Quantification of biotransformation of chlorinated hydrocarbons in a biostimulation study: added value via stable carbon isotope analysis

Stable carbon isotope analysis of chlorinated aliphatic compounds was performed at an in situ biostimulation pilot test area (PTA) at a site where 1,2-dichloroethane (1,2-DCA) and trichloroethene (TCE) were present in groundwater. Chlorinated products of TCE reductive dechlorination (cis-dichloroethene (cDCE) and vinyl chloride (VC)) were present at concentrations of 17.5 to 126.4 micromol/L. Ethene, a potential degradation product of both 1,2-DCA dihaloelimination and TCE reductive dechlorination was also present in the PTA. Emulsified soybean oil and lactate were added as electron donors to stimulate anaerobic dechlorination in the PTA. Stable carbon isotope analysis provided evidence that dechlorination was occurring in the PTA during biostimulation, and a means of monitoring changes in dechlorination efficiency over the 183 day monitoring period. Stable carbon isotope analysis was also used to determine if ethene production in the PTA was due to dechlorination of TCE, 1,2-DCA, or both. Fractionation factors (alpha) were determined in the laboratory during anaerobic biotransformation of 1,2-DCA via a dihaloelimination reaction in four separate enrichment cultures. These alpha values (as well as the previously published ranges of alpha for the dechlorination of TCE, cDCE and 1,2-DCA) were used, along with isotopic values measured during the pilot test, to derive quantitative estimates of biotransformation during the pilot test. Dechlorination was found to account for 10.7 to 35.9%, 21.9 to 74.9%, and 54.4 to 67.8% of 1,2-DCA, TCE and cDCE concentration loss respectively in the PTA. Stable carbon isotope analysis indicates that dechlorination of 1,2-DCA, TCE and cDCE were all significant processes during the pilot test, while ethene production during the pilot test was dominated by 1,2-DCA dihaloelimination. This study demonstrates how stable carbon isotope analysis can provide more conservative estimates of the extent of biotransformation than do conventional protocols. In addition, in a complex mixed plume such as this, compound specific isotope analysis is shown to be one of the few methods available for clarifying dominant biotransformation pathways where breakdown products are non-exclusive (i.e. ethene).     

Characterizing natural degradation of tetrachloroethene (PCE) using a multidisciplinary approach

A site in mid-western Sweden contaminated with chlorinated solvents originating from a previous dry cleaning facility, was investigated using conventional groundwater analysis combined with compound-specific isotope data of carbon, microbial DNA analysis, and geoelectrical tomography techniques. We show the value of this multidisciplinary approach, as the different results supported each interpretation, and show where natural degradation occurs at the site. The zone where natural degradation occurred was identified in the transition between two geological units, where the change in hydraulic conductivity may have facilitated biofilm formation and microbial activity. This observation was confirmed by all methods and the examination of the impact of geological conditions on the biotransformation process was facilitated by the unique combination of the applied methods. There is thus significant benefit from deploying an extended array of methods for these investigations, with the potential to reduce costs involved in remediation of contaminated sediment and groundwater.Electronic supplementary materialThe online version of this article (10.1007/s13280-020-01418-5) contains supplementary material, which is available to authorized users.     

Products of methotrexate during chlorination

Methotrexate(MTX)is a cytotoxic drug widely used in the treatment of tumors,autoimmune diseases and severe asthma. jen00883 This drug has been frequently detected in the aquatic environment with concentrations up to μg/L levels. The MTX present in environmental water might be transformed and removed during chlorination disinfection treatment. In this work,the fate of MTX during aqueous chlorination was investigated in laboratory batch experiments,and the transformation products of MTX were identified. Aqueous solutions of MTX(1 mg/L)were chlorinated by sodium hypochlorite solution at room temperature under neutral p H conditions. Chlorinated products were pre-concentrated with solid-phase extraction(SPE)cartridges and determined by liquid chromatography electrospray ionization tandem mass spectrometry(LC–ESI–MS/MS). The reaction of MTX chlorination exhibited pseudo-first-order kinetics and the half-life time of MTX degradation was calculated to be 1.65 min,when the initial chlorine concentration was 2 mg/L. Two chlorinated MTX congeners,4-amino-3-chlorinated-N10-methylpteroylglutamic(monochloro-MTX)and 4-amino-3,5-dichloro-N10-methylpteroylglutamic(dichloro-MTX)were found in the chlorinated solution. Monochloro-MTX was successfully fractionated by high performance liquid chromatography(HPLC)and its structure was further identified using ~1H nuclear magnetic resonance(NMR)analysis. The presence of the two products in real hospital wastewater was then examined and both compounds were detected. Finally,the effects of MTX and monochloro-MTX on the cell cycle progression in vitro were evaluated using zebrafish liver cell line. It was found that both compounds could inhibit the proliferation of zebrafish liver cells through S phase arrest and their effects on the cell cycle profile had no significant difference.     

酚类物质在棉花对枯萎病抗性中的作用

分析了枯萎病菌侵染及氟乐灵诱发处理后，棉苗叶片和根茎部组织中可溶性酚和黄酮醇以及不溶性细胞结合酚（胞壁结合简单酚、胞壁结合复杂酚聚合物及胞壁结合黄酮醇）含量的变化．结果表明：抗病品种棉苗组织中酚类物质的含量高于感病品种棉苗中的含量，氟乐灵诱发处理促进了棉苗组织中酚类物质的积累；枯萎病菌侵染可明显提高棉苗体内的酚含量，但抗病品种棉苗及经氟乐灵诱发处理并产生诱导抗性的棉苗受侵后其组织中酚含量的增加幅度更大．由此认为，棉花体内的酚类物质与棉花对枯萎病的抗病性以及由氟乐灵诱发的诱导抗性有关．     

利用攀钢氯化残渣生产低熟料水泥

较系统地研究了氯化残渣、矿渣、熟料、激发剂等掺量对低熟料水泥强度的影响；找出了利用氯化残渣生产低熟料水泥的最佳条件；并对低熟料水泥性能进行了初步探索。试验表明，利用氯化残渣可生产４２５＾＊低熟料水泥，工业废渣的利用率可达７０％。     

Batch-test study on the dechlorination of 1,1,1-trichloroethane in contaminated aquifer material by zero-valent iron

Chlorinated aliphatic hydrocarbons are common groundwater contaminants. One possible remediation option is in-situ reductive dechlorination by zero-valent iron, either by direct injection or as reactive barriers. Chlorinated ethenes (tetrachloroethene: PCE; trichloroethene: TCE) have received extensive attention in this context. However, another common groundwater pollutant, 1,1,1-trichlorethane (TCA), has attracted much less attention. We studied TCA reduction by three types of granular zero-valent irons in a series of batch experiments using polluted groundwater, with and without added aquifer material. Two types of iron were able to reduce TCA completely with no daughter product concentration increases (1,1-dichloroethane: DCA; chloroethane: CA). One type of iron showed slower reduction, with intermediate rise of DCA and CA concentrations. When evaluating the formation of daughter products, the tests on the groundwater alone showed different results than the groundwater plus aquifer batches: DCA did not temporarily accumulate in the batches with added aquifer material, contrary to the batches without added aquifer material. 1,1-dichloroethene (DCE, also present in the groundwater as an abiotic degradation product of TCA) was also reduced slower in the batches without added aquifer material than in the batches with aquifer material. Redox potentials gradually decreased to low values in batches with aquifer material without iron, while the batches with groundwater alone maintained a constant higher redox potential. Either adsorption processes or microbiological activity in the samples could explain these phenomena. Polymerase Chain Reaction (PCR: a targeted gene probe technique) for chlorinated aliphatic compound (CAH)-degrading bacteria confirmed the presence of Dehalococcoides sp. (chloroethene-degraders) but was negative for Desulfobacterium autotrophicum (a known co-metabolic TCA degrader). DCA reduction was rate determining: first-order half-lives of 300-350 h were observed. TCA was fully removed within hours. CA is resistant to reduction by zero-valent iron but it is known to hydrolyze easily. Since CA did not accumulate in our batches, it may have disappeared by the latter mechanism or it may not have formed as a major daughter product.     

Effect of source variability and transport processes on carbon isotope ratios of TCE and PCE in two sandy aquifers

Chlorinated ethenes often migrate over extended distances in aquifers and may originate from different sources. The aim of this study was to determine whether stable carbon isotope ratios remain constant during dissolution and transport of chlorinated ethenes and whether the ratios can be used to link plumes to their sources. Detailed depth-discrete delineation of the carbon isotope ratio in a tetrachloroethene (PCE) plume and in a trichloroethene (TCE) plume was done along cross-sections orthogonal to groundwater flow in two sandy aquifers in the Province of Ontario, Canada. At the TCE site, TCE concentrations up to solubility were measured in one high concentration zone close to the bottom of the aquifer from where dense non-aqueous phase liquid (DNAPL) was collected. A laboratory experiment using the DNAPL indicated that only very small carbon isotope fractionation occurs during dissolution of TCE (0.26 per thousand), which is consistent with field observations. At most sampling points, the delta(13)C of dissolved TCE was similar to that of the DNAPL except for a few sampling points at the bottom of the aquifer close to the underlying aquitard. At these points, a (13)C enrichment of up to 2.4 per thousand was observed, which was likely due to biodegradation and possibly preferential diffusion of TCE with (12)C into the aquitard. In contrast to the TCE site, several distinct zones of high concentration were observed at the PCE site and from zones to zone, the delta(13)C values varied substantially from -24.3 per thousand to -33.6 per thousand. Comparison of the delta(13)C values in the high concentration zones made it possible to divide the plume in the three different domains, each probably representing a different episode and location of DNAPL release. The three different zones could still be distinguished 220 m from the DNAPL sources. This demonstrates that carbon isotope ratios can be used to differentiate between different zones in chlorinated ethene plumes and to link plume zones to their sources. In addition, subtle variations in delta(13)C at plume fringes provided insight into mechanisms of plume spreading in transverse vertical direction. These variations were identified because of the high-resolution provided by the monitoring network.     

A History of the Production and Use of Carbon Tetrachloride,Tetrachloroethylene, Trichloroethylene and 1,1,1-Trichloroethane in the United States: Part 2--Trichloroethylene and 1,1,1-Trichloroethane

Carbon tetrachloride (CTC), tetrachloroethylene (PCE), trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) were four of the most widely used cleaning and degreasing solvents in the United States. Part 2 of this article describes the history of TCE and TCA. TCE production in the United States began in the early 1920s. TCE was used as a replacement for petroleum distillates in the dry-cleaning industry, and became the solvent of choice for vapor degreasing in the 1930s. TCE's use as a degreaser decreased in the 1960s due to toxicity concerns and the increasing popularity of TCA. Significant TCA use began in the 1950s with the development of suitable stabilizer formulations. In the 1990s, TCA was phased out under the Montreal Protocol due to its role in stratospheric ozone depletion.     

Pesticide Residues in Water From River Kaveri,South India

The residue levels of presistent chlorinated pesticides such as HCH (hexachlorocyclo-hexane) isomers and DDT (dichlorodiphenyl trichloroethane) compounds were quantified in water samples collected from the River Kaveri and its distributor River Coleroon in Tamil Nadu, South India. HCH showed higher levels in River Kaveri during premonsoon (July to September) and monsoon (October to December) months, reflecting the HCH usage during that season for paddy crops. But in the case of DDT no clear trend in residue level was observed. the α-HCH was detected as the dominant isomer in all the three sampling sites. Among DDT compounds, p,p'-DDT and p,p'-DDE showed higher percentage of the total. International comparison of residue levels revealed that the present values are comparable to the waters from Asian and South East Asian nations, but lower than some samples from other parts of India. the value of DDT is well below the EEC's maximum acceptable concentration for surface waters and lower than the recommended limit of 2000ng 1^-1 in USA water for protection of aquatic life (Water Quality Criteria, 1972).     

利用共代谢机制降解水体中的氯代芳烃

氯代芳烃及其衍生物是一类毒性强、难降解的持久性有机化合物。在我国江河水体中检出率高，其中许多是优先监测污染物。水中的难降解有机污染物，可能通过几种微生物的一系列共代谢作用得到大部分，甚至是彻底的降解。本文针对水环境中的氟代芳烃污染物，分析了共代谢的类型、发生原因及影响因素。对利用共代谢机制修复水中氯代芳烃的最新研究进展进行了综述，并对本领域的发展前景进行了探讨。