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。     

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     

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。     

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。     

紫外光降解硝酸盐体系中四环素

为了考察紫外光照射下四环素(tetracycline,TC)在硝酸盐(NO_3~-)体系中的降解过程,研究了初始pH、TC初始浓度、NO_3~-浓度、腐殖酸以及磷酸盐等环境因子对TC光降解的影响,利用ESR检测和自由基猝灭实验,量化分析体系中不同氧化途径对TC去除的贡献率。结果表明:TC在NO_3~-体系中的光降解受pH影响显著;腐殖酸和磷酸盐对TC的降解表现出不同程度的抑制作用;TC通过直接光解、HO·、~1O_2和O_2~(·-)氧化4种途径降解,当TC浓度为10.0 mg·L~(-1),NO_3~-浓度为1.0 mmol·L~(-1),pH为7.0时光照150 min后,不同途径的贡献率分别为60.4%、25.6%、8.9%和5.1%。结果有助于了解TC的环境化学行为,为TC治理提供参考。     

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。     

用于四氯乙烯降解的厌氧污泥的培养与驯化研究

由于四氯乙烯(PCE)的大量使用和不合理的处置使其成为常见的污染物之一。PCE在好氧条件下不发生生物降解，只在厌氧条件下通过还原脱氯发生生物降解。本研究主要是对从不同处理厂获得的厌氧污泥进行培养，选出合适的厌氧污泥，进行降解PCE的厌氧污泥的驯化，为以后进行降解PCE的动力学研究和优势菌种的筛选做准备。同时，在实验中检测到了三氯乙烯(TCE)，表明PCE是通过还原脱氯发生生物降解的。     

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%.     

茜素绿的微波无极紫外光降解及产物分析

以茜素绿为研究对象,探讨了蒽醌类染料在微波无极紫外灯光辐射下的降解行为。结果表明,茜素绿的脱色反应符合一级反应动力学规律,反应120 min后COD和TOC的去除率分别为65.79%和60.98%;采用荧光色谱仪和电子顺磁共振仪检测到降解过程中羟基自由基和超氧自由基为主要活性物种;利用红外光谱仪、离子色谱仪和电子喷雾质谱仪分析了反应过程中的中间产物;采用电喷雾等技术和离子色谱测定了茜素绿降解的中间产物,并推断了茜素绿微波紫外光降解可能的历程;采用大肠杆菌和锦鲤对溶液进行了生物毒性检测与评价,由于中间产物的产生降解溶液的毒性先升后降。     

紫外光与超声波耦合对氯酚水溶液的降解研究

选择超声波(US)、紫外光(UV)、紫外光与超声波耦合(UV/US)3种方式对不同位置取代基的单氯酚和不同数目取代基的氯酚进行降解研究。结果表明,UV、US、UV/US对取代基位置不同的单氯酚的降解率大小均为3-氯酚4-氯酚2-氯酚;UV、UV/US对不同取代基数量的氯酚的降解率大小为2-氯酚2,4-二氯酚2,4,6-三氯酚,US单独作用下的降解率大小为2,4,6-三氯酚2,4-二氯酚2-氯酚;UV与US的耦合呈现出较优的协同效应,且耦合降解均以US的降解作用占主导;UV、US、UV/US对氯酚的降解均符合表观一级反应动力学。     

Reductive dechlorination of non-ortho substituted polychlorinated biphenyls by ultraviolet irradiation in alkaline 2-propanol

The photodechlorination pathways of 3,3′,4,5,5′-pentachlorobiphenyl (3,3′,4,5,5′-PentaCB) and the related lower polychlorinated biphenyl congeners irradiated at 254 nm in alkaline 2-propanol were elucidated. Steric effect is the most important factor for controlling the dechlorination pattern of these substrates. Electronic effect also influences the photoreactivity of chlorine substituents.     

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.     

Microbial transformation and degradation of polychlorinated biphenyls

This paper reviews the potential of microorganisms to transform polychlorinated biphenyls (PCBs). In anaerobic environments, higher chlorinated biphenyls can undergo reductive dehalogenation. Meta- and para-chlorines in PCB congeners are more susceptible to dechlorination than ortho-chlorines. Anaerobes catalyzing PCB dechlorination have not been isolated in pure culture but there is strong evidence from enrichment cultures that some Dehalococcoides spp. and other microorganisms within the Chloroflexi phylum can grow by linking the oxidation of H(2) to the reductive dechlorination of PCBs. Lower chlorinated biphenyls can be co-metabolized aerobically. Some aerobes can also grow by utilizing PCB congeners containing only one or two chlorines as sole carbon/energy source. An example is the growth of Burkholderia cepacia by transformation of 4-chlorobiphenyl to chlorobenzoates. The latter compounds are susceptible to aerobic mineralization. Higher chlorinated biphenyls therefore are potentially fully biodegradable in a sequence of reductive dechlorination followed by aerobic mineralization of the lower chlorinated products.     

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。     

混合洗脱剂对土壤中重金属和多氯联苯的同步高效洗脱

针对电子垃圾拆解、焚烧场地周边污染土壤中的重金属和疏水性有机物的复合污染问题,对重金属和有机物同步高效洗脱方法进行了研究。将皂素、吐温-80和柠檬酸按照不同浓度配比组合并制成混合洗脱剂,采用批量平衡振荡的方法,研究其对Cu、Pb、Cd和多氯联苯（PCBs）复合污染土壤的洗脱效果,以及浓度配比、pH和洗脱时间对洗脱效果的影响,并找出最优的洗脱条件。结果表明：在混合洗脱剂中皂素、吐温-80和柠檬酸的浓度分别为12、10和5 g·L-1,pH值为5,批量平衡振荡洗脱时间为6 h的条件下,洗脱效果最佳,对Cu、Pb、Cd和PCBs的洗脱率分别为88.32%、82.75%、94.89%和80.56%,实现了复合污染土壤中重金属和疏水性有机物的同步高效洗脱。     

Effects of black carbon on bioturbation-induced benthic fluxes of polychlorinated biphenyls

It is unknown whether carbonaceous geosorbents, such as black carbon (BC) affect bioturbation by benthic invertebrates, thereby possibly affecting sediment-water exchange of sediment-bound contaminants. Here, we assess the effects of oil soot on polychlorinated biphenyl (PCB) mass transfer from sediment to overlying water, for sediments with and without tubificid oligochaeta as bioturbators. PCB levels were so low that toxicity to the oligochaeta played no role, whereas soot levels and binding affinity of PCBs to soot were so low that pore water PCB concentrations were not significantly affected by binding of PCBs to soot. This setup left direct effects of BC on bioturbation activity as the only explanation for any observed effects on mass transfer. Mass transfer coefficients (K_L) for benthic boundary layer transport were measured by a novel flux method using Empore™ disks as a sink for PCBs in the overlying water. For the PCBs studied (logK_ow 5.2-8.2), K_L values ranged from 0.2 to 2 cm × d⁻¹ in systems without tubificids. Systems with tubificids showed K_L values that were a factor of 10-25 higher. However, in the presence of oil soot, tubificids did not cause an increase in mass transfer coefficients. This suggests that at BC levels as encountered under field conditions, the mechanism for reduction of sediment-water transfer of contaminants may be twofold: (a) reduced mass transfer due to strong binding of the contaminants to BC, and (b) reduced mass transfer of contaminants due to a decrease in bioturbation activity.     

Bioaccessibility of polychlorinated biphenyls in workplace dust and its implication for risk assessment

Human exposure to bioaccessible PCBs via indoor dust is limited around the world. In the present study, the workplace dust sample from commercial office, hospital, secondary school, shopping mall, electronic factory and manufacturing plant were collected from Hong Kong for PCBs analyses. Total PCBs concentrations ranged from 46.8 to 249 ng g⁻¹, with a median of 107 ng g⁻¹. Manufacturing plant showed the highest concentration among all of sampling sites. PCB 77 was found as the dominant congeners. The bioaccessibility of PCBs in small intestinal juice ranging from 8.3% to 26.0% was significantly higher than that in gastric condition, ranging from 4.8% to 12.4%. In addition, significant negative correlations (p < 0.05) were observed between K_OW and bioaccessibility for all workplace dust samples. Risk assessment indicated that the averaged daily dose of dioxin-like PCBs via non-dietary intake of workplace dust, considering the bioaccessibility of PCBs, were much lower than the TDI of dioxins (2.3 pg WHO-TEQ kg bw⁻¹ d⁻¹) established by Joint FAO/WHO Expert Committee on Food Additives.     

Trend studies of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans in human milk

Human milk has been used in studies of long-term changes in the concentrations of organochlorine contaminants in mothers from the Stockholm region. The previously observed decline (1972 to 1985) in the levels of polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) seems to have ceased for certain compounds since the levels were about the same in samples collected in 1985 and 1989. Calculating with the proposed toxicity equivalency factors for the different congeners of PCDDs, PCDFs and PCBs it is seen that the congeners of PCBs contribute more to the possible toxicity than those of PCDDs and PCDFs. The mono-ortho substituted congener 2,3′,4,4′,5-pentachlorobiphenyl (IUPAC No. 118) contributes with the largest part.     

Dry deposition and soil-air gas exchange of polychlorinated biphenyls (PCBs) in an industrial area

Ambient air and dry deposition, and soil samples were collected at the Aliaga industrial site in Izmir, Turkey. Atmospheric total (particle + gas) ∑₄₁-PCB concentrations were higher in summer (3370 ± 1617 pg m⁻³, average + SD) than in winter (1164 ± 618 pg m⁻³), probably due to increased volatilization with temperature. Average particulate ∑₄₁-PCBs dry deposition fluxes were 349 ± 183 and 469 ± 328 ng m⁻² day⁻¹ in summer and winter, respectively. Overall average particulate deposition velocity was 5.5 ± 3.5 cm s⁻¹. The spatial distribution of ∑₄₁-PCB soil concentrations (n = 48) showed that the iron-steel plants, ship dismantling facilities, refinery and petrochemicals complex are the major sources in the area. Calculated air-soil exchange fluxes indicated that the contaminated soil is a secondary source to the atmosphere for lighter PCBs and as a sink for heavier ones. Comparable magnitude of gas exchange and dry particle deposition fluxes indicated that both mechanisms are equally important for PCB movement between air and soil in Aliaga.