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Is the isotopic composition of nitrous oxide an indicator for its origin from nitrification or denitrification? A theoretical approach from referred data and microbiological and enzyme kinetic aspects
Author(s) -
Schmidt HannsLudwig,
Werner Roland A.,
Yoshida Naohiro,
Well Reinhard
Publication year - 2004
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.1586
Subject(s) - isotopomers , chemistry , isotopologue , nitrous oxide , denitrification , nitrification , kinetic isotope effect , nitrous oxide reductase , isothermal microcalorimetry , isotope , isotopic signature , isotopes of nitrogen , environmental chemistry , inorganic chemistry , stereochemistry , nitrogen , organic chemistry , molecule , denitrifying bacteria , deuterium , quantum mechanics , enthalpy , physics
Literature data on the isotopic composition of nitrous oxide indicate a general predominance of the α ‐ 15 N‐isotopomer and a parallel 18 O‐enrichment in N 2 O from nitrification and denitrification, respectively. As the kinetic isotope effects on any individual reactions of the two processes lead to depletions of the heavy isotopes of nitrogen and oxygen in the products, the observed enrichments could mainly be caused by enzymatic reduction of NO, provided it occurs via a symmetric intermediate like hyponitrite; infrared data are in favour of large differences between the binding constants of the isotopomers and isotopologues of this compound. As a matter of fact one of the mechanisms discussed for the nitric oxide reductase from certain microorganisms implies the parallel binding of two NO molecules and the formation of a symmetrical intermediate, while that of the enzyme from other microorganisms reduces NO in a sequential mechanism. In addition, isotope effects on the reduction of N 2 O to N 2 must contribute to the observed isotope characteristics of N 2 O, especially in context with denitrification. Therefore, the known enzymatic reaction pathways suggest that the α ‐ 15 N‐isotopomer preference and the 18 O‐signature of the produced N 2 O is not essentially characteristic for its origin from nitrification or denitrification, respectively, but rather from the involved population of microorganisms and the type of their nitric oxide reductases. This has to be confirmed experimentally. Copyright © 2004 John Wiley & Sons, Ltd.