Kinetic Isotope Fractionation Factors Research Articles

Isotope fractionation of alkaline and alkaline-earth elements (Li, K, Rb, Mg, Ca, Sr, Ba) during diffusion in aqueous solutions

In this study, we used an improved “diffusion cell” method to precisely determine the diffusion-driven kinetic isotope fractionation factors of the Li, K, Rb, Mg, Ca, Sr, and Ba cations in aqueous solutions under room temperature. The obtained isotope fractionation factors (±2σ errors) are, α7/6Li = 0.996139 ± 0.000140, α41/39K = 0.998572 ± 0.000072, α87/85Rb = 0.999333 ± 0.000020, α26/24Mg = 0.999877 ± 0.000010, α44/42Ca = 0.999704 ± 0.000010, α88/86Sr = 0.999781 ± 0.000014, α138/135Ba = 0.999716 ± 0.000018. The results show that the charge of the cation and the ion-water bond length for the aquo ions are the two predominant factors affecting the mass dependence of isotope fractionation (β factor) during cation diffusion in aqueous solutions. Cations with higher charge numbers and shorter ion-water bond lengths exhibit less kinetic isotope fractionation during diffusion. Therefore, the isotope separation effect during diffusion (or β factor) in fluids is fundamentally controlled by the intensity of ion-water interaction. Weaker ion-water interaction (e.g., lower charge number, longer ion-water bond length) leads to less prominent hydrodynamic behavior for diffusing ions at the molecular level, thus more significant isotope fractionation in bulk solutions, and vice versa. Ions of larger radius would show stronger mass dependence of isotope fractionation (β factor), which can cancel the effect of decreasing relative isotope mass difference for heavier elements, thus kinetic isotope fractionation during diffusion in aqueous solutions remains prominent even for heavy elements such as Rb, Sr, and Ba. The diffusion-driven kinetic isotope fractionation factors measured in this study could provide a useful basis for interpreting specific natural isotopic variability of alkaline and alkaline-earth elements in supergene environments where chemical diffusion takes place.

Experimental and theoretical investigations of stable Sr isotope fractionation during its incorporation in aragonite

Strontium partitioning and isotope fractionation between aragonite and fluid have been determined experimentally at low values of the fluid saturation state (Ω) with respect to this mineral (1.1 ≤ Ωaragonite ≤ 2.2), and the measured isotope fractionation has been compared with the results of first-principles simulations. For the latter, Density Functional Theory (DFT) was used for estimation of the equilibrium Sr isotope fractionation between aragonite and Sr2+(aq). The obtained results suggest that, for values of Ωaragonite close to unity, the apparent distribution coefficient of Sr in aragonite (DSr,aragonite=XSrCO3XCaCO3(CaSr)fluid) exhibits values higher than one that rapidly decrease at increasing aragonite growth rate. Under equilibrium conditions (i.e. Ωaragonite=1) a DSr,aragoinite value of 2.7 can be extrapolated. Additionally, for aragonite growth rates rp ≤ 10−8.0±0.2 (mol/m2/s) the Sr isotope fractionation between aragonite and the fluid (i.e. Δ88/86Sraragonite-fluid) shows a constant value of −0.1±0.05‰, whereas it decreases to −0.40‰ when the growth rate increases to 10−7.7(mol/m2/s). The surface reaction kinetic model (SRKM) developed by DePaolo (2011) has been used to describe the dependence of DSr,aragonite and Δ88/86Sraragonite-fluid on mineral growth rate. In this model the best fit for DSr,aragonite and Δ88/86Sraragonite-fluid were 4 and −0.01‰, respectively, whereas the kinetic isotope fractionation factor for Δ88/86Sraragonite-fluid was −0.6‰. The results of first-principles calculations yield an equilibrium Sr isotope fractionation factor of −0.04‰ which is in excellent agreement with the experimental value of the present study. These results are the first experimental measurements of Sr isotope fractionation during inorganic aragonite precipitation as a function of growth rate and the first DFT calculations of Sr equilibrium fractionation in the aragonite-fluid system. The results of this study provide new insight into the mechanisms controlling stable Sr isotope composition in aragonite, which has implications for using Sr isotopes for paleo-reconstructions of natural archives, particularly those of abiogenic origin.

Kinetic zinc isotope fractionation in olivine phenocrysts records magma evolution history of intra-plate basalts

In the past few years, zinc isotope systematics of basaltic magmas have been widely used as novel proxies for terrestrial mantle heterogeneity induced by recycled crustal materials and for planet formation and evolution. The influence of crystal-melt isotope disequilibrium during magma differentiation on the zinc isotopic composition of basaltic melts, nonetheless, has received little attention. In addition, no quantitative constraint has yet been given for the diffusion-driven Zn isotope fractionation between olivine crystals and melts. Here we present high-precision zinc isotope data (δ66ZnJMC-Lyon) for a series of olivine phenocrysts separated from intra-plate alkali basalts from the Jiaodong Peninsula in Eastern China, together with in-situ chemical analysis. Olivine phenocrysts have Zn isotopic compositions which are too light in comparison with the host basaltic melts (Δ66Znol-melt = −0.41‰ to −0.10‰; n = 16) to be explained by equilibrium isotope fractionation at magmatic temperatures. Instead, the decrease of δ66Zn values with decreasing Mg# (i.e., Mg/[Mg + Fe2+] × 100) and increasing Zn + Fe2+ contents in olivine phenocrysts suggests diffusion-driven kinetic fractionation during olivine crystallization. The data is well-fitted with a diffusion model in which Zn together with Fe2+ diffuse from surrounding melt into olivine crystals and approximately equal flux of Mg diffuses into melt due to the large chemical gradient, yielding a kinetic Zn isotope fractionation factor βZn of 0.07. By utilizing the fractional crystallization model under equilibrium or disequilibrium conditions, it is suggested that diffusion-induced isotope disequilibrium during olivine crystallization may drive Zn isotopic composition of the residual melt toward heavier values. When using zinc isotope systematics of any basaltic magma to probe the source heterogeneity, this impact must be taken into account if the Zn isotope disequilibrium widely exists in olivine phenocrysts. Based on the time-related quantitative diffusion model, our results show that the magma residence time for strongly alkali basaltic lavas (∼20 days) is 10–60 times shorter than that for weakly alkali basaltic lavas (6 months to 4 years). This supports the generation of weakly alkali basalts via interaction between silica-undersaturated melts and the surrounding lithospheric mantle, implying a probable common mechanism in intra-plate basalts that could be comparable globally. Thus, Zn isotope disequilibrium between olivine crystals and melts could provide valuable information on the evolution history of intra-plate basaltic magmas.

Effect of growth rate and pH on Li isotope fractionation during its incorporation in calcite

Lithium isotope compositions were determined for synthetic calcite and fluid, reported in Füger et al. (2019). Calcite was precipitated at 25 °C, and mineral growth rate and pH varied within the range of 10−8.1 ≤ rp (mol m−2 s−1) ≤ 10−7.2 and 6.3 ≤ pH ≤ 9.5, respectively. At pH = 8.25 ± 0.15, the Δ7Licalcite-fluid = δ7Licalcite - δ7Lifluid value of −2.76 ± 0.22‰ (n = 4) was yielded when calcite growth rate was lower than ∼ 10−7.7 (mol m−2 s−1). As calcite growth rate increased, Δ7Licalcite-fluid values progressively decreased to about −4.5‰. The dependence of Li isotope fractionation on calcite growth rate is described by the surface reaction kinetic model developed by DePaolo (2011). In this model the equilibrium and kinetic isotope fractionation factors obtain values of −2.7 ± 0.1‰ and −8.8 ± 0.1‰, respectively. In addition, for experiments performed under similar surface-normalized growth rate of 10−7.7±0.2 (mol m−2 s−1) a significant decrease in Δ7Licalcite-fluid from pH 9.5 to 6.3 was observed. These variations of Δ7Licalcite-fluid as a function of pH for experiments performed under low degrees of solution saturation with respect to calcite point towards the incorporation of two or more Li-bearing species in the solid phase. Thus, the Li isotope composition of the solid reflects the abundance of these species, which depends on solution pH and fluid composition.Overall the results of this study suggest that both calcite growth rate and pH are parameters that can significantly affect the measured Li isotope fractionation between calcite and fluid. The high sensitivity of Δ7Licalcite-fluid to calcite growth rate observed in this study suggests that a high variability of δ7Licalcite in natural samples, such as foraminifera, brachiopods, and speleothems can be expected in natural environments. The implications for the potential use of elemental and isotope fractionation of Li during calcite formation are discussed in the light of reconstruction of paleo-environmental conditions.

Isotopic fractionation accompanying CO2 hydroxylation and carbonate precipitation from high pH waters at The Cedars, California, USA

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 (<0.01). Precipitation of aragonite is likely promoted by the high pH (11.5–12.0) of pool waters, in agreement with published experiments illustrating the effect of pH on calcium carbonate polymorph selection.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 HCO3-, 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.

Ideas and perspectives: The same carbon behaves like different elements – an insight into position-specific isotope distributions

Abstract. It is expected that information on the source, reaction pathway, and reaction kinetics of an organic compound can be obtained from its position-specific isotope compositions or intramolecular isotope distribution (Intra-ID). To retrieve the information, we could use its predicted equilibrium Intra-ID as a reference for understanding the observed Intra-IDs. Historically, observed, apparently close-to-equilibrium carbon Intra-ID has prompted an open debate on the nature of biosystems and specifically the pervasiveness of reversible biochemical reactions. Much of the debate remains unresolved, and the discussion has not clearly distinguished between two states of equilibrium: (1) the equilibrium among the corresponding bond-breaking and bond-forming positions in reactant and product and (2) the equilibrium among all carbon positions within a compound. For an organic molecule with multiple carbon positions, equilibrium carbon Intra-ID can be attained only when a specific reaction is in equilibrium and the sources of each position are also in equilibrium with each other. An observed Intra-ID provides limited information on if the sources and pathways are both unconstrained. Here, we elaborate on this insight using examples of the observed Intra-IDs of hydroxyl-bearing minerals, N2O, and acetic acid. Research effort aiming to calibrate position-specific equilibrium and kinetic isotope fractionation factors for defined processes will help to interpret observed Intra-IDs of a compound accurately and fully.

Experimental investigation of lithium isotope fractionation during kaolinite adsorption: Implications for chemical weathering

The feedback between CO2 sources and sinks through chemical weathering is one of the important reasons why Earth has maintained a habitable climate for over four billion years. The lithium (Li) isotopic system is a promising tracer of silicate weathering, but the mechanisms causing its isotope fractionation during weathering remain ambiguous. Here, we performed batch experiments of Li adsorption to one of the common clay minerals -kaolinite in three sets, including the time-series, pH-dependent, and concentration-control sets. Our results demonstrate that the liquid-solid Li isotope fractionation reaches up to 36‰, with up to 99% initial Li being adsorbed on kaolinite. The magnitudes of Li adsorption and isotope fractionation increase with reaction time, and reach the steady-state after ∼1000 min. The magnitude of Li isotope fractionation increases with the adsorption ratio of Li, in positive relationships with solute pH and ionic strength. At constant solute pH = 8.5 and ionic strength of 0.001 M, the adsorption ratio and isotope fractionation of Li on kaolinite reach the maximum with the lowest initial Li concentration of 2 μM. In experiments, Li is removed by kaolinite as the inner-sphere and/or outer-sphere complexes, likely followed by structural occupation as supported by incomplete desorption. We model the Li isotope fractionation in all three sets, which can be best described by Rayleigh distillation models. In summary, significant Li isotope fractionation occurs following a kinetic law in closed-systems during adsorption on kaolinite. Adsorption-driven isotope fractionation conforms to a kinetic solid-liquid isotope fractionation factor α ∼ 0.992, consistent with theoretical ion-desolvation between complexed and dissolved ions (α = 0.9925, Hofmann et al., 2012). This study reveals a vital kinetic role of clay uptake in Li isotope fractionation during chemical weathering, suggesting rapid forward adsorption reaction versus relatively slow backward reaction. The dominance of the kinetic mechanism over the equilibrium mechanism further explains field observations from rivers worldwide. Given above, the outcome of this study calls for additional attention on low-temperature kinetic Li isotope fractionation at Earth’s surface and further refinement of quantitative models using geological Li records to trace weathering and reconstruct climate.

Stable isotope fractionations in the evaporation of water: The wind effect

AbstractWe performed pan evaporation experiments with the objective of exploring the behaviour of the long‐standing Craig–Gordon (C–G) stable isotope model for evaporation under different conditions of air turbulence. The water lost through evaporation was automatically replenished so that a steady isotopic composition was reached, the value of which depended on the isotopic composition of the replenishment water and environmental parameters like temperature, relative humidity and isotopic composition of the atmospheric vapour, and the air turbulence index. The pans were exposed to artificial winds ranging from 0 to 2.5 m/s to change the air turbulence index, which governs the repartition between vapour transported by molecular diffusion and turbulent diffusion. Our data revealed that for wind speeds &gt;0.5 m/s the isotopic composition of the evaporating water deviated from that predicted by the C–G model. This deviation was hypothetically attributed to microdroplets of liquid water removed by the wind without any isotopic fractionation. Isotope mass balance equations allowed us to quantify this water loss, which at wind speeds of ~2 m/s reached 10% of the total evaporation losses. An alternative kinetic evaporation model was proposed whereby the equilibrium layer and the atmospheric laminar layer above the evaporating water of the C–G model were destroyed by the wind and evaporated water molecules were directly injected into the atmosphere. In this model, the isotopic fractionations were due to the slower kinetics of hydrogen bond breakage between molecules in liquid water when heavy isotopes are involved. Accordingly, our data suggested that for isotope water balance studies where winds are frequently above 2 m/s, the C–G model may be inadequate without appropriate corrections for spray vaporization, or the introduction of appropriate kinetic isotope fractionation factors.

Molecular simulations of kinetic stable calcium isotope fractionation at the calcite-aqueous interface

The measurement of calcium stable isotope fractionation during crystal growth can provide insights into the dominant pathways and mechanisms of crystal growth, but these interpretations require a detailed understanding of mass dependent reaction rates and free energy states at the molecular scale. Here we report the results of free energy calculations used to determine the rate-limiting step controlling kinetic stable isotope fractionation during calcium ion attachment to active growth sites – kink sites – at the calcite surface. The free energy profile for attachment is combined with ion coordination states to reconstruct the multi-step molecular pathway for the ion attachment process. Dissociative desolvation of a water molecule coordinating the calcium ion approaching the kink is identified as the rate-limiting step, with a free energy barrier of ∼18kJ/mol, which is equal to the energetic cost of water molecule leaving Ca2+ coordination shell in the aqueous phase. Molecular dynamics simulations were used to investigate the dependence of this desolvation step on calcium ion mass. Both brute force MD and an analysis of mass dependent water exchange coefficients (kwex) give identical kinetic stable isotope fractionation factor values αf44/40=0.992, which corresponds to Δ44/40Ca of ∼ -8‰, originating from a mass-dependent transition frequency for the Ca-bound solvation water at the kink. This value is significantly higher than the fractionation factor associated with water exchange dynamics around Ca2+ in bulk aqueous solution determined here (αf44/40=0.999). Our results confirm that the growing calcite surface should be depleted in 44Ca with respect to the aqueous phase due to kinetically preferred desolvation of the lighter isotope. We conclude that the maximum kinetic stable isotope fractionation associated with calcium attachment to surfaces is not constant but can vary due to changes in the interfacial environment that affect local solvent dynamics during desolvation.

Chemical and Isotopic Evidence for Organic Matter Sulfurization in Redox Gradients Around Mangrove Roots

Coastal environments like mangrove forests are increasingly recognized as potential hotspots for organic carbon burial, giving them a crucial and yet poorly constrained role in the global carbon cycle. Mangrove sediments are frequently anoxic, which facilitates elevated organic matter (OM) burial via several mechanisms, including sulfurization – abiotic reactions between dissolved (poly)sulfide and OM that decrease its lability. Although sulfurization was estimated to account for roughly half of OM preservation in a Bermuda mangrove forest, both its mechanisms and its global significance remain poorly understood. In this study, we investigate S cycling in mangrove forest sediments from Little Ambergris Cay, Turks and Caicos Islands, an environment with predominantly microbial OM inputs and no major source of terrestrial iron. We characterize the S- and C-isotope composition and organic S speciation of sedimentary OM fractions with varying degrees of resistance to acid hydrolysis, along with other inorganic S phases. Near the surface of a 3-mm-diameter, O2-releasing root, abundant organic and elemental S with a 34S-depleted composition indicates microbial sulfur cycling and OM sulfurization. A mixture of pyrite, elemental S, and organic S form a plaque within the outer 50 m of the root, which also contains strongly 34S-depleted sulfate in its xylem. OM sulfurization products in the sediments include both the alkyl sulfides and disulfides associated with the root plaque and more oxidized forms, especially sulfonates. Hydrolysis-resistant organic S in the sediments is consistently 3–5‰ more 34S-enriched than coexisting elemental S, matching the reported kinetic isotope fractionation factor for OM sulfurization via reaction with polysulfides. These sediments also contain a substantial pool of solid-phase, hydrolysable organic S with a seawater sulfate-like isotope composition, largely in the form of sulfate esters, which may represent excretions from abundant gastropods. The coexistance of sulfurized OM and aerobic macrofauna highlights how understanding spatial scales and/or temporal cycles in local redox state is critical for predicting net OM preservation, especially in dynamic, coastal environments. Future attempts to mechanistically predict changes in carbon storage in coastal systems will benefit from incorporating OM sulfurization as both a sink for microbially produced sulfide and a mechanism for enhanced carbon sequestration.

Triple oxygen isotope fractionation in the DIC-H2O-CO2 system: A numerical framework and its implications

Triple oxygen isotope composition of carbonate minerals reflects the isotope composition of the water from which carbonates precipitate, and is emerging as a promising proxy for constraining past changes in Earth hydroclimate and surface environment. However, quantitative interpretation of this proxy is not straightforward when carbonate minerals do not form under isotope equilibrium with water. For these carbonates, isotope composition of dissolved inorganic carbon (DIC) in the precipitating solution usually exerts the dominant control on their isotope composition. Here we examine the systematics of triple oxygen isotope fractionation in the DIC-H2O-CO2 system by deriving the fundamental equilibrium and kinetic triple oxygen isotope fractionation factors in this system and simulating the evolution of triple oxygen isotope composition of DIC during three common isotope fractionation processes, i.e., DIC-H2O isotope exchange, CO2 degassing and CO2 absorption.We show that under thermodynamic equilibrium dissolved HCO3– and CO32– both exhibit similar Δ′17O as calcite and aragonite (within 10 per meg at 25 °C), with temperature dependences around 0.61 per meg/°C. However, kinetic isotope fractionations associated with CO2 hydration and hydroxylation and their reverse reactions can produce a range of disequilibrium triple oxygen isotope effects in DIC during all three processes we simulated. The magnitudes of these disequilibrium effects vary with both time and the physicochemical conditions of the solution, e.g., temperature, pH and initial composition. Particularly, we predict correlated enrichments in Δ′17O and δ18O of DIC during CO2 degassing but depletions during CO2 absorption. The slopes of these correlations vary mainly as a function of solution pH but not temperature, DIC concentration or air pCO2, yielding values of 8.8 and 12.0 per meg/‰ at pH = 8 and 9, respectively, at 25 °C. Such disequilibrium isotope effects in DIC are expected to be inherited by carbonate minerals that form from these solutions (e.g., speleothem, coral skeleton, and high pH travertine) and, if not accounted for, could lead to inaccurate estimates of the triple oxygen isotope compositions of the parent water and carbonate formation temperatures. Our numerical model provides a quantitative framework for interpreting triple oxygen isotope composition of DIC and for correcting disequilibrium triple oxygen isotope effects in natural carbonates.

Nitrogen isotope fractionation factors (α) measured and estimated from the volatilisation of ammonia from water at pH 9.2 and pH 8.5

ABSTRACTThis paper examines the nitrogen isotope fractionation factors (α) associated with the volatilisation of ammonia from water under controlled conditions at two pH values (8.5 and 9.2). This experiment assumed the continuous removal of ammonia at a single purge rate of 10 mL air min−1. The fractionation resulting from the removal of total ammonia from the water into an acid trap was named the observed isotope fractionation factor (αobs), and it was measured as 1.019 (±0.0025) at pH 8.5 and 1.030 (±0.0025) at pH 9.2. The observed isotope fractionation factor includes the equilibrium isotope fractionation factor (αeq) and the kinetic isotope fractionation factor (αkin), each one mathematically derived from the experimental data. The equilibrium and kinetic isotope fractionation factors were estimated as αeq = 1.036 (±0.0014) and αkin = 1.050 (±0.003), respectively. Our results are compared to other previously measured and estimated fractionation factors.

Oxygen isotope analysis of bacterial and fungal manganese oxidation.

The ability of micro-organisms to oxidize manganese (Mn) from Mn(II) to Mn(III/IV) oxides transcends boundaries of biological clade or domain. Many bacteria and fungi oxidize Mn(II) to Mn(III/IV) oxides directly through enzymatic activity or indirectly through the production of reactive oxygen species. Here, we determine the oxygen isotope fractionation factors associated with Mn(II) oxidation via various biotic (bacteria and fungi) and abiotic Mn(II) reaction pathways. As oxygen in Mn(III/IV) oxides may be derived from precursor water and molecular oxygen, we use a twofold approach to determine the isotope fractionation with respect to each oxygen source. Using both 18 O-labeled water and closed-system Rayleigh distillation approaches, we constrain the kinetic isotope fractionation factors associated with O atom incorporation during Mn(II) oxidation to -17.3‰ to -25.9‰ for O2 and -1.9‰ to +1.8‰ for water. Results demonstrate that stable oxygen isotopes of Mn(III/IV) oxides have potential to distinguish between two main classes of biotic Mn(II) oxidation: direct enzymatic oxidation in which O2 is the oxidant and indirect enzymatic oxidation in which superoxide is the oxidant. The fraction of Mn(III/IV) oxide-associated oxygen derived from water varies significantly (38%-62%) among these bio-oxides with only weak relationship to Mn oxidation state, suggesting Mn(III) disproportionation may account for differences in the fraction of mineral-bound oxygen from water and O2 . Additionally, direct incorporation of molecular O2 suggests that Mn(III/IV) oxides contain a yet untapped proxy of δ18OO2 of environmental O2 , a parameter reflecting the integrated influence of global respiration, photorespiration, and several other biogeochemical reactions of global significance.

Experimental investigation of nitrogen isotopic effects associated with ammonia degassing at 0–70 °C

Ammonia degassing is a common process in natural alkaline waters and in the atmosphere. To quantitatively assess the nitrogen cycle in these systems, the essential parameter of nitrogen isotope fractionation factors associated with ammonia degassing is required, but still not constrained yet. In this study, we carried out laboratory experiments to examine the nitrogen isotope behavior during ammonia degassing in alkaline conditions. The experiments started with ammonium sulfate solution with excess sodium hydroxide. The reaction can be described as: NH4+ + OH− (excess) → NH3·nH2O → NH3 (g)↑. Two sets of experiments, one with ammonia degassing under static conditions and the other with ammonia degassing by bubbling of N2 gas, were carried out at 2, 21, 50, and 70 °C. The results indicate that kinetic isotopic effects are dominated during efficient degassing of ammonia in the bubbling experiments, which yielded kinetic nitrogen isotope fractionation factors αNH3(g)–NH3(aq) of 0.9898 at 2 °C, 0.9918 at 21 °C, 0.9935 at 50 °C and 0.9948 at 70 °C. These values show a good relationship with temperature as 103lnαNH3(g)–NH3(aq) = 14.6 − 6.8 × 1000/T. In contrast, isotopic effects during less efficient degassing of ammonia in the static experiments are more complicated. The results do not match either kinetic isotope fractionation or equilibrium isotope fractionation but sit between these two. The most likely cause is that back dissolution of the degassed ammonia occurred in these experiments and consequently shifted kinetic isotope fractionation toward equilibrium isotope fractionation. Our experimental results highlight complicated isotopic effects may occur in natural environments, and need to be fully considered in the interpretation of field data.

Equilibrium and kinetic Si isotope fractionation factors and their implications for Si isotope distributions in the Earth’s surface environments

Abstract Several important equilibrium Si isotope fractionation factors among minerals, organic molecules and the H4SiO4 solution are complemented to facilitate the explanation of the distributions of Si isotopes in Earth’s surface environments. The results reveal that, in comparison to aqueous H4SiO4, heavy Si isotopes will be significantly enriched in secondary silicate minerals. On the contrary, quadra-coordinated organosilicon complexes are enriched in light silicon isotope relative to the solution. The extent of 28Si-enrichment in hyper-coordinated organosilicon complexes was found to be the largest. In addition, the large kinetic isotope effect associated with the polymerization of monosilicic acid and dimer was calculated, and the results support the previous statement that highly 28Si-enrichment in the formation of amorphous quartz precursor contributes to the discrepancy between theoretical calculations and field observations. With the equilibrium Si isotope fractionation factors provided here, Si isotope distributions in many of Earth’s surface systems can be explained. For example, the change of bulk soil δ30Si can be predicted as a concave pattern with respect to the weathering degree, with the minimum value where allophane completely dissolves and the total amount of sesqui-oxides and poorly crystalline minerals reaches their maximum. When, under equilibrium conditions, the well-crystallized clays start to precipitate from the pore solutions, the bulk soil δ30Si will increase again and reach a constant value. Similarly, the precipitation of crystalline smectite and the dissolution of poorly crystalline kaolinite may explain the δ30Si variations in the ground water profile. The equilibrium Si isotope fractionations among the quadra-coordinated organosilicon complexes and the H4SiO4 solution may also shed light on the Si isotope distributions in the Si-accumulating plants.

Silicon isotope fractionation during the precipitation of quartz and the adsorption of H4SiO4(aq) on Fe(III)-oxyhydroxide surfaces

Equilibrium Si isotope fractionation factors among orthosilicic acid (i.e.,H4SiO4(aq)), quartz and the adsorption complexes of H4SiO4(aq) on Fe(III)-oxyhydroxide surface were calculated using the full-electron wave-function quantum chemistry methods [i.e., B3LYP/6-311G(2df,p)] with a new cluster-model-based treatment. Solvation effects were carefully included in our calculations via water-droplet method combined with implicit solvent models (e.g., PCM). The results revealed that, if it is under equilibrium conditions, heavy Si isotopes would be significantly enriched in quartz in comparison to H4SiO4(aq). However, most of the field observations suggested that quartz would have identical or even depleted δ30Si values compared to that of H4SiO4(aq). To explain this discrepancy between the equilibrium calculation results and the field observations, the kinetic isotope effect (KIE) associated with the formation of amorphous silica, which usually is the precursor of crystalline quartz, was investigated using quantum chemistry methods. The KIE results showed that amorphous silica would be significantly enriched in light Si isotopes during its formation. Our equilibrium fractionation results, however, matched a special type of quartz (i.e., Herkimer “diamond”) very well, due to its nearly equilibrated precipitation condition. Opposite to the case of precipitated quartz, a large equilibrium Si isotope fractionation (i.e., −3.0 ‰) was found between the absorbed bidentate Si surface complexes (i.e., 2C > Fe2O2Si(OH)2) and H4SiO4(aq). This calculated equilibrium Si isotope fractionation factor largely differed from a previous experimental result (ca. −1.08 ‰). We found that the formation of transient or temporary surface complexes [e.g., 1V > Fe2OSi(OH)3] may have accounted for the smaller net fractionation observed. With the equilibrium and kinetic Si isotope fractionation factors provided here, the distributions and changes of Si isotope compositions in the Earth’s surface systems can be better understood.

Enrichment of nitrogen and 13C of methane in natural gases from the Khuff Formation, Saudi Arabia, caused by thermochemical sulfate reduction

Permian Khuff reservoirs along the east coast of Saudi Arabia and in the Arabian Gulf produce dry sour gas with highly variable nitrogen concentrations. Rough correlations between N2/CH4, CO2/CH4 and H2S/CH4 suggest that non-hydrocarbon gas abundances are controlled by thermochemical sulfate reduction (TSR). In Khuff gases judged to be unaltered by TSR, methane δ13C generally falls between −40‰ and −35‰ VPDB and carbon dioxide δ13C between −3‰ and 0‰ VPDB. As H2S/CH4 increases, methane δ13C increases to as much as −3‰ and carbon dioxide δ13C decreases to as little as −28‰. These changes are interpreted to reflect the oxidation of methane to carbon dioxide.Khuff reservoir temperatures, which locally exceed 150°C, appear high enough to drive the reduction of sulfate by methane. Anhydrite is abundant in the Khuff and fine grained nodules are commonly rimmed with secondary calcite cement. Some cores contain abundant pyrite, sphalerite and galena. Assuming that nitrogen is inert, loss of methane by TSR should increase N2/CH4 of the residual gas and leave δ15N unaltered. δ15N of Paleozoic gases in Saudi Arabia varies from −7‰ to 1‰ vs. air and supports the TSR hypothesis. N2/CH4 in gases from stacked Khuff reservoirs varies by a factor of 19 yet the variation in δ15N (0.3–0.5‰) is trivial.Because the relative abundance of hydrogen sulfide is not a fully reliable extent of reaction parameter, we have attempted to assess the extent of TSR using plots of methane δ13C versus log(N2/CH4). Observed variations in these parameters can be fitted using simple Rayleigh models with kinetic carbon isotope fractionation factors between 0.98 and 0.99. We calculate that TSR may have destroyed more than 90% of the original methane charge in the most extreme instance. The possibility that methane may be completely destroyed by TSR has important implications for deep gas exploration and the origin of gases rich in nitrogen as well as hydrogen sulfide.

Si stable isotope fractionation during adsorption and the competition between kinetic and equilibrium isotope fractionation: Implications for weathering systems

The adsorption of Si onto amorphous Al-hydroxides is the cause for the light Si isotope signature that secondary crystalline clay minerals in weathering systems carry. We propose this hypothesis from a series of adsorption experiments in which the light isotopes are being favored during Si adsorption onto crystalline gibbsite and in which the associated fractionation factor depends on the solution's initial Si concentration.Three adsorption experiments were carried out at pH7 with different initial Si concentrations of 0.36, 0.71 and 1.42mmol/l Si start concentrations. As Al-hydroxide adsorbent, 30g/l crystalline gibbsite were used to provide equal surface area in all experiments. Adsorption rates are higher with higher initial Si concentration. At the same time, calculated apparent isotope fractionation factors 103lnαadsorbed/solution decrease from −1.8 to −3‰ with increasing initial Si concentration. As care was taken to avoid isotope fractionation during transport of dissolved Si to the gibbsite surface, the mass dependence of the activation energy barrier at the interface is causing the kinetic isotope fractionation. Within the mass balance framework of DePaolo (2011) the shift in Si isotope fractionation with initial Si concentration is interpreted to be induced by different kinetic isotope fractionation factors associated with the forward reaction. Only after ca. two months do the isotope ratios begin to adjust to an equilibrium isotope fractionation factor that is close to 0‰. With such slow re-equilibration Si adsorption differs fundamentally from transition metals that re-equilibrate isotopically within hours after adsorption onto Fe and Mn oxide surfaces.These observations may provide an explanation for the light Si isotope signature clay minerals formed during weathering carry: the light Si isotope composition is being inherited early on during Si adsorption onto amorphous Al-hydroxides and is potentially carried over during all further stages of transformation.

Assessing the control on the effective kinetic Cr isotope fractionation factor: A reactive transport modeling approach

The fractionation of stable Cr isotopes is a well-accepted proxy for demonstrating Cr(VI) reduction occurring in geological systems. Published values for experimentally determined effective kinetic Cr isotope enrichment factors (εkin) vary over the range of 0.4–5.0‰. Most published studies propose a variation in Cr(VI) reduction mechanisms as being responsible for the wide range of εkin. Alternatively, varying reaction rates and/or transport limitations have been addressed. In this study the different contributions on εkin were quantitatively addressed by performing a series of reactive transport model simulations. The proposed reaction network is based on a novel multi-continuum approach and expressing isotope fractionation through the formation of a 53Cr(OH)3(s)–52Cr(OH)3(s) solid solution as the product of Cr(VI) reduction. In doing so, Cr(VI) reduction was considered to occur at solid surfaces and Cr isotope fractionation was modeled by defining an equilibrium enrichment factor.Simulating Cr(VI) reduction occurring along a 1D flow path suggested that for a given reaction mechanism εkin can vary over a large range. According to our simulations the upper range of εkin is defined by a reaction mechanism's theoretical equilibrium enrichment factor. In contrast, high reduction rate and/or transport limitations can shift εkin to very low values. In a second model simulation our modeling approach was used to propose an alternative kinetic interpretation for the low εkin observed in Fe(II)–Cr(VI) reduction experiment by others.Our simulations suggest that the individual contributions of reaction rates, transport limitations and reaction mechanisms should be addressed more carefully when interpreting experimentally determined kinetic Cr isotope enrichment factors and Cr isotope data derived from field sites. Reactive transport modeling is a powerful tool, which should be more commonly used to quantitatively assess these individual contributions in experimental systems.

Isotope fractionation and mixing in methane plumes from the Logatchev hydrothermal field

As methane is consumed in the deep sea, its 13C/12C ratio progressively increases because of kinetic isotope fractionation. Many submarine hydrothermal vents emit methane with carbon isotope ratios that are higher than those of background methane in the surrounding ocean. Since the latter exists at low concentrations, mixing of background methane with vent fluid tends to decrease the 13C/12C ratio as concentration decreases, opposite to the trend produced by consumption. We investigated CH4 concentration and δ13C together with δ3He in plumes from the Logatchev hydrothermal field (LHF) located at 14°45′N, 45°W, which generates relatively heavy methane (δ13C ≈ −13‰) by serpentinization of ultramafic rock. The measured methane and δ3He were well correlated at high concentrations, indicating a CH4/3He ratio of 1 × 108 in the vent fluids. These tracer distributions were also simulated with an advection‐diffusion model in which methane consumption only occurs above a certain threshold concentration. We utilized δ3He to calculate the methane remaining in solution after oxidation, f, and the deviation of δ13C from the value expected from mixing alone, Δδ13C. Both in the model and in the data, the entire set of Δδ13C values are not correlated with log f, which is due to continuous oxidation within the plume while mixing with background seawater. A linear relationship, however, is found in the model for methane at concentrations sufficiently above background, and many of the samples with elevated CH4 north of LHF exhibit a linear trend of Δδ13C versus log f as well. From this trend, the kinetic isotope fractionation factor in the LHF plumes appears to be about 1.015. This value is somewhat higher than found in some other deep‐sea studies, but it is lower than found in laboratory incubation experiments.