加速溶剂同时萃取和净化-气相色谱-三重四极杆串联质谱测定土壤和沉积物中8种多溴联苯醚

建立了土壤和沉积物中8种多溴联苯醚(PBDEs,BDE-28、BDE-47、BDE-99、BDE-100、BDE-153、BDE-154、BDE-183和BDE-209)加速溶剂同时萃取和净化-气相色谱-三重四极杆串联质谱(ASE-GC-MS-MS)的分析方法。通过优化加速溶剂萃取与弗罗里硅土在线净化和串联质谱多反应监测模式的条件,较好地去除基质干扰,并提高了三重四极杆串联质谱定性的准确性及定量的灵敏性。该方法采用改进的色谱柱能同时分析包括高溴代联苯醚BDE-209在内的8种PBDEs,其浓度范围为1～100 ng/mL(BDE-209为10～1 000 ng/mL),线性良好,线性回归系数均大于0.997。方法检出限为0.004～0.1 ng/g,方法回收率为75%～110%,方法精密度为2.4%～15.6%。适于批量处理土壤和沉积物中含有多组分痕量PBDEs的样品。     

高效液相色谱串联质谱法分析土壤中多溴联苯醚类化合物

建立了一种超高效液相色谱串联质谱法(UPLC-MS/MS)同时测定土壤中8种多溴联苯醚化合物(PBDEs)的方法,采用快速溶剂萃取(ASE)和凝胶净化色谱(GPC),经BEH反相C₁₈色谱柱分离,10 min内完成分离,使用含0.1%氨水的甲醇和水进行梯度洗脱,采用液相色谱-负离子-大气压化学电离(APCI)串联质谱,多反应监测模式(MRM),加入 ¹³C₁₂-BDE-139和¹³C₁₂-BDE-209内标作定量分析。结果表明:在优化的分析条件下,PBDEs的线性相关系数为0.998 8～0.999 5,方法检出限为0.22～0.59 μg/kg,在2个添加水平下,平均回收率为71%～126%,标准偏差为3%～18%,土壤实际质控样测定结果均在允许范围内。适合于土壤中PBDEs的快速分析,特别对于高溴代PBDEs,相比气相色谱质谱方法具有更快的分析速度和更好的稳定性。     

DPX快速萃取程序升温大体积进样GC/MS法测定水中19种多溴联苯化合物

建立DPX快速吸附萃取、程序升温(PTV)大体积进样与气相色谱/质谱(GC/MS)联用,SIM模式同时测定水中19种多溴联苯(PBBs)单体的方法。该方法在PBBs质量浓度1~50μg/L范围内线性良好,19种PBBs单体检出限为0.147~0.230μg/L,相对标准偏差为6.61%~10.5%,加标回收率为61.5%~82.6%。     

加速溶剂萃取-凝胶净化色谱-气相色谱质谱法测定农用地土壤中有机氯农药方法研究

通过对加速溶剂萃取、平行蒸发及净化方法等环节的优化实验,建立了加速溶剂萃取-凝胶净化色谱-气相色谱质谱法测定农用地土壤中23种有机氯农药的检测方法。结果表明,方法检出限为0.0034~0.0052 mg/kg;对化合物质量分数为0.25 mg/kg的土壤加标样品进行平行实验,回收率为82.0%~93.7%;测定结果的相对标准偏差（RSD）≤8.7%。对土壤有证标准质控样品进行分析,测定结果均在验收范围之内。该方法准确可靠,灵敏度较高,样品净化效果较好,能够满足农用地土壤中有机氯农药残留痕量分析的要求。     

液相色谱-串联质谱法测定水体、沉积物及土壤中全氟化合物

建立了水、沉积物及土壤中13种全氟化合物(PFCs)的富集、净化、浓缩的前处理方法及快速液相色谱三重四级杆串联质谱的分析方法。9种全氟羧酸、2种典型全氟磺酸、2种磺酰铵衍生前体物的响应因子与质量浓度的线性关系良好。添加回收实验表明,13种全氟化合物在水、土壤和沉积物中的回收率为52.3%~119.3%,变异系数为2.3%~19.4%,方法检出限分别为0.015~0.472 ng/L、0.012~0.875 ng/g、0.004~0.743 ng/g。该法成功应用于实际样品的测定,沉积物和土壤中分别检测到3种和10种全氟化合物。     

液相色谱-质谱法测定土壤中四溴双酚A和六溴环十二烷

文章建立了液相色谱-串联四级杆质谱仪同时测定土壤中四溴双酚A及3种六溴环十二烷同分异构体的分析方法。土壤样品经快速溶剂仪萃取，全自动凝胶净化系统净化后，使用液相色谱-串联四级杆质谱仪，负离子电喷雾多反应监测模式监测，内标法定量分析。结果表明，土壤中四溴双酚A、α-六溴环十二烷、β-六溴环十二烷和γ-六溴环十二烷的检出限为0.1~1.2 pg/g，加标回收率为81.8%~113%，相对标准偏差小于10%。该方法分析时间短，灵敏度高，操作简单，对电子固废拆解场地中的179个土壤样品进行分析，取得满意结果。     

固相萃取-LC-MS/MS测定土壤中多溴联苯醚

采用快速溶剂萃取-固相萃取-液相色谱串联质谱法（LC-MS/MS）测定土壤中8种多溴联苯醚类（PBDEs）化合物，通过优化试验条件，使方法在100 μg/L～1 000 μg/L范围内线性良好，方法检出限为085 μg/kg～125 μg/kg。不同土壤样品的8种多溴联苯醚回收率为68.6%～127%，4次测定结果的RSD为4.8%～27.6%。将该方法用于测定电子废物拆解点周边的土壤样品，结果BDE-209测定值为未检出～168 μg/kg，BDE-183为未检出～560 μg/kg，其余6种BDEs均为未检出。     

加速溶剂萃取/气相色谱-质谱法测定小麦中多环芳烃

建立了小麦中8种多环芳烃的分析方法.样品通过加速溶剂萃取,经全自动在线凝胶渗透色谱-浓缩联用系统和硅胶柱净化,最后用GC-MS测定.实验中优化了加速溶剂萃取条件和凝胶渗透色谱净化条件.结果表明,在120℃用正己烷-丙酮(V∶V=1∶1)提取8min,萃取3次的提取效果最好,1000～1800s是凝胶渗透色谱净化的最佳收...     

土壤中20种磺酰脲类除草剂的超高效液相色谱-串联质谱测定方法

建立了加速溶剂提取、凝胶渗透色谱法净化-超高效液相色谱/串联质谱快速测定土壤中20种磺酰脲类除草剂的方法。土壤经过冷冻干燥、粉碎过筛,用加速溶剂仪提取(ASE),经凝胶渗透色谱净化(GPC),以超高效液相色谱/串联质谱(UPLC-MS/MS)多级监测模式(MRM)外标法进行定性定量分析。结果表明:土壤中20种磺酰脲类除藻剂的检出限为2～5 ng/kg。对同一环境样品进行了3个不同添加量(1、5、10μg/L)的加标回收实验,平均回收率为65. 7%～106. 1%,相对标准偏差为2. 3%～12. 1%。该方法快速、灵敏、准确,可有效应用于土壤中20种磺酰脲类除草剂的快速监测。     

加速溶剂提取气-质联用分析土壤中的多环芳烃

建立了加速溶剂提取-凝胶渗透色谱净化和气相色谱-质谱联用快速分析土壤中16种多环芳烃的新方法。方法的检出限、定量限分别为1.1~12μg/kg、3.7~40μg/kg。16种PAHs的回收率为76.6%~96.8%,相对标准偏差为2.9%~9.5%。应用于多个环境样品的分析测试,结果满意。     

测量土壤中多溴联苯和多溴联苯醚含量不确定度评定

通过对气相色谱-质谱联用法测定土壤中多溴联苯和多溴联苯醚类化合物含量的不确定度进行评定,分析了测量过程中引入的不确定度来源,求出各不确定度分量,最后合成标准不确定度并计算相对扩展不确定度。结果表明,各化合物最大的不确定度分量是方法回收率,约占50%~90%,方法相对扩展不确定度为0.12~0.20。     

Short-range transport of contaminants released from e-waste recycling site in South China

The transport behaviors of a suite of contaminants released from electronic waste (e-waste) recycling operations, including polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and heavy metals, were evaluated by analyzing the contaminant residues in surface soils sampled in the surrounding area of an e-waste recycling site in South China. Concentrations of PBDEs and PCBs in the soil samples ranged from 0.565 to 2908 ng g(-1) dw and from 0.267 to 1891 ng g(-1) dw, respectively, while soil residues were 0.082-2.56, 3.22-287, and 16.3-162 μg g(-1) dw for Cd, Cu, and Pb, respectively. Concentrations of PBDEs and PCBs in soil decreased with increasing distance from the source of pollution, indicating possible PBDE and PCB contamination in the surrounding areas due to the short-range transport of these compounds from the e-waste recycling site. Although no significant difference in the short-range transport potential among PBDE and PCB congeners was observed, reductions in concentrations of the highly-brominated-BDEs and highly-chlorinated-CBs were slightly quicker than those of their less-halogen-substituted counterparts. Conversely, heavy metals showed the lowest transport potential due to their low vapor pressure, and results showed metals would remain near the pollution source instead of diffusing into the surrounding areas. Finally, mass inventories in areas near the e-waste site were 0.920, 0.134, 0.860, 4.68, 757, and 673 tons for BDE209, PBDEs (excluding BDE209), PCBs, Cd, Cu, and Pb, respectively.     

Temporal trend studies on polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in ringed seals from east Greenland

The concentrations of polybrominated diphenyl ethers (PBDEs) 17, 28, 47, 49, 66, 85, 99, 100, 153, 154, and 183 were determined in ringed seal blubber from central East Greenland collected in 1986, 1994, 1999 and during the period 2001 to 2004. The trend of PBDEs was compared with the trends of polychlorinated biphenyls (PCBs) 28, 31, 52, 101, 105, 118, 138, 153, 156, and 180 during the same period. The levels of sigmaPBDE in East Greenland ringed seals ranged from 21.8 ng g(-1) lipid weight (1w) in 1986 to 39.3 ng g(-1) lw in 2001 and are among the highest observed in ringed seal from the Arctic. The dominating congeners were BDE-47 (75.4%) and BDE-99 (9.7%). The concentrations of PBDEs and PCBs increased with the age of the seals, and therefore only young seals < or =4 years old) were included in the temporal trend analyses. No significant trend (p > 0.14) was observed in sigmaPBDE or the congeners BDE 28, 47 and, 99 during the period while sigmaPCB decreased significantly (p = 0.004) over the period from 1986 to 2004 with an estimated annual rate of 4.3%.     

Occurrence,sources, and ecological risks of PBDEs,PCBs, OCPs,and PAHs in surface sediments of the Yangtze River Delta city cluster,China

Polybrominated diphenyl ethers (PBDEs), organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs) in 25 surface sediments in three cities (Nantong, Wuxi, and Suzhou) in the Yangtze River Delta, eastern China were measured. The mean concentrations were 378, 45.8, 1.98, 4,002 ng/g for PBDEs, OCPs, PCBs, and PAHs, respectively. Their levels in the sediments in the three cities were generally consistent with the city industrialization. PBDEs and OCPs were markedly dominated by deca-BDE (>90 %) and DDTs (>70 %). A principle component analysis of the analytes identified three major factors suggesting different sources of the contaminants in the sediments. PBDEs and the organic carbon in the sediments have common sources from industrial activities; whereas OCPs and PCBs, correlated with the second factor, were mainly from historical sources. The third factor with loadings of PAHs is indicative of various combustion sources. Ecological risk assessment indicated that the potential highest risk is from DDTs, for which 22 sites exceed the effects range low (ERL) values and three sites exceed the effects range median (ERM) value.     

Levels and congener profiles of polybrominated diphenyl ethers (PBDEs) in primipara breast milk from Shenzhen and exposure risk for breast-fed infants

This study aimed at revealing the levels of polybrominated diphenyl ethers (PBDEs) in breast milk from primipara in Shenzhen (China), and estimating daily intake of PBDEs for breast-fed infants. Concentrations of 7 PBDEs were measured in 60 breast milk samples by isotope dilution HRGC/HRMS (high-resolution gas chromatography/high-resolution mass spectrometry). The intake of PBDEs for breast-fed infants was estimated based on the infant's daily milk consumption. The range of total concentration of 7 PBDEs congeners in samples was 2.6-188.6 ng g(-1) lipid (mean: 14.8 ng g(-1) lipid; median: 7.2 ng g(-1) lipid). The mean estimated daily intake of PBDEs by breast-fed infants ranged from 9.9 to 335.9 ng kg(-1) body weight (bw) per day (mean: 52.5 ng kg(-1) bw per day; median: 28.6 ng kg(-1) bw per day). The levels of PBDEs body burden in the recruited mothers of Shenzhen were higher than those reported previously for the general population from other areas in China. No significant correlations were found between the body burden of PBDEs and the mothers' age, pre-pregnancy BMI, dietary habits, duration of residence in Shenzhen, weight and length of the newborns. BDE-47 and BDE-153 were major PBDE congeners in milk samples, while the congeners of BDE-183 and BDE-28 were also high in Shenzhen. The situation may be attributed to the special economic pattern including electronic production in Shenzhen in the past three decades. Continuous surveillance on PBDEs levels in human milk is needed in order to accurately evaluate the environmental impact of PBDEs to human health in Shenzhen.     

建设项目中常见的内分泌干扰物的污染和控制建议

建设项目常见排放的内分泌干扰物主要包括二噁英类、多氯联苯和多溴联苯、砷及重金属、双酚A、苯并[a]芘和氯乙烯等。生物质燃烧和掺烧污泥的锅炉废气中的二噁英、掺烧石油焦的锅炉废气中的苯并[a]芘和化工项目排放的双酚A等均存在执行标准缺失问题。电子类项目中的多氯联苯和多溴联苯、冶炼项目中的砷及重金属、化工类项目中的氯乙烯等也应加强全过程监管。建议研究建立优控清单,系统地提出相关控制政策,管理建设项目环境激素类的产生和排放。     

Assessment of sorbent impregnated PUF disks (SIPs) for long-term sampling of legacy POPs

Two field studies were conducted for one year using sorbent-impregnated polyurethane foam (SIP) disks for PCB and PBDE air sampling. SIP disks were introduced by Shoeib et al. (2008) as an alternative passive air sampling medium to the polyurethane foam (PUF) disk and have the advantage of a higher holding capacity for organic chemicals. The first study on SIP disks confirmed their application for measuring volatile perfluorinated compounds (PFCs) and their ability to maintain time-integrated (linear) air sampling. In this study, the suitability of the SIP disks for long-term sampling of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and hexachlorobenzene (HCB) was assessed. SIP disks were deployed at a rural site in the UK and harvested after periods ranging from 35-350 days. Atmospheric POP concentrations were monitored with a high-volume air sampler during the deployment period. Linear uptake was observed for all monitored PCBs and PBDEs over the full exposure time. Air-sampler equilibrium was observed for HCB after 6 months. In a second field study, SIP disks were deployed for one year at 10 sites on a latitudinal transect in the UK and Norway, at which air sampling has been undertaken previously with different passive air sampling media since 1994. The estimated concentrations and spatial distributions derived from the SIP disks were largely in agreement with previously reported data.     

Environmental Specimen Bank in Ehime University (es-BANK), Japan for global monitoring

During the last 40 years, The Center for Marine Environmental Studies (CMES), Ehime University collected a variety of environmental and biological material comprising about 1000 species and 100,000 samples from many developing and developed countries and also open seas and oceans all over the world. They were categorically archived, catalogued and stocked in our Environment Specimen Bank (es-BANK) facility equipped with a -25 degrees C cold room. We have already exchanged specimens with many scientific institutions and are also eager to widen our collaboration with other specimen banks. In our survey using the air, water, wildlife and human samples, we found that the major emission sources for the industrial chemicals like polychlorinated biphenyls (PCBs) are in the developed nations while those of organochlorine (OC) pesticides like dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), etc. are located in developing countries. However, significant emission of modern environmental contaminants such as polybrominated diphenyl ethers (PBDEs) also seems to occur predominantly in countries with high economic growth rates. Apart from the modern incinerators and other industrial installations in developed nations, the compounds, like dioxins and related compounds (DRCs), were also found to be released in significant levels from the municipal solid waste dumping sites of developing countries. By evaluating the distribution patterns of various persistent toxic substances (PTSs) in our studies, we could conclude that DRCs and DDTs are regional contaminants, while PCBs, PBDEs, HCHs and hexachlorobenzene (HCB) are global contaminants. We also found that the pollution by PBDEs has been increasing in the last two decades while that of the legacy OCs has been decreasing.