表面活性剂增强修复地下水中PCE的砂箱实验及模拟

在石英砂充填的二维砂箱中开展表面活性剂（Tween 80）冲洗四氯乙烯（PCE）的修复实验,基于图像分析技术监测不同污染源区结构条件下NAPL相的去除过程.由于实验条件限制,实验中缺乏溶解相浓度数据.为此进一步基于UTCHEM数值模拟方法来理解NAPL相和溶解态之间的质量传输过程,并探讨表面活性剂浓度、注入速率等因素对修复效率的影响.综合砂箱实验和数值模拟结果表明：介质均质和非均质条件下会形成不同类型DNAPL污染源区结构,表现为离散状PCE与池状PCE体积比（GTP）差异.由于离散状污染物与表面活性剂的接触面积更大,更易被优先去除;初始GTP值越高,污染物的修复速率和修复效率也越高.增大表面活性剂浓度或提高表面活性剂的注入速率,虽然能提高DNAPL的修复速率,但会明显降低表面活性剂的修复效率,实验过程中修复效率降幅可达93%.线性驱动溶解模型可以有效地模拟表面活性剂修复DNAPLs过程,基于数值模拟方法选择合适的表面活性剂配比可有效的节省实际污染场址修复经费和时间成本.     

Comparative assessment of wet and dry garment cleaning Part 1. Environmental and human health assessment

Water-based cleaning of specialty garments is emerging as a potential alternative to dry cleaning. Perchloroethylene, the solvent used in dry cleaning, poses significant human and ecosystem health concerns. This paper is part 1 of a two part series that analyzes the key environmental, human health, performance, economic, and regulatory factors which influence the future of the garment cleaning industry. This paper inventories the environmental releases and wastes associated with the consumption of perchloroethylene in modern dry cleaning machines which ranges from 2.0 to 5.2 kg per 100 kg of clothing cleaned. In addition, water, electricity, and other inputs for both perchloroethylene-based and water-based garment cleaning are compared using data from previous demonstration projects. Toxicological and epidemiological studies provide evidence for the carcinogenicity of perchloroethylene although this classification is controversial. Cancer risks at low levels of exposure associated with modern dry cleaning equipment and good housekeeping practices are unknown and require further investigation. Regardless of these uncertainties, water-based cleaning is preferable to dry cleaning from a human and environmental health perspective.     

The distribution of the chlorinated solvents dichloromethane,perchloroethylene, and trichloroethylene in the global atmosphere

Dichloromethane, perchloroethylene, and trichloroethylene are commercially important chlorinated solvents whose health and environmental impacts are under scrutiny in the industrial world. Their distributions in the global atmosphere have been computed based on data from the Reactive Chlorine Emissions Inventory (RCEI) project using the Global Balance Environment (GLOBE) model, a 3-D radiative-dynamical-chemical model. Their atmospheric lifetimes, scaled to an observed methyl chloroform lifetime of 4.8 years, are 158 days, 105 days, and 4.3 days, respectively. They have strong interhemispheric gradients, with maximum zonal mean surface concentrations in the winter mid-latitude northern hemisphere of approximately 40 ppt, 9 ppt, and 2.5 ppt, respectively. Their spatial distributions show significant seasonal variability, and are sensitive to vertical mixing by cumulus convection and horizontal mixing by synoptic-scale turbulence. While the model interhemispheric exchange time (1.0 years) and computed atmospheric lifetimes are very sensitive to sub-grid scale diffusion, interhemispheric gradients of the chlorinated solvents are not. The simulated results suggest a greater importance for oceanic emissions of perchloroethylene and trichloroethylene than has previously been assumed.     

Physiological changes associated with aging result in lower internal doses of toluene and perchloroethylene in simulations using pharmacokinetic modeling

Physiologically based pharmacokinetic (PBPK) models were developed in order to translate external concentrations into internal dose estimates, but most PBPK models were developed for younger adults. A set of physiological parameters for ages 65, 75, and 85 of both genders were developed and were used with previously established human PBPK models of exposure to toluene and perchloroethylene (PERC) in order to investigate internal dose changes with increasing age. The predicted compartmental concentrations of toluene and PERC for aged adults were lower than predicted concentrations for younger adults, and this suggests that body composition changes with aging do not increase internal doses of inhaled toxicants alone after acute exposure. Hence, susceptibility to either toxicant was not expected to increase solely based on the physiological changes associated with aging. Predictions for a metabolite of PERC, however, were similar in magnitude across ages, which may lead to enhanced susceptibility if metabolic capacity changes with aging.     

采用筛板塔吹脱模拟处理四氯乙烯污染地下水

利用自主设计的筛板塔装置模拟吹脱四氯乙烯(PCE)污染废水,综合考察了影响吹脱的各因素(气液体积比、初始浓度和筛板数等),同时对吹脱工艺条件进行了优化,并建立了吹脱模型.研究表明:25.68mg/L PCE废水经吹脱后出水浓度降至0.62mg/L,去除率可达97.59%;气液比对废水的吹脱效果影响很大, 且最佳气液比在200左右;PCE初始浓度对去除率的影响并不明显;采用4层塔板时PCE去除效果较好;实验数据很好地遵从一级衰变模型;吨水吹脱成本约为0.31元,可作为后续生化处理的预处理工艺.     

四氯乙烯胁迫对草鱼抗氧化酶活性的影响及其机理

研究了四氯乙烯(PCE)对草鱼的肝胰脏、肾脏和鳃组织的超氧化物歧化酶(SOD)和过氧化物酶(POD)的影响.结果表明:草鱼肝胰脏SOD活性,在PCE低浓度胁迫时其SOD活性“先升后降”[72h SOD是(6665.84±106.87)U/g·FW,168h SOD是(3021.26±16.96)U/g·FW],高浓度胁迫时“先降后升再降”[24h SOD是(2175.16±185.14)U/g·FW, 96h SOD是(5692.19±44.17)U/g·FW,168h SOD是(1297.70±11.52)U/g·FW];草鱼肾脏SOD活性在PCE所有浓度组胁迫均是“先降后升再降”的趋势;草鱼鳃组织SOD酶活性只有在PCE较低浓度短时间内没有显著变化,其它情况始终降低.在PCE低浓度和中等浓度胁迫时,草鱼肝胰脏POD活性始终降低,较低浓度和高浓度胁迫时肝胰脏POD活性“先降后升再降”;草鱼肾脏POD活性在PCE低浓度胁迫时“先升后降再升又降”的趋势,而高浓度胁迫时“先降后升又降”;PCE对草鱼鳃组织POD活性“先升后降”的趋势.但是草鱼鳃组织的SOD和POD活性明显低于肝胰脏和肾脏组织的SOD和POD活性.     

Solubilization and degradation of perchloroethylene （PCE） in cationic and nonionic surfactant solutions

Solubilization of perchloroethylene (PCE) in a nonionic (Triton X-100) and a cationic (cetyltrimethylammonium bromide (CTAB)) surfactant solutions and the degradation of surfactant solubilized PCE using fine to nanosize Fe and bi-metallic Fe-Ni particles were investigated. Micelle partition coefficients (Km) and molar solubility ratio (MSR) for PCE in 10 g/L of surfactant solutions have been quantified and the solubility of PCE (100 mg/L in water) in the surfactant solutions increased by about ten fold. Of the two surfactants studied, Triton X-100 solubilized the higher amount of PCE per gram of surfactant. To degrade solubilized PCE, both iron and bimetallic Fe-Ni particles were used in continuously stirred batch reactors. The iron and bi-metallic particles were synthesized using the solution method and the particles were characterized using the SEM, EDS, TEM and XRD. The PCE solubilized up to 500 mg/L in both surfactant solutions were totally degraded at various rates by 200 g/L of bi-metallic Fe-Ni particles in less than 20 hr, which is the highest concentration of PCE degraded in the shortest time compared to data in the literature. The degradations of PCE solubilized in surfactant solutions were represented by nonlinear kinetic relationships which depended on the type of surfactant used for solubilizing the PCE.     

电子鼻检测污染土壤中挥发性氯代烃的适用性研究

开发了一套以光离子化传感器（PID）为核心的电子鼻系统,用于污染土壤中挥发性氯代烃的快速检测.用气相色谱（GC）分析评价了预处理管对苯系物等干扰物质的去除效果;用标准气体发生装置发生不同浓度的四氯乙烯和三氯乙烯气体,比较评价了电子鼻与GC检测结果的吻合程度及测试重现性.在此基础上,选取我国长三角地区三类典型水稻土进行模拟污染土壤的通风净化实验,评价了电子鼻系统用于实时监测挥发性氯代烯烃污染土壤修复进程的可行性.结果表明：①采用RAE-SEP卤代烃分离管进行预处理,甲苯、乙苯等苯系干扰物的去除率可达80%～97%,而四氯乙烯和三氯乙烯等挥发性氯代烃的选择性透过率高于90%;②电子鼻对不同浓度四氯乙烯和三氯乙烯气体的定量检测结果与GC结果相近,线性拟合斜率为1.012,相关系数R2〉0.99;③电子鼻对三类典型土壤通气脱附过程中污染物浓度的变化趋势的实时监测结果与GC检测结果基本一致,判定系数R2〉0.99（n=47）.因此,该电子鼻系统有望用于挥发性氯代烯烃污染土壤的快速检测,提高污染场地的风险评估和修复效率.     

铁还原环境四氯乙烯生物降解及其影响因素

通过实验研究了铁还原环境下四氯乙烯(PCE)的生物降解。以醋酸为共代谢基质,在20℃时,PCE可以顺序脱氯为TCE和DCEs。反应速率常数为0.2489d-1,半衰期为2.78d。在实验的第1天和第10天分别检测到了TCE和DCEs。TCE最高浓度为358.98nmol/L,是最主要的反应产物。碳平衡为88.7%～109.3%。在13d的实验周期中,微生物的数量和活性都有所增加。同时研究了不同的影响因素,如低温、不同pH和电子受体对PCE生物降解的影响。结果表明,在12℃时,PCE可以脱氯为TCE,半衰期为6.45d,降解速率为0.1075d-1,较20℃时的降解速率要低。脱氯的最佳pH值在7.0左右,较高和较低的pH值均会抑制脱氯微生物的活性。加入不同电子受体NO3-和SO42-,PCE脱氯受到不同程度的抑制,前者可能是由于NO3-是相对强的氧化剂,造成微环境中的氧化还原电位升高;后者则可能是SO42-的存在,会抑制脱氯菌的作用。     

脉冲电晕法藕合Ca(OH)2固体吸收处理四氯乙烯废气研究

采用线-筒式脉冲电晕反应器对四氯乙烯去除效果进行了研究.结果表明,四氯乙烯去除率随电压的增大而增大.在氮气中加入氧气,四氯乙烯降解效果低于纯氮气下的降解效果.四氯乙烯在氮气下的主要气相产物为Cl_2和少量的CCl_4.当氧气加入后,四氯乙烯主要降解为CO_2、CO、COCl_2、O_3和C_2Cl_4O.为了去除有害中间产物,在反应器中加入Ca(OH)_2固体吸收剂,这明显提高了有害中间产物的去除,存在水汽及含Ca(OH)_2固体吸收剂时并未检测到COCl_2、O_3和有害中间产物C_2Cl_4O,但水汽不利于四氯乙烯去除.