Carbon and Chlorine Isotope Fractionation during Aerobic Oxidation and Reductive Dechlorination of Vinyl Chloride andcis-1,2-Dichloroethene

Abstract. The stratospheric degradation of chlorofluorocarbons (CFCs) releases chlorine, which is a major contributor to the destruction of stratospheric ozone (O3). A recent study reported strong chlorine isotope fractionation during the breakdown of the most abundant CFC (CFC-12, CCl2F2, Laube et al., 2010a), similar to effects seen in nitrous oxide (N2O). Using air archives to obtain a long-term record of chlorine isotope ratios in CFCs could help to identify and quantify their sources and sinks. We analyse the three most abundant CFCs and show that CFC-11 (CCl3F) and CFC-113 (CClF2CCl2F) exhibit significant stratospheric chlorine isotope fractionation, in common with CFC-12. The apparent isotope fractionation (&varepsilon;app) for mid- and high-latitude stratospheric samples are respectively −2.4 (0.5) and −2.3 (0.4) ‰ for CFC-11, −12.2 (1.6) and −6.8 (0.8) ‰ for CFC-12 and −3.5 (1.5) and −3.3 (1.2) ‰ for CFC-113, where the number in parentheses is the numerical value of the standard uncertainty expressed in per mil. Assuming a constant isotope composition of emissions, we calculate the expected trends in the tropospheric isotope signature of these gases based on their stratospheric 37Cl enrichment and stratosphere–troposphere exchange. We compare these projections to the long-term δ (37Cl) trends of all three CFCs, measured on background tropospheric samples from the Cape Grim air archive (Tasmania, 1978–2010) and tropospheric firn air samples from Greenland (North Greenland Eemian Ice Drilling (NEEM) site) and Antarctica (Fletcher Promontory site). From 1970 to the present day, projected trends agree with tropospheric measurements, suggesting that within analytical uncertainties, a constant average emission isotope delta (δ) is a compatible scenario. The measurement uncertainty is too high to determine whether the average emission isotope δ has been affected by changes in CFC manufacturing processes or not. Our study increases the suite of trace gases amenable to direct isotope ratio measurements in small air volumes (approximately 200 mL), using a single-detector gas chromatography–mass spectrometry (GC–MS) system.

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Auxiliary Substrates for Elimination of Trichloroethene, Monochlorobenzene, and Benzene in a Sequential Anaerobic–Aerobic GAC Biobarrier

ASEAN Journal of Chemical Engineering ◽

10.22146/ajche.50129 ◽

2007 ◽

Vol 7 (1 & 2) ◽

pp. 68

Author(s):

M. Gozan ◽

A. Mueller ◽

A. Tiehm

Keyword(s):

Vinyl Chloride ◽

Reductive Dechlorination ◽

Biological Degradation ◽

Anaerobic Conditions ◽

Batch Studies ◽

Second Stage ◽

Competitive Reactions ◽

Novel Concept ◽

Tce Degradation ◽

Granulated Activated Carbon

Sequential anaerobic-aerobic barrier is a novel concept for groundwater bioremediation. Trichloroethene (TCE), monochlorobenzene (MCB), and benzene (BZ) were used as model contaminants representing contaminant cocktails frequently found in the contaminated subsurface. The autochthonous microflora from a contaminated field was inoculated to eliminate model contaminants in a set of sequential anaerobic–aerobic granulated activated carbon (GAC) columns and batch studies. In the anaerobic column, the TCE was reductively dechlorinated through cis-dichloroethene (cis-DCE), vinyl chloride (VC), and ethene (ETH). Ethanol and sucrose as auxiliary substrates were added to donate electrons. In the second stage, MCB, BZ, and the lower chlorinated metabolites of TCE degradation, i.e. cis-Dichloroethene (cisDCE) and vinyl chloride (VC), were oxidatively degraded with addition of hydrogen peroxide and nitrate. This paper examines the influence of auxiliary substrates on the biological degradation of model pollutants. In the anaerobic barrier, the auxiliary substrates supply should be maintained low but stoichiometrically adequate for supporting reductive dechlorination. Supplying higher amount of auxiliary substrates provoked competitive reactions in anaerobic conditions, such as sulfate reduction and methanogenesis. If the auxiliary substrates are not utilized completely in the anaerobic phase, the remaining compounds flow into the aerobic phase. This led to unwanted conditions, i.e. oxidation of auxiliary substrates instead of pollutant elimination, and a higher consumption of electron acceptors. In the aerobic barrier, in particular, ethene proved to be a suitable auxiliary substrate for cometabolic degradation of cisDCE.

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Chlorine isotope composition in chlorofluorocarbons CFC-11, CFC-12 and CFC-113 in firn, stratospheric and tropospheric air

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-14-31813-2014 ◽

2014 ◽

Vol 14 (23) ◽

pp. 31813-31841

Author(s):

S. J. Allin ◽

J. C. Laube ◽

E. Witrant ◽

J. Kaiser ◽

E. McKenna ◽

...

Keyword(s):

Isotope Fractionation ◽

Isotope Composition ◽

Stratospheric Ozone ◽

Isotope Ratios ◽

Gas Chromatography Mass Spectrometry ◽

Chlorine Isotope ◽

Site Model ◽

Tropospheric Measurements ◽

Single Detector

Abstract. The stratospheric degradation of chlorofluorocarbons (CFCs) releases chlorine, which is a major contributor to the destruction of stratospheric ozone (O3). A recent study reported strong chlorine isotope fractionation during the breakdown of the most abundant CFC (CFC-12, CCl2F2), similar to effects seen in nitrous oxide (N2O). Using air archives to obtain a long-term record of chlorine isotope ratios in CFCs could help to identify and quantify their sources and sinks. We analyse the three most abundant CFCs and show that CFC-11 (CCl3F) and CFC-113 (CClF2CCl2F) exhibit significant stratospheric chlorine isotope fractionation, in common with CFC-12. The apparent isotope fractionation (&varepsilon;app) for mid- and high-latitude stratospheric samples are (−2.4 ± 0.5) and (−2.3 ± 0.4)‰ for CFC-11, (−12.2 ± 1.6) and (−6.8 ± 0.8)‰ for CFC-12 and (−3.5 ± 1.5) and (−3.3 ± 1.2)‰ for CFC-113, respectively. Assuming a constant source isotope composition, we estimate the expected trends in the tropospheric isotope signature of these gases due to their stratospheric 37Cl enrichment and stratosphere–troposphere exchange. We compare these model results to the long-term δ(37Cl) trends of all three CFCs, measured on background tropospheric samples from the Cape Grim air archive (Tasmania, 1978–2010) and tropospheric firn air samples from Greenland (NEEM site) and Antarctica (Fletcher Promontory site). Model trends agree with tropospheric measurements within analytical uncertainties. From 1970 to the present-day, we find no evidence for variations in chlorine isotope ratios associated with changes in CFC manufacturing processes. Our study increases the suite of trace gases amenable to direct isotope ratio measurements in small air volumes, using a single-detector gas chromatography-mass spectrometry system.

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Sequential anaerobic/aerobic biodegradation of chlorinated hydrocarbons in activated carbon barriers

Water Science & Technology Water Supply ◽

10.2166/ws.2002.0045 ◽

2002 ◽

Vol 2 (2) ◽

pp. 51-58 ◽

Cited By ~ 3

Author(s):

A. Tiehm ◽

M. Gozan ◽

A. Müller ◽

H. Schell ◽

H. Lorbeer ◽

...

Keyword(s):

Hydrogen Peroxide ◽

Biological Activity ◽

Activated Carbon ◽

Vinyl Chloride ◽

Reductive Dechlorination ◽

Chlorinated Hydrocarbons ◽

Aerobic Biodegradation ◽

Anaerobic Conditions ◽

Biological Activated Carbon ◽

Batch Tests

The aim of this study is to develop a long lasting, sequential anaerobic/aerobic biological activated carbon barrier. In the biobarrier, pollutant adsorption on granular activated carbon (GAC) and biodegradation occur simultaneously. Trichloroethene (TCE), chlorobenzene (CB), and benzene were used as model pollutants. In the first barrier, that was operated under anaerobic conditions with sucrose and ethanol as auxiliary substrates, TCE was completely converted to lower chlorinated metabolites, predominantly cis-dichloroethene (cis-DCE). The reductive dechlorination process was stable for about 300 d, although the concomitant sulphate-reducing and methanogenic processes varied considerably. In the second barrier, that was operated with addition of hydrogen peroxide and nitrate, dechlorination was limited by a lack of oxygen and restricted mainly to CB biodegradation. Additional aerobic batch tests revealed that the metabolites of anaerobic TCE dechlorination, i.e. cis-DCE and vinyl chloride, were oxidatively dechlorinated in the presence of suitable auxiliary substrates such as ethene, CB, benzene, or sucrose and ethanol. During periods of low biological activity, elimination of TCE and CB occurred by adsorption in the GAC barriers. The pre-sorbed pollutants were available for subsequent biodegradation resulting in a bioregeneration of the activated carbon barriers.

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