Comparison of PCE and TCE disappearance in heated volatile organic analysis vials and flame-sealed ampules

The rates of hydrolysis reported for tetrachloroethylene (PCE) and trichloroethylene (TCE) at elevated temperatures range over two orders-of-magnitude, where some of the variability may be due to the presence of a gas phase. Recent studies suggest that volatile organic analysis (VOA) vials provide a low-cost and readily available zero headspace system for measuring aqueous-phase hydrolysis rates. This work involved measuring rates of PCE and TCE disappearance and the corresponding appearance of dechlorination products in water-filled VOA vials and flame-sealed ampules incubated at 21 and 55 °C for up to 95.5 days. While PCE and TCE concentrations readily decreased in the VOA vials to yield first-order half lives of 11.2 days for PCE and 21.1 days for TCE at 55 °C, concentrations of anticipated dechlorination products, including chloride, remained constant or were not detected. The rate of PCE disappearance was 34 times faster in VOA vials at 55 °C compared to values obtained with flame-sealed ampules containing PCE-contaminated water. In addition, the concentration of TCE increased slightly in flame-sealed ampules incubated at 55 °C, while a decrease in TCE levels was observed in the VOA vials. The observed losses of PCE and TCE in the VOA vials were attributed to diffusion and sorption in the septa, rather than to dechlorination. These findings demonstrate that VOA vials are not suitable for measuring rates of volatile organic compound hydrolysis at elevated temperatures.     

Endophytic bacteria improve phytoremediation of Ni and TCE co-contamination

The aim of this work was to investigate if engineered endophytes can improve phytoremediation of co-contaminations by organic pollutants and toxic metals. As a model system, yellow lupine was inoculated with the endophyte Burkholderia cepacia VM1468 possessing (a) the pTOM-Bu61 plasmid, coding for constitutive trichloroethylene (TCE) degradation, and (b) the ncc-nre Ni resistance/sequestration system. Plants were exposed to Ni and TCE and (a) Ni and TCE phytotoxicity, (b) TCE degradation and evapotranspiration, and (c) Ni concentrations in the roots and shoots were determined. Inoculation with B. cepacia VM1468 resulted in decreased Ni and TCE phytotoxicity, as measured by 30% increased root biomass and up to 50% decreased activities of enzymes involved in anti-oxidative defence in the roots. In addition, TCE evapotranspiration showed a decreasing trend and a 5 times higher Ni uptake was observed after inoculation.     

活性炭对天然水体中甲基对硫磷和三氯乙烯的吸附特性研究

采用序批式试验研究了3种粉末活性炭(PAC)对天然水体中甲基对硫磷(MP)和三氯乙烯(TCE)的吸附平衡特性,利用均相表面扩散模型(HSDM)对不同投炭量下的吸附动力学进行拟合与预测,并探讨了天然有机物(NOM)对MP、TCE在PAC上的竞争吸附效应.研究结果表明,天然水体条件下,3种PAC对MP和TCE的吸附符合Langmuir模型和Freundlich模型;MP比TCE更易于被PAC吸附;3种PAC对MP、TCE的吸附能力由大到小依次为YK炭、SL炭和JC炭;HSDM模型可以很好地对吸附动力学进行拟合,并能够有效地预测不同投炭量时的吸附动力学;天然水体中的NOM会与MP和TCE在PAC上发生竞争吸附,NOM对MP的竞争吸附作用相对TCE更为显著.     

Potential of the TCE-degrading endophyte Pseudomonas putida W619-TCE to improve plant growth and reduce TCE phytotoxicity and evapotranspiration in poplar cuttings

The TCE-degrading poplar endophyte Pseudomonas putida W619-TCE was inoculated in poplar cuttings, exposed to 0, 200 and 400 mg l⁻¹ TCE, that were grown in two different experimental setups. During a short-term experiment, plants were grown hydroponically in half strength Hoagland nutrient solution and exposed to TCE for 3 days. Inoculation with P. putida W619-TCE promoted plant growth, reduced TCE phytotoxicity and reduced the amount of TCE present in the leaves. During a mid-term experiment, plants were grown in potting soil and exposed to TCE for 3 weeks. Here, inoculation with P. putida W619-TCE had a less pronounced positive effect on plant growth and TCE phytotoxicity, but resulted in strongly reduced amounts of TCE in leaves and roots of plants exposed to 400 mg l⁻¹ TCE, accompanied by a lowered evapotranspiration of TCE. Dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA), which are known intermediates of TCE degradation, were not detected.     

Sorption and transport of trichloroethylene in caliche soil

Sorption of TCE to the caliche soil exhibited linear isotherm at the high TCE concentrations (Co = 122-1300 mg L⁻¹) but Freundlich isotherm at the low concentration range (1-122 mg L⁻¹). Sorption strength of the carbonate fraction of the soil was about 100-fold lower than the sorption strength of soil organic matter (SOM) in the caliche soil, indicating weak affinity of TCE for the carbonate fraction of the soil. Desorption of TCE from the caliche soil was initially rapid (7.6 × 10⁻⁴ s⁻¹), then continued at a 100-fold slower rate (7.7 × 10⁻⁶ s⁻¹). Predominant calcium carbonate fraction of the soil (96%) was responsible for the fast desorption of TCE while the SOM fraction (0.97%) controlled the rate-limited desorption of TCE. Transport of TCE in the caliche soil was moderately retarded with respect to the water (R = 1.75-2.95). Flow interruption tests in the column experiments indicated that the rate-limited desorption of TCE controlled the non-ideal transport of TCE in the soil. Modeling studies showed that both linear and non-linear nonequilibrium transport models provided reasonably good match to the TCE breakthrough curves (r² = 0.95-0.98). Non-linear sorption had a negligible impact on both the breakthrough curve shape and the values of sorption kinetics parameters at the high TCE concentration (Co = 1300 mg L⁻¹). However, rate-limited sorption/desorption processes dominated at this concentration. For the low TCE concentration case (110 mg L⁻¹), in addition to the rate-limited sorption/desorption, contribution of the non-linear sorption to the values of sorption kinetics became fairly noticeable.     

细胞色素P450代谢污染物的化学模拟与优化

利用Fe2+EDTAH2O2联氨混合体系模拟了生物细胞色素P450的代谢功能,选择三氯乙烯作为典型污染物与模拟体系反应,产生的活性中间体与4(对硝基苄基)吡啶(NBP)反应生成紫红色物质,用分光光度法检测.根据产生活性中间体的多少对模拟体系的组成和反应条件进行了优化,对活化机理进行了初步探讨.结果发现联氨等还原剂的存在对模拟体系的代谢活化能力有重要影响,是体系区别于Fenton试剂的重要标志.在优化条件下,低至2×10-6mol·L-1的三氯乙烯在模拟体系中可以代谢产生活性中间体,表明该体系能够较好地模拟细胞色素P450的代谢功能.