利用紫外光降解多氯联苯（PCBs）的研究进展

本文综述了PCBs在各种溶剂中的紫外光化学反应特性和降解途径：PCB的光化学反应以氢取代氯的脱氯反应为主,除此之外,在水或醇等极性溶液中,还存在羟基化反应;PCB的光化学反应活性与其氯原子的数量和取代位置有关。文章最后还简述了光降解在治理受PCB污染土壤方面的应用。     

紫外光照射与生物降解耦合用于PCBs降解的研究

介绍了PCBs紫外光降解的机理及研究进展，讨论了影响PCBs光降解的主要因素，即环上的氯原子数目、取代位置及所处的微环境均显著地影响PCBs的光降解速率。简述了PCBs生物降解的研究进展，重点概述了好氧降解、厌氧降解及好氧厌氧协同作用的机理及特点。最后，讨论了PCBs生物降解和光降解的互补性，介绍了最近的研究进展，指出光降解和生物降解耦合格加快PCBs的移走速率，提出了PCBs污染土壤原位修复需要进一步解决的问题。     

紫外光照射与生物降解耦合用于PCBs降解的研究

介绍了PCBs紫外光降解的机理及研究进展 ,讨论了影响PCBs光降解的主要因素 ,即环上的氯原子数目、取代位置及所处的微环境均显著地影响PCBs的光降解速率。简述了PCBs生物降解的研究进展 ,重点概述了好氧降解、厌氧降解及好氧厌氧协同作用的机理及特点。最后 ,讨论了PCBs生物降解和光降解的互补性 ,介绍了最近的研究进展 ,指出光降解和生物降解耦合将加快PCBs的移走速率 ,提出了PCBs污染土壤原位修复需要进一步解决的问题。     

水中安替比林的紫外光降解研究

以波长为254 nm的紫外杀菌灯为光源,研究了水溶液中消炎镇痛药物安替比林（PZ）的光降解行为;考察了初始pH值及水中其他物质对PZ光降解的影响,探讨了PZ光解机制,并分析其降解产物及光解途径。结果表明,安替比林的光降解遵循拟一级反应动力学规律,pH值变化对光解速率基本没有影响。安替比林直接光降解占主导作用,活性氧类物种（ROS）对安替比林间接光解基本没有贡献。腐殖酸对安替比林光降解有抑制作用,而NO^-₃,HCO^-₃,Cl^-对安替比林光降解没有明显作用。GC-MS分析表明安替比林在紫外辐射下生成甲酰胺,乙酰胺,2-羟基吲哚-3-酮,2,4（1氢,3甲基）-喹唑啉二酮,1-甲基-2-羟基苯并咪唑,2-羟基苯并恶唑等一系列具有安替比林母体苯环结构的化合物,表明安替比林侧链上N—N键断裂导致其最终降解。     

水和废水中多氯联苯(PCBs)的测定方法及进展

本文引用了七十余篇近几年国内外的有关著文,对水和废水中的多氯联苯(PCBs)的测定方法进行了评述,全面系统地介绍了水样的采集、富集、净化和分析测定等操作程序,着重于样品的前处理和气相色谱分析,并提出了这一领域今后的发展趋势。     

真空紫外光降解五氯酚钠以及过硫酸盐对反应的促进作用

研究了真空紫外光(VUV,185 am)对于水溶液中五氯酚钠的降解,反应2 h后,初始浓度为10 mg/L的五氯酚钠的去除率达到99%以上,有机氯的脱除率达到70%以上,有效地实现了五氯酚钠的脱毒.溶液初始pH值对五氯酚钠的真空紫外光解有很大影响,pH=10.9时的降解速率常数是pH=3.1时的3倍.表观一级反应速率常数随初始浓度的增加而线性下降.在反应溶液中加入过硫酸盐,可有效提高五氯酚钠的真空紫外光降解速率和矿化速率,过硫酸盐和五氯酚钠摩尔比为24时,降解速率提高3倍,反应4 h后TOC去除率达到95%.     

气相中嗅味物质—壬醛的真空紫外光降解研究

在建立热脱附-气相色谱法分析气相中低浓度壬醛的基础上,研究了不同条件下真空紫外光对气相中低浓度壬醛的光化学降解。结果表明,壬醛的真空紫外光降解率基本不受初始浓度的影响,在所研究的浓度范围(0.13～1.74mg/m3)内符合一级动力学,其表观反应速率常数为2.3 min-1。相对湿度一开始增加时均使得不同浓度的壬醛的去除率降低,但低浓度壬醛的降解随后几乎不再受相对湿度变化的影响,而较高浓度壬醛的去除率则先随相对湿度增加而下降,随后则又上升。壬醛能在极干燥的氮气气氛中被真空紫外光降解,同时它在氮气气氛中的降解率随相对湿度的增加而增加,壬醛在极干燥的氮气、空气和氧气气氛中的降解率依次上升,说明真空紫外光直接光解、光解产生的羟基自由基、光解产生的氧原子或臭氧均能导致壬醛的有效降解,且这3种机制相互影响。     

真空紫外光降解苯的研究

为了考察真空紫外光辐射在气体净化中的应用,以苯作为目标污染物,分别进行了紫外光波长、气体湿度、反应时间、初始浓度以及辐射功率对苯光解率的影响实验。实验结果表明,真空紫外光辐射方法净化气相污染物中的苯效果良好,在一定条件下,浓度为348.2 mg/m³苯污染气体真空紫外光降解率可达到90%。通过在不同条件下苯的降解率以及臭氧浓度变化,初步探讨了苯降解的机理以及降解途径。苯的降解主要是通过氢氧自由基（·OH）的加成以及后续一系列的氧化反应,降解产物为苯酚以及含有羟基的长链烃。     

土壤中多氯联苯分析方法研究进展

文中综述了多氯联苯的分析技术及其研究进展。介绍了样品前处理技术如索氏萃取法、超声萃取法、微波辅助萃取、超临界流体萃取、加速溶剂萃取等在土壤样品中多氯联苯分析中的应用;阐述了气相色谱、液相色谱、气质联用技术在土壤样品中多氯联苯的检测,并对土壤中未来多氯联苯检测技术的发展提出了展望。     

紫外光协助高锰酸钾降解四环素的研究

高锰酸钾氧化法在实际水处理中得到了一定的应用,但对有机污染物的去除和降解能力相对有限,为此提出了以外加紫外光照射协助高锰酸钾氧化的方法。以四环素作为模型污染物,考察了四环素浓度、高锰酸钾浓度、反应时间、初始pH条件和不同紫外光照射等的影响。结果表明,高锰酸钾能够氧化并去除四环素,紫外光照射明显提高了高锰酸钾对四环素的降解效果,并且254 nm紫外光照射对降解的促进作用远大于365 nm紫外光。在所考察的pH范围内,无论紫外光照射与否,高锰酸钾在酸性条件下的降解效率最高,中性条件较高,碱性条件次之。     

多氯联苯污染沉积物质量评价研究进展

介绍了多氯联苯污染沉积物质量评价的研究进展 ,其中 ,简单介绍了多氯联苯的有关概况及环境行为、沉积物质量评价方法及基准研究进展 ;最后 ,重点介绍了包括多氯联苯在内的憎水性有机物污染沉积物质量评价的研究现状及存在问题。     

Detailed study on the levels of polychlorinated dibenzo-p-dioxins,polychlorinated dibenzofurans and polychlorinated biphenyls in Yusho rice oil

One bottle of Yusho rice oil was obtained from a Yusho family in 1998. The levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in the causal oil were investigated with two different approaches and the individual concentrations of all the 17 2,3,7,8-substituted PCDD/F and 14 coplanar PCB (Co-PCB) congeners were elucidated for the first time. The concentrations of PCDDs and PCDFs were found to be 0.60 and 8.8 ppm, respectively. For PCBs, more than 130 PCB peaks were observed and a total concentration of 850 ppm including 170 ppm of Co-PCBs was obtained. The toxic equivalents (TEQs) of PCDDs, PCDFs, and Co-PCBs were calculated to be 17, 470, and 120 ppb, respectively. The relative contribution of these classes to the total TEQ in Yusho oil is 3%, 77%, and 20%, respectively, indicating that PCDFs play a major role in the toxicity of Yusho oil. Furthermore, it was confirmed that 2,3,4,7,8-penta-CDF contributes 58% to the total TEQ, supporting the view that this compound is the principal causal agent in Yusho poisoning. It is noteworthy that the most toxic 2,3,7,8-tetra-CDD was newly discovered, although it contributes only 0.1% to the total TEQ. Based on our data, the smallest TEQ intake during the latent period was estimated to be 0.067 mg for Yusho patients. This value is about 60% of that previously reported, suggesting a lower minimum threshold level for the development of the toxic symptoms of Yusho.     

碳纳米管对水中多氯联苯的吸附动力学

通过静态吸附实验研究了碳纳米管（CNTs）对水中多氯联苯（PCBs）的吸附动力学特性,包括1种单壁碳纳米管（SWCNTs）和3种多壁碳纳米管（MWCNTs）,并对4种CNTs的物理特征及孔径分布进行了分析。结果表明,SWCNTs的比表面积和总孔容最大,分别为228.210 m2·g-1和1.515 4 cm3·g-1。CNTs对PCBs的吸附速率很快,40 min吸附量可达到平衡时的90%以上,80 min左右达到吸附平衡,且SWCNTs的吸附能力远大于MWCNTs。运用拟一级和拟二级动力学模型对实验数据进行拟合,表明拟二级模型更适合描述CNTs对PCBs的吸附过程。     

Accumulation of hydroxylated polychlorinated biphenyls (OH-PCBs) and implications for PCBs metabolic capacities in three porpoise species

The present study investigated polychlorinated biphenyls (PCBs) and hydroxylated metabolites of PCBs (OH-PCBs) in blood from three porpoise species: finless porpoises (Neophocaena phocaenoides), harbor porpoises (Phocoena phocoena), and Dall’s porpoises (Phocoenoides dalli). The porpoises were found stranded or were bycaught along the Japanese coast. Concentrations of OH-PCB were the highest in Dall’s porpoises (58 pg g⁻¹ wet wt), second highest in finless porpoises (20 pg g⁻¹ wet wt), and lowest in harbor porpoises (8.3 pg g⁻¹ wet wt). The concentrations in Dall’s porpoises were significantly higher than the concentrations in finless porpoises and harbor porpoises (p < 0.05 and p < 0.01, respectively). There was a positive correlation between PCB and OH-PCB concentrations (r = 0.67, p < 0.001), suggesting the possible concentration-dependent induction of CYP enzymes. The three porpoise species may have exceptionally low metabolic capacities compared with other marine and terrestrial mammals, because low OH-PCB/PCB concentration ratios were found, which were 0.0016 for Dall’s porpoises, 0.0013 for harbor porpoises, and 0.00058 for finless porpoises. Distinct differences in the OH-PCB congener patterns were observed for the three species, even though they are taxonomically closely related.     

生物与化学表面活性剂协同洗脱土壤中PCBs的研究

通过序批实验和土柱淋洗实验研究了由生物表面活性剂鼠李糖脂(RL)与非离子化学表面活性剂十二烷基醇聚氧乙烯(6)醚(POE(6))混合得到的复配试剂洗脱污染土壤中多氯联苯(PCBs)的作用效果及其作用机理。结果表明,同一土样中,从批实验得到的PCBs洗脱率略高于土柱淋洗实验。RL与POE(6)两种单一试剂对人工污染土样中的PCBs洗脱率均大于60%,而对陈化土样中的洗脱率均不到20%,且土壤中的TOC含量越高,PCBs的洗脱率越低。在质量浓度为301 mg/L(10 CMC)及1 505 mg/L(50 CMC)的RL-POE(6)复配试剂中,RL与POE(6)对人工污染土壤中PCBs的洗脱具有一定的协同作用。当复配试剂的浓度为301 mg/L时,RL与POE(6)对陈化土样中PCBs的洗脱没有协同作用;但当RL-POE(6)的浓度增加到1 505 mg/L时,RL与POE(6)对陈化土样中PCBs的洗脱具有明显的协同作用。     

Occurrence of pesticides and polychlorinated biphenyls in water of the Nile river at the estuaries of Rosetta and Damiatta branches,north of delta,Egypt

Abstract

A study was conducted from summer 1995 to summer 1997 to assess the seasonal occurrence of pesticide residues and other organic contaminants, polychlorinated biphenyls (PCBs), in water at the estuaries of Rosetta and Damiatta branches of the Nile river. The results indicated that organochlorine compounds (OCs) including HCB, lindane, p,p‘‐DDE, p,p‘DDD, p,p‘‐DDT, aroclor 1254 and aroclor 1260 were present in all the water samples at concentration levels ranging between 0.195–0.240, 0.286–0.352, 0.035–0.067, 0.019–0.033, 0.024–0.031, 0.390–0.70 and 0.166–0.330 μg/l, respectively. The levels of these compounds were higher in water of Damiatta branch than those found in water of Rosetta branch. Aldrin, dieldrin and endrin were not detected in all water samples. Only 4 compounds from 36 organophosphorus insecticides, fungicides and s‐triazine herbicides tested were detected in water samples collected during summer and autumn seasons from Rosetta branch. The concentration levels of these detected compounds, dimethoate, malathion, captan, and ametryne, ranged from 0.011 to 0.340 μg/l, respectively. Similar compounds during the same seasons as found in water of Rosetta branch were also detected in water of Damiatta branch except ametryne. The levels of the detected compounds (dimethoate, malathion and captan) ranged between 0.030 and 0.330 μg/l. The levels of detected organophosphorus insecticides, fungicides and s‐triazine herbicides were in the order: dimethoate > malathion > captan > ametryne.     

Monofluorinated analogues of polychlorinated biphenyls (F-PCBs): synthesis using the Suzuki-coupling, characterization, specific properties and intended use

An improved method, a palladium-catalyzed cross-coupling reaction the so-called Suzuki-coupling, was used to synthesize 19 monofluorinated analogues (F-PCBs) of polychlorinated biphenyls (PCBs), including analogues of PCBs 28, 52 and 81. The coupling of chlorinated and/or fluorinated isomers of aryl boronic acids with bromo- and/or iodobenzenes gave the desired F-PCB congeners in good to excellent yields. The self-coupling product of the aryl boronic acids was the major impurity, but this limitation could be minimized. The influence of ortho-substitution by chlorine on the reaction time was studied in detail. The F-PCBs were characterized by means of ¹H and ¹⁹F NMR and mass spectrometry (MS). F-PCBs show remarkably similar characteristics in many aspects to those of the corresponding non-fluorinated parent PCBs. Since fluorine is generally resistant to degradation, once incorporated into a substrate it functions as an indelible label that can be used to monitor structures and dynamics. F-PCBs may prove their usefulness as markers and tracers in mechanistic and toxicological studies. The aim of further research will be to test the suitability of fluorine as a sensitive probe in a broad range of applications, including synthesis, analytical, mechanistic and toxicological studies.     

Reductive dechlorination for remediation of polychlorinated biphenyls

Technologies such as thermal, oxidative, reductive, and microbial methods for the remediation of polychlorinated biphenyls (PCBs) have previously been reviewed. Based on energy consumption, formation of PCDD/F, and remediation efficiency, reductive methods have emerged as being advantageous for remediation of PCBs. However, many new developments in this field have not been systematically reviewed. Therefore, reductive technologies published in the last decade related to remediation of PCBs will be reviewed here. Three categories, including catalytic hydrodechlorination with H₂, Fe-based reductive dechlorination, and other reductive dechlorination methods (e.g., hydrogen-transfer dechlorination, base-catalyzed dechlorination, and sodium dispersion) are specifically reviewed. In addition, the advantages of each remediation technology are discussed. In this review, 108 articles are referenced.     

A national survey of polybrominated diphenyl ethers (PBDEs) and indicator polychlorinated biphenyls (PCBs) in Chinese mothers' milk

Seven polybrominated diphenyl ethers (PBDEs) congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154 and BDE-183) and six indicator polychlorinated biphenyls (PCBs) congeners (CB-28, CB-52, CB-101, CB-138, CB-153 and CB-180) were measured in 24 pooled human milk samples comprised of 1237 individual samples from 12 provinces in China. The samples were taken to estimate the background body burden of general population and assess nursing infant exposure via human milk in China. The median concentrations of ∑₇PBDEs and ∑₆PCBs were 1.49 and 10.50 ng g⁻¹ lipid weight (lw), respectively. BDE-28, BDE-47 and BDE-153 were predominant PBDE congeners accounting for nearly 70% of ∑₇PBDEs. As for indicator PCBs, CB-153 was the most abundant congener, followed by CB-138. In our study, there was no significantly statistical relationship between concentrations of PBDEs in milk samples and maternal age as well as dietary habits. ∑₇PBDEs did not correlate to ∑₆PCBs in Chinese mothers’ milk. The human exposure to indicator PCBs in China was found to be significantly determined by maternal age, dietary habits and geographical factors. It is suggested that Chinese general population is probably exposed to PBDEs with multiple sources and pathways. The estimated daily intakes (EDI) of BDE-47, BDE-99 and BDE-153 for the Chinese nursing infant were much lower than corresponding threshold reference values suggested by USEPA.     

Occurrence and sources of polychlorinated dibenzo-p-dioxins, dibenzofurans and dioxin-like polychlorinated biphenyls in surficial sediments of Lakes Superior and Huron

Concentrations and congener profile patterns of 2378-substituted PCDD/Fs and DLPCBs in offshore, nearshore and tributary sediments of Lakes Superior and Huron are reported, and spatial trends and source contributions assessed. PCDD/F concentrations ranged from 5 to 18 000 pg/g dw (Lake Superior) and 3 to 6100 pg/g dw (Lake Huron); DLPCBs ranged from 9 to 11 000 pg/g dw (Lake Superior) and 9 to 27 000 pg/g dw (Lake Huron). Our analysis indicated atmospheric deposition is a primary source to depositional areas of both lakes; however, greater PCDD/F and DLPCB concentrations were observed at several nearshore and tributary sites, and were attributed to corresponding land use in the watershed. Statistical analysis and pattern comparison suggested that industrial inputs mainly associated with wood treatment plants, pulp and paper mills, mining operations, and chlorine-based chemical manufacturing also contributed to contamination by PCDD/Fs and DLPCBs in certain nearshore and offshore areas of Lakes Superior and Huron.