Formation pathways of brominated products from benzophenone-4 chlorination in the presence of bromide ions

The brominated products, formed in chlorination treatment of benzophenone-4 in the presence of bromide ions, were identified, and the formation pathways were proposed.Under disinfection conditions, benzophenone-4 would undertake electrophilic substitution generating mono- or di-halogenated products, which would be oxidized to esters and further hydrolyzed to phenol derivatives. The generated catechol intermediate would be transformed into furan-like heterocyclic product. The product species were p H-dependent,while benzophenone-4 elimination was chlorine dose-dependent. When the chlorination treatment was performed on ambient water spiked with benzophenone-4 and bromide ions, most of brominated byproducts could be detected, and the acute toxicity significantly increased as well.     

Mutagenic and cytotoxic potential of Endosulfan and Lambda-cyhalothrin - In vitro study describing individual and combined effects of pesticides

Excessive use of pesticides poses increased risks to non target species including humans. In the developing countries, lack of proper awareness about the toxic potential of pesticides makes the farmer more vulnerable to pesticide linked toxicities, which could lead to diverse pathological conditions. The toxic potential of a pesticide could be determined by their ability to induce genetic mutations and cytotoxicity. Hence, determination of genetic mutation and cytotoxicity of each pesticide is unavoidable to legislate health and safety appraisal about pesticides. The objective of current investigation was to determine the genotoxic and cytotoxic potential of Endosulfan（EN） and Lambda-cyhalothrin（LC）; individually and in combination. 3-（4,5-Dimethylthiazol-2-yl）-2,5-Diphenyltetrazolium Bromide（MTT） assay was utilized to determine cytotoxicity, while two mutant histidine dependent Salmonella strains（TA98, TA100） were used to determine the mutagenicity of EN and LC.Moreover, mutagenicity assay was conducted with and without S9 to evaluate the effects of metabolic activation on mutagenicity. Even though a dose dependent increase in the number of revertant colonies was detected with EN against both bacterial strains, a highly significant（p 〈 0.05） increase in the mutagenicity was detected in TA98 with S9. In comparison, data obtained from LC revealed less mutagenic potential than EN. Surprisingly,the non-mutagenic individual-concentrations of EN and LC showed dose dependent mutagenicity when combined. Combination of EN and LC synergistically induced mutagenicity both in TA98 and TA100. MTT assay spotlighted comparable dose dependent cytotoxicity effects of both pesticides. Interestingly, the combination of EN and LC produced increased reversion and cytotoxicity at lower doses as compared to each pesticide, concluding that pesticide exposure even at sub-lethal doses can produce cytotoxicity and genetic mutations, which could lead to carcinogenicity.     

维生素B_(12)催化降解三氯乙烯的碳氯同位素分馏机理

挥发性氯代烃(volatile chlorinated hydrocarbons,VCHs)是地下水中一类重要的有机污染物,维生素B12是催化VCHs还原脱氯的高效催化剂。该文选取VCHs中典型的污染物三氯乙烯(TCE)作为研究对象,以Ti(Ⅲ)为电子供体,探索不同pH条件下,维生素B12催化TCE还原脱氯过程中碳、氯同位素分馏机理。反应溶液初始pH为7.5~9.0时,其表观一级动力学反应速率系数k值为0.06~0.15 h-1;碳同位素富集系数εC为-1.8‰~-2.4‰,氯同位素富集系数εCl均值为-1.5‰。这说明,pH增大,Ti(Ⅲ)还原势能增大,反应的速率提高;还原脱氯不同反应途径所占份额改变,碳、氯同位素分馏程度变化。碳、氯的单体同位素分析(CSIA)技术可以用来评价地下水氯代烃污染降解程度和效率,结合分析2种元素能够提高污染物修复评价的准确性,同位素富集系数的稳定性研究可为其不同环境条件下的精确评价提供理论依据。     

还原脱氯-生物联合降解2,4-二氯苯氧乙酸

采用Pd/Fe双金属对2,4-二氯苯氧乙酸(2,4-D)进行催化还原脱氯,以活性污泥对2,4-D脱氯产物进行生物氧化,考察初始pH、活性污泥量、污染物初始浓度、温度等因素对生物氧化的影响情况.通过PCR-变性梯度凝胶电泳分析污泥体系菌群变化情况,高效液相色谱测定来推测目标污染物的降解过程.结果表明:1 Pd/Fe双金属可有效还原2,4-D,其主要先还原为2-氯苯氧乙酸(2-CPA),最终顺序脱氯为苯氧乙酸(PA).2 2,4-D具有较大生物毒性,其脱氯产物毒性下降,更易被生物降解.3 pH=7、污泥量50 mL/200 mL、适量的初始PA浓度(14.6 mg·L-1)和30℃均有利于PA的去除.在该条件下反应96 h,PA去除率可达84.3%.     

改性粉煤灰处理黑化集团焦化含酚废水的研究

焦化废水是一种典型的含有难降解有机污染物的工业废水,除含有酚类化合物外,还含有多种芳香烃和杂环类有机污染物,成分复杂,水量大,对环境污染严重。因此,焦化废水处理技术越来越受到环保部门的重视。本文摸索了改性粉煤灰处理焦化含酚废水的试验工艺条件,确定了反应条件,反应时间和反应温度。     

电化学还原-氧化工艺降解4-氯酚的毒性研究

采用紫外光还原法制备了Pd-Fe/石墨烯催化阴极,并以Ti/IrO_2/RuO_2为阳极,构成三电极体系(双阴极)和两电极体系(单阴极)的电化学还原-氧化降解工艺,分别对4-氯酚进行降解.采用离子色谱、高效液相色谱、TOC仪对4-氯酚降解过程中中间产物及其浓度进行测定.根据公式计算降解过程中理论计算毒性值,应用发光细菌法测定降解过程中的实际毒性值,对理论计算毒性值与实际毒性值进行比较,分析不同体系下降解过程中毒性的变化规律.结果表明,两种工艺体系在最佳降解条件下,阴极室毒性均呈下降的趋势,由于降解过程中在阳极室生成高毒性的苯醌,阳极室毒性均先升高后降低.通过相关性分析得到,两种体系理论计算毒性与实际毒性在P=0.01水平下,相关性系数均为1,显著相关,表明降解过程中实际毒性的测定结果真实可靠.降解至120 min时,三电极体系毒性小于两电极体系,表明三电极体系优于两电极体系.据此提出实际毒性测定方法在电化学还原-氧化工艺降解氯酚类有机废水毒性测试的工业应用中有着广泛的前景.     

EDTA优化纳米Pd/Fe对2,4-D的催化脱氯研究

采用EDTA优化纳米Pd/Fe催化脱氯水中2,4-二氯苯氧乙酸(2,4-D),并考察了EDTA投加浓度、pH、钯化率、温度等因素对2,4-D还原的影响.结果表明,EDTA的加入络合了纳米Pd/Fe在催化脱氯过程中生成的铁离子,抑制纳米Pd/Fe颗粒表面钝化层的形成,提高了体系的反应活性.适宜的EDTA浓度、低pH、高钯化率、低温等有利于2,4-D的还原脱氯.当EDTA浓度为25.0 mmol·L-1,纳米铁含量为1.0 g·L-1,初始pH=4.3、钯化率为0.5%,温度为25.0℃,搅拌速率为200 r·min~(-1)时,反应50 min,10.0 mg·L-1的2,4-D去除率及苯氧乙酸(PA)生成率均达到100%.     

金属氧化物降解六氯苯的活性比较及催化机理研究

以氧化铝(α-Al_2O_3、γ-Al_2O_3)、氧化钙(CaO)、过渡金属氧化物(Mn O_2、α-Fe_2O_3、γ-Fe_2O_3、Ni_2O_3、CuO)为催化剂,考察了催化剂种类、添加比例等因素对六氯苯(Hexachlorobenzene,HCB)降解效果和产物组分的影响.结果表明,催化效果随催化剂添加比例的提高显著增加.在反应温度为350℃,反应时间1 h,金属氧化物添加比例为100∶1的条件下,碱土金属氧化物CaO及过渡金属氧化物中的α-Fe_2O_3和Ni_2O_3降解活性较好,这3种氧化物对HCB的降解率分别达到65.5%、100.0%和100.0%,脱氯率D_1分别为54.4%、81.9%和77.5%.HCB降解有机产物分析结果显示,8种金属氧化物与HCB样品反应产物中均存在低氯代苯,在α-Fe_2O_3和Ni_2O_3的催化作用下有2~4氯代低氯苯检出,说明在降解过程中存在明显的逐级脱氯/加氢反应;与CaO反应后的产物中低氯代苯较少,经拉曼光谱定性分析,有无序碳的检出,说明除了脱氯/加氢还存在脱氯缩合反应.     

苯酚、菲在BS-12/DTAB复配修饰膨润土上吸附的差异

为了探究复配修饰膨润土吸附疏水性不同的污染物的差异,采用阳离子型表面修饰剂十二烷基三甲基溴化铵(DTAB)对两性表面修饰剂十二烷基二甲基甜菜碱(BS-12)修饰膨润土进行复配修饰,采用批处理法研究复配修饰膨润土总修饰比例对苯酚和菲的等温吸附影响,并对比不同温度、pH值和离子强度条件下供试土样对苯酚和菲吸附量、热力学参数的差异.结果表明:随着总修饰比例的增大,复配修饰膨润土对苯酚及菲的吸附能力逐渐增强,0~50%CEC修饰比例下,菲的吸附率大于苯酚的吸附率,当修饰比例超出50%CEC后,苯酚的吸附率大于菲的吸附率,总修饰比例超出150%CEC后,膨润土对苯酚的吸附率变化趋于平缓,而对菲的吸附率开始呈下降趋势;随着土样总修饰比例的增大,温度对苯酚及菲吸附量的抑制效果降低;在KNO_3浓度为0.001~0.1 mol·L~(-1)时,苯酚及菲的吸附量均随着KNO_3浓度的增大而增大;随着pH值的升高,苯酚的吸附量逐渐增大,在pH=7处达到最大,而菲的吸附量则始终呈降低趋势.热力学参数显示,随着总修饰比例的增大,复配修饰土样对苯酚和菲的吸附自发性增强,混乱度增大,当总修饰比例超出150%CEC后,自发性减弱,混乱度下降.     

钙、氯对磷酸盐稳定污染土壤中铅的促进作用研究

为探讨促进磷酸盐稳定污染土壤中铅的方法,在全铅含量为517 mg·kg-1的铅冶炼污染土壤中加入5 mmol·kg-1磷酸盐,同时加入10mmol·kg-1硝酸钙或5 mmol·kg-1氯化钾,在15%或30%的含水率下培养40 d,之后种植黑麦草.结果表明,与单独施用磷酸盐相比,采用磷酸盐与钙、氯结合或增加培养期间的土壤含水率后,土壤DTPA-Pb含量下降3.92%~26.1%;对于同一添加剂处理,培养期间土壤含水率从15%增加到30%,土壤有效铅(DTPA-Pb)含量下降8.83%~24.4%.增加土壤含水率后,土壤有效磷(Olsen-P)含量均显著升高(p0.05).土壤铅的EXAFS分析表明,与未施用磷酸盐的对照相比,土壤中加入磷酸盐后矿物态铅的比例由57%上升至81%,加施钙、氯或增加土壤含水率后,多数处理矿物态铅的比例有所下降,而有机结合态铅比例上升.与对照相比,污染土壤中施用磷酸盐后,植物产量大幅增加,但施用钙、氯或增加培养期间含水率后,部分处理植物产量有所下降.以上结果表明,在铅冶炼污染土壤中加入磷酸盐时,加入钙、氯或者增加土壤含水率均有利于铅的稳定,但以上措施可能对植物生长产生不利影响.