东部沿海典型城市食用鱼和鸭中二恶英的评价

通过对青岛海鱼和上海崇明岛淡水鱼、鸭样品中二英(PCDD/Fs)质量分数(以脂肪计)的分析测定,并根据每日摄入量可能带来的健康风险进行了初步探讨. 青岛海鱼和崇明岛淡水鱼中w(2,3,7,8-PCDD/Fs)的平均值分别为54.5 和33.2 pg/g. 崇明岛鸭肉中w(2,3,7,8-PCDD/Fs)平均值为12.6 pg/g. 与国内外相比,w(2,3,7,8-PCDD/Fs)较低. PCDD/Fs的毒性当量浓度(WHO-TEQ)平均值为7.04 pg/g. 通过每日摄入量估计,两地人群的PCDD/Fs每日摄入量不会对人体健康产生严重的负面影响.      

上海崇明农业土壤中共平面多氯联苯的初步研究

采用同位素稀释质谱法,用高分辨率气相色谱-高分辨率质谱仪(HRGC-HRMS)对上海崇明农业土壤中12个共平面多氯联苯(co-PCBs)的含量进行了测定,并且对可能的来源进行了初步探讨。31个农业土壤中co-PCBs浓度范围为24.86~814.50 pg/g,平均值为92.65 pg/g,毒性当量浓度(I-TEQ)为0.032~0.486 pg/g,平均值为0.142 pg/g。经过比较,其浓度远远低于国内外污染土壤水平,和一般的农业土壤水平比较接近,认为该地区基本未受co-PCBs的污染。其中个别位点的毒性当量浓度较高,认为有必要对该地区可能的来源进行分析。主成分分析结果表明,崇明土壤co-PCBs可能来自市售Arcolor和各种燃烧,包括室内煤炭、木料燃烧以及固体或医疗废物燃烧的影响。作为生态岛屿建设的崇明,需要特别关注防止土壤中的co-PCBs进一步升高降低生态系统良性循环的完整性。     

蚀刻废液及其回收后生产的铜盐产品中PCDD/Fs含量水平及分布特征

通过高分辨气相色谱-高分辨磁质谱联用仪(HRGC-HRMS)测定了蚀刻废液及其回收利用后生产的铜盐产品中17种2,3,7,8取代PCDD/Fs的浓度.结果表明,蚀刻废液中PCDD/Fs浓度范围为0～3 460 pg·L-1,平均值为616 pg·L-1,毒性当量浓度WHO-TEQ范围为0～246 pg·L-1,平均值为42.9 pg·L-1;铜盐产品中PCDD/Fs浓度范围为1.08～24.6 ng·kg-1,平均值为8.83 ng·kg-1,毒性当量浓度WHO-TEQ范围为0.112～0.715 ng·kg-1,平均值为0.338 ng·kg-1.通过净化处理工艺可以除去蚀刻废液中大部分PCDD/Fs.在蚀刻废液生产的各级产品中,工业级产品中PCDD/Fs浓度高于饲料级与电镀级产品.各铜盐产品中PCDD/Fs具有相似的单体分布特征:①PCDFs的百分含量明显高于PCDDs;②除硫酸铜类产品中的2,3,7,8-TCDF外,单体的氯取代数越大,百分比含量越高.     

苏南地区表层土壤中多氯萘的浓度及来源

采用气相色谱-三重四极杆质谱联用技术对苏南地区34个表层土壤中的多氯萘(PCNs)进行了分析测定,并对其组成特征及污染来源进行了研究.结果表明,苏南地区土壤中SPCNs的浓度水平在0.263~2.48ng/g dw之间,除16号采样点PCNs浓度(2.48ng/g dw)显著偏高外,其余各点平均值为0.464ng/g dw,毒性当量(TEQs)的变化范围在0.045~0.157pg/g dw之间,整体处于较低水平.所有样品中PCNs均以一氯代萘和二氯代萘为主,所占比例为39.3%~91.4%.CN-66/67、CN-69和CN-73对该区域PCNs的TEQs值贡献最大,分别为25.6%,29.1%和28.7%.SPCN_(Com)/∑PCNs比值表明,高温燃烧过程对整个苏南地区PCNs的污染影响较大.相关性分析与主成分分析研究表明,老电气设备的使用及交通排放过程也是造成该区域PCNs污染的可能来源.但该地区PCNs污染来源较复杂,各点位PCNs的来源需深入研究.     

鄱阳湖康山和湖口水域鱼、贝类体内有机氯农药残留现状

为了解鄱阳湖生物体内有机氯农药的残留和富集状况,分析了康山水域的2种鱼类和1种贝类以及湖口水域的3种鱼类和3种贝类体内的六六六(BHCs)、滴滴涕(DDTs)和六氯苯(HCB)的质量分数. 结果表明:康山水域鱼、贝类体内w(BHCs)为0.04～1.53 μg/kg(平均值为0.282 μg/kg),w(DDTs)为0.09～5.38 μg/kg(平均值为1.856 μg/kg),w(HCB)为0.075～0.55 μg/kg(平均值为0.210 μg/kg);湖口水域鱼、贝类体内w(BHCs)为nd～0.43 μg/kg(平均值为0.168 μg/kg),w(DDTs)为0.56～18.76 μg/kg(平均值为4.172 μg/kg),w(HCB)为0.15～1.28 μg/kg(平均值为0.723 μg/kg). DDTs和HCB的检出率和质量分数显著高于BHCs,其中p,p′-DDE和α-BHC分别为DDTs和BHCs的优势组分. 所检测样品的残留水平均未超过我国农业部、美国食品与药品管理局(FDA)和联合国粮农组织(FAO)颁布的标准.      

我国苏南地区香樟树皮赋存的二英类污染特征及来源

为分析长江下游经济高速发展区的POPs污染特征,于2012年8月在苏南地区典型城市10个采样点采集香樟树皮,应用高分辨气相色谱-高分辨质谱(HRGC-HRMS)联用技术对二英(PCDD/Fs)浓度水平进行监测,同时采用主成分分析(PCA)法探讨其可能来源. 结果表明:苏南地区香樟树皮中二英的毒性当量(I-TEQ)浓度(以干质量计,下同)为5.6～12.2 pg/g,平均值为7.2 pg/g;4～8氯代二英同族体质量分数(以干质量计)范围为418～938 pg/g,平均值为635 pg/g. 由于二英在大气中的长距离迁移潜力较强,在研究的苏南地区区域尺度上,其含量在城市中心区和对照区之间的差异性并不明显;苏南地区香樟树皮二英质量分数及毒性当量浓度均高于国外报道的背景区及典型城市中树皮的水平. 对比典型二英排放源及树皮中二英特征谱图,可推断苏南地区香樟树皮中二英可能主要来源于危险(医疗)废物焚烧、机动车尾气排放和工业燃烧源.      

我国苏南地区香樟树皮赋存的二噁英类污染特征及来源

为分析长江下游经济高速发展区的POPs污染特征,于2012年8月在苏南地区典型城市10个采样点采集香樟树皮,应用高分辨气相色谱-高分辨质谱(HRGC-HRMS)联用技术对二噁英(PCDD/Fs)浓度水平进行监测,同时采用主成分分析(PCA)法探讨其可能来源.结果表明:苏南地区香樟树皮中二噁英的毒性当量(I-TEQ)浓度(以干质量计,下同)为5.6~12.2 pg/g,平均值为7.2 pg/g;4~8氯代二噁英同族体质量分数(以干质量计)范围为418~938 pg/g,平均值为635 pg/g.由于二噁英在大气中的长距离迁移潜力较强,在研究的苏南地区区域尺度上,其含量在城市中心区和对照区之间的差异性并不明显;苏南地区香樟树皮二噁英质量分数及毒性当量浓度均高于国外报道的背景区及典型城市中树皮的水平.对比典型二噁英排放源及树皮中二噁英特征谱图,可推断苏南地区香樟树皮中二噁英可能主要来源于危险(医疗)废物焚烧、机动车尾气排放和工业燃烧源.     

广州市不同功能区大气二噁英含量和分布特征研究

应用气相色谱-高分辨率质谱仪(GC-HRMS)对广州市秋冬季6个区域环境空气样品中的17种2,3,7,8-氯代二英含量进行了检测.结果表明,广州市各观测区域大气中二英毒性当量浓度范围为0.151～2.230pg.m-3,均值为0.418pg.m-3.各观测区域空气中二英毒性当量浓度分布存在一定的差异,本研究的背景区、居民住宅区和商业区二英毒性当量浓度较低且水平相近,分别为(0.294±0.099)、(0.305±0.115)、(0.308±0.102)pg.m-3.交通枢纽区、郊区和工业区二英毒性当量浓度相对较高,分别为(0.342±0.049)、(0.423±0.113)和(0.838±0.704)pg·m-3.广州市不同功能区二英毒性当量浓度呈现背景区<住宅区<商业区<交通枢纽区<郊区<工业区的分布特点.与2004年相比,广州市城区二英毒性当量浓度有所下降,郊区毒性当量浓度有所上升.     

渤海湾脉红螺中多氯联苯和多溴联苯醚的测定分析

应用GC/HRMS对渤海湾脉红螺中的PCBs(多氯联苯)和PBDEs(多溴联苯醚)2类持久性有机污染物进行了测定分析.结果表明:雄性脉红螺中PCB(3～10氯代)的质量分数(10.1 ng/g,以干质量计)和PBDEs(BDE28、BDE47、BDE99、BDE100、BDE153、BDE154、BDE209)的质量分数(1.74 ng//g)均高于雌性脉红螺(分别为8.09和1.38 ng/g);雄性脉红螺中PCBs的WHO-TEQ(毒性当量,8.41 pg/g,以脂肪质量计)高于雌性脉红螺(4.34 pg/g),其中PCB118和PCB126的贡献率分别为13%和77%.脉红螺的不同组织中,性腺和消化腺中w(PCBs)和w(PBDEs)最高,肌肉组织中最低;主要同类物为PCB118、PCB101、PCB28、PCB138、PCB180、PCB52、PCB153和5-PCB以及BDE209.渤海湾脉红螺的消化腺可以作为PCBs和PBDEs的生物指示物.     

Spatial distribution of polychlorinated biphenyls in soil around a municipal solid waste incinerator

The impact of a typical municipal solid waste incinerator (MSWI) on polychlorinated biphenyl (PCB) concentrations in the surrounding soil was studied. Six stack gas samples were taken from the MSWI and 21 soil samples were collected from sampling sites between 300 and 1700 m from the MSWI stack. The total (∑PCB) concentrations of dioxin-like (dl) PCBs and indicator PCBs in the stack gas samples were between 3.41 and 34.3 ng/m3, and the corresponding toxic equivalents (TEQs) ranged from 4.45 to 66.9 pg WHO-TEQ/m3, with a mean of 28.6 pg WHO-TEQ/m3. A total of 2.43 g WHO-TEQ of PCBs per year was calculated to be released into the environment from MSWIs in China. The ∑PCB concentrations in the soil samples ranged from 28.0 to 264.4 pg/g, with mean and median values of 127.6 and 127.7 pg/g, respectively, while the TEQ values were between 0.020 and 0.18 pg WHO-TEQ/g, with mean and median values of 0.074 and 0.062 pg WHO-TEQ/g, respectively. Comparing this study with other studies performed around the world suggest that PCB emission from incinerators has a critical influence on PCB concentrations in the surrounding soil. An exponential function equation is proposed, which indicates a clear decline in ∑PCB concentrations with increasing distance from the stack. A contour map created using an ordinary kriging interpolation technique showed that a limited area (1250 m radius) from the stack was clearly influenced by PCB emission from the MSWI.     

胶州湾内外沉积物岩芯中多氯萘的分布特征研究

利用13 C同位素稀释-高分辨率气相色谱-高分辨率质谱法测定了胶州湾内、外沉积物岩芯中多氯萘(PCNs)异构体的含量,对其同系物分布、可能来源、沉积通量及毒性当量进行了初步探讨,并研究了由各类来源PCNs进入到胶州湾的历史沉积趋势.结果表明,胶州湾内、外沉积物岩芯中∑PCNs含量范围分别为3.9～56.4 Pg·g-1...     

广东东江流域多氯萘的大气沉降研究

为考察多氯萘(PCNs)通过大气沉降作用对东江流域的影响,利用通用型大气沉降采样器,在东江流域广东省境内代表性地段布设11个采样点,于2010年冬季(1、2月)和夏季(7、8月)分别采集和分析了沉降样品中PCNs的通量及组成.结果表明,东江流域总PCNs日均沉降通量为828 pg.(m2.d)-1,对应毒性当量(TEQ)为0.14 pg.(m2.d)-1,由此估算东江流域广东境内PCNs年沉降总量为8.5 kg,相应TEQ年沉降总量为1.3 g.地域上,广州和东莞地区沉降通量明显高于惠州,同时城镇采样点的沉降通量显著高于农村;季节上,各采样点总体呈现夏季高于冬季的特点;组成上,三氯萘(tri-CNs)是主要的污染物,占总量的50%以上,但广州、东莞的5～8氯萘含量比惠州高.来源分析表明,东江流域PCNs的大气沉降可能受燃烧源与非燃烧源的共同影响;东莞大气沉降中PCNs多来自燃烧源,广州点大气沉降的PCNs以非燃烧源为主.     

Patterns and dietary intake of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in food products in China

The health risk of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like PCBs (dl-PCBs) to human being should be assessed regularly. To evaluate the contamination levels in various food products in the Chinese market and to assess the dietary exposure of the Chinese population, 11 varieties of food groups totaling 634 samples including beef and mutton, chicken and duck, pork, fish and seafood, milk and dairy products were evaluated. The average concentrations of PCDD/Fs in all groups ranged from 0.291 to 8.468 pg/g whole weight (w.w.). The average toxic equivalency concentrations were from 0.012 pg TEQ/g w.w. for cereal to 0.367 pg TEQ/g fat for marine oil. OCDD and 2,3,7,8-TCDF were the dominant congeners in foodstuffs. The dietary estimated mean intake for the Chinese rural and urban populations were 0.656 and 0.514 pg TEQ/kg body weight/day, respectively, however, the cereal group exposure were higher to the estimate daily intake and contributed 81% for rural and 48% for urban population, followed by fish and seafood which contributed 4% and 16% to the estimate daily intake. The estimated dietary intakes were compared with the toxicological reference values and showed that both rural and urban populations were well below those values.     

Burden levels of polychlorinated dibenzo-p-dioxins, dibenzofurans, and polychlorinated biphenyls in typical edible meat animals

The concentrations and distributions of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) in the whole blood and meat of eight typical edible animals (chicken, donkey, horse, cattle, rabbit, sheep, duck, and pig) were illustrated. Total concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and PCBs (on a basis of liquid volume) in animal bloods were 142-484 pg/L and 46-62 ng/L, respectively. Total concentrations of PCDD/Fs and PCBs (on a basis of dry weight (dw) and lipid weight (lw)) in animal meat samples were 0.47-1090 pg/g dw (0.47-4513 pg/g lw) and 7.2-23 ng/g dw (10-776 ng/g lw), respectively. TEQs for both PCDD/Fs and PCBs in animal blood and meat samples were (67 ± 27) pg/L and (5.3 ± 14) pg/g dw (24 ± 56 pg/g lw), respectively. Besides, the dietary intakes of PCDD/Fs and PCBs were also estimated. Chicken and pig contributed more TEQs than other animals. Chicken contributed the most (95%) with high toxicity, followed by pig (3.4%) with high consumption. The dietary intake of chicken might pose risks to consumers who prefer to eat chicken products, who should comprehensively consider the essential nutrients and contaminants in food during dietary intake.     

废物焚烧厂烟气中PCDD/Fs和PCNs的排放特征

采用同位素内标稀释高分辨气质联用分析法,对废物焚烧厂的烟气样品PCDD/Fs和PCNs进行了测定,分析了其排放特征以及相关性,为有组织排放的PCDD/Fs和PCNs的控制提供理论依据.实验结果表明,空白实验中未发现明显的背景干扰;样品中PCDD/Fs的采样内标回收率范围为74.0%~90.1%,提取内标的回收率范围为53.3%~120.0%,均符合US EPA23和CHN HJ77.2-2008的质量控制标准;PCDD/Fs的同系物浓度均随着氯取代数目的增加而增加,而PCNs同系物则随着氯取代数目的增加表现出先增大后减小的规律.同系物之间的皮尔森相关系数分析结果可知,这两类污染物相邻同系物相关性系数明显大于非相邻同系物相关性系数,表明低氯代同系物可能是生成高氯代同系物的一个重要途径.此外,PCNs和PCDD/Fs同系物的线性相关分析结果表明,一些PCNs化合物（PeCN、HxCN、HpCN、OCN）与某些PCDD/Fs（OCDD、PeCDF、HxCDF、HpCDF）具有良好的相关性（R²=0.55~0.78）,由此推断在废物焚烧过程中这些同系物可能具有相类似的生成机制.     

SCR装置对焦炉煤气燃烧废气中PCDD/Fs、PCBs和PCNs的协同脱除

研究了某大型焦化厂的选择性催化还原(SCR)装置对焦炉煤气燃烧废气中典型非故意产生持久性有机污染物(UPPOPs)的脱除效果,对SCR装置入口和出口废气和SCR装置降尘中二英(PCDD/Fs)、多氯联苯(PCBs)和多氯萘(PCNs)的全部异构体进行了分析.结果表明,SCR装置对总PCDD/Fs的脱除效率最高,为94.6%,对总PCBs和总PCNs的脱除率分别为74.7%和78.4%.SCR装置入口和出口废气中UP-POPs同系物的分布模式明显不同,入口处以高氯取代为主,出口处以低氯取代为主.SCR装置对高氯取代UP-POPs有更好的脱除效果.催化还原和催化氧化降解同时发生是SCR装置脱除废气中UP-POPs的重要机制.     

电子废物拆解区农业土壤中PCNs的污染水平、分布特征与来源解析

用GC-NCI-MS法测定了路桥农业表层土壤中46种多氯萘(PCNs)的含量.目的是了解该地区表层土壤中PCNs的污染水平、空间分布特征和来源.结果表明,所有表层土壤样品中ΣPCNs的含量为0.062～2.92 ng.g-1,平均值为0.630 ng.g-1.多数样品中tetra-CNs和penta-CNs是最主要的同族体,分别占18.4%～88.8%(平均值为46.7%)和8.40%～53.1%(平均值为30.7%),其次是tri-CNs,范围为0～47.3%,平均值为10.6%.聚类分析和燃烧指示物分析表明,采样点主要受Halowax1014和Halowax 1013工业品污染,PCBs工业品和电子废物燃烧也可能对污染有贡献.与国内外其它研究相比,研究区域内土壤中PCNs污染处于中等水平.     

Levels of polychlorinated biphenyls in 1,4-dichlorobenzene mothballs

Although polychlorinated biphenyls(PCBs) are globally recognized pollutant, an understanding of their resources as by-products in chemical industry is poorly investigated. This paper presents data from a study that was conducted in order to determine the extent of PCBs in 1,4-dichlorobenzene(p-DCB) mothballs. Total PCBs and dioxin-like PCBs were detected in five mothball samples. Total PCB concentrations ranged from 328 ng/g to 1798 ng/g, while the levels of WHO-TEQ were between 0.16 pg/g and 13 pg/g. Mean concentrations of total PCBs and WHO-TEQ in the samples were 724 ng/g and 3.2 pg/g, respectively. The highest level of PCB congeners was that of trichlorinated biphenyls(537 ng/g), which maybe due to the relatively low chlorination in the process of p-DCB production. A mechanism of the formation of PCBs from polychlorinated benzene in the presence of chlorine is also suggested. The results suggested that re-estimation on the risk of p-DCB products, especially the products for daily use such as mothballs, is expected.