超高效液相色谱-串联质谱联法测定茶园用农药制剂中烷基酚聚氧乙烯醚含量
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摘要
建立了超高效液相色谱-串联质谱法测定茶园用农药制剂中烷基酚聚氧乙烯醚(APEOs)的检测方法。APEOs经Waters-BEH C_(18)色谱柱分离,电喷雾正离子源(ESI+)条件下多反应监测模式(MRM)测定,外标法定量。APEOs(n=3～20)在水剂、水乳剂、悬浮剂、乳油、颗粒剂和可湿性粉剂中的基质标准曲线在0.047～1503.6 mg·kg~(-1)范围内线性关系良好,相关系数(r)为0.996 1～0.999 9;在0.5～1 503.6 mg·kg~(-1)添加范围内,添加回收率为83.8%～120.4%,相对标准偏差(RSD)为0.6%～13.7%,LOQ为0.5～150.4 mg·kg~(-1)。测定的51种茶园农药制剂中,辛基酚聚氧乙烯醚(OPEOs)百分数含量均低于0.5%;壬基酚聚氧乙烯醚(NPEOs)质量分数为ND～32.1%,检出率90.2%,NPEOs在茶园用农药中应用普遍。
This study established an ultra high performance liquid chromatography-tandem mass spectrometry method for the determination of alkylphenol polyoxyethylene(APEOs) in pesticide formulations. APEOs were separated on a Waters-BEH C_(18) column, measured by a multi-reaction monitoring mode(MRM) with an electrospray positive ion source(ESI+), and quantified by an external standard method. The matrix standard curve of APEOs(n=3-20) in aqueous solutions, water emulsion, suspension concentrate, emulsifiable concentrate,granules and wettable powder had a good linearity in the range of 0.047~(-1) 503.6 mg·kg~(-1)with the correlation coefficient(r) between 0.996 1 and 0.999 9. The recovery of APEOs spiked in the level of 0.5~(-1) 503.6 mg·kg~(-1) ranged from 83.8~(-1)20.4% with relative standard deviation(RSD) of 0.6~(-1)3.7%, and the limits of quantity(LOQs) of 0.5～150.4 mg·kg~(-1). Among the 51 pesticide formulations used in tea gardens, the percentage of Octylphenol ethoxylates(OPEOs) was less than 0.5%. The mass fraction of nonylphenol ethoxylates(NPEOs) was ND-32.1% and the detection rate was 90.2%, indicating the wide use of NPEOs in pesticides in tea gardens.
This study established an ultra high performance liquid chromatography-tandem mass spectrometry method for the determination of alkylphenol polyoxyethylene(APEOs) in pesticide formulations. APEOs were separated on a Waters-BEH C_(18) column, measured by a multi-reaction monitoring mode(MRM) with an electrospray positive ion source(ESI+), and quantified by an external standard method. The matrix standard curve of APEOs(n=3-20) in aqueous solutions, water emulsion, suspension concentrate, emulsifiable concentrate,granules and wettable powder had a good linearity in the range of 0.047~(-1) 503.6 mg·kg~(-1)with the correlation coefficient(r) between 0.996 1 and 0.999 9. The recovery of APEOs spiked in the level of 0.5~(-1) 503.6 mg·kg~(-1) ranged from 83.8~(-1)20.4% with relative standard deviation(RSD) of 0.6~(-1)3.7%, and the limits of quantity(LOQs) of 0.5～150.4 mg·kg~(-1). Among the 51 pesticide formulations used in tea gardens, the percentage of Octylphenol ethoxylates(OPEOs) was less than 0.5%. The mass fraction of nonylphenol ethoxylates(NPEOs) was ND-32.1% and the detection rate was 90.2%, indicating the wide use of NPEOs in pesticides in tea gardens.
引文
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[9]Jiang Z J,Cao X L,Li H,et al.Fast determination of alkylphenol ethoxylates in leafy vegetables using a modified QuEChERS and ultra-high performance supercritical fluid chromatography-tandem mass spectrometry[J].Journal of Chromatography A,2017,1525:161-177.
[10]Lu Y Y.A simplified method for simultaneous quantitation of alkylphenols and alkylphenol ethoxylates in meat and fish using high-performance liquid chromatography with fluorescence detection[J].International Journal of Environmental Analytical Chemistry,2006,86(10):713-722.
[11]Ferrara F,Ademollo N,OrrùM A,et al.Alkylphenols in adipose tissues of Italian population[J].Chemosphere,2011,82(7):1044-1049.
[12]Chen M J,Zhu P F,Xu B,et al.Determination of nine environmental phenols in urine by ultra-high-performance liquid chromatography-tandem mass spectrometry.[J].Journal of Analytical Toxicology,2012,36(9):608-615.
[13]Ademollo N,Ferrara F,Delise M,et al.Nonylphenol and octylphenol in human breast milk[J].Environment International,2008,34(7):984-987.
[14]郭文建,王超,吕怡兵,等.固相萃取-液相色谱/荧光检测法同时测定水中8种烷基酚和烷基酚聚氧乙烯醚[J].环境化学,2018(3):497-504.
[15]高俊伟,叶平,谢坚,等.高效液相色谱-质谱法测定车用清洗剂中烷基酚聚氧乙烯醚[J].化学试剂,2018(1):57-59.
[16]江泽军,曹晓林,李辉,等.液体农药制剂中烷基酚及其聚氧乙烯醚类助剂的高效液相色谱分析[J].农药学学报,2017,19(2):245-253.
[17]Chen J,Mullin C A.Determination of nonylphenol ethoxylate and octylphenol ethoxylate surfactants in beehive samples by high performance liquid chromatography coupled to mass spectrometry[J].Food Chemistry,2014,158(158):473-479.
[18]张鹏,赵楠楠,苏杭,等.高效液相色谱-串联质谱法检测三苯乙烯基苯酚聚氧乙烯醚[J].色谱,2017,35(7):730-734.
[2]霍鹏.茶叶中重金属污染物残留及消减研究[J].福建茶叶,2016,38(6):253-254.
[3]Wang X,Zhou L,Luo F J,et al.9,10-Anthraquinone deposit in tea plantation might be one of the reasons for contamination in tea[J].Food Chemistry,2018:254-259.
[4]卜元卿,王昝畅,智勇,等.368种农药制剂中助剂使用状况调查研究[C]//2014中国环境科学学会学术年会.2014.
[5]Bennie D T.Review of the environmental occurrence of alkylphenols and alkylphenol ethoxylates[J].Water Quality Research Journal of Canada,1999,34(1):79-122.
[6]佚名.农业部农药检定所《关于征求〈农药助剂禁限用名单〉(征求意见稿)意见的通知》[J].中国食品,2015(15):135-135.
[7]Koh Y K,Chiu T Y,Boobis A R,et al.A sensitive and robust method for the determination of alkylphenol polyethoxylates and their carboxylic acids and their transformation in a trickling filter wastewater treatment plant[J].Chemosphere,2008,73(4):551-556.
[8]王艳平.高风险农药助剂在土壤的残留特征及环境行为初探[D].北京:中国农业科学院研究生院,2011:1-70.
[9]Jiang Z J,Cao X L,Li H,et al.Fast determination of alkylphenol ethoxylates in leafy vegetables using a modified QuEChERS and ultra-high performance supercritical fluid chromatography-tandem mass spectrometry[J].Journal of Chromatography A,2017,1525:161-177.
[10]Lu Y Y.A simplified method for simultaneous quantitation of alkylphenols and alkylphenol ethoxylates in meat and fish using high-performance liquid chromatography with fluorescence detection[J].International Journal of Environmental Analytical Chemistry,2006,86(10):713-722.
[11]Ferrara F,Ademollo N,OrrùM A,et al.Alkylphenols in adipose tissues of Italian population[J].Chemosphere,2011,82(7):1044-1049.
[12]Chen M J,Zhu P F,Xu B,et al.Determination of nine environmental phenols in urine by ultra-high-performance liquid chromatography-tandem mass spectrometry.[J].Journal of Analytical Toxicology,2012,36(9):608-615.
[13]Ademollo N,Ferrara F,Delise M,et al.Nonylphenol and octylphenol in human breast milk[J].Environment International,2008,34(7):984-987.
[14]郭文建,王超,吕怡兵,等.固相萃取-液相色谱/荧光检测法同时测定水中8种烷基酚和烷基酚聚氧乙烯醚[J].环境化学,2018(3):497-504.
[15]高俊伟,叶平,谢坚,等.高效液相色谱-质谱法测定车用清洗剂中烷基酚聚氧乙烯醚[J].化学试剂,2018(1):57-59.
[16]江泽军,曹晓林,李辉,等.液体农药制剂中烷基酚及其聚氧乙烯醚类助剂的高效液相色谱分析[J].农药学学报,2017,19(2):245-253.
[17]Chen J,Mullin C A.Determination of nonylphenol ethoxylate and octylphenol ethoxylate surfactants in beehive samples by high performance liquid chromatography coupled to mass spectrometry[J].Food Chemistry,2014,158(158):473-479.
[18]张鹏,赵楠楠,苏杭,等.高效液相色谱-串联质谱法检测三苯乙烯基苯酚聚氧乙烯醚[J].色谱,2017,35(7):730-734.
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