分散固相萃取/气相色谱-三重四极杆串联质谱法检测纸张中的20种芳香胺
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摘要
建立了纸张中的20种芳香胺的分散固相萃取/气相色谱-三重四极杆串联质谱分析方法。纸张中的偶氮染料于(70±2)℃经预处理后还原为芳香胺,向反应后的悬浮液中先加入4 mL 10 mol/L氢氧化钠溶液,将pH值由弱酸性调至碱性,再加入0.5 mL的3内标(氘代萘、2,4,5-三氯苯胺和氘代蒽)工作溶液、10 mL的叔丁基甲醚,最后加入15 g无水硫酸钠除水,振摇40 min萃取芳香胺。萃取液经分散固相萃取试剂盒(d-SPE)进一步净化、离心后,取上层清液以气相色谱-三重四极杆串联质谱法(GC-MS/MS),在多反应离子监测(MRM)模式下检测,内标法定量。目标物在各自浓度范围内线性关系良好(r~2>0.99),在10、20、50 ng/mL 3个加标水平下的回收率为80.7%～128%,相对标准偏差(RSDs)为0.79%～6.5%,检出限(LOD)为0.05～2.1 ng/mL,定量下限(LOQ)为0.18～5.5 ng/mL。该方法简便快捷,灵敏度高,可用于纸张中芳香胺的快速检测。
A gas chromatography-triple quadrupole tandem mass spectrometry(GC-MS/MS) with dispersive solid phase extraction(d-SPE) was developed for the determination of azo colorants in paper.The azo colorants were reduced as aromatic amines after pretreatment.Sequentially,4 mL 10 mol/L sodium hydroxide solution,0.5 mL three internal standards(naphthalene-D_8,2,4,5-trichloro-aniline and anthracene-D_(10))working solution,10 mL tert-butyl methyl ether and 15 g anhydrous sodium sulfate were added into the suspension to adjust the pH value from faintly acid to alkaline and absorb water.The aromatic amines were extracted with 10 mL tert-butyl methyl ether via 40 min thorough oscillation.The extract was further purified with d-SPE kits.After centrifugation,the supernatant was determined by GC-MS/MS in highly sensitive and selective multiple reaction monitoring mode(MRM),and quantified by internal standard method.There existed good linear relationships for the target compounds in respective concentration ranges,with their correlation coefficients(r~2) larger than 0.99.The recoveries at three spiked levels of 10,20 and 50 ng/mL were between 80.7% and 128%,with the relative standard deviations(RSDs) of 0.79%-6.5%.The limits of detection(LODs) and limits of quantification(LOQs) were in the ranges of 0.05-2.1 ng/mL and 0.18-5.5 ng/mL,respectively.Results showed that the method was simple,rapid and sensitive,was applicable for the rapid detection of aromatic amines in paper.
A gas chromatography-triple quadrupole tandem mass spectrometry(GC-MS/MS) with dispersive solid phase extraction(d-SPE) was developed for the determination of azo colorants in paper.The azo colorants were reduced as aromatic amines after pretreatment.Sequentially,4 mL 10 mol/L sodium hydroxide solution,0.5 mL three internal standards(naphthalene-D_8,2,4,5-trichloro-aniline and anthracene-D_(10))working solution,10 mL tert-butyl methyl ether and 15 g anhydrous sodium sulfate were added into the suspension to adjust the pH value from faintly acid to alkaline and absorb water.The aromatic amines were extracted with 10 mL tert-butyl methyl ether via 40 min thorough oscillation.The extract was further purified with d-SPE kits.After centrifugation,the supernatant was determined by GC-MS/MS in highly sensitive and selective multiple reaction monitoring mode(MRM),and quantified by internal standard method.There existed good linear relationships for the target compounds in respective concentration ranges,with their correlation coefficients(r~2) larger than 0.99.The recoveries at three spiked levels of 10,20 and 50 ng/mL were between 80.7% and 128%,with the relative standard deviations(RSDs) of 0.79%-6.5%.The limits of detection(LODs) and limits of quantification(LOQs) were in the ranges of 0.05-2.1 ng/mL and 0.18-5.5 ng/mL,respectively.Results showed that the method was simple,rapid and sensitive,was applicable for the rapid detection of aromatic amines in paper.
引文
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[28] GB 19601-2013.Limit and Determination of 23 Harmful Aromatic Amines in Dye Products.National Standards of the People's Republic of China(染料产品中23种有害芳香胺的限量及测定.中华人民共和国国家标准).2013.
[29] GB 18401-2010.National General Safety Technical Code for Textile Products.National Standards of the People's Republic of China(国家纺织产品基本安全技术规范.中华人民共和国国家标准).2010.
[2] Qian H F,Wang A,Jiang H.China Fiber Inspection(钱霍飞,王安,蒋红.中国纤检),2013,(7):85-88.
[3] EN 14362-1:2012.Textiles-Methods for Determination of Certain Aromatic Amines Derived From Azo Colorants-Part 1:Detection of the Use of Certain Azo Colorants Accessible with and without Extracting the Fibres.European Committee for Standardization.
[4] EN 14362-3:2012.Textiles-Methods for Determination of Certain Aromatic Amines Derived From Azo Colorants — Part 3:Detection of the Use of Certain Azo Colorants which may Release 4-Aminoazobenzene.European Committee for Standardization.
[5] GB/T 19942-2005.Leather and Fur-Chemical Tests-Determination of Banned Azo Colourants.National Standards of the People's Republic of China(皮革和毛皮化学试验禁用偶氮染料的测定.中华人民共和国国家标准).2005.
[6] GB/T 17592-2011.Textiles-Determination of the Banned Azo Colourants.National Standards of the People's Republic of China(纺织品禁用偶氮染料的测定.中华人民共和国国家标准).2011.
[7] GB/T 23344-2009.Textiles-Determination of 4-aminoazobenzene.National Standards of the People's Republic of China(纺织品 4-氨基偶氮苯的测定.中华人民共和国国家标准).2009.
[8] Liu P,Xu Y,Guo J.J.Anal.Sci.(刘鹏,徐烨,郭静.分析科学学报),2011,27(4):451-454.
[9] Xiao D Q,Chen S H,Zhu X Y,Liu Z M,Ma M,Cao G Z.J.Instrum.Anal.(肖道清,陈少鸿,朱晓艳,刘在美,马明,曹国洲.分析测试学报),2009,28(10):1155-1159.
[10] Zhao Y,Wang Y F.Chem.Anal.Meterage(赵洋,王元凤.化学分析计量),2009,18(5):14-18.
[11] Hong X Y,Wen Y Y,Lin F,Liang J,Gong Z B.J.Instrum.Anal.(洪小燕,温裕云,林芳,梁婧,弓振斌.分析测试学报),2010,29(1):31-34.
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[13] Wang C Y,Yang Z J,Xie T T,Shen Y L,Zhang E S,Liu C M.China Pulp & Paper(王成云,杨左军,谢堂堂,沈雅蕾,张恩颂,刘彩明.中国造纸),2011,30(11):7-12.
[14] Wang C Y,Chu N Q,Xie T T,Shen Y L,Zhang E S,Feng Z R,Liu C M.China Fiber Inspection(王成云,褚乃清,谢堂堂,沈雅蕾,张恩颂,冯泽锐,刘彩明.中国纤检),2011,(12):53-57.
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[16] Niu Z Y,Luo X,Ye X W,Wang H H,Li J Y.Chin.J.Chromatogr.(牛增元,罗忻,叶曦雯,王卉卉,李晶莹.色谱),2014,32(1):34-39.
[17] Wen Y Y,Ou Y,He M C,Gong Z B.Chin.J.Chromatogr.(温裕云,欧延,何明超,弓振斌.色谱),2013,31(4):380-385.
[18] Zhong X L,Lu J Y,Hu Y Q.China Fiber Inspection(钟雪莲,陆佳英,胡燕琴.中国纤检),2015,(24):68-71.
[19] China Tobacco Quality Supervision and Inspection Center.China Patent(国家烟草质量监督检验中心.中国专利),CN201410041729.3.[2014-04-30].
[20] Zhang T G,Deng Q X,Lin Y,Liu Z C,Xu H C,Xie W.China Pulp & Paper(张廷贵,邓其馨,林艳,刘泽春,许寒春,谢卫.中国造纸),2015,34(4):43-47.
[21] Si X X,Zhang R,Zhang F M,Liu Z H,He P,Shen Q P,Su Z B,Zhu R Z.J.Instrum.Anal.(司晓喜,张蓉,张凤梅,刘志华,何沛,申钦鹏,苏钟璧,朱瑞芝.分析测试学报),2015,34(11):1240-1245.
[22] Liu H,Zhou F,Li Y E.Env.Sci.Manage.(刘浩,周芳,李月娥.环境科学与管理),2008,33(5):137-139,185.
[23] Xu P J,Gao X S,Tao B,Zhang H Y,Jiang S R.Chin.J.Anal.Chem.(许鹏军,高晓莎,陶晡,张红艳,江树人.分析化学),2008,36(11):1515-1520.
[24] YC 171-2009.Tipping Paper for Cigarette.Chinas Tobacco Industrial Criteria of the People's Republic of China(烟用接装纸.中华人民共和国烟草行业标准).2009.
[25] YC 264-2008.Inner Liner for Cigarette.Chinas Tobacco Industrial Criteria of the People's Republic of China(烟用内衬纸.中华人民共和国烟草行业标准).2008.
[26] YC/T 207-2006.Determination of Volatile Organic Compounds in Cigarette Carton and Packet Packaging Papers – Headspace – Gas chromatography.Chinas Tobacco Industrial Criteria of the People's Republic of China(卷烟条与盒包装纸中挥发性有机化合物的测定顶空-气相色谱法.中华人民共和国烟草行业标准).2006.
[27] Luo H T,Huang X L,Wu H Q,Zhang Q Y,Zhu Z X,Huang F,Lin X S,Ma Y F,Deng X.Chin.J.Chromatogr.(罗辉泰,黄晓兰,吴惠勤,张秋炎,朱志鑫,黄芳,林晓珊,马叶芬,邓欣.色谱),2017,35(8):816-825.
[28] GB 19601-2013.Limit and Determination of 23 Harmful Aromatic Amines in Dye Products.National Standards of the People's Republic of China(染料产品中23种有害芳香胺的限量及测定.中华人民共和国国家标准).2013.
[29] GB 18401-2010.National General Safety Technical Code for Textile Products.National Standards of the People's Republic of China(国家纺织产品基本安全技术规范.中华人民共和国国家标准).2010.