杭州市环境空气中二噁英类物质检测与分析

为了解二噁英类物质(PCDD/Fs)在环境空气中污染现状及不同季节不同时段浓度、组成和存在形式等的变化情况,于夏、冬两季对杭州西湖区空气中PCDD/Fs进行了采样分析。结果表明,空气中PCDD/Fs毒性当量浓度与国内其他城市(北京、上海、广州)相近,夏、冬两季空气中PCDD/Fs质量浓度和毒性当量浓度分别为4.92 pg/m3、0.34 I-TEQ pg/m3和4.51 pg/m3、0.40 I-TEQ pg/m3,夏季PCDD/Fs毒性当量浓度略低于冬季;在分时段采样检测结果中,晚间空气中PCDD/Fs质量浓度和毒性当量浓度均高于白天空气中的PCDD/Fs浓度;夏季样品中TCDD/Fs、PeCDD/Fs主要以气相的形式存在,HpCDD/Fs、OCDD/F主要以颗粒相的形式存在,冬季样品中PCDD/Fs主要以颗粒相形式存在。     

同位素稀释高分辨气相色谱-高分辨质谱法测定氯化石蜡工业品中二噁英

氯化石蜡（CPs）作为一种用途广泛、产量大的有机氯化学工业品,具有组成多样、基质复杂等特点,对其中产生的二噁英（PCDD/Fs）检测是当前工作面临的难题。建立了同位素稀释高分辨气相色谱-高分辨质谱法检测CPs工业品中PCDD/Fs的分析方法。对样品净化过程进行了优化,通过提取溶剂筛选,去除固体CPs中部分基质,建立的双活性炭柱法可高效去除CPs基质。方法采用¹³ C₁₂标记的PCDD/Fs内标物进行定性和定量分析。17种PCDD/Fs同系物的检出限为0.1～3 pg/g,回收率为31.7%～100%。该方法可对高纯度工业品中痕量持久性有机污染物进行高效的定性和定量分析,能够满足国家标准方法对PCDD/Fs检测的要求。     

珠三角地区造纸行业排水中二 NFDA1 英(PCDD/Fs)特征分析

研究采用¹³C同位素内标稀释定量法,高分辨气相色谱质谱法(HRGC-HRMS)对珠三角地区造纸行业排水中PCDD/Fs特征进行了分析。结果表明,该地区造纸行业PCDD/Fs含量为:4.75~80.05 pg/L,且以OCDD占主导地位;同时该类行业PCDD/Fs的TEQ为:0.21~2.02 pg TEQ/L。最后通过对该类行业排水中PCDD/Fs的TEQ年排放量进行讨论,其结果为0.30~12.97 mg TEQ,且年平均排放量(4.42 mgTEQ)只占我国造纸行业TEQ总排放量的很小一部分。     

上海市崇明岛农业土壤中二噁英的现状研究及来源分析

为了解上海市崇明岛农用土壤中二噁英类化合物(PCDD/Fs)现状水平及其来源,于2021年6-7月采集上海市崇明岛31个农业土壤样品,采用同位素稀释法测定样品中17种2,3,7,8-PCDD/Fs的含量,并且对其现状水平、异构体特征以及来源进行初步分析。结果表明,31个土壤样品中均检出PCDD/Fs,质量分数为88.14~356.55 pg/g,对应毒性当量为0.64~2.20 pg I-TEQ/g,统计频率分析发现呈右侧拖尾的偏态分布,中位数为1.05 pg I-TEQ/g。经过比较,崇明岛农用土壤属于典型的背景土壤,土壤中二噁英类物质的污染属于较低水平。利用主成分分析(PCA)和正定矩阵因子分解法(PMF)对可能的来源进行分析,结果显示上海市崇明岛农业土壤中PCDD/Fs的主要来源为五氯酚(PCP)、水稻秸秆烟(RSS)和交通源(TS),占比分别为61.6%,23.2%和15.2%。结合采样地理位置推断,上海市崇明岛农业土壤中PCDD/Fs可能受到来自崇明岛自身农耕以及交通等因素的影响。     

济南市大气细颗粒物中二(口恶)英污染水平及季节变化

2021年对济南市大气PM_2.5中17种2,3,7,8氯取代二(口恶)英(PCDD/Fs)污染现状进行监测。对其异构体分布、指示性单体、季节变化规律等特征及其与常规污染物相关性进行了分析。结果表明:大气PM_2.5中PCDD/Fs浓度范围和年平均值分别为0.157~1.595 pg/m³和0.785 pg/m³,而毒性当量(以I-TEQ计)范围和年平均值分别为0.009~0.116 pg TEQ/m³和0.052 pg TEQ/m³。PCDD/Fs浓度与毒性当量季节变化特征显著,均呈现出冬季>春季>秋季>夏季的情况,可能由季节性排放源和气象条件不同导致。不同季节PCDD/Fs异构体分布模式一致,主要由高氯代(1,2,3,4,6,7,8-HpCDF、OCDD、OCDF和1,2,3,4,6,7,8-HpCDD)单体组成;而对毒性当量贡献最大的单体是2,3,4,7,8-PeCDF,其与总毒性当量具有较好的相关性。同时,PCDD/Fs浓度与SO₂、NO₂、PM_2.5等大气常规污染物呈显著正相关。这表明,大气PM_2.5中PCDD/Fs与常规污染物的生成和排放密切相关。     

上海大气中二噁英类化合物污染水平及人群呼吸暴露评估

为了获取上海环境大气中二噁英类化合物（PCDD/Fs）的浓度水平、季节和空间变化，评估上海地区人群PCDD/Fs呼吸暴露风险，选取上海16个行政区域中44个市级环境大气监控点作为采样点位，利用被动采样技术采集2019年夏、冬季大气样品共83个，分析了其中17种2，3，7，8-PCDD/Fs的浓度。结果表明：（1）2019年上海大气中PCDD/Fs的质量浓度为136~3 939 fg/m³，对应的毒性当量浓度为11.84~94.9 fg WHO₂₀₀₅-TEQ/m³；（2）上海冬季大气中PCDD/Fs毒性当量浓度（13.3~94.9 fg WHO₂₀₀₅-TEQ/m³）高于夏季（11.84~78.52 fg WHO₂₀₀₅-TEQ/m³）。上海郊区由于受工业生产影响，PCDD/Fs平均毒性当量浓度（夏季: 40.7 fg WHO₂₀₀₅- TEQ/m³; 冬季:57.4 fg WHO₂₀₀₅-TEQ/m³）高于中心城区（夏季: 28.5 fg WHO₂₀₀₅-TEQ/m³; 冬季:38.6 fg WHO₂₀₀₅-TEQ/m³）；（3）中心城区人群PCDD/Fs呼吸暴露量［成人：6.82 fg WHO₂₀₀₅-TEQ/(kg·d)；儿童：13.7 fg WHO₂₀₀₅-TEQ/(kg·d)］小于郊区［成人：19.17 fg WHO₂₀₀₅-TEQ/(kg·d)；儿童：18.4 fg WHO₂₀₀₅-TEQ/(kg·d)］。儿童呼吸暴露量高于成人。经对比，上海城市背景区域居民PCDD/Fs呼吸暴露风险低于上海垃圾焚烧厂周边居民，且都远低于人体PCDD/Fs每日耐受量［4 pg WHO₂₀₀₅-TEQ/(kg·d)］的10%，表明上海地区居民PCDD/Fs呼吸暴露风险处于可接受水平。     

深圳市大气中PCDD/Fs污染水平初步研究

目的:了解深圳市大气中二噁(PCDD/Fs)的污染水平和分布特征。方法:利用大流量空气采样器分别采集6个采样点的空气样品,每个采样点采集两个平行样品。参照美国环保总局(US EPA Method TO-9A)二噁的检测方法,通过高分辨气相色谱-高分辨双聚焦磁式质谱仪(HRGC/HRMS)对大气样品中17种具有毒性当量因子(TEF)的单体进行了定性和定量分析。结果:∑PCDD/Fs的浓度范围为0.23～11.88pg/m3(平均值为3.84 pg/m3)。毒性当量浓度范围为0.014～0.29 pg I-TEQ/m3(平均值为0.135 pg I-TEQ/m3)。OCDD、HpCDD、HpCDF、OCDF、HxCDF是丰度较大的单体,分别占总浓度的48.21%、15.85%、11.37%、7.40%、6.59%。PCDDs和PCDFs单体浓度(除OCDF之外)均随氯原子取代个数的增加而增大。2,3,4,7,8-PeCDF对总的毒性当量贡献最大,占总毒性当量浓度的38.87%。六个采样点中有三个地点二噁同系物分布显示了"源"的特征,而另外三个地点则显示了"汇"的特征。成人的PCDD/Fs暴露量为0.0023～0.047 pg I-TEQ/kg.day;儿童PCDD/Fs暴露量为0.0052～0.11 pg I-TEQ/kg.day。结论:深圳市大气样品中二噁浓度低于国内一些城市研究水平,而高于日本、欧美国家的研究水平。     

自动净化-高分辨气相色谱/高分辨质谱测定废气中二(口恶)英

采用自动净化-高分辨气相色谱/高分辨质谱(HRGC/HRMS)测定废气中的17种2,3,7,8位取代的多氯代二噁英和呋喃(PCDD/Fs)。废气样品经索氏提取,DEXTech系统全自动净化,浓缩和定容后,以HRGC/HRMS对废气样品中的PCDD/Fs进行了定性和定量分析。结果表明,17种二噁英和呋喃采样内标平均回收率为93%~99%,提取内标平均回收率为80%~97%;17种二噁英和呋喃自动净化实测结果与手工净化测试结果基本一致。该方法不但满足相关国家标准要求,还极大提高了样品的净化速度,减少人体对有机试剂的暴露。     

交通限行对大气颗粒物及PM_(2.5)中二■英的影响

为了研究北京大气颗粒物和二■英(PCDD/Fs)的污染状况以及评估交通限行对大气颗粒物和PCDD/Fs的影响。利用同位素稀释高分辨率气相色谱/高分辨率质谱(HRGC/HRMS)联用法和USEPA 1613B标准方法,以中国地质大学(北京)东门为采样点,采集大气PM_(2.5)、PM_(10)、TSP样品,对北京市交通限行期间以及交通限行前后等不同交通状况下颗粒物浓度及大气PM_(2.5)中17种2,3,7,8-PCDD/Fs污染特征进行了监测。结果表明,PM_(2.5)、PM_(10)、TSP的日均质量浓度在交通限行前分别为126、202、304μg/m~3,限行期间分别为39、78、93μg/m~3,限行结束后分别为79、126μg/m~3。PM_(2.5)中17种PCDD/Fs的质量浓度(毒性浓度) 3个时段分别为1 804 fg/m~3(70 fg I-TEQ/m~3)、252 fg/m~3(9 fg I-TEQ/m~3)和1 196 fg/m~3(48 fg I-TEQ/m~3)。北京市交通限行期间颗粒物浓度和二■英浓度显著低于交通限行前后,交通源减排措施的实施是大气颗粒物和二■英污染水平降低的主要原因,从减排效果看,交通源减排措施对大气细颗粒物(PM_(2.5))的控制效果明显好于大气粗颗粒物。     

交通限行对大气颗粒物及PM2.5中二NFDA1英的影响

为了研究北京大气颗粒物和二NFDA1英(PCDD/Fs)的污染状况以及评估交通限行对大气颗粒物和PCDD/Fs的影响。利用同位素稀释高分辨率气相色谱/高分辨率质谱(HRGC/HRMS)联用法和USEPA 1613B 标准方法,以中国地质大学(北京)东门为采样点,采集大气PM_2.5、PM₁₀、TSP样品,对北京市交通限行期间以及交通限行前后等不同交通状况下颗粒物浓度及大气PM_2.5中17种2,3,7,8-PCDD/Fs污染特征进行了监测。结果表明,PM_2.5、PM₁₀、TSP的日均质量浓度在交通限行前分别为126、202、304 μg/m³,限行期间分别为39、78、93 μg/m³,限行结束后分别为79、126 μg/m³。PM_2.5中17种PCDD/Fs的质量浓度(毒性浓度)3个时段分别为1 804 fg/m³(70 fg I-TEQ/m³)、252 fg/m³ (9 fg I-TEQ/m³)和1 196 fg/m³ (48 fg I-TEQ/m³)。北京市交通限行期间颗粒物浓度和二 NFDA1 英浓度显著低于交通限行前后,交通源减排措施的实施是大气颗粒物和二 NFDA1英污染水平降低的主要原因,从减排效果看,交通源减排措施对大气细颗粒物(PM_2.5)的控制效果明显好于大气粗颗粒物。     

Chlorinated and brominated dibenzo-p-dioxins and dibenzofurans in surface sediment from Taihu Lake, China

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in surface sediment samples from Taihu Lake--an important water supply of the Yangtze River Delta, China--were investigated in the present study. Concentrations of PCDD/Fs ranged from 0.91 to 4.8 pg TEQ g(-1) dw (mean: 2.9 pg TEQ g(-1) dw, TEQ: Toxic Equivalent), which were all higher than the threshold effect level established by interim sediment quality guidelines in Canada (0.85 pg TEQ g(-1) dw). The levels of PBDD/Fs ranged from 0.16 to 1.6 pg TEQ g(-1) dw (mean: 0.52 pg TEQ g(-1) dw) and accounted for 5-33% (mean: 14%) of the total PCDD/Fs and PBDD/Fs TEQ. Comparatively, the abundance of sedimentary PCDD/Fs in the three regions (Meiliang Bay, Gonghu Bay, and Xukou Bay) showed a decreasing trend from the inflow region to the outflow region, while no significant difference was observed among their 2,3,7,8-PBDD/Fs levels, which suggested that the sources of PCDD/Fs and PBDD/Fs differed in this area. Principal component analysis suggested that the historical production/usage of pentachlorophenol and sodium pentachlorophenate was the dominant source of PCDD/Fs in the sediment of these regions. Although the specific sources of PBDD/Fs in the sediment of Taihu Lake were unclear, it was suspected to be due to atmospheric deposition; however, an additional study is needed to confirm this.     

广州天河区大气中二噁英年度监测及气固分配规律

对广州天河区大气中二噁英进行年度监测和气固分配模式的研究。结果表明,天河区大气中存在较高浓度的二噁英;低氯代二噁英对毒性当量贡献较大,其主要分布在气相,2,3,4,7,8-PeCDF对毒性当量贡献最大,其贡献超过35%;高氯代二噁英(主要是OCDF、OCDD、1,2,3,4,6,7,8-HpCDF和1,2,3,4,6,7,8-HpCDD)对浓度贡献较大,其主要分布在颗粒相。     

Development of a new automated clean-up system for the simultaneous analysis of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and 'dioxin-like' polychlorinated biphenyls (dl-PCB) in flue gas emissions by GPC-SPE

A comprehensive clean-up method for quantitative analysis of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzo-furans (PCDD/Fs) in one single extract of environmental samples was developed. Since the chemical nature and toxicity of planar PCBs are similar to those of PCDD/Fs, dioxin-like PCBs and PCDD/Fs are often surveyed together in their exposure assessments. The development of a method for the simultaneous analysis of PCBs and PCDD/Fs in environmental samples is invaluable. The automated clean-up system evaluated in this work consists of three additional steps after traditional extraction: the chromatography on gel permeation (GPC), the concentration of the solvent through the use of an in-line evaporation module and the further purification and separation of PCDDs/Fs and dl-PCBs on an alumina cartridge in the 'SPE module'. In this work, three fly ash samples from an interlaboratory study with different PCDD/F and PCB levels were Soxhlet-extracted and then cleaned up using an automated system. PCDD/Fs and PCBs were determined using isotope dilution and high resolution gas chromatography/high resolution mass spectrometry. The determined values of 17 PCDD/Fs were consistent with the certified values and the relative standard deviations (RSDs) of the determined values were less than 20%. The recoveries of (13)C labeled PCDD/Fs and planar PCBs, and their RSDs were within the ranges specified in EPA1613 and 1668a methods, respectively. An accurate and reliable method was successfully developed and can be used in the simultaneous analysis of PCDD/Fs and planar PCBs in environmental samples.     

上海市危险废物焚烧行业二噁英排放特征研究

通过对上海市危险废物焚烧行业焚烧炉排放烟气数据的分析，结果表明：不管是医疗废物焚烧炉还是一般危险废物焚烧炉，其二蟋英分布规律大致相同；PCDFs对二曝英的贡献率远高于PCDDs；实测检出的二嚼英异构体中，占二嚼英总量比例较大的依次为1，2，3，4，6，7，8-HpCDF、1，2，3，4，6，7，8-HpCDD和OCDD；I—TEQ贡献最高的二嚼英异构体为2，3，4，7，8-PeCDF，贡献率达31．08％～53．56％。17种二喏英异构体与I—TEQ的相关性分析表明，仅2，3，4，7，8-PeCDF在2类焚烧炉中与I—TEQ均存在相关性，其相关系数分别为0．989和0．998，可以作为潜在的测定指示物。     

Contributions of dry and wet depositions of polychlorinated dibenzo-p-dioxins and dibenzofurans to a contaminated site resulting from a penetachlorophenol manufacturing process

The soils at a factory for manufacturing pentachlorophenol were heavily contaminated by polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). In order to verify the contributions of dry and wet deposition of PCDD/Fs from the ambient air, the concentration of PCDD/Fs in ambient air and soil were measured, the partition of particle- and gas-phases of atmospheric PCDD/Fs was calculated, and the annual fluxes of total dry and wet PCDD/F depositions were modeled. Average atmospheric PCDD/F concentration was 1.24 ng Nm^???3 (or 0.0397 ng I-TEQ Nm^???3). Moreover, over 92.8% of total PCDD/Fs were in the particle phase, and the dominant species were high chlorinated congeners. The total PCDD/F fluxes of dry and wet deposition were 119.5 ng m^???2 year^???1 (1.34 ng I-TEQ m^???2 year^???1) and 82.0 ng m^???2 year^???1 (1.07 ng I-TEQ m^???2 year^???1), respectively. By scenario simulation, the total fluxes of dry and wet PCDD/F depositions were 87.1 and 68.6 ng I-TEQ, respectively. However, the estimated PCDD/F contents in the contaminated soil were 839.9 ?? g I-TEQ. Hence, the contributions of total depositions of atmospheric PCDD/F were only 0.02%. The results indicated that the major sources of PCDD/F for the contaminated soil could be attributed to the pentachlorophenol manufacturing process.     

Concentrations and accumulation profiles of PCDDs, PCDFs and dioxin-like PCBs in adipose fat tissues of Korean women

Reports on residue levels and accumulation profiles of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in human adipose tissue are scarce in Korea. In this study, concentrations and accumulation features of PCDD/Fs and DL-PCBs were determined in the samples of adipose tissue collected from Korean women in 2007-2008. The total dioxin-like toxic equivalent (TEQ) concentrations (3.4-42 pg g(-1) lipid wt) in Korean adipose tissues were similar to those reported in European and other Asian countries. The relative contributions of individual compounds to total TEQs were as follows: non-ortho PCBs (mean: 45%) > PCDFs (28%) > PCDDs (24%) > mono-ortho PCBs (3%), a pattern similar to those reported for seafoods in Korea. The dominant PCDD/F congeners found in adipose tissues were OCDD and 2,3,4,7,8-PeCDF and dominant PCBs were 118, 156 and 105. No correlation was found between subject's age and concentrations of dioxin-like contaminants. Body mass index was not correlated with concentrations of PCDD/Fs and was negatively (p < 0.001) correlated with concentrations of DL-PCBs. The results of this study provide baseline information on PCDD/Fs and DL-PCBs in adipose tissues of the general population in Korea.     

Distribution patterns of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in sediments of the Xiangjiang River, China

We investigated the occurrence and distribution patterns of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in six sediment samples from the Xiangjiang River, Hunan Province, People’s Republic of China. Total concentrations of PCDD/Fs ranged from 876 to 497,759 (mean 160,766) ng/kg dw, the highest of which exceeded that have ever been reported for sediment samples. World Health Organization total toxicity equivalent (WHO-TEQ) concentrations in three out of six samples were significantly higher than the guidance level (21.5?ng WHO-TEQ/kg dw) suggested by Canadian Sediment Quality Guideline. A predominance of octachlorodibenzo-p-dioxin (OCDD) was observed with an average contribution of 90.8% to the total PCDD/F concentrations, while 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (HpCDD) was the major contributor to the PCDD/F WHO-TEQ concentrations in most of the sites. Such high levels of OCDD and HpCDD may be attributed to the presence of PCP/PCP-Na pollution, although MB-WW, agricultural straw open burning, and boilers–hazardous wastes were also the potential sources of PCDD/Fs. This is the first report for the concentrations and congener profiles of PCDD/Fs in sediment samples from the Xiangtan, Zhuzhou, and Changsha sections of the Xiangjiang River, providing scientific evidence for establishing priorities to reduce ecological risks posed by PCDD/Fs in the rapidly developing areas of Hunan Province and elsewhere.     

杭州城区环境空气中二口恶英浓度状况研究

依据2009年7月至2012年2月连续3年对杭州城区环境空气中二英（PCDD/Fs）采样分析结果得知，杭州城区环境空气中二英毒性当量质量浓度变化范围为0.13～0.55 pg TEQ/m³，均值为0.34 pg TEQ/m³。城区环境空气中二英浓度季节变化不显著，夏季略低于冬季；城区范围内不同功能区之间二英浓度差别不显著；连续3年监测结果未显现二英年度变化趋势。沙尘暴天气环境空气中二英浓度显著增高，日常天气和烟花爆竹集中燃放天气环境空气中二英形态分布存在明显区别，烟花爆竹集中燃放期间八氯代二苯并-对-二英（OCDD）占总质量浓度比例显著提高。利用IBM SPSS Statistics 19.0统计软件对24个监测结果聚类分析发现，杭州城区环境空气中二英的同类物分布具有明显的“源”分布特征。     

广州大气颗粒物中二噁含量的初步研究

2004年夏季在广州四个不同区域采集大气颗粒物样品,参照美国环保局(US EPA)标准方法测定其中二噁的含量,采用热分解光学分析法测定元素碳和有机碳的含量。结果表明,花都、荔湾、天河、黄埔大气颗粒物中二噁浓度(毒性当量)平均值分别为3815fg/m3(104.6fg I-TEQ/m3)、12777fg/m3(430.5fg I-TEQ/m3)、6963fg/m3(163.7fg I-TEQ/m3)、10953fg/m3(769.3fg I-TEQ/m3)。简单地分析了广州大气颗粒物中二噁的含量特征,以及与元素碳、有机碳之间的相关性。