有机化合物动态定量结构——生物降解关系(QSBR)模型研究

本文通过分析一般ＱＳＢＲ模型应用的特点、不足和影响有机物生物降解的基本因素，指出ＱＳＢＲ模型应综合反映影响有机物生物降解的四个方面（以氯代芳香化合物为例）：氯代苯系物的摄入、氯代苯系物的诱导作用、毒性物质的形成和基础酶的缺乏。在此基础之上给出了动态ＱＳＢＲ的概念模式及方法学基础。     

难降解氯代有机物污染环境的生物修复技术研究进展

氯代有机物是一类在生产和生活中广泛应用并被大量排放到环境中的难降解有机污染物质,一旦进入生态环境,就会在水体、土壤和底质中长期残留,并在食物链中不断积累、富集,从而对生物体产生危害。因此,对受这类难降解有机物污染的环境修复是目前所迫切需要解决的环境问题之一。基于物理和化学修复方法成本较高易造成二次污染,文中探讨了国内外生物修复技术的研究进展,并对难降解氯代有机物污染环境修复的研究方向进行了展望,由于环境中的污染物质复杂多变,联合生物修复技术将成为未来的研究热点。     

超声波和零价铁联用对氯代苯酚脱氯降解作用的研究

采用超声波和零价铁联用对氯代有机物3氯苯酚(CP)、2,4-二氯苯酚(DCP)和2,4,6-三氯苯酚(TCP)模拟废水进行了脱氯处理研究。以单因素法, 考察了铁粉初始投加量、溶液的初始浓度、超声波功率和溶液的pH值等因素对氯代酚降解的影响,并探讨了降解反应动力学。结果表明,超声波和零价铁联用对氯酚具有显著的降解效果,当水样初始浓度为25 mg/L,溶液pH呈弱酸性,超声波功率为200 W时,氯代酚的脱氯效率达到最大值。降解反应符合准一级反应,CP、DCP和TCP的反应速率常数分别0.0613 h^-1、0.374 h^-1和0.197 h^-1。     

TiO2光催化法在饮用水处理中的应用

针对目前水源水普遍受到有机物污染,而且氯消毒具有副作用的状况,因此,探讨了用TiO2光催化法去除水中的有机物及进行消毒的可能性.     

城市污水再生氯消毒过程中HAAs生成及迁移转化

针对城市污水再生处理工艺中卤乙酸类(HAAs)消毒副产物和卤乙酸生成潜能(HAAFP),结合三维荧光光谱,分析HAAs及其前体物的变化规律。结果表明,二级出水经2次加氯过程后,再生出水中的总卤乙酸浓度增加了90%,其中溴代乙酸的增幅最大,占增加量的82%。卤乙酸生成潜能较大的为氯代乙酸类物质,说明水中存在大量的氯代乙酸前体物。从工艺过程来看,总卤乙酸生成潜能与总有机物荧光强度分别下降了32%和28%,表明该再生处理工艺对HAAs前体物有一定的去除作用。     

纳米钯?铝双金属对水中3-氯酚的脱氯降解研究

采用置换沉积法制备了纳米钯/铝双金属催化剂,氢解还原去除水相中难降解有毒有机物3-氯酚(3-CP),考察了溶液pH、钯负载量、纳米钯/铝双金属投加量、反应温度对脱氯效果的影响并解析相关反应机制。结果表明:(1)初始pH 3.0时,沉积液中93.25%(质量分数,下同)～96.67%的钯可有效负载于铝材上。(2)在pH为3.0、纳米钯/铝双金属投加量为2g/L、钯负载量为1.16%(质量分数)、反应温度为25℃下降解初始摩尔浓度为0.389mmol/L的3-CP,反应终了时脱氯率在99%以上。利用纳米钯/铝双金属降解氯代有机污染物具有高效低耗的优势,在实际应用上具有较好的前景。     

松花江中游(哨口-松花江村段)水中有毒有机物污染研究

1983—1990年,在松花江中游(哨口—松花江村)138公里江段中,进行七次五断面追踪水团采样,采用高分子微球GDX—502吸附富集,GC定性定量,GC/MS定性验证。依据有机物检出率、毒性持久性、有点源排放、分析方法适用等因素,筛选出65种主要有毒有机物。化合物总浓度逐年降低,石油烷烃、芳烃浓度增加;属致癌致变性化合物21种,EPA优测物21种,建议的优先控制黑名单20种;有点源排入的占90％以上,污染源来自吉化主要入江污水口;封冰期比其它水文期污染增强;该江段污染特征为氯代链烃、氯代苯类、硝基芳烃种类多、浓度高,应为重点控制对象。     

生物流化床反应器在处理含氯代芳香化合物废水中的应用

氯代芳香化合物是工业废水中重要污染物之一。本文介绍了氯代芳香化合物的降解机理、生物流化床的特点及其处理氯代芳香化合物的应用 ,为含氯代芳香化合物的废水处理提供参考     

生物流化床反应器在处理含氯代芳香化合物废水中的应用

氯代芳香化合物是工业废水中重要污染物之一。本文介绍了氯代芳香化合物的降解机理、生物流化床的特点及其处理氯代芳香化合物的应用，为含氯代芳香化合物的废水处理提供参考。     

南方某水源水中天然有机物的特点及氯胺对氯化消毒副产物的控制

在对天然有机物分类的基础上进行了水体中有机物的特性研究，并采用氯胺对不同特性有机物的氯化消毒副产物进行了控制研究。结果表明，疏水酸占有机物总量的24%，疏水中性物质占41%，疏水性有机物占67%；对于三卤甲烷类消毒副产物生成势，疏水酸所产生的最多，疏水碱次之，亲水酸最少；对于卤乙酸类消毒副产物生成势，疏水碱产生的三卤乙酸最多，其次为疏水酸，亲水酸最少。氯胺对不同类有机物氯化消毒副产物控制程度不同，氯胺对疏水中性物质控制三卤甲烷类消毒副产物最好，其次是疏水碱和亲水碱；对疏水酸的三卤甲烷生成量控制较弱，对亲水酸的控制效果最差；氯胺对亲水碱氯化产生卤乙酸的控制效果最好，其次是疏水碱，控制效果最差的为疏水中性物质。     

The health effects and ecological significance of chlorine residuals in water

During the past several years, chlorine residuals and chlorinated organic compounds in drinking waters and aquatic environments have become a significant topic of study for scientists concerned about the quality of life in aquatic ecosystems as well as general public health. The effects of direct toxicity and/or carcinogenicity to human and aquatic life are the focal points for this concern.The effects of chloramines and chlorinated organic compounds present in the water distribution system after chlorination treatments are reviewed. Also discussed are the effects of chlorinated discharges from municipal secondary treatment plants and power plants on human health and aquatic life. The toxic significance of environmental chemicals are described.     

Degradation of PCDD, PCDF, PAH, PCB and chlorinated phenols during the destruction-treatment of landfill seepage water in laboratory model reactor (UV, Ozone, and UV/Ozone)

Seepage water of toxic waste landfills is polluted with high concentrations of toxic organic compounds. The concentrations in the seepage water we applied for chlorinated phenols are between 2 μg/1 and 1 mg/l, for PCB between 800 pg/l and 250 ng/l, for PAH between 200 ng/l and 12 μg/l and for PCDD and PCDF between 20 pg/l and 1 ng/l. Usual purification methods produce highly contaminated residues, which have to be treated by pyrolysis or are deposited again at a landfill. A better way is to destruct these contaminants by UV/ozone treatment. The treatment of seepage water by UV-irradiation, ozone and UV/ozone is compared. Results show no significant effect during all treatments for PCB and PCDD/PCDF. The chlorinated phenols and PAH were mostly destroyed by UV/ozone treatment more than 90 %. The pH value has no influence on the UV/ozone treatment of seepage water.     

Transformation of phenol, catechol, guaiacol and syringol exposed to sodium hypochlorite

Germs, xenobiotics and organic matter that influence the colour, turbidity and organoloeptic properties of water are removed by chlorination. Unfortunately, chlorine oxidants including sodium hypochlorite, used in water treatment induce processes that partly convert the treated compounds to unwanted chlorinated derivatives. The purpose of this work was to analyse the efficiency of transformation of phenol, catechol, guaiacol and syringol exposed to sodium hypochlorite and determine the intermediates formed during oxidative conversion of these compounds. The analysis was performed in aerobic conditions, both in acidic (pH 4.0) and alkaline (pH 8.0) medium. The effectiveness of transformation was slightly higher in acidic in comparison to alkaline conditions. Some chlorophenols, such as 2-chlorophenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol and pentachlorophenol were determined as the products of phenol conversion. Chlorophenols were also formed during catechol, guaiacol and syringol transformation by replacement of hydroxy and methoxy residues by chlorine atoms. Moreover, some chlorocatechols and chlorinated methoxyphenols were determined during catechol and methoxyphenols transformations. Higher concentrations of chlorinated compounds were observed in the alkaline environment during phenol transformation. Conversion of catechol and methoxyphenols generated higher amounts of chlorinated intermediates in the acidic medium. In samples carboxylic acids like acetic and formic acids were determined. The formation of these compounds was the result of the cleavage of aromatic structure of phenols.     

Dioxins,chlorophenols and other chlorinated organic pollutants in colloidal and water fractions of groundwater from a contaminated sawmill site

BACKGROUND, AIM, AND SCOPE: The distribution of chlorinated organic contaminants in groundwater and the importance of colloids were studied in groundwater from a sawmill site contaminated by chlorophenol preservatives. MATERIALS AND METHODS: The groundwater was fractionated into three different size ranges: (1) >0.7 mum, (2) 0.4-0.7 mum and (3) 0.2-0.4 mum and the filtered water phase. The concentrations of chlorophenols (CP), chlorinated phenoxy phenols (PCPP), chlorinated diphenyl ethers (PCDE), chlorinated dibenzofurans (PCDF) and chlorinated dibenzo-p-dioxins (PCDD) were determined in each fraction. The colloids were characterised regarding the chemical composition using X-ray photoelectron spectroscopy (XPS). RESULTS: Chlorophenols were mostly found in the water fraction and PCDD/Fs were found almost exclusively in the particulate fractions. For example, the filtered water phase contained 2,100 mug l(-1) and 0.72 ng l(-1) for CPs and PCDD/Fs, respectively, and the particulate fractions contained 27 mug l(-1) and 32 ng l(-1) for CPs and PCDD/Fs, respectively. XPS evaluation of the particulate phases showed no correlation between the surface chemistry of the particle properties and the distribution of chlorinated compounds. DISCUSSION: The results suggest that groundwater transport of CPs, PCPPs, PCDEs and PCDD/Fs may occur from contaminated sawmill sites and that the colloid-facilitated transport, especially of PCDD/Fs, is substantial. The results correlated well with previous studies of compounds sorbed to dissolved organic carbon, which indicate that dissolved and colloidal organic carbon facilitated the transport of PCDEs, PCDFs and PCDDs particularly. CONCLUSIONS: Several classes of chlorinated compounds were readily detected in the groundwater samples. Due to the differences in their physicochemical properties, CPs, PCPPs, PCDEs and PCDD/Fs vary in their partitioning between colloidal fractions and the filtered groundwater. The proportion of the bound fraction increased with an increasing hydrophobicity of the chlorinated compounds. The groundwater transport of colloid-associated pollutants from the site may be significant. RECOMMENDATIONS AND PERSPECTIVES: The results imply that colloidal particles <0.7 mum are freely mobile in groundwater from this site. The groundwater transport of colloid-associated pollutants may be significant. However, the extent of the problem is not yet known and, thus, further research is needed to evaluate the impact of colloidal transport of hydrophobic organic contaminants. In Sweden alone, 400 to 500 sawmill sites are estimated to be contaminated with PCDD/Fs as a result of the former use of CP-based wood preservatives. The widespread use of CP mixtures for a variety of applications, including wood preservation, indicates that potential colloidal transport will be an issue of concern in many countries.     

Screening of organic halogens and identification of chlorinated benzoic acids in carbonaceous meteorites

The occurrence of halogenated organic compounds measured as a sum parameter and the evidence of chlorinated benzoic acids in four carbonaceous meteorites (Cold Bokkeveld, Murray, Murchison and Orgueil) from four independent fall events is reported. After AOX (Adsorbable organic halogen) and EOX (Extractable organic halogen) screening to quantify organically bound halogens, chlorinated organic compounds were analyzed by gas chromatography. AOX concentrations varying from 124 to 209 microg Cl/g d.w. were observed in carbonaceous meteorites. Ion chromatographic analysis of the distribution of organically bound halogens performed on the Cold Bokkeveld meteorite revealed that chlorinated and brominated organic compounds were extractable, up to 70%, whereas only trace amounts of organofluorines could be extracted. Chlorinated benzoic acids have been identified in carbonaceous meteorite extracts. Their presence and concentrations raise the question concerning the origin of halogenated, especially chlorinated, organic compounds in primitive planetary matter.     

The effect of inorganic and organic chlorine on formation of highly chlorinated organic compounds during incineration: Laboratory pilot study

Aliphatic liquid as a basic fuel was incinerated in a laboratory scale pilot plant. Inorganic chlorine and organic chlorine mixed with basic fuel were used as additive chemicals. Sodium chloride (NaCl) and tetrachloroethylene (C₂Cl₄) were used as the sources of inorganic and organic chlorine. Combustion parameters were adjusted for optimum combustion and, consequently, the amount of particles in flue gases was low. The concentrations of chlorine in flue gases were high enough for possible formation reactions of organic chlorinated compounds in all of the chlorine input tests. An increase in chlorine input did not significantly increase the amounts of highly chlorinated organic compounds, like PCDD/Fs. The main result was that chlorophenol concentrations increased in parallel with organic chlorine input. Comparing organic chlorine to inorganic chlorine tests showed that more highly substituted PCDD/F congeners were formed when organic chlorine was the additive chlorine source. The formation of highly chlorinated organic compounds such as PCDD/Fs requires not only chlorine and aliphatic fuel to be formed, but some catalysts are also needed.     

Quantification of bisphenol A, 353-nonylphenol and their chlorinated derivatives in drinking water treatment plants

Bisphenol A (BPA) and nonylphenols (NP) are of major concern to public health due to their high potential for human exposure and to their demonstrated toxicity (endocrine disruptor effect). A limited number of studies have shown that BPA and NP are present in drinking water. The chlorinated derivatives that may be formed during the chlorination step in drinking water treatment plants (DWTP) exhibit a higher level of estrogenic activity than their parent compounds. The aim of this study was to investigate BPA, 353NP, and their chlorinated derivative concentrations using an accurate and reproducible method of quantification. This method was applied to both surface and treated water samples from eight French DWTPs producing from surface water. Solid-phase extraction followed by liquid chromatography?Ctandem mass spectrometry was developed in order to quantify target compounds from water samples. The limits of detection ranged from 0.3 to 2.3?ng/L for BPA and chlorinated BPA and from 1.4 to 63.0?ng/L for 353NP and chlorinated 353NP. BPA and 353NP were found in most analyzed water samples, at a level ranging from 2.0 to 29.7?ng/L and from 0 to 124.9?ng/L, respectively. In most of DWTPs a decrease of BPA and 353NP was observed between surface water and treated water (36.6 to 78.9?% and 2.2 to 100.0?% for BPA and 353NP, respectively). Neither chlorinated BPA nor chlorinated 353NP was detected. Even though BPA and 353NP have been largely removed in the DWTPs studied, they have not been completely eliminated, and drinking water may consequently remain a source of human exposure.     

Remediation of BTEX and trichloroethene

The widespread use of industrial chemicals in our highly industrialized society has often caused contamination of large terrestrial and marine areas due to the deliberate and accidental release of organic pollutants into the soil and groundwater. In this review, environmental problems arising from the use of chlorinated solvents and BTEX compounds are described, and an overview about active management strategies for remediation with special emphasis on phytoremediation are presented to achieve a reduction of the total mass of chlorinated solvents and BTEX compounds in contaminated areas. Phytoremediation has been proposed as an efficient, low-cost remediation technique to restore areas contaminated with chlorinated solvents and BTEX compounds. The feasibility of phytoremediation as a remediation tool for these compounds is discussed with particular reference to the uptake and metabolism of these compounds, and a future perspective on the use of phytoremediation for the removal of chlorinated solvents and BTEX compounds is given.     

Contaminated site remedial investigation and feasibility removal of chlorinated volatile organic compounds from groundwater by activated carbon fiber adsorption

Groundwater contaminated by dense, non-aqueous phase liquids (DNAPLs) such as chlorinated solvents has become a serious problem in some regions of Taiwan. The sources of these contaminants are due to industrial discharges. These chlorinated volatile organic compounds (VOCs) have been proven to be carcinogenic to humans. The groundwater is used for domestic drinking water supply in some cities of Taiwan and the severely contaminated groundwater has to be treated in order to meet the requirement of drinking water standards. This study covers two areas of work. In the first part, polluted groundwater samples were collected from the contaminated site and analytical results indicated measurable concentrations of 12 representative chlorinated VOCs in water samples. The primary VOCs detected included trichloroethene (TCE), tetrachloroethene (PCE), 1,1,2-trichloroethane (1,1,2-TCA), and 1,1-dichloroethene (1,1-DCE). Second, to remove VOCs groundwater was treated using adsorption on activated carbon fiber (ACF). This involved pumping groundwater through vessels containing ACF. Most VOCs, including TCE, PCE, 1,1,2-TCA, and DCE, were readily adsorbed onto ACF and are removed from the water stream. Our study showed that the technology was able to significantly reduce chlorinated VOCs concentrations in groundwater.     

Degradation of 2,4,6-trichlorophenol in aqueous systems through the association of zero-valent-copper-mediated reduction and UVC/H2O2: effect of water matrix and toxicity assessment

Environmental Science and Pollution Research - The presence of toxic chlorinated compounds in drinking water, generated during the disinfection step in water treatment plants, is of great concern...