Stable isotope fractionation analysis as a tool to monitor biodegradation in contaminated acquifers

The assessment of biodegradation in contaminated aquifers has become an issue of increasing importance in the recent years. To some extent, this can be related to the acceptance of intrinsic bioremediation or monitored natural attenuation as a means to manage contaminated sites. Among the few existing methods to detect biodegradation in the subsurface, stable isotope fractionation analysis (SIFA) is one of the most promising approaches which is pronounced by the drastically increasing number of applications. This review covers the recent laboratory and field studies assessing biodegradation of contaminants via stable isotope analysis. Stable isotope enrichment factors have been found that vary from no fractionation for dioxygenase reactions converting aromatic hydrocarbons over moderate fractionation by monooxygenase reactions (epsilon=-3 per thousand) and some anaerobic studies on microbial degradation of aromatic hydrocarbons (epsilon=-1.7 per thousand) to larger fractionations by anaerobic dehalogenation reactions of chlorinated solvents (epsilon=between -5 per thousand and -30 per thousand). The different isotope enrichment factors can be related to the respective biochemical reactions. Based on that knowledge, we discuss under what circumstances SIFA can be used for a qualitative or even a quantitative assessment of biodegradation in the environment. In a steadily increasing number of cases, it was possible to explain biodegradation processes in the field based on isotope enrichment factors obtained from laboratory experiments with pure cultures and measured isotope values from the field. The review will focus on the aerobic and anaerobic degradation of aromatic hydrocarbons and chlorinated solvents as the major contaminants of groundwater. Advances in the instrumental development for stable isotope analysis are only mentioned if it is important for the understanding of the application.     

Ambient air analysis round robin

A laboratory intercomparison study was carried out to determine the current capability of Canadian laboratories for the analysis of dioxins and furans in ambient air. Seven laboratories (government and private) participated in the analysis of exposed foam/filter samples, ambient air extracts and standard mixtures. The results indicated that a number of laboratories were capable of the aforementioned analyses; however, further analytical methodology development is also required.     

Occurrence and fate of chlorinated methylsiloxanes in surrounding aqueous systems of Shengli oilfield, China

Mono-chlorinated products of cyclic volatile methylsiloxanes (cVMS), i.e., Monochlormet-hylheptamethylcyclotetrasiloxane [D3D(CH₂Cl)], monochlormethylnonamethylcyclopenta-siloxane [D4D(CH₂Cl)], and monochlormethylundemethylcyclohexasiloxane [D5D(CH₂Cl)], were detected in water [<LOQ (Limit of quantitation) -86.3 ng/L, df (detection frequency) = 23%-38%, n=112] and sediment samples [<LOQ-504 ng/g dw (dry weight), df = 33%-38%, n=112] from 16 lakes located in Shengli oilfield of China, and had apparent increasing trends (31%-34% per annum) in sediments during Year 2014-2020. Simulated experiments showed that chloro-cVMS in sediment-water system had approximately 1.7-2.0 times slower elimination rates than parent cVMS. More specifically, compared with those of parent cVMS, volatilization (86-2558 days) and hydrolysis (135-549 days) half-lives of chloro-cVMS were respectively 1.3-2.0 and 1.8-2.1 times longer. In two species of freshwater mussels (n=1050) collected from six lakes, concentrations of chloro-cVMS ranged from 9.8-998 ng/g dw in Anodonta woodiana and 8.4-970 ng/g dw in Corbicula fluminea. Compared with parent cVMS, chloro-cVMS had 1.1-1.5 times larger biota-sediment accumulation factors (2.1-3.0) and 1.1-1.7 times longer half-lives (13-42 days). Their stronger persistence in sediment and bioaccumulation in freshwater mussels suggested that environmental emission, distribution and risks of chloro-cVMS deserve further attention.     

毛细管色谱柱分离氯苯类化合物的优化

介绍了不同极性毛细管色谱柱分离11种氯苯类化合物的方法,通过实验证明,随着色谱柱极性的增加,11种化合物的分离得到改善,采用DB-5和AC-20双柱定性可以避免各种氯代物的干扰,达到准确定性的目的。     

果园土壤有机氯农药残留的时间趋势研究

以天然荒地和蔬菜基地作为对照 ,于 1993年和 2 0 0 3年对北京市某果园中具有不同树龄的老果园和新果园的土壤有机氯农药 (HCH ,DDT)残留情况进行了定位监测 .结果表明 ,在禁用 2 0年后 ,土壤中的有机氯农药残留水平大幅度降低 ,其中老果园的有机氯农药残留浓度显著高于新果园 (P <0 0 5 ) .果园土壤有机氯残留浓度显著高于荒地和蔬菜基地对照 (P <0 0 5 ) .DDT是当地主要的有机氯污染物 ,利用绿色食品生产基地环境质量标准作为评价标准对该果园土壤的污染程度进行了评估 .评估结果表明 ,新果园的土壤质量能够满足绿色食品生产的要求 ,老果园由于土壤中DDT和HCH残留超标严重不适合作为绿色食品生产基地     

挥发性氯代烃检测管速测技术

在阐述检测管测试原理的基础上,介绍了国内外挥发性氯代烃气体检测管的发展现状,展望了检测管在我国土壤和地下水污染快速诊断方面应用推广的前景及存在的问题。     

Henry's law constants of chlorinated solvents at elevated temperatures

Henry’s law constants for 12 chlorinated volatile organic compounds (CVOCs) were measured as a function of temperature ranging from 8 to 93 °C, using the modified equilibrium partitioning in closed system (EPICS) method. The chlorinated compounds include tetrachloroethylene, trichloroethylene, cis-1,2-dichloroethylene, vinyl chloride, 1,1,1-trichloroethane, 1,1-dichloroethane, 1,2-dichloroethane, chloroethane, carbon tetrachloride, chloroform, dichloromethane, and chloromethane. The variation in Henry’s constants for these compounds as a function of temperature ranged from around 3-fold (chloroethane) to 30-fold (1,2-dichloroethane). Aqueous solubilities of the pure compounds were measured over the temperature range of 8-75 °C. The temperature dependence of Henry’s constant was predicted using the ratio of pure vapor pressure to aqueous solubility, both of which are functions of temperature. The calculated Henry’s constants are in a reasonable agreement with the measured results. With the improved data on Henry’s law constants at high temperatures measured in this study, it will be possible to more accurately model subsurface remediation processes that operate near the boiling point of water.     

Contamination by chlorinated pesticides, PCBs and PBDEs in Atlantic spotted dolphin (Stenella frontalis) in western South Atlantic

Chlorinated pesticides, PCBs and PBDEs were analysed in nine blubber samples of Atlantic spotted dolphins, Stenella frontalis, incidentally captured during fishing operations in southern and southeastern Brazil between 2005 and 2007. The majority of compounds analysed were detected, suggesting widespread contamination over the region. Although the samples came from a location far from main coastal industrial areas, the results revealed an influence from such sources. Therefore, levels of PCBs (774-23 659 ng g⁻¹ lipid wt.) and PBDEs (23-1326 ng g⁻¹ lipid wt.) detected seem to be related to the movement of individuals throughout near-shore and offshore waters. The sample from a lactating female exhibited a lower level of contamination and a distinct pattern, indicating selective transfer favouring less lipophilic compounds.     

Variations in expression of carbon isotope fractionation of chlorinated ethenes during biologically enhanced PCE dissolution close to a source zone

The stable carbon isotope values of tetrachloroethene (PCE) and its degradation products were monitored during studies of biologically enhanced dissolution of PCE dense nonaqueous phase liquid (DNAPL) to determine the effect of PCE dissolution on observed isotope values. The degradation of PCE was monitored in a 2-dimensional model aquifer and in a pilot test cell (PTC) at Dover Air Force Base, both with emplaced PCE DNAPL sources. Within the plume down gradient from the source, the isotopic fractionation of dissolved PCE and its degradation products were consistent with those observed in biodegradation laboratory studies. However, close to the source zone significant shifts in the isotope values of dissolved PCE were not observed in either the model aquifer or PTC due to the constant input of newly dissolved, non fractionated PCE, and the small isotopic fractionation associated with PCE reductive dechlorination by the mixed microbial culture used. Therefore the identification of reductive dechlorination in the presence of PCE DNAPL was based upon the appearance of daughter products and the isotope values of those daughter products. An isotope model was developed to simulate isotope values of PCE during the dissolution and degradation of PCE adjacent to a DNAPL source zone. With the exception of very high degradation rate constants (>1/day) stable carbon isotope values of PCE estimated by the model remained within error of the isotope value of the PCE DNAPL, consistent with measured isotope values in the model aquifer and in the PTC.     

受氯代烃类污染的地下水环境修复研究进展

越来越多的地下水源正遭受氯代烃类有机物的污染,氯代烃类的地下环境行为及其污染环境的修复技术是当前环境学界的一个热点。目前修复这类污染环境的技术主要有抽出处理、渗透性反应墙和生物修复等。其中研究最多、应用最广的是利用表面活性剂强化抽出处理技术、零价铁降解氯代烃类的渗透性反应墙技术以及原位强化生物修复技术。零价铁反应墙如何长期稳定运行是目前的研究难题,也是该技术的发展目标。强化生物修复是具有巨大发展潜力的一项新兴技术,构建一个能同时降解多组分污染物的微生物生态群落并成功引入污染场地发挥最大功效,是地下水环境生物修复技术研究中的难点,也将是热点。