Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
22
pubmed:dateCreated
2008-12-11
pubmed:abstractText
Compound-specific nitrogen isotope analysis was shown to be a promising tool for the quantitative assessment of abiotic reduction of nitroaromatic contaminants (NACs) under anoxic conditions. To assess the magnitude and variability of 15N fractionation for reactions with dissolved reductants, we investigated the reduction of a series of NACs with a model quinone (anthrahydroquinone-2,6-disulfonate monophenolate; AHQDS-) and a Fe(II)-catechol complex (1:2 Fe(II)-tiron complex; Fe(II)L2(6-)) over the pH range from 3 to 12 and variable reductant concentrations. Apparent kinetic isotope effects, AKIEN, for the reduction of four mononitroaromatic compounds by AHQDS- ranged from 1.039 +/- 0.003 to 1.045 +/- 0.002 (average +/- 1sigma), consistent with previous results for various mineral-bound reductants. 15N fractionation for reduction of 1,2-dinitrobenzene and 2,4,6-trinitrotoluene by AHQDS- and that of 4-chloronitrobenzene by Fe(II)L2(6-), however, showed substantial variability in AKIEN-values which decreased from 1.043 to 1.010 with increasing pH. We hypothesize that the isotope-sensitive and rate-limiting step of the overall NAC reduction can shift from the dehydration of substituted N,N-dihydroxyanilines (large 15N fractionation upon N-O bond cleavage) to protonation or reduction of nitroaromatic radical anions (small 15N isotope effect upon electron transfer) consistent with calculations of semiclassical 15N isotope effects. Our results imply that a quantitative assessment of NAC reduction using compound-specific isotope analysis (CSIA) might need to account for homogeneous and heterogeneous reactions separately.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Nov
pubmed:issn
0013-936X
pubmed:author
pubmed:issnType
Print
pubmed:day
15
pubmed:volume
42
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
8352-9
pubmed:meshHeading
pubmed:year
2008
pubmed:articleTitle
Variability of nitrogen isotope fractionation during the reduction of nitroaromatic compounds with dissolved reductants.
pubmed:affiliation
Institute of Biogeochemistry and Pollutant Dynamics (IBP), ETH Zurich, Universitätstrasse 16, 8092 Zurich, Switzerland.
pubmed:publicationType
Journal Article, Research Support, U.S. Gov't, Non-P.H.S., Research Support, Non-U.S. Gov't