水体中27种有机磷阻燃剂(OPFRs)的检测及风险评价  

Determination and risk assessment of 27 organophosphorus flame retardants(OPFRs)in water

作　　者：韩超 梁存珍[1] 高欲乾 关东 HAN Chao;LIANG Cunzhen;GAO Yuqian;GUAN Dong(Department of Environmental Engineering,Beijing Institute of Petrochemical Technology,Beijing 102617,China)

机构地区：[1]北京石油化工学院环境工程系,北京102617

出　　处：《环境工程学报》2022年第5期1737-1747,共11页Chinese Journal of Environmental Engineering

基　　金：第三次新疆综合科学考察项目资助(2021xjkk1400)。

摘　　要：有机磷阻燃剂(organophosphorus flame retardants,OPFRs)具有致畸、致癌、致突变风险以及神经毒性作用。为了更好地研究其存在水平和健康风险,建立了固相萃取与高效液相色谱-串联质谱仪和气相色谱-质谱联用仪检测水体中27种OPFRs的分析方法,并对OPFRs进行了健康风险评价。20种OPFRs采用MCX固相萃取柱预处理和LC-MS/MS进行检测,以甲醇和含10 mmol·L^(−1)的甲酸水溶液作为流动相进行梯度洗脱,7种OPFRs采用HLB串联Envi-18固相萃取柱进行预处理并利用GC-MS进行检测。检测结果表明,27种OPFRs的检出限为0.02~2.53 ng·L^(−1);定量限为0.06~8.43 ng·L^(−1);回收率为65.82%~108.48%。2021年4月份,采集北京市潮白河地表水和地下水8个水样并检测其OPFRs。实测结果表明:除磷酸三(2-异丙基苯)酯、磷酸异癸基二苯酯、磷酸叔丁基苯二苯酯、磷酸二苄酯外,其余23种OPFRs均有不同程度检出,质量浓度为0~973.17 ng·L^(−1);磷酸三(2-乙基己基)酯、磷酸三乙酯、磷酸三丙酯、磷酸三异丙酯含量相对较高,分别高达973.17、459.90、315.47、298.41 ng·L^(−1)。采用USEPA模型对水样中的OPFRs进行了健康风险评价,13种OPFRs的非致癌风险值为0~6.17×10^(−4),4种OPFRs致癌风险值为1.37×10^(−9)~1.07×10^(−7);在高暴露条件下,OPFRs的非致癌风险值为1.61×10^(−5)~6.17×10^(−4),致癌风险值为1.00×10^(−8)~1.07×10^(−7),均低于风险阈值。上述结果说明,水体中OPFRs产生的健康风险处于较低水平。此次采集的潮白河地表水和地下水水中OPFRs的致癌风险和非致癌风险均处于较低水平。本研究结果可为地表水和地下水水体中OPFRs的检测及风险评价提供参考。Organophosphorus flame retardants(OPFRs)have been demonstrated to be teratogenic,carcinogenic,mutagenic and neurotoxic.In order to better study its existing level and health risks,the analytical methods with solid-phase extraction(SPE)pretreatment followed by liquid chromatography-tandem mass spectrometry(HPLC-MS/MS)and gas chromatography-mass spectrometry(GC-MS)were developed to determine 27 OPFRs in the surface and ground water,and their health risk assessment was performed.Twenty OPFRs were determined by MCX cartridge pretreatment coupled by LC-MS/MS method,and gradient elution was performed using methanol and 10 mmol·L^(−1) formic acid as the mobile phases in the positive mode.Seven OPFRs were determined by GC-MS method with HLB and Envi-18 double cartridge pretreatment.The results showed that the detection limit(LODs),quantitation limit(LOQs)and recoveries for the 27 OPFRs were 0.02~2.53 ng·L^(−1),0.06~8.43 ng·L^(−1),and 65.82%~108.48%,respectively.In April 2021,eight samples from the surface and ground water in Chaobai River,Beijing were collected,and the concentrations of 27 OPFRs in these samples were analyzed.in which only 4 kinds of OPFRs,namely Tri-(2-isopropyl phenyl)phosphate(TIPPP),Isodecyl diphenyl phosphate(IDPP),Tertbutyl phenyl diphenyl phosphate(BPDP)and Dibenzyl phosphate(DBPP)were undetectable,the rest of 23 OPFRs was detected with the concentration range of 0~973.17 ng·L^(−1),and relative high concentrations for Tris(2-ethylhexyl)phosphate(TEHP),Tri-ethyl phosphate(TEP),Tri-propyl phosphate(TnPP),Tri-isopropyl phosphate(TiPP)were 973.17,459.90,315.47,298.41 ng·L^(−1),respectively.The health risks posed by OPFRs in Chaobai River water environment were evaluated using the USEPA health risk assessment model.The non-carcinogenic risk values of 13 OPFRs were in the range of 0~6.17×10^(−4),whereas the carcinogenic risk values of 4 OPFRs were in the range of 1.37×10^(−9)~1.07×10^(−7).At the high exposure concentrations,the non-carcinogenic risk values of the above 13 OPFRs w

关 键 词：有机磷阻燃剂(OPFRs) 高效液相色谱-串联质谱仪 气相色谱-质谱联用仪 固相萃取 风险评价 

分 类 号：X703[环境科学与工程—环境工程]