气相色谱法同时测定贝类中15种持久性有机污染物残留量
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摘要
建立了气相色谱-电子捕获检测器(GC-ECD)同时测定贝类中15种持久性有机污染物(POPs)(包括8种有机氯农药和7种多氯联苯)残留的分析方法。采用丙酮超声提取样品中的有机氯农药和多氯联苯,提取液经液液萃取、凝胶渗透色谱和固相萃取(LLE-GPC-SPE)联合净化,采用外标法定量。结果显示,在1.0～100.0μg/L质量浓度范围内,15种持久性有机污染物均呈良好的线性关系,相关系数不小于0.995 0,定量限为1.0～2.0μg/kg,检出限为0.3～0.8μg/kg,回收率在60.1%～111.0%范围内,相对标准偏差小于10%。该方法重现性好,准确度、精密度高,能满足残留分析技术要求,适用于贝类中有机氯农药和多氯联苯的同时测定。将此方法应用于检测蛤蜊、牡蛎和扇贝等贝类样品中将POPs的残留量,检出率最高的是p,p′-dichlorodiphenyl dichloroethylene(p,p′-DDE),其在样品中均有检出。本研究可为进一步深入研究持久性有机污染物对水产品质量安全的影响提供技术支持。
A gas chromatography-electron capture detector(GC-ECD) method was developed for simultaneous determination of 15 persistent organic pollutants(POPs) residues in shellfish. Organochlorine pesticides(OCPs) and polychlorinated biphenyls(PCBs) residues were obtained from samples by ultrasonic extraction with acetone. And then, the extracts were purified by liquid-liquid extraction(LLE), gel permeation chromatography(GPC) and solid phase extraction(SPE) in turn. In addition, external standard method was used for quantitative analysis. The results showed that 15 POPs had a good linear relationship in the mass concentration range of 1.0-100.0 μg/L, and the correlation coefficient was no less than 0.995 0. The limit of quantification was 1.0-2.0 μg/kg, and the detection limit was 0.3-0.8 μg/kg. The recovery rates ranged from 60.1% to 111.0%, and the relative standard deviation was less than 10%. The method has good reproducibility, high accuracy and precision, which can meet the technical requirements of residual analysis and is suitable for simultaneous determination of organochlorine pesticides and polychlorinated biphenyls in shellfish. Therefore, this method was applied to detect 15 POPs in shellfish samples, such as cockroaches, oysters and scallops. The p,p′-DDE was showed the highest positive rate and detected in all samples. The experiment will provide technical support for further in-depth study on the impact of persistent organic pollutants on the quality and safety of aquatic products.
A gas chromatography-electron capture detector(GC-ECD) method was developed for simultaneous determination of 15 persistent organic pollutants(POPs) residues in shellfish. Organochlorine pesticides(OCPs) and polychlorinated biphenyls(PCBs) residues were obtained from samples by ultrasonic extraction with acetone. And then, the extracts were purified by liquid-liquid extraction(LLE), gel permeation chromatography(GPC) and solid phase extraction(SPE) in turn. In addition, external standard method was used for quantitative analysis. The results showed that 15 POPs had a good linear relationship in the mass concentration range of 1.0-100.0 μg/L, and the correlation coefficient was no less than 0.995 0. The limit of quantification was 1.0-2.0 μg/kg, and the detection limit was 0.3-0.8 μg/kg. The recovery rates ranged from 60.1% to 111.0%, and the relative standard deviation was less than 10%. The method has good reproducibility, high accuracy and precision, which can meet the technical requirements of residual analysis and is suitable for simultaneous determination of organochlorine pesticides and polychlorinated biphenyls in shellfish. Therefore, this method was applied to detect 15 POPs in shellfish samples, such as cockroaches, oysters and scallops. The p,p′-DDE was showed the highest positive rate and detected in all samples. The experiment will provide technical support for further in-depth study on the impact of persistent organic pollutants on the quality and safety of aquatic products.
引文
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[22] 邹琴,许均图,陈德斌,等.气相色谱法测定贝类中指示性多氯联苯的优化研究[J].广东化工,2016,43(14):220-222.
[23] 唐健.几种海洋贝类中砷的含量和形态分析及体外生物利用度研究[D].杭州:浙江大学,2006.
[24] Li W,Liu D,Li J,et al.Matrix Solid-Phase Dispersion Combined with GC-MS/MS for the Determination of Organochlorine Pesticides and Polychlorinated Biphenyls in Marketed Seafood[J].Chromatographia,2017,80(5):813-824.
[25] 孙秀梅,胡红美,钟志,等.气相色谱法测定贻贝中的多氯联苯和有机氯农药[J].广州化工,2014,42(14):134-136.
[2] 刘云兴,王国梁.多氯联苯生物降解技术研究进展[J].环境科学与管理,2012,37(12):72-75.
[3] Cetin B.Investigation of PAHs,PCBs and PCNs in soils around a Heavily Industrialized Area in Kocaeli,Turkey:Concentrations,distributions,sources and toxicological effects[J].Sci Total Environ,2016,560/561:160-169.
[4] Wu Y,Wang X,Li Y,et al.Polybrominated diphenyl ethers,organochlorine pesticides,and polycyclic aromatic hydrocarbons in water from the Jiulong River Estuary,China:levels,distributions,influencing factors,and risk assessment[J].Environ Sci Pollut Res,2017,24(10):8933-8945.
[5] 邓力,余轶松.同位素稀释-高分辨气相色谱-高分辨质谱法测定土壤和沉积物中27种有机氯农药[J].理化检验-化学分册,2015,51(7):907-913.
[6] 周涛,韩彬,徐亚岩,等.南中国海海水中有机氯农药和多氯联苯的含量及分布特征[J].岩矿测试,2014,33(1):90-95.
[7] Chiesa L M,Nobile M,Malandra R,et al.Food safety traits of mussels and clams:distribution of PCBs,PBDEs,OCPs,PAHs and PFASs in sample from different areas using HRMS-Orbitrap? and modified QuEChERS extraction followed by GC-MS/MS[J].Food Addit Contam,Part A,2018,35(4):959-971.
[8] 周京花,马慧慧,赵美蓉,等.持久性有机污染物(POPs)生殖毒理研究进展——从实验动物生殖毒性到人类生殖健康风险[J].中国科学:化学,2013,43(3):315-325.
[9] Grindler N M,Allsworth J E,Macones G A,et al.Persistent Organic Pollutants and Early Menopause in U.S.Women[J].PLOS ONE,2015,10(1):e0116057.
[10] Tiemann U.In vivo and in vitro effects of the organochlorine pesticides DDT,TCPM,methoxychlor,and lindane on the female reproductive tract of mammals:a review[J].Reprod Toxicol,2008,25(3):316-326.
[11] 唐子刚.海产品及海水中有机氯农药及多氯联苯的前处理方法及应用研究[D].宁波:宁波大学,2015.
[12] Lee Y J,Jang J S,Yang J H.Potential Health Risks from Persistent Organic Pollutants (POPs) in Marine Ecosystem[J].J Mar Biosci Biotechnol,2016,8(1):10-17.
[13] 黄冬梅,于慧娟,沈晓盛,等.水产品中多氯联苯检测方法的研究[J].食品科学,2008,29(7):359-361.
[14] 曹方方,费金岩,许人骥,等.气相色谱-质谱法测定贝类样品中的有机氯农药[J].中国测试,2017,43(3):53-57.
[15] 胡礼渊,邓集煜,廖和菁,等.分散固相萃取-气相色谱法测定水产品中多氯联苯[J].食品科学,2016,37(14):207-212.
[16] 孙伟红,魏志强,冷凯良,等.气相色谱-串联质谱法测定贝类中指示性多氯联苯[J].分析科学学报,2009,25(6):647-651.
[17] 叶玫,姜琳琳,余颖,等.气相色谱法测定水产品中硫丹及其代谢物残留[J].食品科学,2013,34(10):211-214.
[18] 仝东超.小麦中吡虫啉残留分析方法及残留消解动态研究[D].天津:天津理工大学,2015.
[19] 费勇,杨晓红,张海燕,等.全自动凝胶色谱净化-气相色谱法同时测定淡水鱼类中多氯联苯和有机氯农药等36种残留有机物[J].中国环境监测,2011,27(2):63-68.
[20] 邓巧巧.水产品中有机污染物检测的前处理方法研究与应用[D].烟台:烟台大学,2014.
[21] 许仁杰,蔡春平,丁立平,等.气相色谱法测定水产品有机氯农药和多氯联苯[J].食品工业,2017,38(3):287-292.
[22] 邹琴,许均图,陈德斌,等.气相色谱法测定贝类中指示性多氯联苯的优化研究[J].广东化工,2016,43(14):220-222.
[23] 唐健.几种海洋贝类中砷的含量和形态分析及体外生物利用度研究[D].杭州:浙江大学,2006.
[24] Li W,Liu D,Li J,et al.Matrix Solid-Phase Dispersion Combined with GC-MS/MS for the Determination of Organochlorine Pesticides and Polychlorinated Biphenyls in Marketed Seafood[J].Chromatographia,2017,80(5):813-824.
[25] 孙秀梅,胡红美,钟志,等.气相色谱法测定贻贝中的多氯联苯和有机氯农药[J].广州化工,2014,42(14):134-136.