PMID- 25379605
OWN - NLM
STAT- MEDLINE
DCOM- 20150821
LR  - 20181202
IS  - 1520-5851 (Electronic)
IS  - 0013-936X (Linking)
VI  - 48
IP  - 24
DP  - 2014 Dec 16
TI  - Carbon and chlorine isotope analysis to identify abiotic degradation pathways of 
      1,1,1-trichloroethane.
PG  - 14400-8
LID - 10.1021/es504252z [doi]
AB  - This study investigates dual C-Cl isotope fractionation during 1,1,1-TCA 
      transformation by heat-activated persulfate (PS), hydrolysis/dehydrohalogenation 
      (HY/DH) and Fe(0). Compound-specific chlorine isotope analysis of 1,1,1-TCA was 
      performed for the first time, and transformation-associated isotope fractionation 
      epsilon bulk C and epsilon bulk Cl values were -4.0 +/- 0.2 per thousand and no chlorine isotope 
      fractionation with PS, -1.6 +/- 0.2 per thousand and -4.7 +/- 0.1 per thousand for HY/DH, -7.8 +/- 0.4 per thousand and 
      -5.2 +/- 0.2 per thousand with Fe(0). Distinctly different dual isotope slopes (Deltadelta13C/Deltadelta37Cl): 
      infinity with PS, 0.33 +/- 0.04 for HY/DH and 1.5 +/- 0.1 with Fe(0) highlight the potential 
      of this approach to identify abiotic degradation pathways of 1,1,1-TCA in the 
      field. The trend observed with PS agreed with a C-H bond oxidation mechanism in 
      the first reaction step. For HY/DH and Fe(0) pathways, different slopes were 
      obtained although both pathways involve cleavage of a C-Cl bond in their initial 
      reaction step. In contrast to the expected larger primary carbon isotope effects 
      relative to chlorine for C-Cl bond cleavage, epsilon bulk C < epsilon bulk Cl was observed 
      for HY/DH and in a similar range for reduction by Fe(0), suggesting the 
      contribution of secondary chlorine isotope effects. Therefore, different 
      magnitude of secondary chlorine isotope effects could at least be partly 
      responsible for the distinct slopes between HY/DH and Fe(0) pathways. Following 
      this dual isotope approach, abiotic transformation processes can unambiguously be 
      identified and quantified.
FAU - Palau, Jordi
AU  - Palau J
AD  - Centre for Hydrogeology and Geothermics, University of Neuchatel , Neuchatel 
      CH-2000, Switzerland.
FAU - Shouakar-Stash, Orfan
AU  - Shouakar-Stash O
FAU - Hunkeler, Daniel
AU  - Hunkeler D
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
DEP - 20141201
PL  - United States
TA  - Environ Sci Technol
JT  - Environmental science & technology
JID - 0213155
RN  - 0 (Carbon Isotopes)
RN  - 0 (Isotopes)
RN  - 0 (Sulfates)
RN  - 0 (Trichloroethanes)
RN  - 113C650IR1 (1,1,1-trichloroethane)
RN  - 4R7X1O2820 (Chlorine)
RN  - E1UOL152H7 (Iron)
SB  - IM
MH  - Carbon Isotopes/*analysis/chemistry
MH  - Chemical Fractionation
MH  - Chlorine/*analysis/chemistry
MH  - Iron/chemistry
MH  - Isotopes/analysis/chemistry
MH  - Oxidation-Reduction
MH  - Sulfates/chemistry
MH  - Trichloroethanes/*chemistry
EDAT- 2014/11/08 06:00
MHDA- 2015/08/22 06:00
CRDT- 2014/11/08 06:00
PHST- 2014/11/08 06:00 [entrez]
PHST- 2014/11/08 06:00 [pubmed]
PHST- 2015/08/22 06:00 [medline]
AID - 10.1021/es504252z [doi]
PST - ppublish
SO  - Environ Sci Technol. 2014 Dec 16;48(24):14400-8. doi: 10.1021/es504252z. Epub 
      2014 Dec 1.