Stable Isotope Fractionation Factors Research Articles

An investigation of zinc isotope fractionation in cacao (Theobroma cacao L.) and comparison of zinc and cadmium isotope compositions in hydroponic plant systems under high cadmium stress

This study aims to establish whether zinc (Zn) and cadmium (Cd) share similar physiological mechanisms for uptake and translocation in cacao plants (Theobroma cacao L.). Multiple-collector ICP-MS was used to determine the Zn stable isotope compositions in the roots, stems and leaves of 19 diverse cacao genotypes grown in hydroponics with 20 µmol L−1 CdCl2. Additional plants of one genotype were grown in hydroponic solutions containing lower Cd concentrations (0 and 5 µmol L−1 added CdCl2). Regardless of the Cd concentration used in the exposures, the Zn stable isotope compositions show the same systematic patterns in plant organs, with δ66Znroot > δ66Znstem > δ66Znleaf (δ66Zn denotes relative differences in 66Zn/64Zn ratios in parts per thousand). The mean Zn stable isotope fractionation between the plants and the hydroponic solutions was ε66Znuptake = –1.15 ± 0.36‰ (2SD), indicating preferential uptake of isotopically light Zn by plants from the hydroponic solution. The mean stable isotope fractionation factor associated with translocation of Zn from roots to shoots, ε66Znseq-mob = + 0.52 ± 0.36‰ (2SD), shows that isotopically heavy Zn is preferentially sequestered in the cacao roots, whilst isotopically light Zn is mobilised to the leaves. A comparison with the Cd stable isotope compositions of the same plants shows that both isotopically light Zn and Cd are preferentially taken up by cacao plants. In contrast to Zn, however, the cacao roots retain isotopically light Cd and transfer isotopically heavy Cd to the leaves.

Redox-dependent Ti stable isotope fractionation on the Moon: implications for current lunar magma ocean models

In terrestrial magmas titanium is predominantly tetravalent (Ti4+), in contrast, lunar magmas are more reduced (IW-1) and hence approximately 10% of their bulk Ti content is trivalent (Ti3+). Changes in oxidation state and coordination number are both important parameters that can serve to drive Ti stable isotope fractionation. As such, mineral–mineral and mineral-melt Ti stable isotope fractionation factors determined for terrestrial samples may not be appropriate for lunar samples that formed under more reducing conditions. To address this issue, several experiments were carried out in gas mixing furnaces over a range of fO2 (air to IW-1) to determine Ti stable isotope fractionation factors for minerals, such as ilmenite, clinopyroxene and rutile that are highly abundant on the Moon. Results show that the extent of Ti stable isotope fractionation significantly increases with decreasing fO2. For example, the isotopic difference between ilmenite and residual melt (Δ49Tiilmenite-melt) is resolvably lower by ~ 0.44 ‰ from terrestrial-like FMQ-0.5 to lunar-like IW-1 at an intermediate precision of ± 0.003 ‰ (95% c.i. OL–Ti). This confirms that fractionation factors determined for terrestrial conditions are indeed not applicable to lunar settings. Our new fractionation factors for ilmenite, clinopyroxene and silicate melt are mostly consistent with those previously determined by ab initio modelling based on density-functional theory. Using our new experimental data in conjunction with previously published high-precision HFSE data and Ti stable isotope data of lunar basalts, we modelled the solidification of the Lunar Magma Ocean (LMO). The model for LMO solidification included fractionation of Ti stable isotopes not only by Ti-oxides, but also by typical lunar silicate minerals as pyroxene or olivine. The resulting δ49Ti for urKREEP and ilmenite-bearing cumulates are within error of previous estimates, but also indicate that ilmenite-bearing cumulates must have contained around 15% ilmenite.

Anaerobic oxidation of methane coupled with sulphate reduction: high concentration of methanotrophic archaea might be responsible for low stable isotope fractionation factors in methane

ABSTRACT The changes in δ 13CH4 and δ 12C1H3 2H during sulphate-dependent anaerobic oxidation of methane (AOM) were described using dynamic modelling. The batch sulphate-dependent AOM at the nearly linear dynamics of methane oxidation with different enriched cultures originating from three marine sediments was simulated. The traditional Rayleigh equation for carbon and hydrogen stable isotopes in methane was derived from the basic dynamic isotope equation. The general and reduced models, taking into account the reaction stoichiometry and based on balances of chemical elements and their isotopes, describes a redistribution of stable isotope values in the sulphate-dependent AOM process. It was shown that AOM is the first and rate-limiting step in the whole AOM + SR (sulphate reduction) process. The different fractionation factors of carbon and hydrogen isotopes in methane were obtained for three marine sediments. It was concluded that during incubation the highest concentration of methanotrophic archaea might be responsible for the lowest fractionation factors of stable isotopes of carbon and hydrogen in methane. The interpretation of this phenomenon was suggested. Different concentrations of methanotrophic archaea can lead to variations of isotope fractionation factors.

Iron corrosion by methanogenic archaea characterized by stable isotope effects and crust mineralogy.

Carbon and hydrogen stable isotope effects associated with methane formation by the corrosive archaeon Methanobacterium strain IM1 were determined during growth with hydrogen and iron. Isotope analyses were complemented by structural, elemental and molecular composition analyses of corrosion crusts. During growth with H2 , strain IM1 formed methane with average δ13 C of -43.5‰ and δ2 H of -370‰. Corrosive growth led to methane more depleted in 13 C, with average δ13 C ranging from -56‰ to -64‰ during the early and the late growth phase respectively. The corresponding δ2 H were less impacted by the growth phase, with average values ranging from -316 to -329‰. The stable isotope fractionation factors, , were 1.026 and 1.042 for hydrogenotrophic and corrosive growth respectively. Corrosion crusts formed by strain IM1 have a domed structure, appeared electrically conductive and were composed of siderite, calcite and iron sulfide, the latter formed by precipitation of sulfide (from culture medium) with ferrous iron generated during corrosion. Strain IM1 cells were found attached to crust surfaces and encrusted deep inside crust domes. Our results may assist to diagnose methanogens-induced corrosion in the field and suggest that intrusion of sulfide in anoxic settings may stimulate corrosion by methanogenic archaea via formation of semiconductive crusts.

Measurement on Diffusion Coefficients and Isotope Fractionation Factors by a Through-Diffusion Experiment

For radioactive waste disposal, it is important that local groundwater flow is slow as groundwater flow is the main transport medium for radioactive nuclides in geological formations. When the groundwater flow is very slow, diffusion is the dominant transport mechanism (diffusion-dominant domain). Key pieces of evidence indicating a diffusion-dominant domain are the separation of components and the fractionation of isotopes by diffusion. To prove this, it is necessary to investigate the different diffusion coefficients for each component and the related stable isotope fractionation factors. Thus, in this study, through-diffusion and effective-porosity experiments were conducted on selected artificial materials and natural rocks. We also undertook measurements relating to the isotope fractionation factors of Cl and Br isotopes for natural samples. For natural rock samples, the diffusion coefficients of water isotopes (HDO and H218O) were three to four times higher than those of monovalent anions (Cl−, Br- and NO3−), and the isotope fractionation factor of 37Cl (1.0017–1.0021) was slightly higher than that of free water. It was experimentally confirmed that the isotope fractionation factor of 81Br was approximately 1.0007–1.0010, which is equivalent to that of free water. The enrichment factor of 81Br was almost half that of 37Cl. The effective porosity ratios of HDO and Cl were slightly different, but the difference was not significant compared to the ratio of their diffusion coefficients. As a result, component separation was dominated by diffusion. For artificial samples, the diffusion coefficients and effective porosities of HDO and Cl were almost the same; it was thus difficult to assess the component separation by diffusion. However, isotope fractionation of Cl and Br was confirmed using a through-diffusion experiment. The results show that HDO and Cl separation and isotope fractionation of Cl and Br can be expected in diffusion-dominant domains in geological formations.

Evaluating biogeochemical indicators of methanogenic conditions and thermodynamic constraints in peat

Burial of organic matter in deep peat deposits has already been experimentally demostrated to slow down or even inhibit anaerobic decomposition due to lack of diffusive transport and end-product accumulation. However, so far little is known about potential biogeochemical or thermodynamic indicators for the observed inhibition of further decomposition. For example, theoretical energy yields for methanogenesis, hydrogen partial pressures, stable isotope fractionation factors between CO2 and CH4, and electrochemical properties of dissolved organic matter have been proposed as thermodyamic indicators for such inhibition. To test the applicability and explanatory power of these indicators to identify conditions inhibiting organic matter decomposition, we incubated homogenized ombrotrophic peat for 300 days at 20 °C under diffusive flux conditions as control, and compared the observed effects to a treatment with vertical advective transport by water circulation and to a treatment in which both the unsaturated and water-saturated zone of the peat profile were kept anoxic. Results of energy yields of acetoclastic and hydrogenotrophic methanogenesis were compared to hydrogen partial pressures, to 13C isotope fractionation factors and to redox properties of dissolved organic matter as obtained from mediated electrochemical oxidation and reduction. While CO2 and CH4 production slowed substantially in the deep peat profile, a concomitant decrease of Gibs free energy yields available to hydrogenotrophic and acetoclastic methanogensis and hydrogen and acetate concentrations over time supported a thermodynamic constraint on methanogenesis. Although, energy yields for the hydrogenotrophic pathway were close to or below the theoretical energy minimum levels already after 15 days. Transiently elevated H2 concentrations, not related to actual methanogenesis rates were observed for about 150–225 days. Thereafter, hydrogen concentrations diminished to levels below thresholds to thermodynamically support ongoing methanogenesis. Thus even on incubation timescales of 150–225 days, steady-state hydrogen concentrations as would be expected from thermodynamic considerations did not adjust on the bulk scale of observation. Gibbs free energy estimates for methanogenesis based on hydrogen partial pressures were consequently biased and did not reach the minimum required threshold despite ovious net CH4 production. Ratios between electron accepting (EAC) and donating (EDC) capacity of dissolved organic matter, however, turned out to provide suitable indicators of predominant redox conditions along gradients, stabilizing at low values upon onset of methanogenesis. Thus, our study demonstrated that the thermodynamically driven slow down of decomposition in deep peat deposits, preventing the peat to decompose further, cannot be easily identified based on a single indicator. However, constant and high concentrations of decomposition end-products, indicating zero net turnover and low energy yields, and constantly low EAC/EDC ratios, indicating no further availability of terminal electron acceptors, seem to be characteristic of the onset of conditions inhibiting further significant decomposition of peat.

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.

Using stable isotope fractionation factors to identify Cr(VI) reduction pathways: Metal-mineral-microbe interactions

Microbes interact with metals and minerals in the environment altering their physical and chemical states, whilst in turn metals and minerals impact on microbial growth, activity and survival. The interactions between bacteria and dissolved chromium in the presence of iron minerals, and their impact on Cr isotope variations, were investigated. Cr(VI) reduction experiments were conducted with two bacteria, Pseudomonas fluorescens LB 300 and Shewanella oneidensis MR-1, in the presence of two iron oxide minerals, goethite and hematite. Both minerals were found to inhibit the rates of Cr(VI) reduction by Pseudomonas, but accelerated those of Shewanella. The Cr isotopic fractionation factors generated by Shewanella were independent of the presence of the minerals (ε = −2.3‰). For Pseudomonas, the ε value was the same in both the presence and absence of goethite (−3.3‰); although, it was much higher (ε = −4.3‰) in the presence of hematite. The presence of aqueous Fe(III) in solution had no detectable impact on either bacterial Cr reduction rates nor isotopic fractionation factors. The presence of aqueous Fe(II) induced rapid abiotic reduction of Cr(VI). The different effects that the presence of Fe minerals had on the Cr fractionation factors and reduction rates of the different bacterial species may be attributed to the way each bacteria attached to the minerals and their different reduction pathways. SEM images confirmed that Pseudomonas cells were much more tightly packed on the mineral surfaces than were Shewanella. The images also confirmed that Shewanella oneidensis MR-1 produced nanowires. The results suggest that the dominant Cr(VI) reduction pathway for Pseudomonas fluorescens LB 300 may have been through membrane-bound enzymes, whilst for Shewanella oneidensis MR-1 it was probably via extracellular electron transfer. Since different minerals impact differentially on bacterial Cr(VI) reduction and isotope fractionation, variations of mineralogies and the associated changes of bacterial communities should be taken into consideration when using Cr isotopes to quantify Cr redox behaviour in the environment.

Ikaite precipitation in a lacustrine environment – implications for palaeoclimatic studies using carbonates from Laguna Potrok Aike (Patagonia, Argentina)

The monoclinic mineral ikaite (CaCO3 · 6H2O) and its pseudomorphs are potentially important archives for palaeoenvironmental reconstructions. Natural ikaite occurs in a small temperature range near freezing point and is reported mainly from marine and only rarely from continental aquatic environments. Ikaite transforms to more stable anhydrous forms of CaCO3 after an increase in temperature or when exposed to atmospheric conditions. The knowledge about conditions for natural ikaite formation, its stable isotope fractionation factors and isotopic changes during transformation to calcite is very restricted. Here, for the first time, primary precipitation of idiomorphic ikaite and its calcite pseudomorphs are reported from a subsaline lake, Laguna Potrok Aike, in southern Argentina. The calculated stable oxygen isotope fractionation factor between lake water and ikaite-derived calcite (αPAI = 1.0324 at a temperature of 4.1 °C) is close to but differs from that of primarily inorganically precipitated calcite. Pseudomorphs after ikaite rapidly disintegrate into calcite powder that is indistinguishable from μm-sized calcite crystals in the sediment record of Laguna Potrok Aike suggesting an ikaite origin of sedimentary calcites. Therefore, the Holocene carbonates of Laguna Potrok Aike have the potential to serve as a recorder of past hydrological variation.

Factors controlling the carbon isotope fractionation of tetra- and trichloroethene during reductive dechlorination by Sulfurospirillum ssp. and Desulfitobacterium sp. strain PCE-S

Carbon stable isotope fractionation of tetrachloroethene (PCE) and trichloroethene (TCE) was investigated during reductive dechlorination. Growing cells of Sulfurospirillum multivorans, Sulfurospirillum halorespirans, or Desulfitobacterium sp. strain PCE-S, the respective crude extracts and the abiotic reaction with cyanocobalamin (vitamin B(12)) were used. Fractionation of TCE (alphaC=1.0132-1.0187) by S. multivorans was more than one order of magnitude higher than values previously observed for tetrachloroethene (PCE) (alphaC=1.00042-1.0017). Similar differences in fractionation were observed during reductive dehalogenation by the close relative S. halorespirans with alphaC=1.0046-1.032 and alphaC=1.0187-1.0229 for PCE and TCE respectively. TCE carbon isotope fractionation (alphaC=1.0150) by the purified PCE-reductive dehalogenase from S. multivorans was more than one order of magnitude higher than fractionation of PCE (alphaC=1.0017). Carbon isotope fractionation of TCE by Desulfitobacterium sp. strain PCE-S (alphaC=1.0109-1.0122) as well as during the abiotic reaction with cyanocobalamin (alphaC=1.0154) was in a similar range to previously reported values for fractionation by mixed microbial cultures. In contrast with previous results with PCE, no effects due to rate limitations, uptake or transport of the substrate to the reactive site could be observed during TCE dechlorination. Our results show that prior to a mechanistic interpretation of stable isotope fractionation factors it has to be carefully verified how other factors such as uptake or transport affect the isotope fractionation during degradation experiments with microbial cultures.

Stable isotope fractionation during bacterial sulfate reduction is controlled by reoxidation of intermediates

Bacterial sulfate reduction is one of the most important respiration processes in anoxic habitats and is often assessed by analyzing the results of stable isotope fractionation. However, stable isotope fractionation is supposed to be influenced by the reduction rate and other parameters, such as temperature. We studied here the mechanistic basics of observed differences in stable isotope fractionation during bacterial sulfate reduction. Batch experiments with four sulfate-reducing strains ( Desulfovibrio desulfuricans, Desulfobacca acetoxidans, Desulfonatronovibrio hydrogenovorans, and strain TRM1) were performed. These microorganisms metabolize different carbon sources (lactate, acetate, formate, and toluene) and showed broad variations in their sulfur isotope enrichment factors. We performed a series of experiments on isotope exchange of 18O between residual sulfate and ambient water. Batch experiments were conducted with 18O-enriched (δ 18O water = +700‰) and depleted water (δ 18O water = −40‰), respectively, and the stable 18O isotope shift in the residual sulfate was followed. For Desulfovibrio desulfuricans and Desulfonatronovibrio hydrogenovorans, which are both characterized by low sulfur isotope fractionation ( ε S > −13.2‰), δ 18O values in the remaining sulfate increased by only 50‰ during growth when 18O-enriched water was used for the growth medium. In contrast, with Desulfobacca acetoxidans and strain TRM1 ( ε S < −22.7‰) the residual sulfate showed an increase of the sulfate δ 18O close to the values of the enriched water of +700‰. In the experiments with δ 18O-depleted water, the oxygen isotope values in the residual sulfate stayed fairly constant for strains Desulfovibrio desulfuricans, Desulfobacca acetoxidans and Desulfonatronovibrio hydrogenovorans. However, strain TRM1, which exhibits the lowest sulfur isotope fractionation factor ( ε S < −38.7‰) showed slightly decreasing δ 18O values. Our results give strong evidence that the oxygen atoms of sulfate exchange with water during sulfate reduction. However, this neither takes place in the sulfate itself nor during formation of APS (adenosine-5′-phosphosulfate), but rather in intermediates of the sulfate reduction pathway. These may in turn be partially reoxidized to form sulfate. This reoxidation leads to an incorporation of oxygen from water into the “recycled” sulfate changing the overall 18O isotopic composition of the remaining sulfate fraction. Our study shows that such incorporation of 18O is correlated with the stable isotope enrichment factor for sulfur measured during sulfate reduction. The reoxidation of intermediates of the sulfate reduction pathway does also strongly influence the sulfur stable isotope enrichment factor. This aforesaid reoxidation is probably dependent on the metabolic conversion of the substrate and therefore also influences the stable isotope fractionation factor indirectly in a rate dependent manner. However, this effect is only indirect. The sulfur isotope enrichment factors for the kinetic reactions themselves are probably not rate dependent.

Equilibrium mineral-fluid stable isotope fractionation factors in graphitic metapelites

The stable isotopic composition (C, O, H, and S) of a fluid in equilibrium with the common metapelite assemblage graphite + sulfide has been calculated using a modified Redlich-Kwong equation of state at 500°3.5 kbar, and 700°C, 6 kbar, for a range of f O2 and f S2 conditions. The four major fluid species under these conditions are H 2O, CO 2, CH 4 and H 2S. Stable isotope fractionation factors among these fluid species remain significant to large, even at temperatures as high as 700°C. At 500°C, 3.5 kbar, Δ 18O quartz-Σfluid ranges from −3.0 to + 3.1‰, Δ 13C graphite-Σfluid ranges from −10.1 to +4.3‰, and ΔD biotite-Σfluid ( XF, biotite = 0.25) ranges from −31 to + 74‰, depending on the values of f o2 and f S2. At 700°C, 6 kbar, Δ 18O quartz-Σfluid ranges from − 1.7 to + 1.6‰, Δ 13C gaph;te-Σfluid ranges from -7.6 to +1.6‰, and Δ 34S biotite-Σfluid ( X Fe biotite = 0.25) ranges from −17 to + 164‰, depending on the values of f o2 and f s2. Values of Δ j34S pyrite−Σfluid are small and independent of f O 2 and f S 2 . The results have implications for studies using stable isotopic methods to investigate interaction between a fluid and a graphitic metapelite during metamorphism, especially during devolatilization and fluid-rock interaction. Equilibrium values of Δ mineral-Σfluid during metamorphism are dependent upon the composition of the fluid, which in turn is dependent upon f o2 and f s2

Stable isotope fractionation between carbon dioxide and calcite at 900°C

Equilibrium stable isotope fractionation factors between carbon dioxide and calcite were determined by direct equilibration of the two phases at 900°C and 12.5 kbar. The results of six three-day runs gave Δ13C(CO2-calcite) and Δ18O(CO2-calcite) fractionations of +2.70± 0.36% and +3.30 ± 0.16%., respectively (2σ). Runs of 22.5, 45, and 90 min; and 3, 6, 12, and 24 h duration were also conducted. Rapid initial recrystallization accompanied by extensive carbon and oxygen isotope exchange (⪆40%) and a very high oxygen/carbon exchange rate ratio (~5) was seen in runs using both natural and synthetic calcite. Subsequent exchange slowed drastically, and the rate of oxygen exchange decreased relative to that of carbon to a constant value of ~3, implicating the involvement of carbonate ion migration in the later, slower stages of exchange. The lower limits of bulk carbon and oxygen diffusion coefficients determined from the partial exchange experiments were 4 × 10−13 and 9× 10−13 (cm2/s), respectively.

Stable isotope fractionation factors of water in hydrated saline mineral-brine systems

Hydrogen and oxygen isotope fractionation factors of water between water of crystallization of carnallite, bischofite and tachyhydrite and the mother solutions were determined from the isotopic activity ratios of the mother solutions (α a ) in the temperature range of 10–40°C. Deuterium is depleted and 18 O enriched in the water of crystallization of all these minerals. No clear temperature dependence can be observed. The published fractionation factors in the literature, which were all determined from the isotopic concentration ratios of the mother solutions (α c ) were corrected to α a using the “salt effect” coefficients. It is proposed that only the α a values can be applied to the natural settings.