerating equilibrium isotope effect calculations. II. Stochastic implementation of direct estimators.

Path integral calculations of equilibrium isotope effects and isotopic fractionation are expensive due to the presence of path integral discretization errors, statistical errors, and thermodynamic integration errors. Whereas the discretization errors can be reduced by high-order factorization of the path integral and statistical errors by using centroid virial estimators, two recent papers proposed alternative ways to completely remove the thermodynamic integration errors: Cheng and Ceriotti [J. Chem. Phys. 141, 244112 (2015)] employed a variant of free-energy perturbation called "direct estimators," while Karandashev and Vaníček [J. Chem. Phys. 143, 194104 (2017)] combined the thermodynamic integration with a stochastic change of mass and piecewise-linear umbrella biasing potential. Here, we combine the former approach with the stochastic change in mass in order to decrease its statistical errors when applied to larger isotope effects and perform a thorough comparison of different methods by computing isotope effects first on a harmonic model and then on methane and methanium, where we evaluate all isotope effects of the form CH4-xDx/CH4 and CH5-xDx +/CH5 +, respectively. We discuss the reasons for a surprising behavior of the original method of direct estimators, which performed well for a much larger range of isotope effects than what had been expected previously, as well as some implications of our work for the more general problem of free energy difference calculations.

In Situ Infrared Spectra for Hydrous Forsterite up to 1243 K: Hydration Effect on Thermodynamic Properties

Hydrogen substitution has significant effect on the physical properties of olivine, the most abundant mineral in the upper mantle. We collected high-temperature polarized Fourier Transform infrared (FTIR) spectra on hydrous forsterite (Mg-pure olivine) crystals, which were synthesized at 12 GPa, 1473–1673 K. The modes at 3612, 3578, 3566, 3551 cm−1 show comparable negative temperature dependence, and the magnitude of (∂vi/∂T)P decreases dramatically with frequency increasing. Whereas, the peak at 3477 cm−1, which is attributed to protonation along the O1...O2 edge on the Si tetrahedron, has a positive temperature dependence. The absorbance intensities of all these OH bands remained almost the same when quenched to room temperature. On the other hand, we also evaluate the hydration effect on the thermodynamic properties (heat capacities). For the anhydrous forsterite sample, the intrinsic anharmonicity could significantly increase the heat capacity by 5~6% when extrapolated to 2000 K. Hydration further increase such difference to ~9%, in both the cases of M-substitution or Si-substitution. Hence, hydration in olivine has significant impact on the anharmonic contribution to the thermodynamic properties, as well as Equations of State and equilibrium isotope fractionation β-factor at high-P,T conditions in the deep mantle.

Synthesis of In‐House Produced Calibrated Silver Phosphate with a Large Range of Oxygen Isotope Compositions

The large range of stable oxygen isotope values of phosphate‐bearing minerals and dissolved phosphate of inorganic or organic origin requires the availability of in‐house produced calibrated silver phosphate of which isotopic ratios must closely bracket those of studied samples. We propose a simple protocol to synthesise Ag3PO4 in a wide range of oxygen isotope compositions based on the equilibrium isotopic fractionation factor and the kinetics and temperature of isotopic exchange in the phosphate–water system. Ag3PO4 crystals were obtained from KH2PO4 that was dissolved in water of known oxygen isotope composition. Isotopic exchange between dissolved phosphate and water took place at a desired and constant temperature into PYREX™ tubes that were placed in a high precision oven for defined run‐times. Samples were withdrawn at desired times, quenched in cold water and precipitated as Ag3PO4. We provide a calculation sheet that computes the δ18O of precipitated Ag3PO4 as a function of time, temperature and δ18O of both reactants KH2PO4 and H2O at t = 0. Predicted oxygen isotope compositions of synthesised silver phosphate range from −7 to +31‰ VSMOW for a temperature range comprised between 110 and 130 °C and a range of water δ18O from −20 to +15‰ VSMOW.

Factors affecting diurnal dissolved inorganic carbon and its isotopic composition in a small stream on a volcanic island in South Korea

Water samples were collected hourly at a small stream on Jeju Island, South Korea in both wet and dry seasons to identify the factors affecting dissolved inorganic carbon (DIC) and its isotopic composition (δ13CDIC). In the wet season, dissolved oxygen (DO) displayed a diurnal pattern with lower values in samples collected between sunset and sunrise compared to samples at other times. Likewise, a diurnal pattern was observed for pH, DIC and δ13CDIC. An overall negative correlation between DIC and DO indicated that photosynthesis and respiration in the stream are the main factors controlling DIC concentration and behavior. Notably, samples at night displayed two trends in plots of DO and DIC, with different δ13CDIC values. This was due to CO2 outgassing from the stream to the ambient atmosphere. Partial pressure of CO2 (pCO2), calcite saturation index (SIcalcite), and equilibrium isotope fractionation between HCO3− and CO2 gas were related to the δ13CDIC value, verifying that photosynthesis and respiration determined DIC behavior. In addition to microbial activity, CO2 outgassing contributed to DIC in the stream after respiration and before photosynthesis. In comparison, δ13CDIC values in the dry season were similar to those in the wet season but showed no clear relationship with pCO2 and SIcalcite. Unlike the wet season, this indicated that in the dry season, photosynthesis and respiration are not the dominant processes and that CO2 exchange between the atmosphere and water is more important in determining DIC.

Uranium isotope fractionation during slab dehydration beneath the Izu arc

Fluids released from subducted slabs impart characteristic geochemical signatures on volcanic arc magmas and residual slabs transported into the deeper mantle. Yet, the sources and transport mechanisms of trace elements released from the slab are speculative. We investigate fluids released from subducted slabs from the perspective of 238U/235U and radiogenic Pb isotope ratios in lavas from the Izu volcanic arc in the Pacific ocean. Izu arc lavas are fluid-dominated end-member type magmas that allow a close characterisation of slab fluids. The Izu arc lavas have low 238U/235U ratios compared to the bulk Earth and mid-ocean ridge basalt (MORB). The low 238U/235U (δ238U=−0.46 to −0.33‰, where δ238U=238U/235Usample/238U/235UCRM145 − 1) is associated with slab-derived fluids low in Th/U that are added to the magma sources. The radiogenic Pb isotope ratios of the lavas form an array between ‘Indian’ type MORB and subducting sediments that is inconsistent with fluids derived from the altered mafic oceanic crust (AMOC). We infer that ‘fluid-mobile’ elements, including U and Pb are mobilised from largely unaltered, deeper sections of the mafic crust by migrating fluids that are derived from the dehydration of underlying serpentinites. Uranium is only fluid-mobile as UVI and needs to be oxidised from predominant UIV in unaltered magmatic rocks in order to be mobilised by fluids. Uranium isotope fractionation of ∼0.2‰ in δ238U during this process is required to generate the low 238U/235U in the fluids. We propose that channelised fluid flow through the metamorphosed sheeted dyke and gabbroic sections of the mafic crust locally oxidises and mobilises U. We suggest that U isotope fractionation occurs within the fluid channels and is related to equilibrium isotope fractionation during the oxidation of U and the incorporation of UIV into secondary phases such as epidote, apatite and zircon that grow within the channels. These phases are predicted to carry isotopically heavy U into the deeper mantle beyond subduction zones. The δ238U is thus tracing the dehydration process of subducting slabs. Similar observations have been made for other, ‘stable isotope’ systems in different arcs and subduction-related metamorphic rocks, thus highlighting their potential for studying processes occurring within the slabs during subduction. This information is essential for understanding and the partitioning of elements between subducted slabs and the mantle wedge and constraining the role of subduction zones in global geochemical cycles.

Potassium isotope fractionation during magmatic differentiation of basalt to rhyolite

High-temperature equilibrium and kinetic stable isotope fractionation during partial melting, fractional crystallization, and other igneous differentiation processes has been observed in many isotope systems, but due to the relative nascence of high-precision analytical capabilities for K, it is still unclear whether igneous processes induce systematic and resolvable K isotope fractionation. In this study, we look to the natural laboratory of Hekla volcano in Iceland to investigate the behavior of K isotopes during magmatic differentiation of basalt to rhyolite. Using a novel MC-ICP-MS method, we analyzed 24 geochemically diverse samples from Hekla, including 7 basalts, 8 basaltic andesites, 3 andesites, 4 dacites, and 2 rhyolites, along with 2 additional samples from Burfell, Iceland, for comparison (1 basalt and 1 trachyte). We observed extremely limited variation of 41K/39K ratios throughout our suite of samples, which is not resolvable within the best current analytical uncertainty. The average value of all samples is δ41KNIST SRM3141a = −0.46 ± 0.07‰ (2sd). This value agrees with the Bulk Silicate Earth value previously defined by average global oceanic basalts in literature. The lack of variation throughout this suite of samples from a single volcano system indicates that K does not fractionate during magmatic differentiation (of basalt to rhyolite) through processes such as partial melting and fractional crystallization. This conclusion is important to the estimation of the Bulk Silicate Earth K isotope composition, to placing a more robust estimate on the composition bulk continental crust, and to fostering a better understanding of the behavior of K isotopes during differentiation of the terrestrial planets.

H2 Kinetic Isotope Fractionation Superimposed by Equilibrium Isotope Fractionation During Hydrogenase Activity of D. vulgaris Strain Miyazaki.

We determined 2H stable isotope fractionation at natural abundances associated with hydrogenase activity by whole cells of Desulfovibrio vulgaris strain Miyazaki F expressing a NiFe(Se) hydrogenase. Inhibition of sulfate reduction by molybdate inhibited the overall oxidation of hydrogen but still facilitated an equilibrium isotope exchange reaction with water. The theoretical equilibrium isotope exchange δ2H-values of the chemical exchange reaction were identical to the hydrogenase reaction, as confirmed using three isotopically different waters with δ2H-values of – 62, +461, and + 1533‰. Expected kinetic isotope fractionation of hydrogen oxidation by non-inhibited cells was also superimposed by an equilibrium isotope exchange. The isotope effects were solely catalyzed biotically as hydrogen isotope signatures did not change in control experiments without cells of D. vulgaris Miyazaki.

Experimentally determined Si isotope fractionation between zircon and quartz

Abstract The silicon isotope composition of detrital quartz and zircon have the potential to inform us about secular changes to the silica cycle and weathering reactions on Earth. However, inferring source melt Si isotope composition from out-of-context minerals is hampered by the fact that, to-date, there is limited Si isotope equilibrium fractionation data for minerals. Here, we report experimental data to constrain Si isotope equilibrium fractionation between zircon and quartz, using two fundamentally different strategies, but with the same experimental design. First, zircon and quartz were hydrothermally synthesized from Zr(OH)4 and SiO2 at 1.5 GPa and temperatures of 725, 800, and 900 °C. The second experimental strategy utilized the three-isotope method; the starting materials consisted of natural zircon and isotopically-labelled SiO2. Three sets of hydrothermal time-series experiments were conducted at the same pressure and temperatures as the direct synthesis experiments. For all experiments, quartz and zircon were separated and 30Si/28Si and 29Si/28Si ratios were measured by solution multi-collector inductively coupled plasma mass spectrometry. The three-isotope method, which provides the best indicator of equilibrium fractionations, yields the following relationship: Δ 30 S i ( q t z - z r c ) = ( 0.53 ± 0.14 ) × 10 6 / T 2 where Δ30Si(qtz-zrc) is the relative difference in 30Si/28Si between quartz and zircon in permil, T is temperature in K, and the error is 2 s.e. This relationship can be used to calculate the fractionation between zircon and other phases, and to estimate the Si isotope composition of the melt from which a zircon crystallized. The results may be used to assess equilibrium-disequilibrium isotope fractionations between quartz and zircon and co-existing phases in igneous rocks. These data can also be applied to out-of-context zircon (and quartz) to estimate the isotope composition of the host rock. Zircons crystallizing from a melt derived from purely igneous sources – i.e., without the involvement of “weathered” material – are expected to display a δ30SiNBS-28 (permil deviation of the 30Si/28Si from the NBS-28 standard) range from −0.7 to −0.35‰. Deviations from this range indicate assimilation of non-igneous (i.e., sedimentary) material in the melt source.