Oxygen Isotope Effects at Anodes

1956 ◽  
Vol 78 (14) ◽  
pp. 3252-3255 ◽  
Author(s):  
Michael Anbar ◽  
Henry Taube
Keyword(s):  
Oxygen Isotope ◽  
Isotope Effects

Mechanisms of equilibrium and kinetic oxygen isotope effects in synthetic aragonite at 25°C

2006 ◽  
Vol 70 (18) ◽  
pp. A318 ◽  
Author(s):  
Sang-Tae Kim ◽  
Claude Hillaire-Marcel ◽  
Alfonso Mucci
Keyword(s):  
Oxygen Isotope ◽  
Isotope Effects

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.

Sauerstoffisotopieeffekte und Hydratstruktur von Alkalihalogenid-Lösungen in H2O und D2O / Oxygen Isotope Effects and Hydrate Structure of Alkali Halide Solutions in H2O and D2O

1973 ◽  
Vol 28 (2) ◽  
pp. 137-141 ◽  
Author(s):  
D. Götz ◽  
K. Heinzinger
Keyword(s):  
Oxygen Isotope ◽  
Oxygen Isotopes ◽  
Alkali Halide ◽  
Isotope Effects ◽  
Bulk Water ◽  
Hydration Water ◽  
Solvent Isotope Effect ◽  
Anion Effect ◽  
Solvent Isotope ◽  
Fractionation Factors

The fractionation of the oxygen isotopes in solutions of LiCl, NaCl. KCl, KBr, KJ and CsCl with H2O and D2O as solvent has been measured at 25 °C by means of the CO2-equilibration technique. As opposed to earlier measurements a slight anion dependence for the potassium halides has been found in H2O. This anion effect is much more pronounced in D2O. It even leads to a change in the directions of the 180 enrichment between cationic hydration water and bulk water for KCl and KBr. The absolute values of the fractionation factors for LiCl and CsCl, which differ in sign in H2O in agreement with positive and negative cationic hydration, respectively, as known from other kinds of measurements, is increased for LiCl and decreased for CsCl in D2O. There is no fractionation of the oxygen isotopes between hydration water and bulk water in both solvents for NaCl.The solvent isotope effect is explained by the stronger anion influence on the structure of the bulk water in D2O as compared with H2O. This stronger influence is expected because of the higher structural order in D2O than in H2O at the same temperature.

Oxygen Isotope Effects on Electron Transfer to O2Probed Using Chemically Modified Flavins Bound to Glucose Oxidase

2004 ◽  
Vol 126 (46) ◽  
pp. 15120-15131 ◽  
Author(s):  
Justine P. Roth ◽  
Roseanne Wincek ◽  
Gabrielle Nodet ◽  
Dale E. Edmondson ◽  
William S. McIntire ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Glucose Oxidase ◽  
Oxygen Isotope ◽  
Isotope Effects ◽  
Chemically Modified

scholarly journals Nitrogen and Oxygen Isotope Effects of Ammonia Oxidation by Thermophilic Thaumarchaeota from a Geothermal Water Stream

2016 ◽  
Vol 82 (15) ◽  
pp. 4492-4504 ◽  
Author(s):  
Manabu Nishizawa ◽  
Sanae Sakai ◽  
Uta Konno ◽  
Nozomi Nakahara ◽  
Yoshihiro Takaki ◽  
...  
Keyword(s):  
Oxygen Isotope ◽  
Ammonia Oxidation ◽  
Isotope Effects ◽  
Isotope Ratios ◽  
Oxidation Activity ◽  
Content Type ◽  
Ammonia Oxidizing Archaea ◽  
Nitrogen Pools ◽  
Archaeal Ammonia Oxidation

ABSTRACTAmmonia oxidation regulates the balance of reduced and oxidized nitrogen pools in nature. Although ammonia-oxidizing archaea have been recently recognized to often outnumber ammonia-oxidizing bacteria in various environments, the contribution of ammonia-oxidizing archaea is still uncertain due to difficulties in thein situquantification of ammonia oxidation activity. Nitrogen and oxygen isotope ratios of nitrite (δ15NNO2−and δ18ONO2−, respectively) are geochemical tracers for evaluating the sources and thein siturate of nitrite turnover determined from the activities of nitrification and denitrification; however, the isotope ratios of nitrite from archaeal ammonia oxidation have been characterized only for a few marine species. We first report the isotope effects of ammonia oxidation at 70°C by thermophilicThaumarchaeotapopulations composed almost entirely of “CandidatusNitrosocaldus.” The nitrogen isotope effect of ammonia oxidation varied with ambient pH (25‰ to 32‰) and strongly suggests the oxidation of ammonia, not ammonium. The δ18O value of nitrite produced from ammonia oxidation varied with the δ18O value of water in the medium but was lower than the isotopic equilibrium value in water. Because experiments have shown that the half-life of abiotic oxygen isotope exchange between nitrite and water is longer than 33 h at 70°C and pH ≥6.6, the rate of ammonia oxidation by thermophilicThaumarchaeotacould be estimated using δ18ONO2−in geothermal environments, where the biological nitrite turnover is likely faster than 33 h. This study extended the range of application of nitrite isotopes as a geochemical clock of the ammonia oxidation activity to high-temperature environments.IMPORTANCEBecause ammonia oxidation is generally the rate-limiting step in nitrification that regulates the balance of reduced and oxidized nitrogen pools in nature, it is important to understand the biological and environmental factors underlying the regulation of the rate of ammonia oxidation. The discovery of ammonia-oxidizing archaea (AOA) in marine and terrestrial environments has transformed the concept that ammonia oxidation is operated only by bacterial species, suggesting that AOA play a significant role in the global nitrogen cycle. However, the archaeal contribution to ammonia oxidation in the global biosphere is not yet completely understood. This study successfully identified key factors controlling nitrogen and oxygen isotopic ratios of nitrite produced from thermophilicThaumarchaeotaand elucidated the applicability and its limit of nitrite isotopes as a geochemical clock of ammonia oxidation rate in nature. Oxygen isotope analysis in this study also provided new biochemical information on archaeal ammonia oxidation.

Solvent dependence of oxygen isotope effects on the decarboxylation of 4-pyridylacetic acid

1990 ◽  
Vol 112 (5) ◽  
pp. 1894-1896 ◽  
Author(s):  
George W. Headley ◽  
Marion H. O'Leary
Keyword(s):  
Oxygen Isotope ◽  
Isotope Effects ◽  
Solvent Dependence
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