某市市售牛奶及其制品中二噁英类化合物污染水平

目的 了解某市市售牛奶及其制品中二噁英类化合物污染情况.方法 于2007年2-6月采集某市市售液体牛奶和奶粉(各5份),用高分辨气相色谱.高分辨双聚焦磁式质谱联用仪(HRGC-HRMS)定量检测样品中的二噁英及多氯联苯水平.采用索式抽提装置、FMS自动纯化系统对市售液体牛奶及奶粉样品中的二噁英(PCDD/Fs)及多氯联苯(PCBs)组分进行纯化和富集,采用同位素稀释法,以HRGC/HRMS联用仪检测.结果 奶粉和液体牛奶的总TEQ[∑(PCDD/Fs+PCBs)]平均值分别是0.43Pg/g脂肪和3.83ps/g脂肪,中位数分别是0.34Pg/g脂肪和2.04pgg脂肪.所有奶样的总TEQ[∑(PCDD/Fs+PCBs)]均值是2.13 ps/g脂肪,中位数是0.815 pg/g脂肪.本次调查的所有样品的平均总TEQ[∑(PCDD/Fs+PCBs)]远低于欧盟所设定的奶品二噁英类化合物的限量标准.受试样品中除了两种液体牛奶样品二噁英类化合物总TEQ超过欧盟限量标准外,其他液体牛奶和奶粉样品二噁英及多氯联苯含量远低于欧盟的限量标准.但是,液体牛奶的平均二噁英浓度明显高于奶粉样品.结论 本次采集的市售牛奶及其制品存在二噁英类化合物的污染.     

2007年北京市居民母乳中二噁英类化合物负荷水平调查

目的 调查北京地区居民母乳中多氯代苯并二噁英和多氯代苯并呋喃(PCDD/Fs)和二噁英样多氯联苯(dl-PCBs)的污染水平,评价一般人群PCDD/Fs和dl-PCBs的机体负荷状况.方法 2007年在北京市11个区、县中采集母乳样品110份,制成11个混合样品后,采用同位素稀释技术以高分辨气相色谱-高分辨质谱(HRGC-HRMS)测定母乳样品中的PCDD/Fs和dl-PCBs.结果 北京市母乳样品中二噁英类化合物含量最高的组分为八氯代二苯并二噁英(OCDD)和多氯联苯(PCB)-118、PCB-105,其含量中位数分别为20.6 pg/g脂肪、4.07和1.63 ng/g脂肪.按毒性当量(TEQ)计,北京市11个母乳混合样品中总二噁英类化合物含量中位数为7.4 pg TEQ/g脂肪;最高的为通州区,含量中位数为13.5 pg TEQ/g脂肪;最低的为平谷区,为4.3 pg TEQ/g脂肪.结论 目前北京市母乳中PCDD/Fs和dl-PCBs处于较低水平,但随着我国的快速工业化,人群此类物质的机体负荷水平有可能会上升,因此有必要持续跟踪监测.     

某市市售牛奶及其制品中二[口][恶]英类化合物污染水平

目的了解某市市售牛奶及其制品中二[口][恶]英类化合物污染情况。方法于2007年2-6月采集某市市售液体牛奶和奶粉（各5份），用高分辨气相色谱-高分辨双聚焦磁式质谱联用仪（HRGC-HRMS）定量检测样品中的二[口][恶]英及多氯联苯水平。采用索式抽提装置、FMS自动纯化系统对市售液体牛奶及奶粉样品中的二[口][恶]英（PCDD／Fs）及多氯联苯（PCBs）组分进行纯化和富集，采用同位素稀释法，以HRGC／HRMS联用仪检测。结果奶粉和液体牛奶的总TEQ[∑（PCDD／Fs＋PCBs）]平均值分别是0.43pg／g脂肪和3.83pg／g脂肪，中位数分别是0.34pg／g脂肪和2.04pg／g脂防。所有奶样的总TEQ[∑（PCDD／Fs＋PCBs）]均值是2.13pg／g脂肪，中位数是0.815pg／g脂肪。本次调查的所有样品的平均总TEQ[∑（PCDD／Fs＋PCBs）]远低于欧盟所设定的奶品二[口][恶]英类化合物的限量标准。受试样品中除了两种液体牛奶样品二[口][恶]英类化合物总TEQ超过欧盟限量标准外，其他液体牛奶和奶粉样品二嗯[口][恶]英及多氯联苯含量远低于欧盟的限量标准。但足，液体牛奶的平均二[口][恶]英浓度明显高于奶粉样品，结论本次采集的市售牛奶及其制品存在二[口][恶]英类化合物的污染。     

高分辨质谱法测定海鱼中二噁英和多氯联苯

目的采用同位素稀释的HRGC／HRMS法定量检测鱼体中17种2，3，7，8-氯取代的二噁英(PCDD／R)和12种二噁英多氯联苯(PCBs)。方法参照美国EPA1613及EPA1668A方法，采用索式抽提和自动纯化系统(FMS)对鱼体中的PCDD／Fs及PCBs进行纯化和富集、用同位素稀释气相色谱与高分辨质谱联用一多离子检测方法检测。结果该方法可对样品中的PCDD／Fs及PCBs同系物进行有效分离，PCDD／Fs同位索标准物的回收率为83．83％～98．48％，PCBs同位素标准物的回收率为50．06％～90．56％。13种PCDD／Fs在鱼体中可检出，总毒性当量(TEQ)为0．86pg／g，12种二噁英PCBs在鱼体中均可检测出，总TEQ值为2．77pg／g。结论该方法可以同时对同一样品中的17种PCDD／Fs及12种二噁英PCBs进行检测，检测效率高，结果准确可靠。     

废水中二噁英类化合物测定的固相微萃取前处理法

目的探讨废水中二噁英类化合物测定的固相微萃取处理法.方法采用固相微萃取(SPME)装置对样品进行纯化和富集,以HRGC-HRMS分析废水中的二噁英类化合物.结果最佳萃取温度和时间分别为45℃、30 main.检测限为0.05 pg/μl,相对标准偏差＜10%,回收率为99%～102%,样品中二噁英类物质总的浓度为0.78 pg/μl.结论用SPME方法测定废水中的二噁英类化合物,操作简便快速,有广阔的应用前景.     

我国某海域海鱼中二噁英污染分析

目的对我国某海域20个海鱼样品进行了二噁英污染状况的定量分析检测,并对该地区人群从鱼获得的膳食暴露进行了初步评估。方法2003年6月至12月采集海水养殖鱼7类,20个样品。采用索式抽提装置、FMS专用净化装置对样品进行提取、纯化和富集,采用国际权威标准方法高分辨气相色谱/高分辨双聚焦磁式质谱联用(HRGC/HRMS)技术,以HRGC/HRMS多离子检测方式分析了样品中的17种氯化二苯并二噁英和氯化二苯并呋喃(PCDD和PCDF)化合物的含量,用放射性核素稀释技术定量。结果质控样品对方法的验证结果在国际认可的范围内,3次检测数据的相对标准偏差<15%。20个海鱼样品的总PCDD/PCDF平均含量以湿重计是1.48ng/kg,范围分布在0.21～8.10ng/kg湿重,以世界卫生组织毒性当量因子(WHOTEF)计,样品总毒性当量浓度(WHOTEQ)分布于0.030～1.291ng/kg湿重之间,平均总的毒性当量浓度是0.292ng/kg。以该TEQ值进行估算,该地区人群由鱼引起的二噁英污染暴露量估计为每日每公斤体重0.58pgWHOTEQ。结论不同样品间二噁英污染水平相差很大,人群由鱼引起的二噁英暴露量虽然低于世界卫生组织的标准,但若考虑人体多渠道摄入的食品,说明我国二噁英的污染现状不容忽视。     

人体胎盘组织二噁英和多溴联苯醚化合物负荷水平初步研究

目的 建立人体胎盘组织样品氯化二苯并二噁英(PCDD)和呋喃(PCDFs)、多氯联苯(PCBs)、多溴联苯醚(PBDEs)化合物同时准确定量检测分析方法,揭示上述持久性有机污染物人体负荷水平,并初步进行危险性评估.方法 采用国际权威标准方法--核素(同位素)稀释的高分辨气相色谱/高分辨双聚焦磁式质谱联用(HRGC/HRMS)技术,以多离子检测方法对人体胎盘组织样品中17个PCDD/Fs和12个共平面PCBs以及7个PBDEs化合物分别进行定性和定量分析,用WHO-TEF值计算所有样品的毒性当量浓度∑TEQ(PCDD+PCDFs+PCBs)和PBDEs浓度,进一步对人体二嗯英和PBDEs化合物负荷水平进行危险性评估.结果 6个胎盘组织样品中PCDD/Fs和PCBs化合物毒性当量总浓度∑TEQ(PCDD+PCDFs+PCBs)中位数是18.15 WHO-TEQ pg/g脂肪.范围分布在5.14～67.01 WHO-TEQ pg/g脂肪之间.2,3,4,7,8-PeCDFs、1,2,3,7,8-PeCDDs、PCB126是毒性当量的主要贡献者,合计占65%.以7个化合物计算PBDEs总浓度,6个样品的中位数值为2.73 ng/g脂肪,均数为7.17 ng/g脂肪,范围是0.95～25.99 ng/g脂肪.BDE47是最主要的污染同系物,占到35%.浓度最高的一个受试样品其毒性当量总浓度∑TEQ(PCDD+PCDFs+PCBs)已经达到世界上已知高暴露区人体二噁英污染负荷水平.结论 我们在本研究中建立了人体组织样品中持久性有机化合物二噁英和PBDEs化合物同时准确定量检测方法,高二噁英负荷水平的样品提供者可能对胎儿存在健康危害的高暴露风险,对于健康的远期影响还需要深入进行医学追踪研究.     

海水产品甲醛本底值调查分析

[目的]了解本地海域海产品甲醛本底值情况。[方法]对79份样品进行201份次的甲醛含量检测。[结果]除鱿鱼与水潺外，甲醛含量在O～5mg／kg之间，鱿鱼与其新鲜度有较大关系，而水潺甲醛含量普遍较高，在30～120mg／kg之间。[结论]本地海水产品是有一定水平的甲醛本底值，执法者应有清醒的认识。     

断续流动氢化物原子荧光法同时测定聚合氯化铝中的砷和汞

[目的]双道同时测定水处理剂聚合氯化铝中砷(As)和汞(Hg)。[方法]以盐酸溶解样品，硫脲一抗坏血酸作掩蔽剂，氢化物发生原子荧光法同时检测。[结果]水处理剂聚合氯化铝中As含量为0．32mg/kg，Hg为0．0039mg／kg；As检出限0．037ng／111l，Hg检出限0．0043ng／ml；加标回收率As在96．5％～103．2％，Hg在82．7％。105．6％之间，试验了金属离子的干扰及消除。[结论]此法具有操作简便快速，灵敏度高，检出限低，线性范围宽，能够同时检测双元素，适于日常大批水处理剂等样品的检测。     

典型地区食品中二噁英的污染水平分析

目的 评价典型行业所在地区食品样品中17种PCDD/Fs的污染水平.方法 使用同位素稀释技术以高分辨气相色谱-高分辨质谱(HRGC-HRMS)测定采自于垃圾焚烧厂、氯化工厂、铸造厂周边以及对照组地区的猪肉、牛肉、鸡肉、牛奶、鸡蛋、水产类及蔬菜样品中的17种二嗯英(PCDD/Fs).结果 OCDD是主要的污染物,平均含量值为0.75 pg/g wet weight;其次,垃圾焚烧厂、氯化工厂、铸造厂周边地区的食品样品中17种PCDD/Fs的毒性当量浓度(TEQ)会显著高于对照组,蔬菜样品中TEQ值会明显低于其他样品;另外,结合已有的食物消费量,计算标准人的二噁英类物质的每月膳食暴露量会远低于JECFA规定的PTMI(70 pg/kg bw/month).结论 垃圾焚烧厂,铸造厂和对照组周边地区人群目前由膳食摄入PCDD/F而导致的潜在健康风险处于较低的水平.     

Dioxin-Like TEQ of women from the Seveso, Italy area by ID-HRGC/HRMS and CALUX

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) are widespread environmental contaminants that exist as complex mixtures and are frequently detected at part-per-trillion (ppt) levels in humans. Using isotope dilution high-resolution gas chromatography/ high-resolution mass spectrometry (HRGC/HRMS), we measure the PCDDs, PCDFs, and PCBs in serum of a population of 78 women residing in an area near Seveso, Italy where a TCDD explosion occurred in 1976 and where furniture is manufactured. The average total dioxin-like toxic equivalents (TEQ) of these women was 25.3 ppt, lipid-adjusted, comparable to other parts of Europe. TCDD levels, however, were higher among the few women who resided in the exposed area in 1976. We examined the possibility of using the CALUX (chemical-activated luciferase gene expression) bioassay to estimate total TEQ in a small volume of plasma from this population. A total of 32 archived plasma specimens were selected for CALUX bioassay, based on the distribution of Total TEQ by HRGC/HRMS. The CALUX bioassay was performed blind to HRGC/HRMS results with 2 ml plasma per replicate analysis. Of 32 samples, 10 were below detection limits in the CALUX bioassay. For the 32 samples, the CALUX-TEQ averaged 25.4 ppt, lipid-adjusted (range: 0-127.6) and was not significantly different from the HRGC/HRMS Total TEQ average of 31.2 ppt, lipid-adjusted (range: 12.7-88.3) (t = 0.88, P = 0.38), however, the two measures were not significantly correlated (R(s) = 0.04, P=0.82). More validation of the CALUX bioassay with larger sample volume is needed before application as an exposure measure in large-scale epidemiologic studies of health effects of dioxin-like compounds.     

Biomarker measurements in a coastal fish-eating population environmentally exposed to organochlorines

The Lower North Shore region of the St. Lawrence River is home to a fish-eating population that displays an unusually high body burden of several organochlorines, including polychlorinated biphenyls (PCBs) and dioxin-like compounds (DLCs). We measured biomarkers indicative of liver enzyme induction and investigated the relationship with organochlorine body burden in adult volunteers from this population. We determined plasma concentrations of PCBs and chlorinated pesticides by high-resolution gas chromatography (HRGC) with electron capture detection. DLC concentrations were measured by the dioxin-receptor chemically activated luciferase expression (DR-CALUX) assay and in a subset of participants, by HRGC/high-resolution mass spectrometry. We measured cotinine, d-glucaric acid, and porphyrins in morning urine samples and determined liver CYP1A2 activity in vivo using the caffeine breath test. Neither DLC concentrations as measured by the DR-CALUX nor PCB-153 concentrations, the latter representing total PCB exposure, were correlated with biomarkers of effects. Smoking (morning urinary cotinine concentration) was positively related to CYP1A2 activity as measured by the caffeine breath test (p < 0.01). Liver CYP1A2 activity was in turn negatively correlated with PCB-105:PCB-153 and PCB-118:PCB-153 congener ratios (p < 0.05). Hence, despite the relatively high body burden of PCBs and DLCs in this population, only smoking had a significant correlation with biomarkers of hepatic enzyme induction. Our data are consistent with smoking-induced liver CYP1A2 activity altering heme metabolism and increasing the biotransformation of mono-ortho PCB congeners.     

EROD activities in a primary cell culture of grass carp (Ctenopharyngodon idellus) hepatocytes exposed to polychlorinated aromatic hydrocarbonas

Aryl hydrocarbon (Ah) receptor (Ah-agonist) effects of environmental samples containing polychlorinated aromatic hydrocarbons were evaluated using a 7-ethoxyresorufin-O-deethylase (EROD) assay of a primary hepatocyte culture from grass carp (Ctenopharyngodon idellus). The results were compared with those obtained from the assay using the rat hepatoma cell line H4IIE and chemical analysis using high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). A dose-response relationship was observed between the EROD activities, either from primary hepatocyte culture assay or from H4IIE assay, and concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). The results showed that the assay based on the H4IIE cell line (EC50=0.83 pg/mL) is more sensitive to TCDD than the assay based on primary hepatocyte culture (EC50=9.7 pg/mL). In tests of environmental samples, the results from the assay using primary hepatocyte culture were comparable to those from the assay using the H4IIE cell line and chemical analysis of concentrations of mixtures of polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/PCDF). The lack of a change in the activities of glutathione-S-transferase (GST) and lactate dehydrogenase (LDH) in cell culture upon exposure to TCDD indirectly indicates that the compound is persistent to biodegradation in the cell culture system.     

奶粉中二噁英前处理方法的探讨

[目的]建立快速溶剂萃取(ASE)的前处理方法,并改进纯化步骤。采用该前处理方法将国际二噁英标准参考物质进行验证。[方法]采用ASE法和索氏提取2种提取方法对奶粉样品进行充分萃取,再选用FMS专用净化装置对样品进行纯化,采用同位素稀释,以各化合物的同位素标记物为回收率内标,以13C-1,2,3,4-TCDD和13C-1,2,3,7,8,9,-HxCDD为定量内标。用高分辨气相色谱(HRGC)和高分辨双聚焦质谱(HRMS)联用技术进行定性和定量分析。[结果]ASE和索氏提取前处理所得的同位素标记化合物平均回收率分别为66.9%和66.5%,测定实际样品的相对标准偏差分别为18.4%和12.3%。[结论]通过比较ASE与索氏提取2种方法,ASE前处理便捷、时间短、所需溶剂少,回收率和精密度都符合美国EPA1613中的要求,通过用该法测定,结果也接近了欧盟2002/69/EC的规定,即每次测定的同位素标记物回收率不少于60%,如单个化合物的TEQ量小于10%总量TEQ时,不受上述限制。     

奶制品中二恶英类化合物两种提取方法的比较

[目的]比较奶和奶制品中二恶英类化合物索氏抽提法和液液萃取法。[方法]采集市售4种纯牛奶和3种奶粉,分别通过索氏抽提和液液萃取,再用酸性硅胶处理,利用硅胶柱和铝柱净化,用高分辨气相色谱/高分辨质谱检测分析PCDDs/Fs和PCBs。[结果]索氏抽提方法对牛奶和奶制品中脂肪不能提取完全,得到的二恶英类化合物检测结果不能真实反映牛奶和奶制品中二恶英类化合物污染情况。液液萃取法能完全萃取牛奶和奶制品中脂肪以及溶于脂肪中的二恶英类化合物,得到的结果能真实反映牛奶和奶制品中二恶英类化合物污染情况。[结论]液液萃取法是适用于检测牛奶和牛奶制品中二恶英类化合物的检测方法。     

Assessment of the trace organic molecular composition of industrial and municipal wastewater effluents by capillary gas chromatography/real-time high-resolution mass spectrometry: a preliminary report

In summary, the use of HRGC/HRMS and ECC can provide valuable information on the organic constituents of refinery wastewater samples, even when present in extremely complex mixtures. In many cases, the low-resolution (nominal mass) spectra would not have been interpretable without the availability of the corresponding high-resolution (accurate mass and elemental composition) information, since, even with the use of capillary columns, the components of these complex mixtures were not chromatographically resolved. It is apparent that additional components in these fractions could be identified if additional data processing followed by detailed analysis of the ECC data set is carried out incorporating the retention index information derivable from the series of n-alkanes present, although the incomplete chemical fractionation of the samples is a complicating factor in these particular wastewater extracts.     

Correlation between serum and adipose tissue levels of 2,3,7,8-tetrachlorodibenzo-p-dioxin in 50 persons from Missouri

Paired human serum and adipose tissue samples were analyzed from 50 persons for 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). On a lipid weight basis, the range of values in adipose tissue spanned approximately 2.5 orders of magnitude, from 3.3 to 969 parts per trillion (ppt). After adjusting the adipose tissue 2,3,7,8-TCDD levels for total lipid content and the serum 2,3,7,8-TCDD levels for total lipid content, the mean of the partitioning ratio of adipose tissue to serum 2,3,7,8-TCDD was 1.09 (standard deviation = 0.385, standard error = 0.060). On this same total lipid weight basis, the adipose tissue and serum levels of 2,3,7,8-TCDD were highly correlated, r = 0.98. The high correlation between adipose tissue and serum 2,3,7,8-TCDD levels in this study indicates that serum 2,3,7,8-TCDD is a valid measurement of 2,3,7,8-TCDD body burden concentration.     

深圳市城市饮用水中二英污染现状的初步研究

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