Hydrogen isotope fractionation between methanol and diphenylphosphine or dimethylphosphine in the gas phase and in aprotic solvents

1996 ◽  
Vol 74 (8) ◽  
pp. 1465-1469
Author(s):  
Andrzej Wawer ◽  
Jerzy Szydtlowski
Keyword(s):  
Interaction Energy ◽  
Gas Phase ◽  
Hydrogen Isotope ◽  
Isotope Fractionation ◽  
Isotope Effects ◽  
Solvent Polarity ◽  
Exchange Reactions ◽  
Fractionation Factor ◽  
The Given ◽  
Fractionation Factors

D/H fractionation factors between MeOH and Ph2PH in dilute solutions of tetrachloroethylene, benzene, tetrahydrofuran, pyridine, and acetonitrile and T/H fractionation factors between MeOH and Me2PH vapors were measured. The experimental results agree very well with values calculated from the statistical theory of isotope effects formulated by Bigeleisen and Mayer. There are correlations between observed fractionation factors and solvent polarity, and the interaction energy of methanol with the given solvent. Another correlation has been found between enthalpy of the exchange reactions and the interaction energy between methanol and the given solvent. Key words: isotope effects, fractionation factor, diphenylphosphine, methanol.

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

Minerals ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 208
Author(s):  
Takuma Hasegawa ◽  
Kotaro Nakata ◽  
Rhys Gwynne
Keyword(s):  
Groundwater Flow ◽  
Diffusion Coefficients ◽  
Isotope Fractionation ◽  
Free Water ◽  
Effective Porosity ◽  
Diffusion Experiment ◽  
Fractionation Factor ◽  
Through Diffusion ◽  
Geological Formations ◽  
Fractionation Factors

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.

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 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.

scholarly journals Hydrogen Isotope Fractionation between HCl2- Ion and HCl

1975 ◽  
Vol 30 (1) ◽  
pp. 38-43
Author(s):  
J. Szydłowski
Keyword(s):  
Hydrogen Isotope ◽  
Isotope Fractionation ◽  
Theoretical Calculations ◽  
Harmonic Approximation ◽  
Statistical Thermodynamic ◽  
Large Temperature ◽  
Deuterium Isotope Effect ◽  
Fractionation Factor ◽  
Temperature Dependences ◽  
Good Agreement

Abstract Hydrogen isotope fractionation between hydrogen dichloride ion in the condensed phase and gaseous hydrogen chloride has been studied both theoretically and experimentally. Quite good agreement between the experimental tritium fractionation factor and that theoretically calculated for two sets of vibrational data was found. Theoretical calculations of the fractionation factors of both deuterium and tritium over the large temperature range of 100-2000 K revealed some anomalies (minima and crossover points) in their temperature dependences. The relative tritium-deuterium isotope effect has also been discussed within the framework of the presently accepted statistical-thermodynamic theory in the harmonic approximation and recent works by Stern et al.

scholarly journals Equilibrium oxygen- and hydrogen-isotope fractionation between ice and water

1991 ◽  
Vol 37 (125) ◽  
pp. 23-26 ◽  
Author(s):  
M. Lehmann ◽  
U. Siegenthaler
Keyword(s):  
Sea Ice ◽  
Hydrogen Isotope ◽  
Isotope Fractionation ◽  
Water Mass ◽  
Precision Measurements ◽  
Deuterium Excess ◽  
Water Ice ◽  
Equilibrium Oxygen ◽  
Fractionation Factors ◽  
Equilibrium Fractionation

Abstract We have performed high-precision measurements of the isotope-fractionation factors between ice and water. Ice was grown from a stirred water mass on a cooling plate. The freezing velocity was varied, keeping the stirring rate of the water constant, so that the equilibrium fractionation factors could be determined by extrapolating to zero freezing velocity. The resulting values are ∝ (18O/16O) = 1.00291 ± 0.00003 and ∝ (D/H) = 1.0212 ± 0.0004. Non-equilibrium freezing of lake and sea ice is briefly discussed as well as the significance of our results for the deuterium excess in polar precipitation.

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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