Cunfu Liu

Stable carbon isotope fractionation during trichloroethene degradation in magnetite-catalyzed Fenton-like reaction

Mineral-catalyzed Fenton-like oxidation of chlorinated ethylenes is an attractive technique for in situ soil and groundwater remediation. Stable carbon isotope enrichment factors associated with magnetite-catalyzed Fenton-like oxidation of trichloroethylene (TCE) have been determined, to study the possibility of applying stable carbon isotope analysis as a technique to assess the efficacy of remediation implemented by Fenton-like oxidation. The carbon enrichment factors (ε values) ranged from -2.7‰ to -3.6‰ with a mean value of -3.3±0.3‰, and only small differences were observed for different initial reactive conditions. The ε values were robust and reproducible, and were relatively insensitive to a number of environmental factors such as ratios of reactants and PCE co-contamination, which can reduce the uncertainty associated with application of isotope enrichment factors for quantification of in situ remediation by Fenton-like reaction. ε values for Fenton-like oxidation of TCE were intermediate in those previously reported for aerobic biological processes (ε=-1.1 to -20.7‰). Thus, field-derived ε values that are more negative than those for Fenton-like oxidation, may indicate the occurrence of aerobic biodegradation at contaminated sites undergoing in situ remediation with Fenton-like reaction. However, stable carbon isotope analysis is unable to determine whether there is the occurrence of biodegradation processes if field-derived ε values are less negative than those for Fenton-like oxidation.

A technique for carbon and chlorine isotope analyses of chlorinated aliphatic hydrocarbons in groundwater

Chlorinated aliphatic hydrocarbons (CAHs), significant contaminants in groundwater, can be characterized by stable isotopic compositions of carbon and chlorine. Previously published methods were of low analytical sensitivity or not ideal for natural samples with low concentrations of CAHs. This method is reported here to carry out simultaneously carbon and chlorine isotope analyses for micromolar concentrations of dissolved CAHs. It was executed by extracting and converting CAHs to carbon dioxide and methyl chloride (CH3Cl). Specially, a continuous-flow interface GasBench II was used to extract CH3Cl for online chlorine isotope analysis. As a result, it greatly enhances the efficiency for isotope analysis by eliminating procedures for offline CH3Cl preparation and separation. Sample size requirement was reduced to approximately 11 μmol chlorine. The standard deviation of δ13C and δ37Cl for both TCE solvents and water samples was better than 0.30‰ and 0.20‰ (1σ), respectively. Carbon and chlorine isotope analyses can be used as an important tool to study the sources of organic contaminants in groundwater and their behaviors in the aquifers. The method is applicable to manufacturers’ products as well as a sample from a polluted site in principle, which will be validated in our field studies.

Carbon and chlorine isotope fractionation during Fenton-like degradation of trichloroethene.

Dual isotope approach has been proposed as a viable tool for characterizing and assessing in situ contaminant transformation, however, little data is currently available on its applicability to chlorinated ethenes. This study determined carbon and chlorine isotope fractionation during Fenton-like degradation of trichloroethene (TCE). Carbon and chlorine isotope enrichment factors were εC=-2.9 ± 0.3‰ and εCl=-0.9 ± 0.1‰, respectively. An observed small secondary chlorine isotope effect (AKIECl=1.001) was consistent with an initial transformation by adding hydroxyl radicals (OH) to CC bonds without cleavage of CCl bonds. The relative change in carbon and chlorine isotope ratios (Δ=Δδ(13)C/Δδ(37)Cl) was calculated to be 3.1 ± 0.2, approximately equal to the ratio of chlorine and carbon isotope enrichment factors (εC/εCl=3.2). The similarity of the Δ (or εC/εCl) values between Fenton-like degradation and microbial reductive dechlorination of TCE was observed, indicating that application of solely dual isotope approach may be limited in distinguishing the two transformation pathways.

Sources, migration and transformation of antimony contamination in the water environment of Xikuangshan, China: Evidence from geochemical and stable isotope (S, Sr) signatures

The Xikuangshan (XKS) mine in central China is the largest antimony (Sb) mine in the world. The mining activity has seriously contaminated the waters in the area. To determine the sources, migration and transformation of Sb contamination, 32 samples from groundwater (aquifer water), surface water and mine water were collected for water chemistry, trace element and SSO4 and Sr stable isotope analyses. The results showed that the groundwater and surface water were in an oxidized environment. The SSO4 and Sr isotope compositions in the water indicated that dissolved Sb and SO4(2) originated from sulfide mineral (Sb2S3) oxidation, whereas radiogenic Sr may have been sourced from silicified limestone and stibnite in the Shetianqiao aquifer. Furthermore, a positive correlation between δ(34)SSO4 and δ(87)Sr values revealed that the Sr, S and Sb in the waters had a common contamination source, i.e., silicified limestone and stibnite, whereas the Sr, S and Sb in rock and ore were sourced from Proterozoic basement clastics. The analysis also indicated that the isotope composition of dissolved SO4(2-) had been influenced by slight bacterial SO4 reduction in the Magunao aquifer. Mining or rock collapse may have caused Shetianqiao aquifer water to contaminate the Magunao aquifer water via mixing. This study has demonstrated that the stable isotopes of (34)SSO4 and (87)Sr, combined with hydrochemical methods, are effective in tracking the sources, migration and transformation of Sb contamination.