气相色谱-高分辨双聚焦磁质谱测定水中超痕量多氯萘

采用固相萃取法处理水样，气相色谱-高分辨双聚焦磁质谱法测定水中超痕量多氯萘，同位素内标法定量，并对样品前处理条件和仪器条件进行优化。试验表明：方法在0．500 ng/L～500 ng/L范围内线性良好；当取样体积为1 L时，方法检出限为0．005 ng/L～0．01 ng/L；对实际水样进行2个质量浓度水平的加标回收试验，平行测定6次的 RSD为2．7％～8．7％，回收率为70．2％～110％。方法适用性试验表明，水样中复杂的基质对测定无影响。     

Polychlorinated naphthalenes in human adipose tissue from New York, USA

Polychlorinated naphthalenes (PCNs) are persistent, bioaccumulative, and toxic contaminants. Prior to this study, the occurrence of PCNs in human adipose tissues from the USA has not been analyzed. Here, we have measured concentrations of PCNs in human adipose tissue samples collected in New York City during 2003-2005. Concentrations of PCNs were in the range of 61-2500 pg/g lipid wt. in males and 21-910 pg/g lipid wt. in females. PCN congeners 52/60 (1,2,3,5,7/1,2,4,6,7) and 66/67 (1,2,3,4,6,7/1,2,3,5,6,7) were predominant, collectively accounting for 66% of the total PCN concentrations. Concentrations of PCNs in human adipose tissues were 2-3 orders of magnitude lower than the previously reported concentrations of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Concentrations of PCNs were not correlated with PCB concentrations. The contribution of PCNs to dioxin-like toxic equivalents (TEQs) in human adipose tissues was estimated to be <1% of the polychlorinated dibenzo-p-dioxin/dibenzofuran (PCDD/F)-TEQs.     

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.     

四川省卧龙地区土壤中二噁英类化合物和多氯萘的海拔梯度分布及对牦牛的毒性风险评价

初步研究了四川省卧龙地区5个不同海拔高度的表层土壤和2个牦牛样品中二噁英/呋喃(PCDD/Fs)、共平面多氯联苯(co-PCBs)和多氯萘(PCNs)的分布特征、来源、毒性当量以及生态风险状况.土壤样品中总2,3,7,8-PCDD/Fs的含量范围为2.48-4.30 pg·g-1dw,平均3.50 pg·g-1dw,最高含量在海拔3927 m的塘房.co-PCBs的总含量平均为9.14 pg·g-1dw,最高值在海拔4487 m的垭口.总2,3,7,8-PC-DD/Fs和总co-PCBs含量随海拔高度的变化表现出正相关关系.不同海拔高度土壤中的PCDD/Fs和co-PCBs异构体的分布相似,表明具有相同的来源.总PCNs与海拔梯度呈负相关关系,最高含量出现在海拔3345 m的贝母坪,平均21.4 pg·g-1dw,主要以3.氯为主.土壤中PcDD/Fs毒性当量浓度范围为0.29-0.43pg TEQ·g-1dw.牦牛肉和牦牛组织中PcDD,/Fs总浓度分别为27.5和23.6 pg·g-1脂肪,毒性当量浓度为4.04和4.07 pg TEQ·g-1脂肪.结果表明,牦牛中的PCDD/Fg,co-PcBs和PCNs不大可能对卧龙地区人群导致严重的负面效应.     

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.     

Distribution of polychlorinated naphthalenes (PCNs) in the whole blood of typical meat animals

The concentrations and distribution of polychlorinated naphthalenes(PCNs) in the whole blood of eight typical terrestrial meat animals(chicken, duck, rabbit, pig, cattle, sheep,horse and donkey) consumed daily in our life were investigated. The total concentrations(on a liquid volume basis) of PCNs were in a range from 305 to 987 pg/L. Donkey blood contained the highest PCN concentrations. Mono-CNs were the dominant homolog group,accounting for 38%–71% PCNs. Apart from the mono-CNs and tri-CNs homolog groups, two hepta-CNs(mean: 9.5%) contributed most, followed by tetra-CNs(mean: 6.5%). The congeners CN1, 5/7, 24/14, 27/30, 52/60, 66/67, and 73 were the most abundant congeners or congener groups. The highest toxicity equivalencies(TEQs) were observed in cattle blood(117.4 fg TEQ/L) then chicken blood(117.1 fg TEQ/L). CN73 contributed 65% to total TEQs,followed by CN70(20%) and CN66/67(14%). The dietary intakes of PCNs were also estimated.Chicken meat, which forms the second largest component of meat product consumption in China, contributed most to the total TEQs(61%), followed by beef(27%) and pork(5.9%). The consumption of chicken might pose the highest risk from exposure to PCNs than other types of meat to populations who prefer to eat chicken meat.     

Passive air monitoring of PCBs and PCNs across East Asia: a comprehensive congener evaluation for source characterization

A comprehensive congener specific evaluation of polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) in the atmosphere was conducted across East Asia in spring 2008, applying polyurethane foam (PUF) disk passive air sampler (PAS) as monitoring device. Mean concentrations derived for Japan, China and Korea were 184 ± 24, 1100 ± 118, and 156 ± 20 pg m⁻³ for ∑₂₀₂ PCBs, and 9.5 ± 1.5, 61 ± 6, and 16 ± 2.4 pg m⁻³ for ∑₆₃ PCNs, respectively. Relative to reported data from 2004, the present results suggest that air PCBs concentrations have not changed much in Japan and Korea, while it has increased by one order of magnitude in China. From principal component analysis, combustion emerged highly culpable in contemporary emissions of both PCBs and PCNs across the East Asian sub-region. Another factor derived as important to air PCBs was re-emissions/volatilization. Signals from PCBs formulations were also picked, but their general importance was virtually consigned to the re-emissions/volatilization tendencies. On the contrary, counterpart PCNs formulations did not appear to contribute much to air PCNs.     

高分辨率气相色谱/高分辨率质谱同位素内标法测定烟气样品中的多氯萘

多氯萘(PCNs)同二噁英(PCDD/Fs)和类二噁英多氯联苯(PCBs)类似,在烟气中的含量处于痕量水平,一般都在pg·m-3以下,因此分析方法要求有较高的灵敏度和选择性.以国内外的研究方法和参考文献为基础,建立了同位素内标稀释高分辨气相色谱/高分辨率质谱联用对垃圾焚烧发电厂的烟气样品中的PCNs进行分析.结果表明,该方法对17种氯取代位的PCNs单体的空白干扰在N.D.—2.1 pg之间;方法检出限范围为2.8—9.1 pg·nm-3,线性范围为0.40—240 pg·μL-1;空白加标实验中目标化合物的回收率为84.62%—116.21%,提取内标回收率为40.41%—75.79%,采样内标的回收率为88.92%—89.89%.实际烟气样品测得17种PCNs的同系物浓度分布在8.79—509 pg·nm-3之间,PCN-6的含量最高,PCNs-31S含量最低,相对标准偏差在4.43%—14.44%.该分析方法具有较高的准确性和可靠性,适用于烟气样品中多氯萘物质的测定.     

Melting and incineration plants of municipal waste. Chemical and biochemical diagnosis of thermal processing samples (emission,residues)

Control of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in emissions and thermal residues from incinerators has been a cause of public concern for more than one decade. Recently, several studies showed that other persistent organic pollutants (POPs) such as coplanar polychlorinated biphenyls (co-PCBs) also have dioxin-like activity and are released from incinerators. Therefore, the present study was aimed at making a risk assessment about dioxin-like activity in extracts of thermal waste residues (e.g. combustion gas; fly ash, slag) from incineration and melting processes in Germany and Japan. For this purpose, polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), coplanar polychlorinated biphenyls (co-PCBs), polychlorinated naphthalenes (PCNs) and polyaromatic hydrocarbons (PAHs) were analyzed by chemical analysis. Additionally, 2, 3, 7, 8-TCDD equivalents (EROD-TEQs) were determined by in vitro Micro-EROD bioassay using rat H4IIE hepatoma cells. EROD-TEQs could be correlated to I-TEQ values (from PCDD/Fs/co-PCBs) analyzed by chemical analysis resulting in a maximal sixfold higher estimate. Our study indicates minor influences of co-PCBs, PAHs and PCNs to the sum of dioxin-like toxicity in the extracts of thermal waste residues as determined here. Furthermore, we showed that the levels of dioxins and co-PCBs contained in slag from melting processes and bottom ashes from incineration processes were lower by 1-2 orders of magnitude than that in fly ash.     

水泥窑除尘器捕集灰中PCDD/Fs、PCBs和PCNs的分布特征

应用同位素稀释、高分辨气相色谱-质谱联用技术测定了国内3种类型水泥窑(机械立窑、湿法旋窑和新型干法旋窑)以及生活垃圾焚烧炉和医疗垃圾焚烧炉的除尘器捕集灰中PCDD/Fs、PCBs和PCNs的浓度和毒性当量,比较了同族体和同类物的分布特征.结果表明,水泥窑除尘器捕集灰中二英及其类似物PCDD/Fs、PCBs和PCNs的总毒性当量(以TEQ计)分别在4.0～62、 0.069～3.9和0.47～2.8 ng·kg^-1之间,远小于垃圾焚烧炉除尘器捕集灰.占优势的PCDD/Fs同族体都是TCDFs,相对较多的2, 3, 7, 8位氯取代二英同类物有OCDD、 2,3,7,8-TCDF、 1,2,3,4,6,7,8-HpCDF;水泥窑除尘器捕集灰中PCBs同族体的分布特征与垃圾炉相似,占优势的同族体都是四氯联苯,含量较高的共平面PCBs同类物有PCB77、PCB105、PCB118;不同窑型水泥窑除尘器捕集灰中PCNs同族体分布特征相似,占优势的同族体都是四氯萘,没有检测到八氯萘的存在,含量较高的二英类毒性PCNs同类物是毒性最大的PCN 66/67.