Experimental calibration of oxygen isotope fractionation between quartz and zircon

We report the results of an experimental calibration of oxygen isotope fractionation between quartz and zircon. Data were collected from 700 to 1000 °C, 10–20 kbar, and in some experiments the oxygen fugacity was buffered at the fayalite–magnetite–quartz equilibrium. Oxygen isotope fractionation shows no clear dependence on oxygen fugacity or pressure. Unexpectedly, some high-temperature data (900–1000 °C) show evidence for disequilibrium oxygen isotope partitioning. This is based in part on ion microprobe data from these samples that indicate some high-temperature quartz grains may be isotopically zoned. Excluding data that probably represent non-equilibrium conditions, our preferred calibration for oxygen isotope fractionation between quartz and zircon can be described by:

This relationship can be used to calculate fractionation factors between zircon and other minerals. In addition, results have been used to calculate WR/melt–zircon fractionations during magma differentiation. Modeling demonstrates that silicic magmas show relatively small changes in δ¹⁸O values during differentiation, though late-stage mafic residuals capable of zircon saturation contain elevated δ¹⁸O values. However, residuals also have larger predicted melt–zircon fractionations meaning zircons will not record enriched δ¹⁸O values generally attributed to a granitic protolith. These results agree with data from natural samples if the zircon fractionation factor presented here or from natural studies is applied.     

New data on equilibrium iron isotope fractionation among sulfides: Constraints on mechanisms of sulfide formation in hydrothermal and igneous systems

Fe, S, and Cu reduced partition function ratios (β-factors) allow calculation of equilibrium isotope fractionation factors. β-Factors for chalcopyrite are calculated from experimental and theoretical partial phonon densities of state states (Kobayashi et al., 2007). The Fe β-factors for mackinawite are calculated from Mössbauer spectroscopy data (Bertaut et al., 1965). Excellent agreement exists between Fe β-factors for chalcopyrite calculated from the experimental and theoretical ⁵⁷Fe phonon densities of states, supporting the reliability of the Fe β-factors for chalcopyrite. The ³⁴S β-factor for chalcopyrite is consistent with experimental data on equilibrium sulfur isotope fractionation factors among sulfides and theoretical ³⁴S β-factors, except those recently calculated by a DFT approach.Up-to-date experimental isotope-exchange data on equilibrium Fe isotope fractionation factors between minerals and aqueous Fe were critically reevaluated in conjunction with Fe β-factors for minerals, and the following expressions for β-factors for aqueous Fe²⁺ and Fe³⁺ were obtained:

     

Controls on ostracod valve geochemistry: Part 2. Carbon and oxygen isotope compositions

The stable carbon and oxygen isotope compositions of fossil ostracods are powerful tools to estimate past environmental and climatic conditions. The basis for such interpretations is that the calcite of the valves reflects the isotopic composition of water and its temperature of formation. However, calcite of ostracods is known not to form in isotopic equilibrium with water and different species may have different offsets from inorganic precipitates of calcite formed under the same conditions. To estimate the fractionation during ostracod valve calcification, the oxygen and carbon isotope compositions of 15 species living in Lake Geneva were related to their autoecology and the environmental parameters measured during their growth. The results indicate that: (1) Oxygen isotope fractionation is similar for all species of Candoninae with an enrichment in ¹⁸O of more than 3‰ relative to equilibrium values for inorganic calcite. Oxygen isotope fractionation for Cytheroidea is less discriminative relative to the heavy oxygen, with enrichments in ¹⁸O for these species of 1.7 to 2.3‰. Oxygen isotope fractionations for Cyprididae are in-between those of Candoninae and Cytheroidea. The difference in oxygen isotope fractionation between ostracods and inorganic calcite has been interpreted as resulting from a vital effect. (2) Comparison with previous work suggests that oxygen isotope fractionation may depend on the total and relative ion content of water. (3) Carbon isotope compositions of ostracod valves are generally in equilibrium with DIC. The specimens’ δ¹³C values are mainly controlled by seasonal variations in δ¹³C_DIC of bottom water or variation thereof in sediment pore water. (4) Incomplete valve calcification has an effect on carbon and oxygen isotope compositions of ostracod valves. Preferential incorporation of at the beginning of valve calcification may explain this effect. (5) Results presented here as well as results from synthetic carbonate growth indicate that different growth rates or low pH within the calcification site cannot be the cause of oxygen isotope ‘vital effects’ in ostracods. Two mechanisms that might enrich the ¹⁸O of ostracod valves are deprotonation of that may also contribute to valve calcification, and effects comparable to salt effects with high concentrations of Ca and/or Mg within the calcification site that may also cause a higher temperature dependency of oxygen isotope fractionation.     

An experimental study of oxygen isotope fractionation between inorganically precipitated aragonite and water at low temperatures

To determine oxygen isotope fractionation between aragonite and water, aragonite was slowly precipitated from Ca(HCO₃)₂ solution at 0 to 50°C in the presence of Mg²⁺ or SO₄²⁻. The phase compositions and morphologies of synthetic minerals were detected by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The effects of aragonite precipitation rate and excess dissolved CO₂ gas in the initial Ca(HCO₃)₂ solution on oxygen isotope fractionation between aragonite and water were investigated. For the CaCO₃ minerals slowly precipitated by the CaCO₃ or NaHCO₃ dissolution method at 0 to 50°C, the XRD and SEM analyses show that the rate of aragonite precipitation increased with temperature. Correspondingly, oxygen isotope fractionations between aragonite and water deviated progressively farther from equilibrium. Additionally, an excess of dissolved CO₂ gas in the initial Ca(HCO₃)₂ solution results in an increase in apparent oxygen isotope fractionations. As a consequence, the experimentally determined oxygen isotope fractionations at 50°C indicate disequilibrium, whereas the relatively lower fractionation values obtained at 0 and 25°C from the solution with less dissolved CO₂ gas and low precipitation rates indicate a closer approach to equilibrium. Combining the lower values at 0 and 25°C with previous data derived from a two-step overgrowth technique at 50 and 70°C, a fractionation equation for the aragonite-water system at 0 to 70°C is obtained as follows:

     

Hydration in solution is critical for stable oxygen isotope fractionation between carbonate ion and water

Various isotope studies require accurate fractionation factors (α’s) between different chemical compounds in thermodynamic equilibrium. Although numerous isotope systems involve aqueous solutions, the conventional theory is formulated for the gas-phase and predicts incorrect α’s for many compounds dissolved in water. Here I show that quantum-chemistry calculations, which take into account solute–water interactions, accurately predict, for instance, oxygen isotope fractionation between dissolved and H₂O (hereafter ). Simple force field and quantum-chemistry calculations for the ‘gas-phase’ ion predict (15‰) at 25 °C. However, based on -clusters with up to 22 H₂O molecules, I calculate a value of 25‰, which agrees with the experimental value of 24.5 ± 0.5‰. Effects of geometry and anharmonicity on the calculated α were also examined. The calculations reveal the critical role of hydration in solution, which is ignored in the gas-phase theory. The approach presented provides an adequate framework for calculating fractionation factors involving dissolved compounds; it may also be used to predict α’s that cannot (or have not yet been) determined experimentally.     

Oxygen isotope biogeochemistry of pore water sulfate in the deep biosphere: Dominance of isotope exchange reactions with ambient water during microbial sulfate reduction (ODP Site 1130)

Microbially mediated sulfate reduction affects the isotopic composition of dissolved and solid sulfur species in marine sediments. Experiments and field data show that the composition is also modified in the presence of sulfate-reducing microorganisms. This has been attributed either to a kinetic isotope effect during the reduction of sulfate to sulfite, cell-internal exchange reactions between enzymatically-activated sulfate (APS), and/or sulfite with cytoplasmic water. The isotopic fingerprint of these processes may be further modified by the cell-external reoxidation of sulfide to elemental sulfur, and the subsequent disproportionation to sulfide and sulfate or by the oxidation of sulfite to sulfate. Here we report values from interstitial water samples of ODP Leg 182 (Site 1130) and provide the mathematical framework to describe the oxygen isotope fractionation of sulfate during microbial sulfate reduction. We show that a purely kinetic model is unable to explain our data, and that the data are well explained by a model using oxygen isotope exchange reactions. We propose that the oxygen isotope exchange occurs between APS and cytoplasmic water, and/or between sulfite and adenosine monophosphate (AMP) during APS formation. Model calculations show that cell external reoxidation of reduced sulfur species would require up to 3000 mol/m³ of an oxidant at ODP Site 1130, which is incompatible with the sediment geochemical data. In addition, we show that the volumetric fluxes required to explain the observed data are on average 14 times higher than the volumetric sulfate reduction rates (SRR) obtained from inverse modeling of the porewater data. The ratio between the gross sulfate flux into the microbes and the net sulfate flux through the microbes is depth invariant, and independent of sulfide concentrations. This suggests that both fluxes are controlled by cell density and that cell-specific sulfate reduction rates remain constant with depth.     

A new value for the stable oxygen isotope fractionation between dissolved sulfate ion and water

Although the stable oxygen isotope fractionation between dissolved sulfate ion and H₂O (hereafter ) is of physico-chemical and biogeochemical significance, no experimental value has been established until present. The primary reason being that uncatalyzed oxygen exchange between and H₂O is extremely slow, taking ∼10⁵ years at room temperature. For lack of a better approach, values of 16‰ and 31‰ at 25 °C have been assumed in the past, based on theoretical ‘gas-phase’ calculations and extrapolation of laboratory results obtained at temperatures >75 °C that actually pertain to the bisulfate system. Here I use novel quantum-chemistry calculations, which take into account detailed solute-water interactions to establish a new value for of 23‰ at 25 °C. The results of the corresponding calculations for the bisulfate ion are in agreement with observations. The new theoretical values show that sediment -data, which reflect oxygen isotope equilibration between sulfate and ambient water during microbial sulfate reduction, are consistent with the abiotic equilibrium between and water.     

Oxygen isotopic fractionation during inorganic calcite precipitation ― Effects of temperature, precipitation rate and pH

Stable oxygen isotopic fractionation during inorganic calcite precipitation was experimentally studied by spontaneous precipitation at various pH (8.3 < pH < 10.5), precipitation rates (1.8 < log R < 4.4 μmol m^− 2 h^− 1) and temperatures (5, 25, and 40 °C) using the CO₂ diffusion technique.The results show that the apparent stable oxygen isotopic fractionation factor between calcite and water (α_{calcite–water}) is affected by temperature, the pH of the solution, and the precipitation rate of calcite. Isotopic equilibrium is not maintained during spontaneous precipitation from the solution. Under isotopic non-equilibrium conditions, at a constant temperature and precipitation rate, apparent 1000lnα_{calcite–water} decreases with increasing pH of the solution. If the temperature and pH are held constant, apparent 1000lnα_{calcite–water} values decrease with elevated precipitation rates of calcite. At pH = 8.3, oxygen isotopic fractionation between inorganically precipitated calcite and water as a function of the precipitation rate (R) can be described by the expressions

at 5, 25, and 40 °C, respectively.The impact of precipitation rate on 1000lnα_{calcite–water} value in our experiments clearly indicates a kinetic effect on oxygen isotopic fractionation during calcite precipitation from aqueous solution, even if calcite precipitated slowly from aqueous solution at the given temperature range. Our results support Coplen's work [Coplen T. B. (2007) Calibration of the calcite–water oxygen isotope geothermometer at Devils Hole, Nevada, a natural laboratory. Geochim. Cosmochim. Acta 71, 3948–3957], which indicates that the equilibrium oxygen isotopic fractionation factor might be greater than the commonly accepted value.     

Experimental studies of oxygen isotope fractionation in the carbonic acid system at 15°, 25°, and 40°C

In light of recent studies that show oxygen isotope fractionation in carbonate minerals to be a function of HCO₃⁻ and CO₃²⁻ concentrations, the oxygen isotope fractionation and exchange between water and components of the carbonic acid system (HCO₃⁻, CO₃²⁻, and CO_2(aq)) were investigated at 15°, 25°, and 40°C. To investigate oxygen isotope exchange between HCO₃⁻, CO₃²⁻, and H₂O, NaHCO₃ solutions were prepared and the pH was adjusted over a range of 2 to 12 by the addition of small amounts of HCl or NaOH. After thermal, chemical, and isotopic equilibrium was attained, BaCl₂ was added to the NaHCO₃ solutions. This resulted in immediate BaCO₃ precipitation; thus, recording the isotopic composition of the dissolved inorganic carbon (DIC). Data from experiments at 15°, 25°, and 40°C (1 atm) show that the oxygen isotope fractionation between HCO₃⁻ and H₂O as a function of temperature is governed by the equation:

     

Oxygen isotope fractionation factors involving cassiterite (SnO2): I. calculation of reduced partition function ratios from heat capacity and X-ray resonant studies

Oxygen isotope equilibrium fractionation constants (β¹⁸O-factors) of cassiterite were evaluated on the basis of heat capacity and X-ray resonant (Mössbauer spectroscopy and X-ray inelastic scattering) data.The low-temperature heat capacity of cassiterite was measured in the range from 13 to 340 K using an adiabatic calorimeter. Results of measurements of two samples agree very closely but deviate more than 5% from previous heat capacity data used for calculation of thermodynamic functions. The temperature dependence of heat capacity was treated using the modern version of the Thirring expansion, and the appropriate temperature dependence of the vibrational kinetic energy was found.Measurements of temperature-dependent Mössbauer parameters of cassiterite were conducted in the range from 300 to 900 K. The attempt to describe Mössbauer fraction and the second order Doppler (SOD) shift on the basis of the Debye model failed. The first term of the Thirring expansion of the Mössbauer SOD shift agrees with that calculated from the Sn sublattice vibration density of states (VDOS) obtained via synchrotron X-ray scattering. Based on this agreement we calculated the kinetic energy of the cassiterite Sn sublattice from VDOS.From the kinetic energy of the total cassiterite crystalline lattice and its Sn sublattice, β¹⁸O-factors of cassiterite were computed in the temperature range 300-1500 K by the method of Polyakov and Mineev (2000). Appropriate polynomials, which are valid at temperatures above 400 K, are the following:

     

Experimental investigation of the effects of temperature and ionic strength on Mo isotope fractionation during adsorption to manganese oxides

The Mo stable isotope system is being applied to study changes in ocean redox. Such applications implicitly assume that Mo isotope fractionation in aqueous systems is relatively insensitive to frequently changing environmental variables such as temperature (T) and ionic strength (I). A major driver of fractionation is the adsorption of Mo to Mn oxyhydroxide surfaces [Barling J. and Anbar A. D. (2004) Molybdenum isotope fractionation during adsorption by manganese oxides. Earth Planet. Sci. Lett.217(3-4), 315-329]. Here, we report the results of experiments that determine the extent to which Mo isotope fractionation during adsorption of Mo to the Mn oxyhydroxide mineral birnessite is sensitive to T and I. The results are compared to new predictions from quantum chemical computations. We measured fractionation from 1 to 50 °C at I = 0.1 m and found that Δ^97/95Mo_{dissolved-adsorbed} varies from 1.9‰ to 1.6‰ over this temperature range. Experiments were also performed at 25 °C in synthetic seawater (I = 0.7); fractionation at this condition was the same within analytical error as in low ionic strength experiments. These findings confirm that the Mo isotope fractionation during adsorption to Mn oxyhydroxides is relatively insensitive to variations and T and I over environmentally relevant ranges. To relate these findings to potential mechanisms of Mo isotope fractionation, we also report results for density functional theory computations of the fractionation between and various possible structures of molybdic acid as a function of temperature. Because no plausible species fractionates from with a magnitude matching the experiments, we are left with three possibilities to explain the fractionation: (1) solvation effects on the vibrational frequencies of aqueous species considered thus far are significant, such that our calculations in vacuo yield inaccurate fractionations; (2) a trace aqueous species not yet considered fractionates from and then adsorbs to birnessite; or (3) a surface complex not present in solution forms on birnessite in which Mo is not tetrahedrally coordinated. Our findings help validate assumptions underlying paleoceanographic applications of the Mo isotope system and also lead us closer to understanding the mechanism of isotope fractionation during adsorption of Mo to Mn oxyhydroxides.     

Inverse kinetic isotope fractionation during bacterial nitrite oxidation

Natural abundance stable isotopes in nitrate (), nitrite (), and nitrous oxide (N₂O) have been used to better understand the cycling of nitrogen in marine and terrestrial environments. However, in order to extract the greatest information from the distributions of these isotopic species, the kinetic isotope effects for each of the relevant microbial reactions are needed. To date, kinetic isotope effects for nitrite oxidation and anaerobic ammonium oxidation (anammox) have not been reported. In this study, the nitrogen isotope effect was measured for microbial nitrite oxidation to nitrate. Nitrite oxidation is the second step in the nitrification process, and it plays a key role in the regeneration of nitrate in the ocean. Surprisingly, nitrite oxidation occurred with an inverse kinetic isotope effect, such that the residual nitrite became progressively depleted in ¹⁵N as the reaction proceeded. Three potential explanations for this apparent inverse kinetic isotope effect were explored: (1) isotope exchange equilibrium between nitrite and nitrous acid prior to reaction, (2) reaction reversibility at the enzyme level, and (3) true inverse kinetic fractionation. Comparison of experimental data to ab initio calculations and theoretical predictions leads to the conclusion that the fractionation is most likely inverse at the enzyme level. Inverse kinetic isotope effects are rare, but the experimental observations reported here agree with kinetic isotope theory for this simple N-O bond-forming reaction. Nitrite oxidation is therefore fundamentally different from all other microbial processes in which N isotope fractionation has been studied. The unique kinetic isotope effect for nitrite oxidation should help to better identify its role in the cycling of nitrite in ocean suboxic zones, and other environments in which nitrite accumulates.     

Phosphoric acid fractionation factors for smithsonite and cerussite between 25 and 72°C

The intramolecular kinetic oxygen isotope fractionation between CO₂ and CO₃²⁻ during reaction of phosphoric acid with natural smithsonite (ZnCO₃) and cerussite (PbCO₃) has been determined between 25 and 72°C. While cerussite decomposes in phosphoric acid within a few hours at 25°C, smithsonite reacts very slowly with the acid at 25°C providing yields of CO₂ < 25% after 2 weeks. The low yields result in a low precision for oxygen isotope measurements of the acid-liberated CO₂ (±1.65‰, 1σ, n = 9). The yield and reproducibility of oxygen isotope values of the acid-liberated CO₂ from smithsonite can be improved, the latter to ∼±0.15‰, by increasing the reaction temperature to 50°C for 12 h or to 72°C for 1 h. Our new phosphoric acid fractionation factor for natural cerussite at 25°C deviates significantly from a previously published value on synthetic material. The temperature dependence of the oxygen isotope factionation factor, α between acid-liberated CO₂ and carbonate at 25 to 72°C is given by the following equations

     

Isotopic fractionations associated with phosphoric acid digestion of carbonate minerals: Insights from first-principles theoretical modeling and clumped isotope measurements

Phosphoric acid digestion has been used for oxygen- and carbon-isotope analysis of carbonate minerals since 1950, and was recently established as a method for carbonate ‘clumped isotope’ analysis. The CO₂ recovered from this reaction has an oxygen isotope composition substantially different from reactant carbonate, by an amount that varies with temperature of reaction and carbonate chemistry. Here, we present a theoretical model of the kinetic isotope effects associated with phosphoric acid digestion of carbonates, based on structural arguments that the key step in the reaction is disproportionation of H₂CO₃ reaction intermediary. We test that model against previous experimental constraints on the magnitudes and temperature dependences of these oxygen isotope fractionations, and against new experimental determinations of the fractionation of ¹³C-¹⁸O-containing isotopologues (‘clumped’ isotopic species). Our model predicts that the isotope fractionations associated with phosphoric acid digestion of carbonates at 25 °C are 10.72‰, 0.220‰, 0.137‰, 0.593‰ for, respectively, ¹⁸O/¹⁶O ratios (1000 lnα^∗) and three indices that measure proportions of multiply-substituted isotopologues . We also predict that oxygen isotope fractionations follow the mass dependence exponent, λ of 0.5281 (where ). These predictions compare favorably to independent experimental constraints for phosphoric acid digestion of calcite, including our new data for fractionations of ¹³C-¹⁸O bonds (the measured change in Δ₄₇ = 0.23‰) during phosphoric acid digestion of calcite at 25 °C.We have also attempted to evaluate the effect of carbonate cation compositions on phosphoric acid digestion fractionations using cluster models in which disproportionating H₂CO₃ interacts with adjacent cations. These models underestimate the magnitude of isotope fractionations and so must be regarded as unsucsessful, but do reproduce the general trend of variations and temperature dependences of oxygen isotope acid digestion fractionations among different carbonate minerals. We suggest these results present a useful starting point for future, more sophisticated models of the reacting carbonate/acid interface. Examinations of these theoretical predictions and available experimental data suggest cation radius is the most important factor governing the variations of isotope fractionation among different carbonate minerals. We predict a negative correlation between acid digestion fractionation of oxygen isotopes and of ¹³C-¹⁸O doubly-substituted isotopologues, and use this relationship to estimate the acid digestion fractionation of for different carbonate minerals. Combined with previous theoretical evaluations of ¹³C-¹⁸O clumping effects in carbonate minerals, this enables us to predict the temperature calibration relationship for different carbonate clumped isotope thermometers (witherite, calcite, aragonite, dolomite and magnesite), and to compare these predictions with available experimental determinations. The success of our models in capturing several of the features of isotope fractionation during acid digestion supports our hypothesis that phosphoric acid digestion of carbonate minerals involves disproportionation of transition state structures containing H₂CO₃.     

Modeling sulfur isotope fractionation and differential diffusion during sulfate reduction in sediments of the Cariaco Basin

Sulfur isotope composition (δ³⁴S) profiles in sediment pore waters often show an offset between sulfate and sulfide much greater in magnitude than S isotope fractionations observed in pure cultures. A number of workers have invoked an additional reaction, microbial disproportionation of sulfur intermediates, to explain the offset between experimental and natural systems. Here, we present an alternative explanation based on modeling of pore water sulfate and sulfide concentrations and stable isotope data from the Cariaco Basin (ODP Leg 165, Site 1002B). The use of unique diffusion coefficients for and , based on their unequal molecular masses, resulted in an increase in the computed fractionation by almost 10‰, when compared to the common assumption of equal diffusion coefficients for the two species. These small differences in diffusion coefficients yield calculated isotopic offsets between coeval sediment pore water sulfate and sulfide without disproportionation (up to 53.4‰) that exceed the largest fractionations observed in experimental cultures. Furthermore, the diffusion of sulfide within sediment pore waters leads to values that are even greater than those predicted by our model for sulfate reduction with unique diffusion coefficients. These diffusive effects on the sulfur isotope composition of pore water sulfate and sulfide can impact our interpretations of geologic records of sulfate and sulfide minerals, and should be considered in future studies.     

Oxygen isotope fractionation between apatite-bound carbonate and water determined from controlled experiments with synthetic apatites precipitated at 10-37 °C

The oxygen isotope fractionation between the structural carbonate of inorganically precipitated hydroxyapatite (HAP) and water was determined in the range 10-37 °C. Values of 1000 ln α() are linearly correlated with inverse temperature (K) according to the following equation: 1000 ln α() = 25.19 (±0.53)·T⁻¹ − 56.47 (±1.81) (R² = 0.998). This fractionation equation has a slightly steeper slope than those already established between calcite and water ( [O’Neil et al., 1969] and [Kim and O’Neil, 1997]) even though measured fractionations are of comparable amplitude in the temperature range of these experimental studies. It is consequently observed that the oxygen isotope fractionation between apatite carbonate and phosphate increases from about 7.5‰ up to 9.1‰ with decreasing temperature from 37 °C to 10 °C. A compilation of δ¹⁸O values of both phosphate and carbonate from modern mammal teeth and bones confirms that both variables are linearly correlated, despite a significant scattering up to 3.5‰, with a slope close to 1 and an intercept corresponding to a 1000 ln α() value of 8.1‰. This apparent fractionation factor is slightly higher or close to the fractionation factor expected to be in the range 7-8‰ at the body temperature of mammals.     

N/N and O/O stable isotope ratios of nitrous oxide produced during denitrification in temperate forest soils

Anaerobic incubations of upland and wetland temperate forest soils from the same watershed were conducted under different moisture and temperature conditions. Rates of nitrous oxide (N₂O) production by denitrification of nitrate () and the stable isotopic composition of the N₂O (δ¹⁵N, δ¹⁸O) were measured. In all soils, N₂O production increased with elevated temperature and soil moisture. At each temperature and moisture level, the rate of N₂O production in the wetland soil was greater than in the upland soil. The ¹⁵N isotope effect (ε) _{(product − substrate)} ranged from −20‰ to −29‰. These results are consistent with other published estimates of ¹⁵N fractionation from both single species culture experiments and soil incubation studies from different ecosystems.A series of incubations were conducted with ¹⁸O-enriched water (H₂O) to determine if significant oxygen exchange (O-exchange) occurred between H₂O and N₂O precursors during denitrification. The exchange of H₂O-O with nitrite () and/or nitric oxide (NO) oxygen has been documented in single organism culture studies but has not been demonstrated in soils prior to this study. The fraction of N₂O-O derived from H₂O-O was confined to a strikingly narrow range that differed between soil types. H₂O-O incorporation into N₂O produced from upland and wetland soils was 86% to 94% and 64% to 70%, respectively. Neither the temperature, soil moisture, nor the rate of N₂O production influenced the magnitude of O-exchange. With the exception of one treatment, the net ¹⁸O isotope effect (ε_net) _{(product-substrate)} ranged from +37‰ to +43‰.Most previous studies that have reported ¹⁸O isotope effects for denitrification of to N₂O have failed to account for the effect of oxygen exchange with H₂O. When high amounts of O-exchange occur after fractionation during reductive O-loss, the ¹⁸O-enrichment is effectively lost or diminished and δ¹⁸O-N₂O values will be largely dictated by δ¹⁸O-H₂O values and subsequent fractionation. The process and extent of O-exchange, combined with the magnitude of oxygen isotope fractionation at each reduction step, appear to be the dominant controls on the observed oxygen isotope effect. In these experiments, significant oxygen isotope fractionation was observed to occur after the majority of water O-exchange. Due to the importance of O-exchange, the net oxygen isotope effect for N₂O production in soils can only be determined using δ¹⁸O-H₂O addition experiments with δ¹⁸O-H₂O close to natural abundance.The results of this study support the continued use of δ¹⁵N-N₂O analysis to fingerprint N₂O produced from the denitrification of . The utilization of ¹⁸O/¹⁶O ratios of N₂O to study N₂O production pathways in soil environments is complicated by oxygen exchange with water, which is not usually quantified in field studies. The oxygen isotope fractionation observed in this study was confined to a narrow range, and there was a clear difference in water O-exchange between soil types regardless of temperature, soil moisture, and N₂O production rate. This suggests that ¹⁸O/¹⁶O ratios of N₂O may be useful in characterizing the actively denitrifying microbial community.     

First-principles estimates of equilibrium magnesium isotope fractionation in silicate, oxide, carbonate and hexaaquamagnesium(2+) crystals

Equilibrium mass-dependent magnesium isotope fractionation factors are estimated for a range of crystalline compounds including oxides, silicates, carbonates, and salts containing the solvation complex. Fractionation factors for the gas-phase species Mg and MgO are also presented. Fractionation factors are calculated with density functional perturbation theory (DFPT), using norm-conserving pseudopotentials. The results suggest that there will be substantial inter-mineral fractionation, particularly between tetrahedrally coordinated Mg²⁺ in spinel (MgAl₂O₄) and the more common octahedrally coordinated Mg²⁺-sites in silicate and carbonate minerals. Isotope fractionations calculated for Mg²⁺ in hexaaquamagnesium(2+) salts are in good agreement with previous fractionation models of based on large molecular clusters (Black et al., 2007), but show possibly more significant disagreement with a more recent study (Rustad et al., 2010). These models further suggest that solvated , in the form of , will have higher ²⁶Mg/²⁴Mg than coexisting magnesite and dolomite. Calculated fractionations are consistent with Mg-isotope fractionations observed in peridotite mineral separates and inorganic carbonate precipitates. Predicted large, temperature-sensitive spinel-silicate fractionations, in particular, may find use in determining equilibration temperatures of peridotites and other high-temperature rock types.     

Modeling the effects of bond environment on equilibrium iron isotope fractionation in ferric aquo-chloro complexes

Four or five sets of ab initio models, including Unrestricted Hartree Fock (UHF) and hybrid Density Functional Theory (DFT) are calculated for each species in a series of aqueous ferric aquo-chloro complexes: , , , FeCl₃(H₂O)₃, FeCl₃(H₂O)₂, , FeCl₅H₂O²⁻, , ) in order to determine the relative isotopic fractionation among the complexes, to compare the results of different models for the same complexes, to examine factors that influence the magnitude of the isotopic fractionation, and to compare bond-partner-driven fractionation with redox-driven fractionation.Relative to , all models show a nearly linear decrease in ⁵⁶Fe/⁵⁴Fe as the number of Cl⁻ ions per Fe³⁺ ion increases, with slopes of −0.8‰ to −1.0‰ per Cl⁻ at 20 °C. At 20 °C, 1000 ln β (β = ⁵⁶Fe/⁵⁴Fe reduced partition function ratio relative to a dissociated Fe atom) values range from 8.93‰ to 9.73‰ for , 8.04-9.12‰ for , 7.61-8.73‰ for , 7.14-8.25‰ for , and 3.09-4.41‰ for . The fractionation between and ranges from 1.5‰ to 2.6‰, depending on the model; this is comparable in magnitude to fractionation effects due to Fe³⁺/Fe²⁺ redox reactions. β values from the UHF models are consistently higher than those from the hybrid DFT models.Isotopic fractionation is shown to be sensitive to differences in ligand bond stiffness (above), coordination number, bond length, and the frequency of the asymmetric Fe-X stretching vibrational mode, as predicted by previous theoretical studies. Complexes with smaller coordination numbers have higher 1000 ln β (7.46‰, 5.25‰, and 3.48‰ for , ,, respectively, from the B3LYP/6-31G(d) model). Species with the same number of chlorides but fewer waters also show the effect of coordination number on 1000 ln β: (7.46‰ vs. 7.05‰ for FeCl₃(H₂O)₂ vs. FeCl₃(H₂O)₃ and 5.25‰ vs. 4.94‰ for vs. FeCl₅H₂O²⁻ with the B3LYP/6-31G(d) model). As more Fe-Cl bonds substitute for Fe-OH₂ bonds (with a resulting decrease in β), the lengths of the Fe-Cl bonds and the Fe-O bonds increase.Preliminary modeling of shows an Fe³⁺/Fe²⁺ fractionation of 3.2‰ for the B3LYP/6-31G(d) model, in agreement with previous studies. The addition of an explicit outer hydration sphere of 12 H₂O molecules to models of improves agreement with measured vibrational frequencies and bond lengths; 1000 ln β increases by 0.8-1.0‰. An additional hydration sphere around increases 1000 ln β by only 0.1‰.Isotopic fractionations predicted for this simple system imply that ligands present in an aqueous iron environment are potentially important drivers of fractionation, and suggest that significant fractionation effects are likely in other aqueous systems containing sulfides or organic ligands. Fractionation effects due to both speciation and redox must be considered when interpreting iron isotope fractionations in the geological record.