Isotope Effects in Unimolecular Processes: “Mass Independent” Isotope Fractionation and the Ozone Problem

2009 ◽  
pp. 427-451
Author(s):  
Max Wolfsberg ◽  
W. Alexander Van Hook ◽  
Piotr Paneth
Keyword(s):  
Isotope Fractionation ◽  
Isotope Effects

scholarly journals Unravelling the process of petroleum hydrocarbon biodegradation in different filter materials of constructed wetlands by stable isotope fractionation and labelling studies

2021 ◽  
Author(s):  
Andrea Watzinger ◽  
Melanie Hager ◽  
Thomas Reichenauer ◽  
Gerhard Soja ◽  
Paul Kinner
Keyword(s):  
Stable Isotope ◽  
Constructed Wetlands ◽  
Hydrogen Isotope ◽  
Petroleum Hydrocarbon ◽  
Isotope Fractionation ◽  
Isotope Effects ◽  
Filter Material ◽  
Hydrocarbon Biodegradation ◽  
Stable Isotope Fractionation ◽  
Filter Materials

AbstractMaintaining and supporting complete biodegradation during remediation of petroleum hydrocarbon contaminated groundwater in constructed wetlands is vital for the final destruction and removal of contaminants. We aimed to compare and gain insight into biodegradation and explore possible limitations in different filter materials (sand, sand amended with biochar, expanded clay). These filters were collected from constructed wetlands after two years of operation and batch experiments were conducted using two stable isotope techniques; (i) carbon isotope labelling of hexadecane and (ii) hydrogen isotope fractionation of decane. Both hydrocarbon compounds hexadecane and decane were biodegraded. The mineralization rate of hexadecane was higher in the sandy filter material (3.6 µg CO2 g−1 day−1) than in the expanded clay (1.0 µg CO2 g−1 day−1). The microbial community of the constructed wetland microcosms was dominated by Gram negative bacteria and fungi and was specific for the different filter materials while hexadecane was primarily anabolized by bacteria. Adsorption / desorption of petroleum hydrocarbons in expanded clay was observed, which might not hinder but delay biodegradation. Very few cases of hydrogen isotope fractionation were recorded in expanded clay and sand & biochar filters during decane biodegradation. In sand filters, decane was biodegraded more slowly and hydrogen isotope fractionation was visible. Still, the range of observed apparent kinetic hydrogen isotope effects (AKIEH = 1.072–1.500) and apparent decane biodegradation rates (k = − 0.017 to − 0.067 day−1) of the sand filter were low. To conclude, low biodegradation rates, small hydrogen isotope fractionation, zero order mineralization kinetics and lack of microbial biomass growth indicated that mass transfer controlled biodegradation.

scholarly journals Mass spectrometric measurement of hydrogen isotope fractionation for the reactions of chloromethane with OH and Cl

2018 ◽  
Author(s):  
Frank Keppler ◽  
Enno Bahlmann ◽  
Markus Greule ◽  
Heinz Friedrich Schöler ◽  
Julian Wittmer ◽  
...  
Keyword(s):  
Hydrogen Isotope ◽  
Isotope Fractionation ◽  
Isotope Effects ◽  
Isotope Analysis ◽  
Isotope Ratio Mass Spectrometry ◽  
Detailed Knowledge ◽  
Mass Spectrometric Measurement ◽  
Isotopic Analyses ◽  
Chlorine Radicals ◽  
Stable Hydrogen Isotope

Abstract. Chloromethane (CH3Cl) is an important provider of chlorine to the stratosphere but yet lacks detailed knowledge of its budget. Stable isotope analysis is potentially a powerful tool to constrain CH3Cl flux estimates. The largest degree of isotope fractionation is expected to occur for deuterium in CH3Cl in the hydrogen abstraction reactions with its main sink reactant tropospheric OH and its minor sink reactant Cl atoms. We determined the isotope fractionation by stable hydrogen isotope analysis of the fraction of CH3Cl remaining after reaction with hydroxyl and chlorine radicals in a 3.5 m3 Teflon smog-chamber at 293 ± 1 K. We measured the increasing stable hydrogen isotope values of the unreacted CH3Cl using compound specific thermal conversion isotope ratio mass spectrometry. The isotope fractionations of CH3Cl for the reactions with hydroxyl and chlorine radicals were found to be −242 ± 7 mUr (or ‰) and −280 ± 11 mUr, respectively. For comparison, we performed similar experiments using methane (CH4) as the target compound with OH and obtained a fractionation constant of −205 ± 6 mUr which is in good agreement with values previously reported. The observed large kinetic isotope effects are helpful when employing isotopic analyses of CH3Cl in the atmosphere to improve our knowledge of its atmospheric budget.

scholarly journals Oxygen isotope fractionation during N<sub>2</sub>O production by soil denitrification

2016 ◽  
Vol 13 (4) ◽  
pp. 1129-1144 ◽  
Author(s):  
Dominika Lewicka-Szczebak ◽  
Jens Dyckmans ◽  
Jan Kaiser ◽  
Alina Marca ◽  
Jürgen Augustin ◽  
...  
Keyword(s):  
Oxygen Isotope ◽  
Soil Water ◽  
Isotope Effect ◽  
Isotope Exchange ◽  
Isotope Fractionation ◽  
Isotope Effects ◽  
N2o Production ◽  
Oxygen Isotope Fractionation ◽  
Oxygen Isotope Exchange ◽  
Incubation Experiments

Abstract. The isotopic composition of soil-derived N2O can help differentiate between N2O production pathways and estimate the fraction of N2O reduced to N2. Until now, δ18O of N2O has been rarely used in the interpretation of N2O isotopic signatures because of the rather complex oxygen isotope fractionations during N2O production by denitrification. The latter process involves nitrate reduction mediated through the following three enzymes: nitrate reductase (NAR), nitrite reductase (NIR) and nitric oxide reductase (NOR). Each step removes one oxygen atom as water (H2O), which gives rise to a branching isotope effect. Moreover, denitrification intermediates may partially or fully exchange oxygen isotopes with ambient water, which is associated with an exchange isotope effect. The main objective of this study was to decipher the mechanism of oxygen isotope fractionation during N2O production by soil denitrification and, in particular, to investigate the relationship between the extent of oxygen isotope exchange with soil water and the δ18O values of the produced N2O. In our soil incubation experiments Δ17O isotope tracing was applied for the first time to simultaneously determine the extent of oxygen isotope exchange and any associated oxygen isotope effect. We found that N2O formation in static anoxic incubation experiments was typically associated with oxygen isotope exchange close to 100 % and a stable difference between the 18O ∕ 16O ratio of soil water and the N2O product of δ18O(N2O ∕ H2O)  =  (17.5 ± 1.2) ‰. However, flow-through experiments gave lower oxygen isotope exchange down to 56 % and a higher δ18O(N2O ∕ H2O) of up to 37 ‰. The extent of isotope exchange and δ18O(N2O ∕ H2O) showed a significant correlation (R2 = 0.70, p <  0.00001). We hypothesize that this observation was due to the contribution of N2O from another production process, most probably fungal denitrification. An oxygen isotope fractionation model was used to test various scenarios with different magnitudes of branching isotope effects at different steps in the reduction process. The results suggest that during denitrification, isotope exchange occurs prior to isotope branching and that this exchange is mostly associated with the enzymatic nitrite reduction mediated by NIR. For bacterial denitrification, the branching isotope effect can be surprisingly low, about (0.0 ± 0.9) ‰, in contrast to fungal denitrification where higher values of up to 30 ‰ have been reported previously. This suggests that δ18O might be used as a tracer for differentiation between bacterial and fungal denitrification, due to their different magnitudes of branching isotope effects.

scholarly journals Nitrogen cycling in shallow low-oxygen coastal waters off Peru from nitrite and nitrate nitrogen and oxygen isotopes

2016 ◽  
Vol 13 (5) ◽  
pp. 1453-1468 ◽  
Author(s):  
Happy Hu ◽  
Annie Bourbonnais ◽  
Jennifer Larkum ◽  
Hermann W. Bange ◽  
Mark A. Altabet
Keyword(s):  
Isotope Fractionation ◽  
Coastal Upwelling ◽  
Isotope Effects ◽  
Low Oxygen ◽  
N Loss ◽  
Fractionation Factor ◽  
High Productivity ◽  
O Isotopes ◽  
Subsequent Loss ◽  
Matter Flux

Abstract. O2 deficient zones (ODZs) of the world's oceans are important locations for microbial dissimilatory nitrate (NO3−) reduction and subsequent loss of combined nitrogen (N) to biogenic N2 gas. ODZs are generally coupled to regions of high productivity leading to high rates of N-loss as found in the coastal upwelling region off Peru. Stable N and O isotope ratios can be used as natural tracers of ODZ N-cycling because of distinct kinetic isotope effects associated with microbially mediated N-cycle transformations. Here we present NO3− and nitrite (NO2−) stable isotope data from the nearshore upwelling region off Callao, Peru. Subsurface oxygen was generally depleted below about 30 m depth with concentrations less than 10 µM, while NO2− concentrations were high, ranging from 6 to 10 µM, and NO3− was in places strongly depleted to near 0 µM. We observed for the first time a positive linear relationship between NO2−δ15N and δ18O at our coastal stations, analogous to that of NO3− N and O isotopes during NO3− uptake and dissimilatory reduction. This relationship is likely the result of rapid NO2− turnover due to higher organic matter flux in these coastal upwelling waters. No such relationship was observed at offshore stations where slower turnover of NO2− facilitates dominance of isotope exchange with water. We also evaluate the overall isotope fractionation effect for N-loss in this system using several approaches that vary in their underlying assumptions. While there are differences in apparent fractionation factor (ε) for N-loss as calculated from the δ15N of NO3−, dissolved inorganic N, or biogenic N2, values for ε are generally much lower than previously reported, reaching as low as 6.5 ‰. A possible explanation is the influence of sedimentary N-loss at our inshore stations which incurs highly suppressed isotope fractionation.

Why magnesium isotope fractionation is absent from basaltic melts under thermal gradients in natural settings

2019 ◽  
Vol 157 (7) ◽  
pp. 1144-1148
Author(s):  
Yingkui Xu ◽  
Dan Zhu ◽  
Xiongyao Li ◽  
Jianzhong Liu
Keyword(s):  
Isotope Fractionation ◽  
Isotope Effects ◽  
Isotopic Fractionation ◽  
Chemical Diffusion ◽  
Kinetic Isotope Effects ◽  
Thermal Gradients ◽  
Magnesium Isotopes ◽  
Magnesium Isotope ◽  
Natural Systems ◽  
Kinetic Isotope

AbstractLaboratory experiments have shown that thermal gradients in silicate melts can lead to isotopic fractionation; this is known as the Richter effect. However, it is perplexing that the Richter effect has not been documented in natural samples as thermal gradients commonly exist within natural igneous systems. To resolve this discrepancy, theoretical analysis and calculations were undertaken. We found that the Richter effect, commonly seen in experiments with wholly molten silicates, cannot be applied to natural systems because natural igneous samples are more likely to be formed out of partially molten magma and the presence of minerals adds complexity to the behaviour of the isotope. In this study, we consider two related diffusion-rate kinetic isotope effects that originate from chemical diffusion, which are absent from experiments with wholly molten samples. We performed detailed calculations for magnesium isotopes, and the results indicated that the Richter effect for magnesium isotopes is buffered by kinetic isotope effects and the total value of magnesium isotope fractionation can be zero or even undetectable. Our study provides a new understanding of isotopic behaviour during the processes of cooling and solidification in natural magmatic systems.

Stable isotope fractionation by Clostridium pasteurianum. 4. Sulfur isotope fractionation during enzymatic S3O62−, S2O32−, and SO32− reductions

1981 ◽  
Vol 27 (8) ◽  
pp. 824-834
Author(s):  
G. I. Harrison ◽  
E. J. Laishley ◽  
H. R. Krouse
Keyword(s):  
Stable Isotope ◽  
Isotope Fractionation ◽  
Sulfur Isotope ◽  
Isotope Effects ◽  
Growth Conditions ◽  
Enzyme Concentration ◽  
Clostridium Pasteurianum ◽  
Relative Reduction ◽  
Stable Isotope Fractionation ◽  
Sulfur Isotope Fractionation

Cell-free extracts from Clostridium pasteurianum grown on SO32− utilize H2 to reduce S3O62−, S2O32−, and SO32− to H2S at a much faster rate than extracts from SO42−-grown cells. This further supports the concept of an inducible dissimilatory type SO32− reductive pathway in this organism. 35S dilution experiments further support the concept that S3O62− and S2O32− are pathway intermediates. The inducible SO32− reductase is ferredoxin linked and the kinetics of the reduction and the sulfur isotope fractionation of the product can be altered by altering the growth conditions. The attending sulfur isotope fractionations are similar to those observed during the chemical decomposition of these compounds. In the case of S2O32−, 35S labelling experiments verified the conclusions derived from the stable isotope fractionation data concerning the relative reduction rates of the sulfane and sulfonate sulfurs. The reduction rates were also affected by enzyme concentration. The integrity of the whole cell is a necessary requirement for the large inverse isotope effects previously reported.

Thiosulfate formation and associated isotope effects during sulfite reduction by Clostridium pasteurianum

1979 ◽  
Vol 25 (6) ◽  
pp. 719-721 ◽  
Author(s):  
L. A. Chambers ◽  
P. A. Trudinger
Keyword(s):  
Isotope Fractionation ◽  
Sulfur Isotope ◽  
Isotope Effects ◽  
Clostridium Pasteurianum ◽  
Stages Of Growth ◽  
Bacterial Cultures ◽  
Sulfur Isotope Fractionation ◽  
Secondary Chemical Reaction ◽  
Secondary Chemical ◽  
Isotopic Effects

During growth of Clostridium pasteurianum on sulfite, approximately half the sulfite was reduced to sulfide and half to thiosulfate. Sulfide was enriched in 32S or 34S at different stages of growth and thiosulfate was enriched in 32S, particularly in the sulfane atom.It is suggested that thiosulfate in these bacterial cultures arose from a secondary chemical reaction. The chemical formation of thiosulfate from sulfide and sulfite was also accompanied by sulfur isotope fractionation. The implications of these results with respect to 'inverse' isotopic effects are discussed.

scholarly journals Effects of Iron and Nitrogen Limitation on Sulfur Isotope Fractionation during Microbial Sulfate Reduction

2012 ◽  
Vol 78 (23) ◽  
pp. 8368-8376 ◽  
Author(s):  
Min Sub Sim ◽  
Shuhei Ono ◽  
Tanja Bosak
Keyword(s):  
Nitrogen Fixation ◽  
Sulfate Reduction ◽  
Isotope Fractionation ◽  
Sulfur Isotope ◽  
Isotope Effects ◽  
Reducing Power ◽  
Sulfate Reducing ◽  
Microbial Sulfate Reduction ◽  
Sulfur Isotope Fractionation ◽  
S Isotope

ABSTRACTSulfate-reducing microbes utilize sulfate as an electron acceptor and produce sulfide that is depleted in heavy isotopes of sulfur relative to sulfate. Thus, the distribution of sulfur isotopes in sediments can trace microbial sulfate reduction (MSR), and it also has the potential to reflect the physiology of sulfate-reducing microbes. This study investigates the relationship between the availability of iron and reduced nitrogen and the magnitude of S-isotope fractionation during MSR by a marine sulfate-reducing bacterium, DMSS-1, aDesulfovibriospecies, isolated from salt marsh in Cape Cod, MA. Submicromolar levels of iron increase sulfur isotope fractionation by about 50% relative to iron-replete cultures of DMSS-1. Iron-limited cultures also exhibit decreased cytochromec-to-total protein ratios and cell-specific sulfate reduction rates (csSRR), implying changes in the electron transport chain that couples carbon and sulfur metabolisms. When DMSS-1 fixes nitrogen in ammonium-deficient medium, it also produces larger fractionation, but it occurs at faster csSRRs than in the ammonium-replete control cultures. The energy and reducing power required for nitrogen fixation may be responsible for the reverse trend between S-isotope fractionation and csSRR in this case. Iron deficiency and nitrogen fixation by sulfate-reducing microbes may lead to the large observed S-isotope effects in some euxinic basins and various anoxic sediments.

scholarly journals Nitrogen isotope dynamics and fractionation during sedimentary denitrification in Boknis Eck, Baltic Sea

2013 ◽  
Vol 10 (1) ◽  
pp. 681-709 ◽  
Author(s):  
K. Dähnke ◽  
B. Thamdrup
Keyword(s):  
Baltic Sea ◽  
Water Column ◽  
Isotope Fractionation ◽  
Isotope Effects ◽  
Nitrogen Isotope ◽  
Current View ◽  
Underlying Assumption ◽  
Stable Isotope Fractionation ◽  
Seasonal Hypoxia ◽  
Preferential Uptake

Abstract. The global marine nitrogen cycle is constrained by nitrogen fixation as a source of reactive nitrogen, and denitrification or anammox on the sink side. These processes with their respective isotope effects set the marine nitrate 15N-isotope value (δ15N) to a relatively constant average of 5‰. This value can be used to better assess the magnitude of these sources and sink terms, but the underlying assumption is that sedimentary denitrification and anammox, processes responsible for approximately one third of global nitrogen removal, have little to no isotope effect on nitrate in the water column. We investigated the isotope fractionation in sediment incubations, measuring net denitrification and nitrogen and oxygen stable isotope fractionation in surface sediments from the coastal Baltic Sea (Boknis Eck, Northern Germany), a site with seasonal hypoxia and dynamic nitrogen turnover. We found tremendously high denitrification rates, and regardless of current paradigms assuming little fractionation during sediment denitrification, we measured fractionation factors of 18.9‰ for nitrogen and 15.8‰ for oxygen in nitrate. While the input of nitrate to the water column remains speculative, these results challenge the current view of fractionation during sedimentary denitrification and imply that nitrogen budget calculations may need to consider this variability, as both preferential uptake of light nitrate and release of the remaining heavy fraction can significantly alter water column nitrate isotope vales at the sediment-water interface.

scholarly journals Theoretical Estimates of Equilibrium Carbon and Hydrogen Isotope Effects in Microbial Methane Production and Anaerobic Oxidation of Methane

2020 ◽  
Author(s):  
Jonathan Gropp ◽  
Mark Iron ◽  
Itay Halevy
Keyword(s):  
Isotopic Composition ◽  
Methane Production ◽  
Isotope Fractionation ◽  
Isotope Effects ◽  
Anaerobic Oxidation Of Methane ◽  
Anaerobic Oxidation ◽  
Oxidation Of Methane ◽  
Production And Consumption ◽  
Fractionation Factors ◽  
Equilibrium Fractionation

Microbial production and consumption of methane are widespread in natural and artificial environments, with important economic and climatic implications. Attempts to use the isotopic composition of methane to constrain its sources are complicated by incomplete understanding of the mechanisms of variation in methane's isotopic composition. Knowledge of the equilibrium isotope fractionations among the large organic intracellular intermediates in the microbial pathways of methane production and consumption must form the basis of any exploration of the mechanisms of isotopic variation, but estimates of these equilibrium isotope fractionations are currently unavailable. To address this gap, we calculated the equilibrium isotopic fractionation of carbon (<sup>13</sup>C/<sup>12</sup>C) and hydrogen (D/H) isotopes among compounds in anaerobic methane metabolisms, as well as the abundance of multiple isotope substitutions ("clumping," e.g., <sup>13</sup>C--D) in these compounds. The Density Functional Theory calculations employed the M06-L/def2-TZVP level of theory and the SMD implicit solvation model, which we have recently optimized for large organic molecules and tested against measured equilibrium isotope fractionations. The computed <sup>13</sup>beta and <sup>2</sup>beta values decrease with decreasing average oxidation state of the carbon atom in the molecules, resulting in a preference for enrichment of the molecules with more oxidized carbon in <sup>13</sup>C and D. Using the computed $\beta$ values, we calculated the equilibrium isotope fractionation factors in the prominent methanogenesis pathways (hydrogenotrophic, methylotrophic and acetoclastic) and in the pathway for anaerobic oxidation of methane (AOM) over a temperature range of 0-700 degrees Celsius. Our calculated equilibrium fractionation factors compare favorably with experimental constrains, where available, and we used them to investigate the relation between the apparent isotope fractionation during methanogenesis and AOM and the thermodynamic drive for these reactions. We show that a detailed map of the equilibrium fractionation factors along these metabolic pathways allows an evaluation of the contribution of equilibrium and kinetic isotope effects to apparent isotope fractionations observed in laboratory, natural and artificial settings. The comprehensive set of equilibrium isotope fractionation factors calculated in this study provides a firm basis for future explorations of isotope effects in methane metabolism.

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