高效液相色谱-串联质谱法测定食品用纸制品中氯酚类化合物残留量
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摘要
目的建立高效液相色谱-串联质谱(HPLC-MS/MS)同时测定食品用纸制品中2,4-二氯酚、2,4,6-三氯酚、2,3,4,6-四氯酚、五氯酚4种氯酚类化合物残留量的检测方法。方法样品经0.5%甲酸甲醇超声提取后,混合型阴离子交换固相萃取柱净化,以HSS T3色谱柱(2.1 mm×100 mm,1.8μm)分离待测物,采用电喷雾离子化,负离子扫描和多反应监测模式(MRM)检测,以保留时间和特征离子对定性,内标法定量。结果 4种待测物在5～100μg/L浓度范围内线性关系良好,相关系数(r)均大于0.99;方法检出限为0.01～0.02 mg/kg,定量限为0.03～0.06 mg/kg;4种物质的添加水平为0.03～0.14 mg/kg时,平均回收率为80.1%～110.4%,相对标准偏差为3.2%～9.9%(n=6)。结论该方法样品前处理简单,准确性、精密度和灵敏度均较好,适用于食品用纸制品中4种氯酚类化合物残留量的检测。
Objective To establish a method for simultaneous determination of the residues of four chlorophenols compounds(2,4-dichlorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, pentachlorophenol) in food paper products by high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS). Methods The samples were extracted by ultrasonic 0.5% formic acid in methanol and purified by mixed anion exchange solid phase column. The target compounds were separated on HSS T3 column(2.1 mm×100 mm,1.8 μm), and detected under negative ionization and multiple reaction monitoring(MRM) mode. Four compounds were identified by retention time and the ratio of characteristic ions, and were quantified by using the internal standard method. Results The calibration curves of the four compounds were linear within the range from 5 to 100 μg/L. The correlation coefficients of the four compounds were above 0.99.The limits of detection(LOD)were in the range of 0.01-0.02 mg/kg,and the limits of quantification(LOQ)were in the range of 0.03-0.06 mg/kg. The average recoveries of paper samples at spiked levels from 0.03 to 0.14 mg/kg were between 80.1% and 110.4%, and the relative standard deviations(n=6) were between 3.2% and 9.9%. Conclusion The pretreatment of sample was simple. The method was accurate and sensitive, which could be used to determine chlorophenols compounds in food paper products.
Objective To establish a method for simultaneous determination of the residues of four chlorophenols compounds(2,4-dichlorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, pentachlorophenol) in food paper products by high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS). Methods The samples were extracted by ultrasonic 0.5% formic acid in methanol and purified by mixed anion exchange solid phase column. The target compounds were separated on HSS T3 column(2.1 mm×100 mm,1.8 μm), and detected under negative ionization and multiple reaction monitoring(MRM) mode. Four compounds were identified by retention time and the ratio of characteristic ions, and were quantified by using the internal standard method. Results The calibration curves of the four compounds were linear within the range from 5 to 100 μg/L. The correlation coefficients of the four compounds were above 0.99.The limits of detection(LOD)were in the range of 0.01-0.02 mg/kg,and the limits of quantification(LOQ)were in the range of 0.03-0.06 mg/kg. The average recoveries of paper samples at spiked levels from 0.03 to 0.14 mg/kg were between 80.1% and 110.4%, and the relative standard deviations(n=6) were between 3.2% and 9.9%. Conclusion The pretreatment of sample was simple. The method was accurate and sensitive, which could be used to determine chlorophenols compounds in food paper products.
引文
[1] 胡长鹰.食品包装材料及其安全性研究动态[J].食品安全质量检测学报,2018,9(12):3025-3026.
[2] 司晓喜,朱瑞芝,刘志华,等.超高效液相色谱-串联质谱法快速测定纸质包装材料中多类防腐剂[J].分析试验室,2015,34(8):984-988.
[3] 郭耀广,关杰,顾卫星.氯酚类化合物的污染现状及去除方法研究进展[J].上海第二工业大学学报,2016,33(3):198-207.
[4] 谢晟瑜,张佳丽,沈昊宇,等.氯酚类污染物的性质、危害及其检测方法研究进展[J].分析试验室,2017,36(11):1351-1355.
[5] HONDA M,KANNAN K.Biomonitoring of chlorophenols in human urine from several Asian countries,Greece and the United States[J].Environmental Pollution,2018,232(9):487-493.
[6] LEWANDOWSKI K,CIESLIKIEWICZ W,KOBUSINSKA M E,et al.Sorption of pentachlorophenol (PCP) in the marine bottom sediments-batch sorption experiment at varying pressure[J].Environmental Science and Pollution Research,2018,25(1/2):10799-10807.
[7] United Nations Environment.SC-7/13:List of pentachlorophenol and its salts and esters[Z/OL].Stockholm Convention on Persistent Organic Pollutants,2015.[2019-03-08].http://www.pops.int/TheConvention/ThePOPs/TheNewPOPs/tabid/2511/Default.aspx.
[8] Council of Europe Committee.ResAP (2002) 1 No.1 technical document list of substances to be used with the food contact paper and board materials and products [S].2002.
[9] 朱峰,涂貌贞,王丽莉,等.高效液相色谱法同时测定纺织品中10种酚类化合物[J].分析测试学报,2013,32(3):336-340.
[10] 张博,梅勇,邹晓雪,等.顶空固相微萃取-气相色谱法测定尿中五氯酚[J].环境与职业医学,2016,33(12):1187-1190.
[11] 雍宗锋,曹慧,蔡丹丹.全自动固相萃取-内标衍生-气相色谱-串联质谱法测定肉中五氯酚[J].江苏预防医学,2017,28(6):619-625.
[12] 张聪,黄金凤,蔡玮红,等.UPLC-MS/MS法同时测定食品接触纸包装材料中的异噻唑酮类和氯酚类杀菌防腐剂[J].现代食品科技,2015,31(6):303-308.
[13] 王天娇,林勤保,宋欢,等.超高效液相色谱-串联质谱法测定食品包装纸中的酚类化合物[J].分析测试学报,2012,29(12):1153-1157.
[14] 王成云,刘斌斌,林君峰,等.纸和纸制品中含氯酚的快速筛查和确证[J].造纸科学与技术,2017,36(1):70-77.
[15] 中华人民共和国国家卫生和计划生育委员会,中华人民共和国农业部,国家食品药品监督管理总局.食品安全国家标准动物源性食品中五氯酚残留量的测定液相色谱-质谱法:GB 23200.92—2016[S].北京:中国标准出版社,2016.
[16] 杨秋红,程小艳,杨坪,等.固相萃取-高效液相色谱串联质谱同时检测地表水中的2,4-二氯酚、2,4,6-三氯酚和五氯酚[J].分析化学,2011,39(8):1208-1212.
[17] 欧阳培毓,谭建华,汤嘉骏,等.超高效液相色谱-四级杆飞行时间质谱测定沉积物中4种氯酚类物质[J].环境化学,2016,35(7):1486-1492.
[2] 司晓喜,朱瑞芝,刘志华,等.超高效液相色谱-串联质谱法快速测定纸质包装材料中多类防腐剂[J].分析试验室,2015,34(8):984-988.
[3] 郭耀广,关杰,顾卫星.氯酚类化合物的污染现状及去除方法研究进展[J].上海第二工业大学学报,2016,33(3):198-207.
[4] 谢晟瑜,张佳丽,沈昊宇,等.氯酚类污染物的性质、危害及其检测方法研究进展[J].分析试验室,2017,36(11):1351-1355.
[5] HONDA M,KANNAN K.Biomonitoring of chlorophenols in human urine from several Asian countries,Greece and the United States[J].Environmental Pollution,2018,232(9):487-493.
[6] LEWANDOWSKI K,CIESLIKIEWICZ W,KOBUSINSKA M E,et al.Sorption of pentachlorophenol (PCP) in the marine bottom sediments-batch sorption experiment at varying pressure[J].Environmental Science and Pollution Research,2018,25(1/2):10799-10807.
[7] United Nations Environment.SC-7/13:List of pentachlorophenol and its salts and esters[Z/OL].Stockholm Convention on Persistent Organic Pollutants,2015.[2019-03-08].http://www.pops.int/TheConvention/ThePOPs/TheNewPOPs/tabid/2511/Default.aspx.
[8] Council of Europe Committee.ResAP (2002) 1 No.1 technical document list of substances to be used with the food contact paper and board materials and products [S].2002.
[9] 朱峰,涂貌贞,王丽莉,等.高效液相色谱法同时测定纺织品中10种酚类化合物[J].分析测试学报,2013,32(3):336-340.
[10] 张博,梅勇,邹晓雪,等.顶空固相微萃取-气相色谱法测定尿中五氯酚[J].环境与职业医学,2016,33(12):1187-1190.
[11] 雍宗锋,曹慧,蔡丹丹.全自动固相萃取-内标衍生-气相色谱-串联质谱法测定肉中五氯酚[J].江苏预防医学,2017,28(6):619-625.
[12] 张聪,黄金凤,蔡玮红,等.UPLC-MS/MS法同时测定食品接触纸包装材料中的异噻唑酮类和氯酚类杀菌防腐剂[J].现代食品科技,2015,31(6):303-308.
[13] 王天娇,林勤保,宋欢,等.超高效液相色谱-串联质谱法测定食品包装纸中的酚类化合物[J].分析测试学报,2012,29(12):1153-1157.
[14] 王成云,刘斌斌,林君峰,等.纸和纸制品中含氯酚的快速筛查和确证[J].造纸科学与技术,2017,36(1):70-77.
[15] 中华人民共和国国家卫生和计划生育委员会,中华人民共和国农业部,国家食品药品监督管理总局.食品安全国家标准动物源性食品中五氯酚残留量的测定液相色谱-质谱法:GB 23200.92—2016[S].北京:中国标准出版社,2016.
[16] 杨秋红,程小艳,杨坪,等.固相萃取-高效液相色谱串联质谱同时检测地表水中的2,4-二氯酚、2,4,6-三氯酚和五氯酚[J].分析化学,2011,39(8):1208-1212.
[17] 欧阳培毓,谭建华,汤嘉骏,等.超高效液相色谱-四级杆飞行时间质谱测定沉积物中4种氯酚类物质[J].环境化学,2016,35(7):1486-1492.