土壤中多氯联苯监测分析方法

文章综述了国内外现有的土壤中多氯联苯的标准监测方法及其它文献报道方法,评述了各方法的优、缺点,介绍了本文所研制的适用性强、能满足监测需求的方法.     

维生素B12对脱氯功能蓝藻降解2,4,4’-三氯联苯的促进作用研究

多氯联苯(polychlorinated biphenyls,PCBs)是环境中典型的持久性氯代有机污染物.PCBs污染的生物修复问题是当前环境科学领域的热点.以维生素B12(VB12)为实验材料,应用无氯培养体系,研究了VB12对脱氯功能蓝藻Nostoc PD-2脱氯降解2,4,4’-三氯联苯(PCB28)和降解过程基因表达的影响.结果表明,添加不同浓度的VB12能够促进Nostoc PD-2对PCB28的降解,添加浓度分别为10、100和1000μg·L-1的维生素B12时,与未添加VB12组相比,其7 d脱氯百分比分别提高了11.0%、19.7%和21.9%;添加10μg·L-1和100μg·L-1维生素B12条件下,PCB28的降解半衰期从5.53 d缩短至3.08 d.添加维生素B12后,细胞色素b6f复合体铁硫蛋白基因和双加氧酶基因的表达量均与PCB28的降解效果呈现显著相关性,铁硫蛋白基因表达量与PCB28降解效果的相关性更高.上述结果表明添加VB12能够有效促进脱氯功能藻种PD-2对PCB28的降解,并在基因水平上影响功能藻种的降解活性,这能够为开发高效生物降解PCBs的技术和脱氯功能藻种降解PCBs的机制提供科学依据.     

强化的零价铁PRB技术对PCBs污染地下水的修复

本实验强化了零价铁可渗透反应墙（Permeable Reactive Barrier,PRB）技术,分别用还原铁粉、还原铁粉＋锌粉、还原铁粉＋活性炭为主要的反应介质,以Arcolor1242为靶污染物,对强化的零价铁PRB技术治理多氯联苯污染的地下水的可行性和有效性进行了模拟研究。实验结果表明：在温度10℃,有效孔隙率为61%~67%,水的渗透速度为0.7~0.8 m.d-1的条件下,3个反应柱稳定期对PCBs的去除率分别达到94%、85%、79%,pH值从6.87升高到8.78、10.2、7.93;氧化还原电位从-48.6 mV降到-135、-107、-86.4 mV;出水铁离子的平均质量浓度为0.241、0.129和0.201 mg.L-1,脱氯率平均值为49.6%、72.6%、58.6%。综合考虑处理效果与成本,用零价铁PRB技术治理PCBs污染的地下水是可行的。     

SBSE-TDU-GC/MS法同步测定饮用水源水中16种多溴联苯化合物

通过对萃取和解吸条件进行优化,实现搅拌棒吸收萃取(SBSE)-热脱附-气相色谱/质谱联用以同时测定饮用水源水中16种多溴联苯单体。此法在2~50 ng/L范围内线性良好,取10 m L水样,搅拌棒吸收萃取1 h后,16种多溴联苯单体的检出限为0.5~1.1 ng/L。对实际水样进行2个质量浓度的加标回收,平均回收率为89.2%~102%。     

典型电子废物集中处置场地及其周边土壤中多溴联苯的污染特征

采用快速溶剂萃取-凝胶净化-气相色谱质谱法（GC-MS）测定了浙江省台州市某典型电子废物集中处置场地及周边土壤中多溴联苯（polybrominatebiphenyls,PBBs）浓度,研究了10种PBBs（PBB-3、PBB-15、PBB-18、PBB-52、PBB-101、PBB-153、PBB-180、PBB-194、PBB～206和PBB-209）的浓度水平、组成特征和垂直分布规律。结果表明,处置场地及周边临近区域的PBBs污染程度相近,10种PBBs含量平均值分别为2．81×10^-3和2,50×10-1mg·kg-1,污染程度较轻,主要污染物为使用相对较多的PBB-153、PBB-194、PBB-206和PBB-209。PBBs含量的垂直分布规律表现为在〉40～60、0～20、〉20—40和〉60—80cm土层依次降低。PBB-209在10种PBBs中所占比例最高,在进行类似区域的PBBs监测时,可主要监测PBB-209含量,并用PBB-209含量乘以经验系数1．78来初步判断PBBs的污染状况。     

多氯联苯(Aroclor 1254)对非洲爪蟾变态发育的影响

为了研究多氯联苯(Aroclor 1254)对非洲爪蟾变态发育的影响,将非洲爪蟾受精卵暴露在一定浓度(0、400ng·L-1、2μg·L-1、10μg·L-1、20μg·L-1)的Aroclor 1254中,直至完全变态.结果表明,20μg·L-1Aroclor1254暴露可使变态所需时间显著延长(p<0.05),低于20μg·L-1的各组变态所需时间与对照组无显著差异.2μg·L-1以上的Aroclor1254暴露可使蝌蚪甲状腺发生明显的组织学改变,包括甲状腺组织滤泡扩张、胶体面积相对缩小,滤泡细胞增殖、高度增加,并且这种变化随暴露剂量的增加而愈发明显.提示多氯联苯可干扰非洲爪蟾的变态发育,引起甲状腺组织学改变.采用定量组织病理学技术检测甲状腺激素干扰物较为灵敏,方法简单易行,是一种切实可行的筛选和确证甲状腺干扰物的体内方法.     

现代黄河三角洲土壤中多氯联苯来源解析研究

对现代黄河三角洲22个表层土壤样品中类二英类多氯联苯（PCBs）进行双毛细管柱GC-ECD结合MS测试,并对所得数据进行主成分分析,在同系物水平上解析了现代黄河三角洲土壤中PCBs污染的类型、来源、贡献率和同系物组成.结果表明,现代黄河三角洲土壤中PCBs污染存在4类污染源：第1类污染是由地表径流带来的非点源污染,来自黄河沿岸企业的工业生产和使用,其贡献率为49.6％,同系物组成与国产PCBs相似,且与Aroclor1221相对应;第2和第3类同属点源污染,来自沿海地区的油田开采活动,贡献率分别为15.0％和10.1％,第2类同系物组成与Aroclor1221和Aroclor1242叠加的结果类似,第3类与Aroclor1260相似;第4类污染是由大气污染导致的非点源污染,来自大气的干、湿沉降,其贡献率为8.4％,同系物组成与Aroclor1242、Aroclor1248和Aroclor1260叠加的结果类似.     

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.     

PCDD, PCDF, PCB and PBDE concentrations in breast milk of mothers residing in selected areas of Slovakia

The concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (dl-PCBs) and polybrominated diphenylethers (PBDEs) in 33 breast milk samples collected in 2006-2007 from primipara mothers close to four industrial areas of Slovak Republic were determined. The total PCDDs/PCDFs and dl-PCBs expressed as TEQ based on WHO TEFs 1998 in breast milk samples varied from 5.0 to 51.8 pg g⁻¹ fat (median: 13.1 pg g⁻¹ fat; mean: 18.0 pg g⁻¹ fat). The measurements of seven PBDE congeners (IUPAC No. 28, 47, 99, 100, 153, 154, and 183) were performed for the first time in human milk from Slovakia. PBDE levels ranged between 0.22 and 1.62 ng g⁻¹ fat, with median and mean value of 0.43 ng g⁻¹ fat and 0.57 ng g⁻¹ fat respectively. No statistically significant differences were observed between studied areas in total PBDE concentrations.Furthermore, this study presents first results concerning the daily intake (DI) of PCDDs/PCDFs and dioxin-like compounds for the most vulnerable breast-fed infant population in Slovakia. The total PCDD/PCDF and dl-PCB DI for an infant during the first 2 months of life was estimated in a range from 14.4 to 230 pg TEQ kg⁻¹ b.w., with a median value of 58.9 pg TEQ kg⁻¹ b.w.. The DI values substantially exceeded the tolerable daily intake (TDI) 1-4 pg TEQ kg⁻¹ b.w. recommended by WHO. The dietary infant intake concerning PBDEs was estimated to be between 0.69 and 7.1 ng kg⁻¹ b.w. d⁻¹, with median value of 1.7 ng kg⁻¹ b.w. d⁻¹.     

Concentration of DL-PCBs in fish from market of Parma city (north Italy): estimated human intake

The concentrations of 12 congeners of non-ortho and mono-ortho dioxin-like polychlorinated biphenyls (ΣDL-PCB) were measured in 30 fish samples from Parma markets by GC/MS technique. The samples were randomly purchased, choosing the species commonly found in supermarkets. The concentration of DL-PCBs estimated remained under the fixed Italian limit of 4 pg g⁻¹ ww WHO-TEQ (World Health Organization-Toxic Equivalent) in the major part of the samples, so the situation seems to be not at a level sufficient to pose a risk to human health of the Parma population. The medium daily intake for DL-PCBs for Italian consumers (Parma) was also estimated. This value generally resulted minor than 2 pg g⁻¹ ww WHO-TEQ kg⁻¹ body weight, exceeding only in four cases: eel, smooth hound, starry smooth hound and tuna.