Concentrations, profiles and gas-particle partitioning of PCDD/Fs, PCBs and PBDEs in the ambient air of an E-waste dismantling area, southeast China

Polychlorinated diebenzo-p-dioxins （PCDDs）, polychlorinated diebenzofurans （PCDFs）, polychlorinated biphenyls （PCBs） and polybrominated diphenyl ethers （PBDEs） were monitored in the ambient air of Taizhou, an E-waste dismantling area of southeast China to evaluate their concentrations, profiles and gas-particle partitioning. The ∑PCDD/Fs concentrations ranged from 2.91 to 50.6 pg/ma, with an average of 14.3 pg/ma. The I-TEQs for PCDD/Fs were in the range of 0.20-3.45 pg/ma, with an average of 1.10 pg/ma, The ∑PCBs concentrations and TEQs ranged from 4.23 to 11.35 ng/ma, 0.050 to 0.859 pg（TEQ）/ma, respectively. The concentrations of ∑PBDEs ranged from 92 to 3086 pg/ma, with an average of 894 pg/ma, The pollution levels of PCDD/Fs, PCBs and PBDEs were higher than other urban sites, which may be associated with the E-waste dismantling activities. The PCDD/Fs were found exclusively in the particle phase whereas PCBs distributed dominantly in the gas phase. The gas-partilce partitioning was also assessed by correlating the gas-particle partition coefficient （Kp） with the subcooled liquid vapor pressure （pL^0）. The measured particulate sorptions of PCDD/Fs, PCBs and PBDEs were compared with the predictions from Junge-Pankow model and Koa absorption model. The Junge-Pankow model well estimated the particulate fractions of PCBs. However, it underestimated the sorptions of PCDD/Fs and overestimated the fractions of PBDEs. The predicted particulate fractions of PCDD/Fs and PCBs from Koa model fitted well with the measured data.     

Effects of substituent position on the interactions between PBDEs/PCBs and DOM

Dissolved organic matters (DOM) have important influence on the environmental behavior and fate of organic pollutants, therefore rationalization of interaction mechanisms between pollutants and DOM has become a hot topic in the field of environmental studies. In this paper, polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs), widely detected pollutants, were chosen as target compounds. The effects of substituent position on the interaction between PBDEs/PCBs and DOM were explored. Equilibrium dialysis technique combined with quantum chemistry and molecular docking calculations were employed to reveal the interaction mechanism from the view of charge distribution and molecular conformation. It is shown that non-ortho-substituted isomers have larger volumes and stronger hydrophobicity than those of ortho-substituted, therefore non-ortho-substituted isomers bind more favorably with DOM by hydrophobic partition. By calculating the atomic charge distribution of target chemicals and Leonardite humic acid (LHA) molecular model, π-πinteractions between the aromatic rings of target chemicals with LHA are proposed and further proved in molecular docking calculations. There were 10, 8, 6 docking conformations demonstrating π-πinteraction with LHA for CB-77, BDE-77 and BDE-47, respectively, but none was found for CB-47. By comparing the change of dihedral angle of the aromatic rings and energy barrier, non-ortho-substituted PBDEs/PCBs have larger dihedral angle adjustment space and flexibility, which results in stronger interaction and binding capability with DOM than ortho-substituted isomers. This paper shed some lights on the effect of substituent position on the environmental behaviors of PBDEs and PCBs.     

垃圾焚烧厂的环境空气、飞灰和土壤二噁英水平研究及风险评价

为评价珠三角某垃圾焚烧厂内工人和周边村民的二噁英健康风险,采集并分析了该垃圾焚烧厂的厂内环境(空气和飞灰)邻近敏感点(邻近村落)环境(空气和土壤)的二噁英(PCDD/Fs)质量水平,运用美国环保署(USEPA)风险评价体系和蒙特卡洛模拟(Monte Carlo simulation)对厂内工人、邻近敏感点村民(成人、青少年和儿童)在呼吸吸入、皮肤接触和经口摄入等暴露途径的健康风险进行评估.结果表明:(1)该垃圾焚烧厂固化飞灰中的PCDD/Fs毒性当量(以I-TEQ计)范围为8.99~240.00 ng TEQ/kg,环境空气中的为0.03~0.20 pg TEQ/m3,邻近敏感点土壤中的为0.81~2.04 ng TEQ/kg. (2)飞灰、厂内环境空气和邻近敏感点环境空气的PCDD/Fs单体分布特征更加接近,土壤中PCDD/Fs单体分布稍有差别. (3)厂内工人和村民(成人、青少年和儿童)的致癌风险(CR)合计第95%值范围为4.55×10-7~6.04×10-6,为可接受风险范围(＜10-5);非致癌风险(HI)合计第95%值范围为4.61×10-3~4.28×10-2,远低于1,非致癌风险极低;(4)厂内工人和成人村民的CR较高, 第95%值分别占风险安全值的60%和39%.厂内工人的CR从环境空气吸入(包括在厂内和敏感点)和飞灰意外经口摄入方式占比最高,分别达55.12%和38.43%;成人村民的CR中从环境空气吸入占主导(占97.79%).建议加强对环境空气二噁英监控和飞灰经口摄入的风险管控.     

Aspects of formation and degradation of polychlorinated dibenzo-p-dioxins and dibenzofurans

The research progress on the mechanisms of formation and degradation of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) is reviewed. The primary sources of PCDD/Fs are chemical, thermal, photochemical and enzymatic reactions. Most of the thermal sources result in emissions into air. The studies on the photodegradation and biodegradation offer promise for destruction of PCDD/Fs in environment.     

多氯联苯的正辛醇—空气分配系数与分子结构信息的关系研究

以多氯联苯分子的范德华体积、偶极矩、平均分子极化率和分子椭圆度等分子结构信息为基础,通过线性多元回归建立了它们与正辛醇—空气分配系数K OA的定量结构—性质关系(QSPRs),预测了一些多氯联苯的K OA。同时研究了分子结构数据对K OA的影响,结果表明对K OA影响最大的是范德华体积和平均分子极化率。苯环上氯原子数越多,对-log K OA的影响越大,非邻位氯取代的多氯联苯分子的-log K OA较大,其次是单邻位取代的多氯联苯分子的-log K OA,双邻位取代的多氯联苯分子的-log K OA较小。     

Spatial concentration, congener profiles and inhalation risk assessment of PCDD/Fs and PCBs in the atmosphere of Tianjin, China

Polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) were monitored in a seasonal passive sampling scheme during June 2008 and January 2009 to investigate the spatial concentration, congener profiles and evaluate the potential inhalation risk in different functional areas in Tianjin, China. The spatial air concentrations and I-TEQs ranged 1.08×10²–8.19×10³ fg m^?3 (average 2.63×10³ fg m^?3) and 4.08–325 fg I-TEQ m^?3 (average 91.4 fg I-TEQ m^?3) respectively for PCDD/Fs. The concentration and I-TEQs of PCBs were 3.08×10⁴–3.01×10⁵ fg m^?3 (average 1.39×10⁵ fg m^?3) and 1.72–49.6 fg I-TEQ m^?3 (average 18.5 fg I-TEQ m^?3). It is obvious that PCB concentrations were several hundred times higher than the PCDD/Fs. However, the ambient air PCDD/Fs contributed a major part to the total toxicity equivalents, varying from 72.7% to 89.0% (average 81.8%). The atmospheric PCDD/F levels were observed to be higher in winter for most of sampling sites in the downtown. Besides, inhalation risk assessment showed that local residents might suffer more risk near the point sources than those in living area, industrial zones and background area in Tianjin City. However, the total daily dioxin intake was approximately several to hundreds of times lower than the WHO criteria, showing relatively low exposure risks from the impact of industry point sources in Tianjin City.     

痕量PBBs/PBDEsGC/MS分析法中PCB及其衍生物干扰消除方法

电子电气产品中痕量阻燃剂聚溴联苯/聚溴联苯醚(PBBs/PBDEs)的检测通常采用气相色谱/质谱(GC-MS)联用法,但该法是建立在持久性污染物多氯化苯/多氯化萘(PCBs/PCNs)基础上,因此此类物质干扰不可避免。为了解决此类问题,提出了2种解决方法:1)阴离子化学电离-气相色谱/质谱联用法(GC/MS-NICI)和电子轰击-气相色谱/质谱联用法(GC/MS-EI)联合使用;2)以YMC ODS-C18为载体,基质固相分散法(MSPD)吸附分离。结果显示,前者可以同时洞察聚溴联苯和联苯醚的分子链断裂后阴离子碎片[Br]-,[HBr2]-和分子链段碎片[M+2]+,[M+4]+,[M+6]+,[M+8]+的滞留峰,增加了对溴系阻燃剂的选择性。后者可以有效分离多种多氯化苯与聚溴联苯醚的色谱峰,这为溴系阻燃剂气相色谱/质谱联用分析法中多氯化苯及其衍生物干扰提供了新的解决方法。采用此方法对8类电子电气产品中10种聚溴联苯醚和多氯化苯进行加标回收实验及精密度分析,回收率在60%～98%,相对误差在9.5%以内,符合国际电工委员会(IEC)对溴系阻燃剂检测精度要求,说明方法具有较高的可靠性,也为我国电子电气业更好遵守...     

多氯联苯辛醇—水分配系数的QSPR研究和预测

建立了多氯联苯系列分子的正辛醇—水分配系数对数-log Kow的定量结构—性质关系(QSPR)。通过它可以以分子结构参数(例如,范德华体积、偶极矩和分子椭圆度)为基础估算多氯联苯系列分子的正辛醇—水分配系数。预测了一些多氯联苯的Kow。同时研究了分子结构数据对Kow的影响,结果表明对Kow影响大的主要因素是范德华体积和分子椭圆度,而分子偶极矩的影响相对较小,说明较大的有机分子在溶解时,体积因素要比偶极距作用大。非邻位取代的氯原子在苯环中的位置对Kow影响不大。     

市政污泥与生活垃圾协同焚烧的二噁英排放特征及毒性当量平衡

于2016年5月和2017年1月，分别对南方某生活垃圾焚烧发电厂开展生活垃圾与市政污泥(分别为0%、5%、10%和15%)协同焚烧试验，探讨市政污泥掺烧对生活垃圾焚烧过程中PCDD/Fs排放的影响.在不同季节中，PCDD/Fs均主要分布于飞灰与炉渣中.受焚烧过程中PCDD/Fs的结构破合与重组的影响，废渣中以2, 3, 4, 7, 8-PeCDF (13.0%~72.1%)单体为主. 2016年5月，每吨焚烧原料(指生活垃圾跟污泥的混合物)混合焚烧排放的PCDD/Fs毒性当量比原料本身含有的增加了14.1~29.2 μg TEQ/t，而2017年1月则降低了9.2~9.9 μg TEQ /t.生活垃圾焚烧过程中加入市政污泥能够提高焚烧材料中的硫元素与氯元素的质量比，从而抑制PCDD/Fs的再合成.综上所述，在保证生活垃圾焚烧发电厂的电力生产条件下，适当的市政污泥与生活垃圾协同焚烧能够降低焚烧过程中的PCDD/Fs排放，从而实现市政垃圾污泥的安全处理处置.     

多氯联苯在土壤/沉积物中的吸附方程

以三种天然土壤/沉积物为研究对象,研究了多氯联苯(PCBs)在样品中的吸附过程。结果表明,分配作用在吸附过程中起主导作用,Freundlich模型能较好地拟合三种土壤/沉积物的吸附方程,PCBs的吸附容量大小主要受样品中有机碳含量的影响,吸附量随着有机碳含量的增大而增大。     

珠江三角洲垃圾焚烧发电厂烟气污染物的呼吸暴露风险研究

以珠江三角洲中心地带的3座生活垃圾焚烧发电厂(MSWIPPs)为研究对象,利用大气扩散模型(AERMOD)模拟烟气特征污染物的扩散特性,研究了3座生活垃圾焚烧发电厂周边的大气污染现状,并应用美国环境保护署健康风险评价方法评估其对人体健康的影响.结果表明:3座生活垃圾焚烧发电厂的烟气中颗粒物(PM₁₀、PM_2.5)、HCl、NO_x、SO₂、Pb、Cd、Cr和PCDD/Fs(二噁英)等的年平均排放质量浓度范围为1.98×10-9~93.87 mg/m3,预测周边环境大气中各污染物的全时段平均质量浓度范围为5.00×10-14~1.49×10-3 mg/m3,均远低于评价标准限值.呼吸暴露健康风险评价结果显示:HCl、NO_x、SO₂和Pb对人群产生的非致癌风险范围为2.71×10-7~1.38×10-2,Cd、Cr和PCDD/Fs的致癌风险范围为7.12×10-10~2.04×10-5,均处于可接受范围.在成人群体中,所有烟气特征污染物对男性造成的健康风险普遍高于女性,在儿童群体中则相反;儿童的非致癌和致癌风险均明显高于成人.在3座生活垃圾焚烧发电厂的下风向均分布有小学、幼儿园等,建议根据人群分布、风向变化、春夏季节更替等特点做出相应的防护措施,最大程度地保障项目周边环境的空气质量和敏感人群的身体健康.     

Concentrations and gas-particle partitioning of PCDD/Fs in the urban air of Dalian, China

PCDD/Fs in the urban air of Dalian,China were monitored with high-volume active sampler from November 2009 to October 2010.The concentration of Cl 4-8 DD/Fs ranged from 3065 to 49538 fg m-3,with an average of 10249 fg m-3.The international toxic equivalents(I-TEQ) value of that was 61.8 1182 fg m-3,with an average of 235 fg m-3,which was comparable to those in the other urban locations around the world.It was found that the Cl 4 8 DD/Fs appeared to be present mainly in the particle phase during winter,spring and autumn,while during summer which were dominantly in gas phase.The ratio of Cl 4-8 DD/Fs present in particle phase increased with the increasing level of chlorination.The concentrations of PCDFs and PCDDs decreased with the increase of chlorinated level,while the concentrations of 2,3,7,8-PCDDs congeners increased with the increase of chlorination level.The homolog profiles of the concentrations of PCDFs presented were higher than those of the PCDDs,which indicated the PCDD/Fs pollution source of the air in Dalian was characteristic for thermal source pollution.The correlation analysis of meteorological parameters with the concentrations of Cl 4-8 CDD/Fs was conducted using SPSS packages,and it was found that the ambient temperature and atmospheric pressure were important factors influence the concentration of PCDD/Fs in the air.The respiratory risk and intake dioxins of the residents around the sampling sites were studied in the paper.It was found that Junge-Pankow model was much more accurate in predicting the gas-particle partitioning behavior of PCDD/Fs homologues during winter,while the Harner-Bidleman model shows better agreement with the measured data during winter and summer.     

西江二恶英的季节变化、通量及来源

用同位素稀释-高分辨色谱／高分辨质谱（HRGC／HRMS）方法对西江（珠江的主干）进行了1a的水相和颗粒相中多氯代二苯并二恶英／呋喃（PCDD／Fs）测定。结果表明，水相中PCDD／Fs的含量范围在1．567-8．008pg／L之间．颗粒物中PCDD／Fs的含量变化在569．4～279．6pg／g之间，经过分析得出其浓度随着西江流量的季节性变化呈现一定的变化规律，即在丰水期此污染物的浓度比在枯水期高。地表径流和干湿沉降对此有很大的贡献。西江中PCDD／Fs年通量为8．55kg，毒性当量通量（I—TEQ）为0．026kg。通过对同系物和同族物分布图对比显示西江PCDD／Fs来源比较复杂，可能是混合来源。其中大气干湿沉降、地表径流和沿岸与漂白有关的工业对此有很大的贡献．是PCDD／Fs进入西江的3个重要途径。     

焚烧烟气和大气中二噁英类气-固分布比较研究

探讨生活垃圾焚烧烟气和周边大气中二噁英类的气-固浓度分布特性。通过采样实测某生活垃圾焚烧厂焚烧烟气和周边大气中二噁英类浓度,比较分析生活垃圾焚烧烟气和周边大气气-固浓度分布特性。焚烧烟气中不同氯取代的二噁英类气-固相分布较均衡,气相二噁英类占主导,质量浓度比例为82%~93%;大气中不同氯取代的二噁英类气-固分布很不均匀,固相二噁英类质量浓度比例为85%。烟气从出口到大气环境二噁英类气-固分配存在动态平衡。影响其动态平衡的2个重要影响参数为:气-固分布系数和颗粒态二噁英粒径分布特征。     

生物酶对五氯联苯降解的初步研究

多氯联苯（PCBs）是具有代表性的持久性有机污染物（POPs）,其氯代数目越多,降解越难。本文以分离筛选的6株PCBs降解细菌为材料,制备了含有NADH辅酶再生系统关键酶甲酸脱氢酶（FDH）的PCBs降解复合酶,研究了其对PCBs的降解效果。结果表明,Pseudomonas sp. MGB11胞内酶/FDH复合酶对五氯联苯PCB114的降解率在10 h内可达69.4%,对于高毒性、难降解的高氯PCBs的污染修复具有应用价值。     

分子发射光谱法研究外加磁场效应对有机污染物环境行为的影响

讨论了用荧光偏振法、荧光法和室温磷光法（ ＲＴＰ） 研究外加磁场效应（ ＭＦＥ） 对多环芳烃（ ＰＡＨｓ） 与溶解态有机物（ 如腐植酸） 间相互作用的影响, 以及ＭＦＥ 对生物降解ＰＡＨｓ 的影响的２种方法．     

Levels and distribution of polychlorinated biphenyls in the atmosphere close to Chinese Great Wall Station,Antarctica: Results from XAD-resin passive air sampling

Antarctica is an important research region for assessing persistence and long-range atmospheric transport (LRAT) of persistent organic pollutants (POPs). In this study, XAD-resin passive air sampling was conducted near the Chinese Great Wall Station, Antarctica, during a one-year sampling period in 2009-2010. The air concentrations of polychlorinated biphenyls (PCBs) were at a very low level, with total PCBs in the range of 26.74-45.08 pg m 3. PCB profiles were dominated by tetra-PCBs, tri-PCBs and di-PCBs, indicating LRAT was responsible for the pollutants in the Antarctic atmosphere. The sampling site near the Chinese Great Wall Station did not show higher PCB levels than the other sites, suggesting that PCB sources associated with the Great Wall Station were negligible. PCB-11 is a non-Aroclor congener, which has specific sources compared to other Aroclor PCB congeners. PCB-11 was observed in all air samples, with an average concentration of 1.22 pg m 3. To our knowledge, this study is the first investigation of PCB levels and distribution in the atmosphere around the Chinese Great Wall Station, Antarctica.     

Research progress of the endocrine disrupting activities of polychlorinated biphenyls

Polychlorinated biphenyls (PCBs) arc global persistent organic pollutants. Almost all commercial PCBs mixtures, single PCB congener, and their metabolites possess endocrine disrupting activities. They can disrupt the estrogen/androgen system, thyroid hormone system and other endocrine systems by interfering with the synthesis, transport, storage, metabolism, and feedback regulation of hormones. The newest data related to the endocrine disrupting activities of PCBs and their mechanisms arc reviewed and the research perspectives arc also discussed.