Extraction of chlorinated aliphatic hydrocarbons from groundwater at micromolar concentrations for isotopic analysis of chlorine.

A method is described for near-quantitative extraction of micromolar concentrations of chlorinated aliphatic hydrocarbons (CAHs) from water for determination of chlorine (Cl) isotope ratios. A low pressure, carrier-gas procedure of extraction was proven to be applicable to CH2Cl2, CCl4, C2H2Cl2, and C2HCl3. The pH of the water was adjusted with NaOH to prevent extraction of CO2 from air and/or dissolved inorganic carbonate species. Recoveries of CAH samples (approximately 15 mumol), added to and extracted from approximately 340 ml of water, averaged approximately 96%. Average changes in the delta 37Cl values of the CAHs, attributable to the extraction process, were -0.01 +/- 0.06@1000. Significant isotopic fractionation of Cl was measured during partial extraction of C2CHCl3 from water, indicating that near-quantitative extraction is required for reliable stable Cl isotope analysis of CAHs. This method is also suitable for the extraction of dissolved CAH for gas chromatography-combustion-isotope ratio mass spectrometric measurements of hydrogen and carbon.     

Stable chlorine intramolecular kinetic isotope effects from the abiotic dehydrochlorination of DDT

INTENTION, GOAL, SCOPE, BACKGROUND: Identifying different sources and following reaction pathways of chlorinated organic contaminants in the environment can be challenging, especially when only their concentrations are available. Compound-specific stable chlorine measurements of some contaminants have recently been shown to provide additional information and an increased understanding of their biogeochemistry. These studies, however, have been generally limited to volatile molecules. OBJECTIVE: Here, the stable chlorine isotope ratios of the semi-volatile pesticide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) were investigated. Specifically, the intramolecular stable chlorine isotopic compositions of DDT and the kinetic isotope effect (KIE) for the abiotic dehydrochlorination of DDT to 2,2-bis(p-chlorophenyl)-1,1-dichloroethene (DDE) were determined. METHODS: Selective chemical oxidation of DDT to dichlorobenzophenone (DCBP) and analysis of each compound was used to calculate the stable chlorine isotope ratios of the alkyl and aromatic chlorines in DDT. To determine the KIE for dehydrochlorination, DDT was reacted in a basic solution to yield DDE at 52 degrees C, 60 degrees C, and 72 degrees C for 3, 5, and 5 days, respectively. RESULTS AND DISCUSSION: Significant intramolecular stable chlorine isotopic differences were observed in one sample of DDT where the alkyl and aromatic delta 37Cl values were -5.76 +/- 0.45 and -2.21 +/- 0.24%@1000, respectively. Dehydrochlorination of DDT to DDE in basic solutions at 52, 60, and 70 degrees C resulted in a substantial intramolecular KIE where the alkyl chlorines of DDE shifted by approximately 3%@1000 relative to the alkyl chlorines in DDT. However, no temperature dependence was observed. The KIE, calculated by an iterative program, was 1.009. CONCLUSIONS: Intramolecular differences in the stable chlorine isotope ratios were observed in DDT and this is the first such finding. Dehydrochlorination of DDT yields a measurable and distinct intramolecular stable chlorine KIE. RECOMMENDATION AND OUTLOOK: The results of this study demonstrate the existence of significant intramolecular differences in chlorinated organic compounds. Many other chlorinated semi-volatile and volatile organic contaminants are synthesized from multiple sources of chlorine, and we recommend that similar studies be performed on many such molecules in order to attain a clear understanding of their intramolecular chlorine isotopic differences. The existence of a measurable KIE for the dehydrochlorination of DDT to DDE shows the potential strength of using isotopic measurements to investigate the biogeochemistry of these important compounds. For example, the isotopically depleted aqueous chloride produced by dehydrochlorination of DDT to DDE may be a useful tracer of these reactions in freshwater environments.     

Impact of the toxicity of Cylindrospermopsis raciborskii (Woloszynska) Seenayya & Subba Raju on laboratory rats in vivo

In vivo laboratory studies of toxicity were performed on Wistar rats using a methanol extract produced by the natural population of Cylindrospermopsis raciborskii (abundance of 2.13 × 10⁵ trichomes mL⁻¹) collected at Aleksandrovac Lake (Serbia). HPLC analysis showed that the extract contains 6.65 μg cylindrospermopsin (CYN) mg⁻¹. The rats were killed 24 or 72 h after a single intraperitoneal injection of C. raciborskii extract in concentrations of 1500, 3000, 6000 and 12,000 μg kg⁻¹ body weight (bw) and an equivalent amount of CYN as present in the highest dose of the extract (79.80 μg CYN kg⁻¹ bw). The genotoxic effect on the livers treated with C. raciborskii was evaluated using comet assay and potential induction of oxidative stress as the toxicity mechanism associated with the presence of CYN in extract. The results from the analyses of DNA damage in the comet tail length, tail moment and percentage of DNA in the tail in the liver indicated that administration of extract and CYN present statistically significant difference when compared with the negative control group. Although an increase in the frequency of selected parameters induced by the CYN was observed in the liver, this damage was less than the damage resulting from the administration of the highest dose of extract. The changes in the biochemical parameters of the hepatic damage showed that the application of single doses of the extract and CYN did not cause serious liver damage in rats. The extract and CYN significantly increased oxidative stress in rats’ liver after a single exposure.

     

An investigation of aqueous activity coefficients at low concentrations

The activity of a chemical in solution determines its tendency to move into other media. At low concentrations (<0.01M) it is generally considered to be linearly related to concentration. A hypothetical model based on the structure of liquid water is discussed which could cause deviations from this linearity in the ppb region, a concentration much lower than that normally investigated thermodynamically, but one of great importance environmentally. Headspace experiments are reported with carbon tetrachloride and chloroform in water at concentrations down to ～10^?3 ppb but no such deviations were discerned.     

油浸变压器排油注氮装置在500kV变电站的设计与应用

在分析500kV变电站主变压器消防系统的现状,比较3类消防系统优缺点的基础上,详细论述了主变排油注氮装置的结构组成、工作原理、参数计算、控制系统设计以及需要注意的事项等,为下一步排油注氮装置的推广应用打下基础.     

Invariant chlorine isotopic signatures during microbial PCB reductive dechlorination

In order to develop more robust insight into the natural attenuation of polychlorinated biphenyls (PCBs), the chlorine isotopic composition of residual 2,3,4,5-tetrachlorobiphenyl (2,3,4,5-CB) was monitored as it underwent microbial reductive dechlorination to 2,3,5-trichlorobiphenyl (2,3,5-CB) in laboratory cultures. Reverse-phase high performance liquid chromatography (HPLC) was employed to isolate the former compound from the experimental matrix for delta37Cl measurement. No detectable isotopic fractionation was observed over the 90 day incubation with sterile control, standard, and inoculated samples all exhibiting delta37Cl values with a range of approximately 0.5 per thousand. These results show that this type of biological activity can be discriminated from other transformations by the absence of a measurable isotope effect during microbial reductive dechlorination. The utility of HPLC isolation for compound-specific delta37Cl analyses of environmentally relevant species is also demonstrated.