Simultaneous Determination of Bisphenol A and 9 Alkylphenols in Environmental Water by Gas Chromatography-Mass Spectrometry with Solid Phase Extraction and Derivatization
摘 要
提出了固相萃取-衍生化-气相色谱-质谱法同时测定环境水中双酚A (BPA)和9种C4~C9烷基酚类化合物(APs,包括4-叔丁基苯酚、4-丁基苯酚、4-戊基苯酚、4-己基苯酚、4-叔辛基苯酚、4-庚基苯酚、壬基酚、4-辛基苯酚和4-壬基苯酚)含量的方法。取500 mL水样,用50%(体积分数)盐酸溶液调节pH小于2,以50 mL·min-1速率通过以苯乙烯/二乙烯苯聚合物为吸附剂的SDB-XC固相萃取膜,用5 mL丙酮和10 mL二氯甲烷洗脱。收集洗脱液,加入1 mL正己烷,经10 g无水硫酸钠脱水,用旋转蒸发仪浓缩至约0.5 mL后转移至1 mL容量瓶中。用少量二氯甲烷洗涤浓缩瓶,将洗涤液合并至容量瓶中,再依次加入100 μL内标混合溶液和100 μL衍生试剂,用二氯甲烷定容至1 mL,室温衍生1 h。上述溶液中各目标物在气相色谱仪中以程序升温和程序升压方式分离,在质谱仪中以选择离子监测模式测定,内标法定量。结果显示:BPA和9种APs标准曲线的线性范围为5.000~500.0 μg·L-1,检出限为0.002~0.006 μg·L-1;各目标物在空白加标水样中测定值的相对标准偏差(n=6)为1.2%~15%;方法用于实际地表水、生活污水和工业废水分析,均检出壬基酚和BPA,地表水和生活污水中还检出4-叔辛基苯酚,检出量为0.005~0.657 μg·L-1,其余APs未检出,实际样品中BPA和9种APs的加标回收率为73.4%~125%。
Abstract
A method for the simultaneous determination of bisphenol A (BPA) and 9 C4-C9 alkylphenols (APs, including 4-tert-butylphenol, 4-n-butylphenol, 4-n-pentylphenol, 4-n-hexylphenol, 4-tert-octylphenol, 4-n-heptylphenol, nonylphenol, 4-n-octylphenol and 4-n-nonylphenol) in environmental water by gas chromatography-mass spectrometry with solid phase extraction and derivatization was proposed. Water sample (500 mL) was adjusted pH to less than 2 with 50%(φ) hydrochloric acid solution, passed through solid phase extraction membrane with styrene/divinylbenzene polymer as adsorbent at the rate of 50 mL·min-1, and eluted with 5 mL of acetone and 10 mL of dichloromethane. The eluate was collected, and 1 mL of n-hexane was added. The mixture was dehydrated with 10 g of anhydrous sodium sulfate, and concentrated to about 0.5 mL by rotary evaporator. The concentrated solution was transferred to 1 mL-volumetric flask. The concentration bottle was washed with a small amount of dichloromethane, and the washing liquid was combined into the volumetric flask. Then 100 μL of internal standard mixed solution and 100 μL of derivative reagent were added successively, and the volume was made up to 1 mL with dichloromethane. The targets were derived at room temperature for 1 h. The targets in the above solution were separated by gas chromatograph with programmed temperature and programmed pressure, determined by mass spectrometer with selective ion monitoring mode, and quantified by internal standard method. As shown by the results, the linear ranges of standard curves of BPA and 9 APs were 5.000-500.0 μg·L-1, with detection limits in the range of 0.002-0.006 μg·L-1. RSDs (n=6) of the determined values of the targets in the blank water samples were in the range of 1.2%-15%. This method was applied to the analysis of surface water, sanitary sewage and industrial wastewater, in which nonylphenol and BPA were detected, and 4-tert-octylphenol was detected in the surface water and sanitary sewage, with detection amounts in the range of 0.005-0.657 μg·L-1. The other APs were not detected, and the spiked recoveries of BPA and 9 APs in the actual samples were in the range of 73.4%-125%.
中图分类号 O657.63 X833 DOI 10.11973/lhjy-hx202210011
所属栏目 工作简报
基金项目 国家环境保护标准制修订项目(2014-31);东营市科技发展指导计划项目(2021ZD48)
收稿日期 2021/3/26
修改稿日期
网络出版日期
作者单位点击查看
备注周同娜,高级工程师,博士,从事环境监测技术工作
引用该论文: ZHOU Tongna,YIN Hailiang. Simultaneous Determination of Bisphenol A and 9 Alkylphenols in Environmental Water by Gas Chromatography-Mass Spectrometry with Solid Phase Extraction and Derivatization[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2022, 58(10): 1182~1188
周同娜,尹海亮. 固相萃取-衍生化-气相色谱-质谱法同时测定环境水中双酚A和9种烷基酚类化合物的含量[J]. 理化检验-化学分册, 2022, 58(10): 1182~1188
共有人对该论文发表了看法,其中:
人认为该论文很差
人认为该论文较差
人认为该论文一般
人认为该论文较好
人认为该论文很好
参考文献
【1】马强,白桦,王超,等.液相色谱-串联质谱法同时测定纺织品和食品包装材料中的壬基酚、辛基酚和双酚A[J].分析化学, 2010,38(2):197-201.
【2】曹杰,和佳鸳,易承学,等.超高效液相色谱-串联质谱法同时测定食品中双酚A和双酚S[J].理化检验-化学分册, 2018,54(5):573-578.
【3】ZHANG Z W, LI X W, DING S Y, et al. Multiresidue analysis of sulfonamides, quinolones, and tetracyclines in animal tissues by ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Food Chemistry, 2016,204:252-262.
【4】王浩,赵丽,杨红梅,等.液相色谱-串联质谱法测定牛奶中35种四环素类、磺胺类、青霉素类、大环内酯类、氯霉素类抗生素残留[J].色谱, 2015,33(9):995-1001.
【5】张勋,吴连鹏,李玲,等.液相色谱-串联质谱法测定进出口多种食用活动物体液及肉中四环素类药物残留量[J].化学试剂, 2016,38(12):1178-1182.
【6】陈小燕,牛玉玲,朱敏,等.固相萃取-高效液相色谱法测定牛奶中四环素类抗生素[J].中国抗生素杂志,2017,42(2):129-133.
【7】Standard test method for determination of nonylphenol, bisphenol A, p-tert-octylphenol, nonylphenol monoethoxylate and nonylphenol diethoxylate in environmental waters by gas chromatography mass spectrometry:ASTM D7065-2017[S/OL].[2021-03-20]. https://www.astm.org/d7065-17.html.
【8】Standard test method for determination of bisphenol A in environmental waters by liquid chromatography/tandem mass spectrometry:ASTM D7574-2016[S/OL].[2021-03-20]. https://www.astm.org/d7574-16.html.
【9】Water quality-Determination of selected alkylphenols-Part 2:Gas chromatographic-mass spectrometric determination of alkylphenols, their ethoxylates and bisphenol A in non-filtered samples following solid-phase extraction and derivatisation:ISO 18857-2:2009[S/OL].[2021-03-20]. https://www.iso.org/standard/34673.html.
【10】Testing method for bisphenol A in industrial water and waste water:JIS K 0450-10-10:2006[S/OL].[2021-03-20]. https://webdesk.jsa.or.jp/preview/pre_jis_k_00450_010_010_2006_e_ed10_i4.pdf.
【11】SELVARAJ K K, SHANMUGAM G, SAMPATH S, et al. GC-MS determination of bisphenol A and alkylphenol ethoxylates in river water from India and their ecotoxicological risk assessment[J]. Ecotoxicology and Environmental Safety, 2014,99:13-20.
【12】SHEN G, YU G, CAI Z X, et al. Development of an analytical method to determine phenolic endocrine disrupting chemicals in sewage and sludge by GC/MS[J]. Chinese Science Bulletin, 2005,50(23):2681-2687.
【13】SANTHI V A, HAIRIN T, MUSTAFA A M. Simultaneous determination of organochlorine pesticides and bisphenol A in edible marine biota by GC-MS[J]. Chemosphere, 2012,86(10):1066-1071.
【14】DONG C D, CHEN C W, CHEN C F. Seasonal and spatial distribution of 4-nonylphenol and 4-tert-octylphenol in the sediment of Kaohsiung Harbor, Taiwan[J]. Chemosphere, 2015,134:588-597.
【15】王世玉,刘菲,刘玉龙,等.气相色谱-质谱法检测地下水中12种对壬基酚同分异构体[J].分析化学, 2013,41(11):1699-1703.
【16】MEZZATESTA E, PERRAUD A, VIEILLESCAZES C, et al. Analysis of balms taken from Egyptian human mummies using solid-phase extraction and gas chromatography-mass spectrometry[J]. Journal of Separation Science, 2021,44(4):850-859.
【17】杨欢春,魏秋宁,安晶晶,等.固相萃取-气相色谱-质谱法测定饮用水中百菌清含量不确定度评定[J].环境卫生学杂志, 2020,10(3):317-322.
【18】TAN D Q, JIN J, WANG L X, et al. Quantification of bisphenol A and its selected analogs in serum using pre-column derivatization with high-performance liquid chromatography and tandem mass spectrometry[J]. Journal of Separation Science, 2019,42(5):991-998.
【2】曹杰,和佳鸳,易承学,等.超高效液相色谱-串联质谱法同时测定食品中双酚A和双酚S[J].理化检验-化学分册, 2018,54(5):573-578.
【3】ZHANG Z W, LI X W, DING S Y, et al. Multiresidue analysis of sulfonamides, quinolones, and tetracyclines in animal tissues by ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Food Chemistry, 2016,204:252-262.
【4】王浩,赵丽,杨红梅,等.液相色谱-串联质谱法测定牛奶中35种四环素类、磺胺类、青霉素类、大环内酯类、氯霉素类抗生素残留[J].色谱, 2015,33(9):995-1001.
【5】张勋,吴连鹏,李玲,等.液相色谱-串联质谱法测定进出口多种食用活动物体液及肉中四环素类药物残留量[J].化学试剂, 2016,38(12):1178-1182.
【6】陈小燕,牛玉玲,朱敏,等.固相萃取-高效液相色谱法测定牛奶中四环素类抗生素[J].中国抗生素杂志,2017,42(2):129-133.
【7】Standard test method for determination of nonylphenol, bisphenol A, p-tert-octylphenol, nonylphenol monoethoxylate and nonylphenol diethoxylate in environmental waters by gas chromatography mass spectrometry:ASTM D7065-2017[S/OL].[2021-03-20]. https://www.astm.org/d7065-17.html.
【8】Standard test method for determination of bisphenol A in environmental waters by liquid chromatography/tandem mass spectrometry:ASTM D7574-2016[S/OL].[2021-03-20]. https://www.astm.org/d7574-16.html.
【9】Water quality-Determination of selected alkylphenols-Part 2:Gas chromatographic-mass spectrometric determination of alkylphenols, their ethoxylates and bisphenol A in non-filtered samples following solid-phase extraction and derivatisation:ISO 18857-2:2009[S/OL].[2021-03-20]. https://www.iso.org/standard/34673.html.
【10】Testing method for bisphenol A in industrial water and waste water:JIS K 0450-10-10:2006[S/OL].[2021-03-20]. https://webdesk.jsa.or.jp/preview/pre_jis_k_00450_010_010_2006_e_ed10_i4.pdf.
【11】SELVARAJ K K, SHANMUGAM G, SAMPATH S, et al. GC-MS determination of bisphenol A and alkylphenol ethoxylates in river water from India and their ecotoxicological risk assessment[J]. Ecotoxicology and Environmental Safety, 2014,99:13-20.
【12】SHEN G, YU G, CAI Z X, et al. Development of an analytical method to determine phenolic endocrine disrupting chemicals in sewage and sludge by GC/MS[J]. Chinese Science Bulletin, 2005,50(23):2681-2687.
【13】SANTHI V A, HAIRIN T, MUSTAFA A M. Simultaneous determination of organochlorine pesticides and bisphenol A in edible marine biota by GC-MS[J]. Chemosphere, 2012,86(10):1066-1071.
【14】DONG C D, CHEN C W, CHEN C F. Seasonal and spatial distribution of 4-nonylphenol and 4-tert-octylphenol in the sediment of Kaohsiung Harbor, Taiwan[J]. Chemosphere, 2015,134:588-597.
【15】王世玉,刘菲,刘玉龙,等.气相色谱-质谱法检测地下水中12种对壬基酚同分异构体[J].分析化学, 2013,41(11):1699-1703.
【16】MEZZATESTA E, PERRAUD A, VIEILLESCAZES C, et al. Analysis of balms taken from Egyptian human mummies using solid-phase extraction and gas chromatography-mass spectrometry[J]. Journal of Separation Science, 2021,44(4):850-859.
【17】杨欢春,魏秋宁,安晶晶,等.固相萃取-气相色谱-质谱法测定饮用水中百菌清含量不确定度评定[J].环境卫生学杂志, 2020,10(3):317-322.
【18】TAN D Q, JIN J, WANG L X, et al. Quantification of bisphenol A and its selected analogs in serum using pre-column derivatization with high-performance liquid chromatography and tandem mass spectrometry[J]. Journal of Separation Science, 2019,42(5):991-998.
相关信息