青岛近海PCDD/Fs的沉积通量、毒性当量及来源

用高分辨率气相色谱-质谱方法对青岛胶州湾内外表层沉积物、柱状岩心及贻贝样品中的17种毒性多氯代二苯并二 /呋喃(PCDD/Fs)进行了分析和讨论.表层沉积物的SP_4-8CDD/Fs含量范围在11.6～369pg/g dw,主要以P_4-8CDFs为主.S2,3,7,8-PCDD/Fs含量范围4.1～232.4pg/g dw.在环流作用下沉积物中形成了明显的东-西分布格局.除河口处外,PCDD/F同系物分布基本上相同,即低氯代PCDD/Fs占主导.SP_4-8CDD/Fs沉积通量从1951年起逐渐增大,STEQ沉积通量从1980年显著增大.青岛近海PCDD/Fs的来源相对恒定,推测为城市污水污泥和大气沉降.贝肉中S2,3,7,8-PCDD/Fs为2.9～5.1pg/g dw. TEQ的主要来源为2,3,4,7,8-PeCDF(35%)、2,3,7,8-TCDF(30%)、2,3,7,8,-TCDD(30%).     

青岛及崇明岛食用鱼和鸭中共平面多氯联苯与多氯萘的研究

利用HRGC-HRMS测定了青岛海鱼和上海崇明岛淡水鱼、鸭样品中共平面多氯联苯(co-PCBs)和多氯萘(PCNs)(均以脂肪计)的质量分数,并根据每日摄取量可能带来的健康风险进行了初步探讨. 青岛海鱼中w(co-PCBs)和w(PCNs)平均值约为4 041和225 pg/g,崇明岛淡水鱼约为3 318和640 pg/g. 崇明岛鸭肉中w(co-PCBs)和w(PCNs)平均值分别约为966和43.8 pg/g. 青岛海鱼中PCNs同系物组成(以5-CNs和3-CNs为主)与崇明岛淡水鱼完全不同. 与国内外其他地区鱼和家禽相比,其污染物含量均较低. 所有样品中co-PCBs的毒性当量浓度(WHO-TEQ)为0.68～11.40 pg/g,PCNs的毒性当量浓度(WHO-TEQ)为0.001～0.210 pg/g. 根据当地人群的饮食习惯,两地人群co-PCBs和PCNs每日摄入量远低于WHO对普通人群规定的每日容许摄入量,因此不会对人群健康产生严重的负面效应.      

珠江三角洲低丘土壤中二类(口恶)(口英)化合物污染水平

应用高分辨气相色谱/高分辨质谱(HRGC/HRMS)对珠江三角洲佛山市某地山丘土壤中二类化合物(PCDD/Fs)含量进行了分析.结果表明,土壤样品中的2,3,7,8-PCDD/Fs含量为0.90~7.89pg-TEQ/g,与土壤pH值具有显著的相关性.pH值偏离pH7越远,土壤中2,3,7,8-PCDD/Fs含量越高.造成研究区内小范围土壤中2,3,7,8-PCDD/Fs含量差异很大且出现较高含量的原因可能与该地曾堆放与焚烧生活垃圾、废旧电线电缆等固体废物有关.本研究样品中2,3,7,8-PCDD/Fs同系物分布特征与目前报道的工业来源的PCDD/Fs分布特征并不一致,表明该地区的PCDD/Fs的来源或污染过程还应作进一步的研究.     

广州某工业区大气中PCDD/Fs含量水平及其季节性变化特征

通过对广州某工业区大气中2,3,7,8-PCDD/Fs的季节性监测,并对大气中PCDD/Fs的浓度与季节性变化进行了分析.结果表明,该工业区大气中PCDD/Fs的浓度范围为2.33~75.4 pg·m-3,平均值为23.2 pg·m-3,毒性当量浓度I-TEQ范围为0.229~10.7 pg·m-3,平均值为2.00 pg·m-3,高于日本环境空气质量标准推荐年均值0.6 pg·m-3.该工业区PCDD/Fs浓度季节性变化明显,最高的季节为春季(37.8 pg·m-3),浓度最低的季节为夏季(13.5 pg·m-3),其次为秋季(22.3 pg·m-3)和冬季(19.1 pg·m-3);毒性当量浓度变化高低顺序为:春季(5.58 pg·m-3)>夏季(1.06 pg·m-3)>秋季(0.839 pg·m-3)>冬季(0.525 pg·m-3).降雨、季风的季节性变化可能是引起大气中PCDD/Fs浓度季节性变化的原因.     

贵屿某电子垃圾拆解点附近大气颗粒物中氯代/溴代二噁英、四溴双酚A污染水平研究

对贵屿某电子垃圾拆解点附近大气颗粒物中氯代二英(PCDD/Fs)、溴代二英(PBDD/Fs)、四溴双酚A(TBBPA)含量水平进行了调查研究.结果显示,大气颗粒物中17种2,3,7,8-PCDD/Fs和8种2,3,7,8-PBDD/Fs的浓度范围分别为126.54～524.78pg·m-3和376.42～566.76pg·m-3;平均毒性当量(TEQ)分别为16.29pg·m-3、91.28pg·m-3,均高出目前所报道的国内外其它部分城市大气污染水平1～4个数量级,且PBDD/Fs的污染水平远远高于PCDD/Fs.四氯至八氯代PCDD/Fs同系物呈现出明显且特别的分布规律,PCDDs和PCDFs浓度均随着氯原子取代程度增加而降低.TBBPA的浓度范围为66.01～95.04ng·m-3,大气中PBDD/Fs浓度与之显著相关r=0.69.初步的暴露风险评价表明,当地居民每日通过呼吸摄入的二英含量远远超过了世界卫生组织(WHO)规定的人体每日耐受量(TDI)1～4pg(W-TEQ)·kg-·1d-1.     

某造纸厂废水中二（口恶）英含量及其电子束辐照降解

通过对造纸厂废水中2,3,7,8-PCDD/Fs的检测,分析了其在造纸厂废水中的浓度水平与特征,并将不同剂量电子束辐照前后废水中2,3,7,8-PCDD/Fs浓度水平进行对比,初步探讨了电子束辐照造纸废水中2,3,7,8-PCDD/Fs的可行性,降解机制以及降解率.结果表明,该造纸厂未经处理过的原水中2,3,7,8-PCDD/Fs浓度为239 pg·L-1,毒性当量浓度为41.0pg·L-1.通过用30 kGy和60 kGy剂量的电子束辐照处理后,废水中2,3,7,8-PCDD/Fs的浓度均有不同程度地降低,其降解率分别为5.27%和23.6%.     

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.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans and polychlorinated biphenyls in surface soil from the Tibetan Plateau

Concentrations of Polychlorinated dibenzo-p-dioxins and dibenzofurans（PCDD/Fs） and polychlorinated biphenyls（PCBs） in soil samples from Tibetan Plateau were determined. The average concentration of total 2,3,7,8-PCDD/Fs was（2.30 ± 1.02） pg/g, and World Health Organization Toxicity Equivalency（WHO-TEQ） average concentration was（0.013 ± 0.010）pg WHO-TEQ/g. The average concentration of ∑PCBs（7 indicator PCB and 12 dioxin like-PCB congeners） was（16.2 ± 9.25） pg/g, and WHO-TEQ average concentration was 0.043 ±0.049 pg WHO-TEQ/g. Comparing to previous studies in similar environmental conditions,PCDD/Fs and PCBs in this study showed a relatively lower concentration. The altitude dependences of PCDD/Fs and PCBs were also studied. Total organic carbon（TOC） normalized concentrations presented a quadratic relation with the altitudes, and an inflection could be found on the parabola of the total concentrations and some congeners of high concentration.The concentrations decreased with altitudes below about 4500 m above sea level（a.s.l.）, while they increased with altitudes above it. These phenomena indicate that cold condensation of PCDD/Fs and PCBs would happen above 4500 m a.s.l, on the Tibetan Plateau.     

活性污泥与施泥土壤中二英污染水平的研究

研究了北京市大兴污泥堆肥厂不同处理阶段的活性污泥和周边的施泥农田土壤中PCDD/Fs污染水平,并与周边背景土壤进行比较.不同处理阶段活性污泥的PCDD/Fs浓度水平为3118.31～3617.36pg/g,毒性当量(TEQ,下同)为26.19～35.81pg/g,在世界范围处于中等偏下水平.施泥农田土壤和背景土壤中PCDD/Fs总浓度水平分别为55.05～72.07pg/g、8.69～18.06pg/g,毒性当量分别为1.20～2.64pg/g、0.28～0.39pg/g,污泥农用导致施泥农田土壤中PCDD/Fs及其各异构体的浓度含量均有提高,浓度总量增高因子在3.0～8.3之间,施泥农田土壤中PCDD/Fs的浓度与施泥比率呈正相关性.施泥农田土壤与施用的活性污泥中PCDD/Fs的17种异构体浓度分布模式十分相似,而与背景土壤中PCDD/Fs各异构体浓度分布模式差异较大,由此说明,活性污泥是施泥农田土壤中PCDD/Fs的主要来源.本研究探讨了施用活性污泥对农田土壤中PCDD/Fs污染水平的影响,揭示了施泥农田土壤中PCDD/Fs的污染来源和污染模式.     

活性污泥与施泥土壤中二噁英污染水平的研究

研究了北京市大兴污泥堆肥厂不同处理阶段的活性污泥和周边的施泥农田土壤中PCDD/Fs污染水平,并与周边背景土壤进行比较.不同处理阶段活性污泥的PCDD/Fs浓度水平为3118.31～3617.36pg/g,毒性当量(TEQ,下同)为26.19～35.81pg/g,在世界范围处于中等偏下水平.施泥农田土壤和背景土壤中PCDD/Fs总浓度水平分别为55.05～72.07pg/g、8.69～18.06pg/g,毒性当量分别为1.20～2.64pg/g、0.28～0.39pg/g,污泥农用导致施泥农田土壤中PCDD/Fs及其各异构体的浓度含量均有提高,浓度总量增高因子在3.0～8.3之间,施泥农田土壤中PCDD/Fs的浓度与施泥比率呈正相关性.施泥农田土壤与施用的活性污泥中PCDD/Fs的17种异构体浓度分布模式十分相似,而与背景土壤中PCDD/Fs各异构体浓度分布模式差异较大,由此说明,活性污泥是施泥农田土壤中PCDD/Fs的主要来源.本研究探讨了施用活性污泥对农田土壤中PCDD/Fs污染水平的影响,揭示了施泥农田土壤中PCDD/Fs的污染来源和污染模式.     

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.     

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.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in different tissues of the cormorants (Phalacrocorax carbo) from Dongting Lake, China

Tissue distribution provides important information regarding the pharmacokinetic behavior of pollutants and is invaluable when analyzing the risk posed to avian species by the exposure to such kind of pollutants. In this study, concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in muscle, liver, spleen, kidney, stomach, gall bladder, skin, heart, pancreas, intestine and lung tissue extracts of cormorants collected from Dongting Lake, China. Tissue distribution results showed preferential accumulation of PCDD/Fs in both liver and skin. The total concentration of PCDD/Fs ranged from 421 to 5696 pg/g lipid weight. Octachlorinated dibenzo-p-dioxin (OCDD) was the predominant congener in all tissues and contributed between 31% and 82% to all 17 PCDD/Fs in different tissues. The liver/muscle ratios progressively increased with the degree of chlorination of PCDDs, except for OCDD. The relative toxic potential of PCDDs and PCDFs in tissues were calculated using the World Health Organization (WHO) Toxic Equivalency Factors (TEFs) for birds. The concentrations of WHO-toxic equivalent in different tissues ranged between 14.8 and 2021 pg/g lipid weight. These results indicated PCDD/Fs may have been bio-accumulated in cormorant via food-web. Furthermore, when compared with studies reported in the literatures, the PCDD/Fs levels in the cormorant collected from Dongting Lake were still relatively high.     

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.      

垃圾焚烧飞灰或炉渣中二噁的分布特征

分别采集了3种生活垃圾焚烧炉产生的飞灰或熔融炉渣样品,分析了其中的二口恶口英含量及其毒性当量,并讨论了17种2,3,7,8位氯取代的二口恶口英分布特征及其对总毒性当量的贡献.结果表明,机械炉排焚烧炉产生的飞灰中二口恶口英最多,总浓度为319ng/g,毒性当量为6.7ngI-TEQ/g;其次为流化床焚烧炉,产生的飞灰中二口恶口英总浓度为38.7ng/g,毒性当量为0.8ngI-TEQ/g;气化熔融焚烧炉产生的熔融炉渣中二口恶口英很少,总浓度为38.7pg/g,毒性当量仅为1.1pgI-TEQ/g;所有的2,3,7,8位氯取代的13C同位素标记内标化合物回收率在39%~156%之间.尽管不同的垃圾焚烧炉在二口恶口英的生成量上有明显的差别,但是产生的二口恶口英同类物的归一化浓度以及对毒性当量贡献的归一化结果分布特征十分相似,表明3种垃圾焚烧炉在垃圾焚烧过程产生二口恶口英可能具有相似的反应机理.     

Occurrence and impact of polychlorinated dibenzo-p-dioxins/dibenzofurans in the air and soil around a municipal solid waste incinerator

To assess the influence of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans(PCDD/Fs) on the environment in the vicinity of municipal solid waste incinerators(MSWIs), we determined the levels of PCDD/Fs in air and soil samples collected around a MSWI, which is the largest in China. The International Toxicity Equivalency Quantity(I-TEQ) concentrations of PCDD/Fs in air samples were from 0.0300 to 1.03 pg I-TEQ/m~3(0.445–13.6 pg/m~3), with an average of 0.237 pg I-TEQ/m~3, while in soil samples they ranged from 0.520 to 3.40 pg I-TEQ/g(2.41–88.7 pg/g) with an average of1.49 pg I-TEQ/g. The concentrations of PCDD/Fs in air and soil samples were comparable to other areas, and Pe CDFs were the dominant contributors, which was different from stack gas homologue patterns. Multivariate statistical analysis showed that PCDD/Fs emission from the MSWI did not directly affect the profiles of PCDD/Fs in air and soils, so that vehicles and unidentified emission sources should be considered. The daily inhalation levels of PCDD/Fs for children(0.0110 to 0.392 pg I-TEQ/(kg·day) and adults(0.00600 to 0.221 pg I-TEQ/(kg·day) near the MSWI were lower than the tolerable daily intake of 1.00 to 4.00 pg WHO-TEQ/(kg·day), but in winter the values were higher than in summer. These results can be used as basic data for assessing the risk of PCDD/Fs exposure in residents living around this MSWI, and more monitoring programs and studies should be carried out around MSWIs.