Kinetic Isotope Fractionation Factors Research Articles

The NO+O3 reaction: A triple oxygen isotope perspective on the reaction dynamics and atmospheric implications for the transfer of the ozone isotope anomaly

Atmospheric nitrate shows a large oxygen isotope anomaly (Delta 17 O), characterized by an excess enrichment of 17 O over 18 O, similar to the ozone molecule. Modeling and observations assign this specific isotopic composition mainly to the photochemical steady state that exists in the atmosphere between ozone and nitrate precursors, namely, the nitrogen oxides (NOx=NO+NO2). However, this transfer is poorly quantified and is built on unverified assumptions about which oxygen atoms of ozone are transferred to NO(x), greatly weakening any interpretation of the nitrate oxygen isotopic composition in terms of chemical reaction pathways and the oxidation state of the atmosphere. With the aim to improve our understanding and quantify how nitrate inherits this unusual isotopic composition, we have carried out a triple isotope study of the reaction NO+O3. Using ozone intramolecular isotope distributions available in the literature, we have found that the central atom of the ozone is abstracted by NO with a probability of (8+/-5)%(+/-2 sigma) at room temperature. This result is at least qualitatively supported by dynamical reaction experiments, the non-Arrhenius behavior of the kinetic rate of this reaction, and the kinetic isotope fractionation factor. Finally, we have established the transfer function of the isotope anomaly of O3 to NO2, which is described by the linear relationship Delta 17 O(NO2)=A x Delta 17 O(O3)+B, with A=1.18+/-0.07(+/-1 sigma) and B=(6.6+/-1.5)[per thousand](+/-1 sigma). Such a relationship can be easily incorporated into models dealing with the propagation of the ozone isotope anomaly among oxygen-bearing species in the atmosphere and should help to better interpret the oxygen isotope anomaly of atmospheric nitrate in terms of its formation reaction pathways.

Assessment of microbial methane oxidation above a petroleum‐contaminated aquifer using a combination of in situ techniques

Emissions of the greenhouse gas CH4, which is often produced in contaminated aquifers, are reduced or eliminated by microbial CH4 oxidation in the overlying vadose zone. The aim of this field study was to estimate kinetic parameters and isotope fractionation factors for CH4 oxidation in situ in the vadose zone above a methanogenic aquifer in Studen, Switzerland, and to characterize the involved methanotrophic communities. To quantify kinetic parameters, several field tests, so‐called gas push‐pull tests (GPPTs), with CH4 injection concentrations ranging from 17 to 80 mL L−1 were performed. An apparent Vmax of 0.70 ± 0.15 mmol CH4 (L soil air)−1 h−1 and an apparent Km of 0.28 ± 0.09 mmol CH4 (L soil air)−1 was estimated for CH4 oxidation at 2.7 m depth, close to the groundwater table. At 1.1 m depth, Km (0.13 ± 0.02 mmol CH4 (L soil air)−1) was in a similar range, but Vmax (0.076 ± 0.006 mmol CH4 (L soil air)−1 h−1) was an order of magnitude lower. At 2.7 m, apparent first‐order rate constants determined from a CH4 gas profile (1.9 h−1) and from a single GPPT (2.0 ± 0.03 h−1) were in good agreement. Above the groundwater table, a Vmax much higher than the in situ CH4 oxidation rate prior to GPPTs indicated a high buffer capacity for CH4. At both depths, known methanotrophic species affiliated with Methylosarcina and Methylocystis were detected by cloning and sequencing. Apparent stable carbon isotope fractionation factors α for CH4 oxidation determined during GPPTs ranged from 1.006 to 1.032. Variability was likely due to differences in methanotrophic activity and CH4 availability leading to different degrees of mass transfer limitation. This complicates the use of stable isotopes as an independent quantification method.

Elemental and isotopic fractionation of Type B CAI-like liquids by evaporation

Vacuum evaporation experiments with Type B CAI-like starting compositions were carried out at temperatures of 1600, 1700, 1800, and 1900 °C to determine the evaporation kinetics and evaporation coefficients of silicon and magnesium as a function of temperature as well as the kinetic isotope fractionation factor for magnesium. The vacuum evaporation kinetics of silicon and magnesium are well characterized by a relation of the form J = J oe − E/ RT with J o = 4.17 × 10 7 mol cm −2 s −1, E = 576 ± 36 kJ mol −1 for magnesium, J o = 3.81 × 10 6 mol cm −2 s −1, E = 551 ± 63 kJ mol −1 for silicon. These rates only apply to evaporation into vacuum whereas the actual Type B CAIs were almost certainly surrounded by a finite pressure of a hydrogen-dominated gas. A more general formulation for the evaporation kinetics of silicon and magnesium from a Type B CAI-like liquid that applies equally to vacuum and conditions of finite hydrogen pressure involves combining our determinations of the evaporation coefficients for these elements as a function of temperature ( γ = γ 0e − E/ RT with γ 0 = 25.3, E = 92 ± 37 kJ mol −1 for γ Si; γ 0 = 143, E = 121 ± 53 kJ mol −1 for γ Mg) with a thermodynamic model for the saturation vapor pressures of Mg and SiO over the condensed phase. High-precision determinations of the magnesium isotopic composition of the evaporation residues from samples of different size and different evaporation temperature were made using a multicollector inductively coupled plasma mass spectrometer. The kinetic isotopic fractionation factors derived from this data set show that there is a distinct temperature effect, such that the isotopic fractionation for a given amount of magnesium evaporated is smaller at lower temperature. We did not find any significant change in the isotope fractionation factor related to sample size, which we interpret to mean that recondensation and finite chemical diffusion in the melt did not affect the isotopic fractionations. Extrapolating the magnesium kinetic isotope fractionations factors from the temperature range of our experiments to temperatures corresponding to partially molten Type B CAI compositions (1250–1400 °C) results in a value of α Mg ≈ 0.991, which is significantly different from the commonly used value of α Mg = 0.97977 = 23.98504 / 24.98584 .

Modelling the budget of middle atmospheric water vapour isotopes

Abstract. A one-dimensional chemistry model is applied to study the stable hydrogen (D) and stable oxygen isotope (17O, 18O) composition of water vapour in stratosphere and mesosphere. In the troposphere, this isotope composition is determined by "physical'' fractionation effects, that are phase changes (e.g. during cloud formation), diffusion processes (e.g. during evaporation from the ocean), and mixing of air masses. Due to these processes water vapour entering the stratosphere first shows isotope depletions in D/H relative to ocean water, which are ~5 times of those in 18O/16O, and secondly is mass-dependently fractionated (MDF), i.e. changes in the isotope ratio 17O/16O are ~0.52 times of those of 18O/16O. In contrast, in the stratosphere and mesosphere "chemical'' fractionation mechanisms, that are the production of HO due to the oxidation of methane, re-cycling of H2O via the HOx family, and isotope exchange reactions considerably enhance the isotope ratios in the water vapour imported from the troposphere. The model reasonably predicts overall enhancements of the stable isotope ratios in H2O by up to ~25% for D/H, ~8.5% for 17O/16O, and ~14% for 18O/16O in the mesosphere relative to the tropopause values. The 17O/16O and 18O/16O ratios in H2O are shown to be a measure of the relative fractions of HOx that receive the O atom either from the reservoirs O2 or O3. Throughout the middle atmosphere, MDF O2 is the major donator of oxygen atoms incorporated in OH and HO2 and thus in H2O. In the stratosphere the known mass-independent fractionation (MIF) signal in O3 is in a first step transferred to the NOx family and only in a second step to HOx and H2O. In contrast to CO2, O(1D) only plays a minor role in this MIF transfer. The major uncertainty in our calculation arises from poorly quantified isotope exchange reaction rate coefficients and kinetic isotope fractionation factors.

Isotopic Fractionation of Carbon and Nitrogen During the Illicit Processing of Cocaine and Heroin in South America

The forensic application of stable isotope analysis to cocaine and heroin for geolocation of exhibits must take into account the possible enrichment and/or depletion of 13C and 15N during the illicit manufacturing process. Continuous-flow elemental analysis-isotope ratio mass spectrometry was utilized to measure changes in the stable isotope ratios of carbon and nitrogen for both cocaine (N = 92) and heroin/morphine (N = 81) exhibits derived from illicit manufacturing processes utilized by South American clandestine chemists. In controlled settings in South America, there was no siginficiant carbon isotope fractionation during the conversion of cocaine base to cocaine HCI using current illict methodologies. In contrast, nitrogen isotope fractionation for this conversion was 1 per thousand. There was a kinetic carbon isotope ratio fractionation during the acetylation of Colombian morphine to heroin and as a result heroin exhibits will almost always have more negative delta13C values than the original morphine. There was an isotopic fractionation against 15N during the acetylation of morphine base to heroin base, but this effect was not expressed since all of the heroin base was precipitated during the manufacturing process. However, the clandestine process of converting a single batch of heroin base usually involved two consecutive crops of heroin HCl and the latter crop was isotopically depleted as expected from a Rayleigh distillation process. When heroin was deacetylated to morphine, the morphine produced resulted in delta13C values that were indistinguishable from the original morphine. The kinetic carbon isotope fractionation factor for the South American process of morphine acetylation was -1.8 per thousand, allowing calculation of the delta13C values of the acetic anhydride from deacetylated heroin delta13C values.

Fe isotope fractionation on FeS formation in ambient aqueous solution

Iron sulfide phases are the ultimate repository of iron and reduced sulfur in sediments. The sulfur isotope geochemistry of pyrite has had much to tell us about modern and ancient Earth environments and it is likely that Fe isotopes will too, once fractionations for key processes are known. We report the results of an experimental study of Fe isotope fractionation on precipitation of FeS, synthetic mackinawite, from excess aqueous Fe(II) solutions by addition of sodium sulfide solution at 2–40 °C. The results show a significant kinetic isotope effect in the absence of a redox process. No detectable effect of temperature on the fractionation factor was observed. The Fe isotope fractionation for zero-age FeS is Δ Fe(II)–FeS = 0.85 ± 0.30‰ across the temperature range studied, giving a kinetic isotope fractionation factor of α Fe(II)–FeS = 1.0009 ± 0.0003. On ageing, the FeS in contact with aqueous Fe(II) becomes progressively isotopically heavier, indicating that the initial fractionations are kinetic rather than equilibrium. From published reaction mechanisms, the opportunity for Fe isotope fractionation appears to occur during inner sphere ligand exchange between hexaqua Fe(II) and aqueous sulfide complexes. Fe isotope fractionation on mackinawite formation is expected to be most significant under early diagenetic situations where a readily available reactive Fe source is available. Since FeS (aq) is a key reactive component in natural pyrite formation, kinetic Fe isotope fractionations will contribute to the Fe isotope signatures sequestered by pyrite, subject to the relative rate of FeS 2 formation versus FeS–Fe(II) (aq) isotopic equilibration.

Quantification of Sequential Chlorinated Ethene Degradation by Use of a Reactive Transport Model Incorporating Isotope Fractionation

Compound-specific isotope analysis (CSIA) enables quantification of biodegradation by use of the Rayleigh equation. The Rayleigh equation fails, however, to describe the sequential degradation of chlorinated aliphatic hydrocarbons (CAHs) involving various intermediates that are controlled by simultaneous degradation and production. This paper shows how isotope fractionation during sequential degradation can be simulated in a 1D reactive transport code (PHREEQC-2). 12C and 13C isotopes of each CAH were simulated as separate species, and the ratio of the rate constants of the heavy to light isotope equaled the kinetic isotope fractionation factor for each degradation step. The developed multistep isotope fractionation reactive transport model (IF-RTM) adequately simulated reductive dechlorination of tetrachloroethene (PCE) to ethene in a microcosm experiment. Transport scenarios were performed to evaluate the effect of sorption and of different degradation rate constant ratios among CAH species on the downgradient isotope evolution. The power of the model to quantify degradation is illustrated for situations where mixed sources degrade and for situations where daughter products are removed by oxidative processes. Finally, the model was used to interpret the occurrence of reductive dechlorination at a field site. The developed methodology can easily be incorporated in 3D solute transport models to enable quantification of sequential CAH degradation in the field by CSIA.

Stable carbon isotope fractionation during aerobic biodegradation of chlorinated ethenes.

Stable isotope analysis is recognized as a powerful tool for monitoring, assessing, and validating in-situ bioremediation processes. In this study, kinetic carbon isotope fractionation factors (epsilon) associated with the aerobic biodegradation of vinyl chloride (VC), cis-1,2-dichloroethylene (cDCE), and trichloroethylene (TCE) were examined. Of the three solvents, the largest fractionation effects were observed for biodegradation of VC. Both metabolic and cometabolic VC degradation were studied using Mycobacterium aurum L1 (grown on VC), Methylosinus trichosporium OB3b (grown on methane), Mycobacterium vaccae JOB5 (grown on propane), and two VC enrichment cultures seeded from contaminated soils of Alameda Point and Travis Air Force Base, CA. M. aurum L1 caused the greatest fractionation (epsilon = -5.7) while for the cometabolic cultures, epsilon values ranged from -3.2 to -4.8. VC fractionation patterns for the enrichment cultures were within the range of those observed for the metabolic and cometabolic cultures (epsilon = -4.5 to -5.5). The fractionation for cometabolic degradation of TCE by Me. trichosporium OB3b was low (epsilon = -1.1), while no quantifiable carbon isotopic fractionation was observed during the cometabolic degradation of cDCE. For all three of the tested chlorinated ethenes, isotopic fractionation measured during aerobic degradation was significantly smaller than that reported for anaerobic reductive dechlorination. This study suggests that analysis of compound-specific isotopic fractionation could assist in determining whether aerobic or anaerobic degradation of VC and cDCE predominates in field applications of in-situ bioremediation. In contrast, isotopic fractionation effects associated with metabolic and cometabolic reactions are not sufficiently dissimilar to distinguish these processes in the field.

Isotope fractionation of toluene: a perspective to characterise microbial in situ degradation.

A concept to assess in situ biodegradation of organic contaminants in aquifers is presented. The alteration of the carbon isotope composition of contaminants along the groundwater flow path indicates microbial degradation processes and can be used as an indicator for in situ biodegradation. The Rayleigh equation was applied to calculate the percentage of the in situ biodegradation (B[%]) using the change in the isotopic composition of contaminants (Rt/R0) along the ground water flow path and a kinetic carbon isotope fractionation factor (αC) derived from defined biodegradation experiments in the laboratory. When the groundwater hydrology is known and a representative source concentration (C0) for a groundwater flow path can be determined, the extent of in situ biodegradation can be quantified.

Stable isotope tracing of anaerobic methane oxidation in the gassy sediments of Eckernfoerde Bay, German Baltic Sea

Methane concentrations in the pore waters of Eckernfoerde Bay in the German Baltic Sea generally reach gas bubble saturation values within the upper meter of the sediment column. The depth at which saturation occurs is controlled by a balance between rates of methane production, consumption (oxidation), and transport. The relative importance of anaerobic methane oxidation (AMO) in controlling dissolved and gas bubble methane distributions in the bay's sediments is indirectly revealed through methane concentration versus depth profiles, depth variations in the stable C and H isotope composition of methane, and the C isotope composition of total dissolved inorganic carbon ({Sigma}CO{sub 2}). Direct radiotracer measurements indicate that AMO rates of over 15 mM/yr are focused at the base of the sulfate reduction zone. Diagenetic equations that describe the depth destructions of the {delta}{sup 13}C and {delta}D values of methane reproduce isotopic shifts observed throughout the methane oxidation zone and are best fit with kinetic isotope fractionation factors of 1.012 {+-} 0.001 and 1.120 {plus{underscore}minus} 0.020 respectively.

13C/12C isotope fractionation of aromatic hydrocarbons during microbial degradation.

The influence of microbial degradation on the 13C/12C isotope composition of aromatic hydrocarbons is presented using toluene as a model compound. Four different toluene-degrading bacterial strains grown in batch culture with oxygen, nitrate, ferric iron or sulphate as electron acceptors were studied as representatives of different environmental redox conditions potentially prevailing in contaminated aquifers. The biological degradation induced isotope shifts in the residual, non-degraded toluene fraction and the kinetic isotope fractionation factors alphaC for toluene degradation by Pseudomonas putida (1.0026 +/- 0.00017), Thauera aromatica (1.0017 +/- 0.00015), Geobacter metallireducens (1.0018 +/- 0.00029) and the sulphate-reducing strain TRM1 (1.0017 +/- 0.00016) were in the same range for all four species, although they use at least two different degradation pathways. A similar 13C/12C isotope fractionation factor (alphaC = 1.0015 +/- 0.00015) was observed in situ in a non-sterile soil column in which toluene was degraded under sulphate-reducing conditions. No carbon isotope shifts resulting from soil-hydrocarbon interactions were observed in a non-degrading soil column control with aquifer material under the same conditions. The results imply that microbial degradation of toluene can produce a 13C/12C isotope fractionation in the residual hydrocarbon fraction under different environmental conditions.

Biodegradation of hydrocarbons and biogeochemical sulfur cycling in the salt dome environment: Inferences from sulfur isotope and organic geochemical investigations of the Bahloul Formation at the Bou Grine Zn/Pb ore deposit, Tunisia

Combined organic geochemical and stable isotope (S) analyses of samples from the Cretaceous Bahloul Formation (Tunisia) provide insight to oil accumulation processes, biogeochemical alteration of hydrocarbons, microbial sulfate reduction, and mineral deposition at the flanks of the Triassic Jebel Lorbeus diapir, forming the Bou Grine Zn/Pb deposit. The sulfur isotopic composition of the metal sulfides correlates with the degree of biodegradation of hydrocarbons, with the base-metal content and with the proportion of aromatics in the organic extracts. The δ 34S-values are interpreted to reflect bacterial sulfate reduction in a more or less closed system rather than a thermogenic contribution. The extent of H 2S production by the activity of the sulfate-reducing bacteria probably was limited by the availability of sulfate, which in turn was governed by the permeability of the respective sedimentary sequence and by the distance to the anhydrite cap rock. Evidence is provided that biodegradation of hydrocarbons and microbial sulfate reduction contribute to the formation of the high-grade mineralization inside the Bahloul Formation at the contact with the salt dome cap rock. The metals probably were derived through leaching of deeper sedimentary sequences by hot hypersaline basinal brines, evolved by dissolution of salt at the flanks of the diapirs. These hot metalliferous brines are proposed to migrate up around the diapir, finally mixing with near-surface, sulfate-rich brines in the roof zone. When the fluids came in contact with the organic-rich sediments of the Bahloul Formation, the dissolved sulfate was reduced by the sulfate-reducing bacteria. Hydrocarbons generated or accumulated in the Bahloul Formation were utilized by sulfate reducers. The occurrence of high amounts of native sulfur in high-grade ore samples suggest that the production rate of H 2S by bacterial sulfate reduction exceeded its consumption by metal-sulfide precipitation. The supply of dissolved metals probably was the limiting reaction. The trend of δ 34S of native sulfur (S 0) towards lower values to the top of the highly mineralized Bahloul profile provides evidence for a biogenic origin of S 0 by sulfide oxidizers. The variation in isotopic fractionation between native sulfur and sulfide sulfur in the ore minerals reflects the kinetic isotope fractionation factor connected with metabolic processes and the respective reaction rate during biogenic oxidation of sulfur.

Carbon isotope fractionation during natural gas generation from kerogen

In petroleum exploration it is important to be able to determine the origin of any gas which is found. This paper describes a new method of estimating the source-type and maturity of a gas based on a Rayleigh fractionation model. Kerogen is divided conceptually into a labile (dominantly oil-generating) fraction and a refractory, gas-prone, component. δ 13C of methane from either kerogen type, and ethane, propane and butane for gases from labile kerogen, can be defined as a function of δ 13C of the gas precursor groups in kerogen, a kinetic isotope fractionation factor, k, and the extent of gas generation. The isotopic ratio of the methane precursors relative to bulk kerogen, determined from laboratory pyrolysis, are −17.5‰ for labile kerogen and −1.4‰ for refractory kerogen. Values for ethane, propane and butane from labile kerogen, based on field correlations, are −4.9‰, −2.2‰ and −1.6‰ respectively. The corresponding fractionation factors are 0.9892, 0.9919, 0.9947 and 0.9975 for methane, ethane, propane and butane respectively from labile kerogen, and 0.9984 for methane from refractory kerogen. Using these parameters, summary diagrams are constructed which allow differentiation of these sources from each other and from biogenic gases and cracked oil, and recognition of gases of mixed origin. If an independent estimate of δ 13C for the source kerogen is possible, then δ 13C of the gas components can be used to estimate maturity in terms of the Gas Generation Index, the fraction of gas potential which has been realized.

The role of organic acid in the abiogenic reduction of sulfate and the sulfur isotope effect.

Abiogenic reduction of sulfate by acetic acid has been conducted at temperatures ranging from 241 to 340°C. The sulfides produced and the remaining sulfates have been chemically and isotopically quantified. The reaction of the aqueous sulfate reduction obey first-order kinetics. The rate constants are strongly dependent on temperature. The temperature dependence of the reaction rate (min-1) is given by the following rate law: log k=-10.3×103/T+15.1. The activation energy for the reaction of sulfate reduction is 208 kJ mol-1. The remaining sulfates display distinct sulfur isotopic variations under a closed system due to the kinetic isotope effect. The kinetic isotope fractionation factor can be expressed as: 103(α-1)=3.32×106/T2-4.19. The kinetic isotope effects during abiogenic reduction of the sulfate may depend on the atomic hydrogen produced, independent of the reducing agents.

Processes controlling the isotopic composition of steam and water discharges from steam vents and steam-heated pools in geothermal areas

On the basis of isotopic analyses of steam and water discharges from the Wairakei, El Tatio and The Geysers geothermal areas, underground steam separation from the rising geothermal fluid appears to be adequately described in terms of a single-step process at temperatures of around 230°C. Absorption of this steam into nearly stagnant pools gives rise to the formation of isotopically enriched waters with compositions following a line with slope σ = ε′ D / ( Δ rw + ε′ 18O − ε 18O .230° C ), where ε′ D and ε′ 18O are the effective kinetic isotope fractionation factors (50‰ and 16‰) for steam heated pools, ε 18O .230° C is the equilibrium fractionation factor for oxygen-18 at 230°C (2‰) and δ rw is the difference in 18O-content of deep chloride and local groundwater (oxygen shift) respectively. The sulfate content of these pools is a function of the proportion of steam absorbed and its H 2S-content.