含苯环有机污染物定量结构与活性相关性研究

定义表征成键原子生物活性的特征值Ei,由Ei建构新的连接性指数nK,并用0阶指数0K、1阶指数1K研究了氯代芳香族化合物的辛醇/水分配系数及取代苯胺、苯酚和硝基苯类化合物的生物毒性,给出了相关的方程.结果表明,该方法计算简单,使用方便,所有QSAR模型的估算结果均明显优于相应的文献方法,为定量评估和预测同类型其他化合物的生物毒性提供了参考依据.nK有望在QSAR/QSPR研究中作为一个新的参数而获得推广应用.     

Microbial responses to combined oxidation and catalysis treatment of 1,4-dioxane and co-contaminants in groundwater and soil

Post-treatment impacts of a novel combined hydrogen peroxide (H₂O₂) oxidation and WO_x/ZrO₂ catalysis used for the removal of 1,4-dioxane and chlorinated volatile organic compound (CVOC) contaminants were investigated in soil and groundwater microbial community. This treatment train removed ~90% 1,4-dioxane regardless of initial concentrations of 1,4-dioxane and CVOCs. The Illumina Miseq platform and bioinformatics were used to study the changes to microbial community structure. This approach determined that dynamic shifts of microbiomes were associated with conditions specific to treatments as well as 1,4-dioxane and CVOCs mixtures. The biodiversity was observed to decrease only after oxidation under conditions that included high levels of 1,4-dioxane and CVOCs, but increased when 1,4-dioxane was present without CVOCs. WO_x/ZrO₂ catalysis reduced biodiversity across all conditions. Taxonomic classification demonstrated oxidative tolerance for members of the genera Massilia and Rhodococcus, while catalyst tolerance was observed for members of the genera Sphingomonas and Devosia. Linear discriminant analysis effect size was a useful statistical tool to highlight representative microbes, while the multidimensional analysis elucidated the separation of microbiomes under the low 1,4-dioxane-only condition from all other conditions containing CVOCs, as well as the differences of microbial population among original, post-oxidation, and post-catalysis states. The results of this study enhance our understanding of microbial community responses to a promising chemical treatment train, and the metagenomic analysis will help practitioners predict the microbial community status during the post-treatment period, which may have consequences for long-term management strategies that include additional biodegradation treatment or natural attenuation.

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Integration of traditional and innovative characterization techniques for flux-based assessment of Dense Non-aqueous Phase Liquid (DNAPL) sites

Key attributes of the source zone and the expanding dissolved plume at a trichloroethene (TCE) site in Australia were evaluated using trends in groundwater monitoring data along with data from on-line volatile organic compound (VOC) samplers and passive flux meters (PFMs) deployed in selected wells. These data indicate that: (1) residual TCE source mass in the saturated zone, estimated using two innovative techniques, is small ( 10 kg), which is also reflected in small source mass discharge ( 3 g/day); (2) the plume is disconnecting, based on TCE concentration contours and TCE fluxes in wells along a longitudinal transect; (3) there is minimal biodegradation, based on TCE mass discharge of  6 g/day at a plume control plane  175 m from source, which is also consistent with aerobic geochemical conditions observed in the plume; and (4) residual TCE in the vadose zone provides episodic inputs of TCE mass to the plume during infiltration/recharge events. TCE flux data also suggest that the small residual TCE source mass is present in the low-permeability zones, thus making source treatment difficult. Our analysis, based on a synthesis of the archived data and new data, suggests that source treatment is unwarranted, and that containment of the large TCE plume ( 1.2 km long,  0.3 km wide; 17 m deep;  2000–2500 kg TCE mass) or institutional controls, along with a long-term flux monitoring program, might be necessary. The flux-based site management approach outlined in this paper provides a novel way of looking beyond the complexities of groundwater contamination in heterogeneous domains, to make intelligent and informed site decisions based on strategic measurement of the appropriate metrics.     

Impacts of the physiochemical properties of chlorinated solvents on the sorption of trichloroethylene to the roots of Typha latifolia

Sorption to plant roots is the first step for organic contaminants to enter plant tissues. Mounting evidence is showing that sorption to plant roots is nonlinear and competitive. The objective of this study was to investigate the effects of physiochemical properties of homologous chlorinated ethenes and ethanes on the competitive sorption of trichloroethylene (TCE) to the roots of Typha latifolia (cattail). The results showed that chlorinated ethenes exerted significantly stronger competition on the sorption of TCE than chlorinated ethanes. Individual physiochemical properties of organic compounds could be related to the competitive capacity of chlorinated ethenes, but the roles appeared secondary, with molecular structures showing primary effects. Based on these observations, a two-step sorption mechanism was proposed, consisting of the interactions between organic compounds and functional groups on the root surface and subsequent pore filling and absorption to the hydrophobic domains in the composition of roots.     

取代苯胺和苯酚类化合物对大型(Daphnia magna Straus)的定量结构-活性关系研究

研究了３６个取代苯胺和苯酚类化合物对大型溲的急性毒性，应用正辛醇／水分配系数，线性溶解能关系参数和分子连接性指数得出了该类化合物的定量构效关系方程，这些方程可以用来进行该化合物危害性初评。ＬＳＥＲ法得到的ＱＳＡＲ方程拟合效果较好，增大分子体积及偶极性－极化性，均可增大毒性，化合物与蛋白质等生物大分子的氢键键合作用是导致该类化合物毒性高于其基本毒性的原因。     

普通小球藻引发水中苯胺光降解的研究

研究了普通小球藻引发水中苯胺的光降解 ,结果表明 :在 2 5 0W高压汞灯 (λ≥365nm)的照射下 ,藻浓度为 2 0× 1 0 1 0 个·1 - 1 时 ,苯胺的光降解率可达 37% ;苯胺浓度为0 0 0 4— 0 0 2mmol·l- 1 范围内 ,苯胺的光降解速率与初始浓度的降低成反比 ,反应是假一级 .另外 ,还研究了光强、藻悬浮液浓度和苯胺初始浓度等对反应体系的影响     

Selective accumulation of chlorinated paraffins (C12 and C16) in the olfactory organ of rainbow trout

Three ¹⁴C-labelled polychloroalkanes (C₁₂ and C₁₆), representing low (23% Cl by weight), medium (51%), and highly (68%) chlorinated paraffin (CP) mixtures, were presented to rainbow trout via the water. The uptake in fat-rich tissues was positively correlated to the degree of chlorination of the preparations. Notably, all preparations gave rise to a high and selective uptake of radioactivity in the olfactory organ and gills. This selective radiolabelling may reflect a general ability of these organs to enrich xenobiotics from the surrounding water. The olfactory organ may be a hitherto unforseen target for toxic environmental pollutants in fish.     

Aerobic biodegradation of vinyl chloride and cis-1,2-dichloroethylene in aquifer sediments

Laboratory batch experiments have been performed with sediment and groundwater obtained from two sites in Denmark to study the aerobic biodegradation of vinyl chloride (VC) and cis-1,2-dichloroethylene (c-1,2-DCE) to assess the natural aerobic biodegradation potential at two sites. The experiments revealed that VC was degraded to below the detection limit within 204 and 57 days at the two sites. c-1,2-DCE was also degraded in the experiments but not completely. At the two sites 50% and 35% was removed by the end of the experimental period of 204 and 274 days. The removal of c-1,2-DCE seems to occur concomitantly with VC indicating that the biodegradation of c-1,2-DCE may depend on the biodegradation of VC. However, in both cases natural groundwater was mixed with sediment and consequently there may be other compounds (e.g. ammonium, natural organic compound etc.) that serves as primary substrates for the co-metabolic biodegradation of c-1,2-DCE. At one of the sites methane was supplied to try to enhance the biodegradation of VC and c-1,2-DCE. That was successful since the time for complete biodegradation of VC decreased from 204 days in the absence of methane to 84 days in the presence of methane. For c-1,2-DCE the amount that was biodegraded after 204 days increased from 50% to 90% as a result of the addition of methane. It seems like a potential for natural biodegradation exists at least for VC at these two sites and also to some degree for c-1,2-DCE.     

Experimental design of Fenton and photo-Fenton reactions for the treatment of cellulose bleaching effluents

Multivariate experimental design was applied to the treatment of a cellulose conventional bleaching effluent in order to evaluate the use of the Fenton reagent under solar light irradiation. The effluent was characterised by the general parameters total organic carbon (TOC), chemical oxygen demand and color, and it was analysed for chlorinated low molecular weight compounds using GC–MS. The main parameters that govern the complex reactive system: Fe(II) and H₂O₂ initial concentration, and temperature were simultaneously studied. Factorial experimental design allowed to assign the weight of each variable in the TOC removal after 15 min of reaction. Temperature had an important effect in the organic matter degradation, especially when the ratio of Fenton reagents was not properly chosen. Fenton reagent under solar irradiation proved to be highly effective for these types of wastewaters. A 90% TOC reduction was achieved in only 15 min of treatment. In addition, the GC–MS analysis showed the elimination of the chlorinated organic compounds initially detected in the studied bleaching effluents.     

The Danish incinerator dioxin study. Part 1

During the last two years an extensive series of dioxin measurements has been conducted on Danish municipal and hospital solid waste incinerators. The study was directed toward finding the total annual dioxin emissions from MSWI in Denmark, now estimated to be 3 kg. of dioxines and furanes. This sum is equivalent to 50 g. of 2,3,7,8-TCDD according to the Nordic Equivalents. Measurements were carried out according to a statistical design following a plan of pre-randomized sampling. This procedure allowed causal interpretation of the correlations found between the dioxin emissions and certain operating parameters. The statistical model obtained describes the emissions by variations between incinerators, by variation in time, and by changes in the load, the excess air and the HCl concentration in the flue gas.