固相膜萃取-气相色谱-串联质谱法测定饮用水中67种农药残留
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摘要
目的建立同时测定饮用水中67种农药残留的固相膜萃取-气相色谱-串联质谱法。方法水样经C_(18)固相膜萃取,二氯甲烷和乙酸乙酯(7∶3,V/V))混合溶剂洗脱,40℃氮吹浓缩,采用DB-5MS毛细管气相色谱柱(30 m×0.25 mm×0.25μm)分离,多反应监测模式进行串联质谱检测,工作曲线法定量。结果本法除敌敌畏、速灭威部分农药外,线性范围为0.050～5μg/L,相关系数为0.9924～0.9999,方法定量限(S/N=10)为1.0×10~(-5)～0.059μg/L。通过3个浓度水平的加标实验测得方法回收率为81.0%～125.0%,相对标准偏差为1.5%～21.4%(n=6)。结论本法准确灵敏、操作简便、环保,适用于生活饮用水中多种农药残留的同时快速分析。
OBJECTIVE To develop a method for the simultaneous determination of 67 pesticides in water by solid phase extration(SPE) disk extraction-gas chromatography-tandem mass spectrometry(GC-MS/MS). METHODS Pesticides in water were extracted and cleaned-up with SPE disk, then eluted with dichloromethane-n-ethyl acetate(7∶3,V/V). After the eluent being concentrated to 1 mL under nitrogen blow at 40 ℃, the supernatant was injected into GC-MS/MS for analysis. The GC separation was performed on a DB-5 MS capillary column(30 m×0.25 mm×0.25 μm). The pesticides were detected by MS/MS in multiple reaction monitoring(MRM) mode and quantified by working curve method. RESULTS The linear range of the method for most of the pesticides were in the range of 0.05-5 μg/L with correlation coefficients of 0.9924-0.9999. The quantitative limits(S/N=10) of the method were in the range of 1.0×10~(-5)-0.059 μg/L. The recoveries for pesticides were 81.0%-125.0% with relative standard deviations of 1.5%-21.4%(n=6).CONCLUSION The method is sensitive, simple, environmentally friendly and suitable to the determination of pesticides in drinking water for rapid screening and quantitative analysis.
OBJECTIVE To develop a method for the simultaneous determination of 67 pesticides in water by solid phase extration(SPE) disk extraction-gas chromatography-tandem mass spectrometry(GC-MS/MS). METHODS Pesticides in water were extracted and cleaned-up with SPE disk, then eluted with dichloromethane-n-ethyl acetate(7∶3,V/V). After the eluent being concentrated to 1 mL under nitrogen blow at 40 ℃, the supernatant was injected into GC-MS/MS for analysis. The GC separation was performed on a DB-5 MS capillary column(30 m×0.25 mm×0.25 μm). The pesticides were detected by MS/MS in multiple reaction monitoring(MRM) mode and quantified by working curve method. RESULTS The linear range of the method for most of the pesticides were in the range of 0.05-5 μg/L with correlation coefficients of 0.9924-0.9999. The quantitative limits(S/N=10) of the method were in the range of 1.0×10~(-5)-0.059 μg/L. The recoveries for pesticides were 81.0%-125.0% with relative standard deviations of 1.5%-21.4%(n=6).CONCLUSION The method is sensitive, simple, environmentally friendly and suitable to the determination of pesticides in drinking water for rapid screening and quantitative analysis.
引文
[1] 吴志凤.谈农药的“植物健康作用”[J].农药科学与管理,2012,33(7): 34-35.
[2] TAMPOURIS S,PAPASSIOPI N.PASPALIARIS I. Removal of contaminant metals from finegrained soil using agglomeration chloride solutions and pile leaching techniques[J]. J Hazard Mater,2001, 84 (2): 297-319.
[3] 中华人民共和国国家卫生健康委员会.生活饮用水卫生标准:GB 5749—2006[S].北京:中国标准出版社,2006.
[4] 黄亮,刘芯成,朱萌萌,等.气相色谱-串联质谱法测定灌溉水中二甲四氯异辛酯的残留量[J].浙江农业科学,2017,58(3):504-507.
[5] 任琳,秦忠雪,朱婧,等. 固相萃取-气相色谱-串联质谱法测定水中16种有机磷和有机氯农药残留[J]. 中国卫生检验杂志, 2017,27(10): 1396-1399.
[6] 华勃,陈小辉,蚁焕钿.固相萃取-气相色谱法测定生活饮用水中的有机磷农药[J].环境科学, 2010,23(2): 62-67.
[7] 邵阳,杨国胜,韩深,等.加速溶剂萃取-硅胶萃取净化-气相色谱/质谱法检测地表水中有机氯农药和多氯联苯[J].分析化学, 2016,44(5): 698-706.
[8] 滕瑞菊,王欢,王雪梅,等.超声辅助分散液液微萃取-高效液相色谱法快速测定水中的6种农药[J].分析化学, 2017,45(2):275-281.
[9] 罗晓飞,杨元,孙成均. 固相膜萃取-毛细管气相色谱法同时测定粮食中45种有机磷农药残留[J].四川大学学报(医学版), 2012,43(1):108-112.
[10] US Environmental Protection Agency. EPA Method 525.2. Determination of organic compounds in drinking water by liquid solid extraction and capillary column gas chromatography/mass spectrometry [S]. Cincinnati, OH: USEPA, 1994.
[11] 廖和菁,胡礼渊,刘瑞芳,等.气相色谱法测定坚果中8种拟除虫菊酯农药残留[J].分析测试学报,2017,36(5):669-673.
[12] NAKSEN W, PRAPAMONTOL T, MANGKLABRUKS A, et al. A single method for detecting 11 organophosphate pesticides in human plasma and breastmilk using GC-FPD[J]. J Chromatogr B, 2016,1025:92-104.
[13] REJCZA T, TUZIMSKI T. QuEChERS-based extraction with dispersive solid phase extraction clean-up using PSA and ZrO2 -based sorbents for determination of pesticides in bovine milk samples by HPLC-DAD[J]. Food Chem, 2017,217:225-233.
[14] 李亚珍,李兆乾,朱华玲,等.磁性石墨烯固相萃取-毛细管电泳联用测定水样中三嗪类农药残留[J].分析化学, 2015,43(15):1182-1187.
[15] 杭莉,杨华梅.超高效液相色谱-串联质谱法同时测定地表水中13种氨基甲酸酯类农药残留[J].江苏预防医学, 2017,28(1):25-28.
[16] 段辉,周密,姜波,等. 疏水性聚合树脂吸附-气相色谱质谱法快速测定地表水农药残留[J].化学工程师, 2016, 245(2):33-38.
[17] SHANSIPUR M, YAZDANFAR N, GHAMBARIAN M. Combination of solid-phase extraction with dispersive liquid-liquid microextraction followed by GC-MS for determination of pesticide residues from water, milk, honey and fruit juice[J]. Food Chem, 2016,204:289-297.
[18] MACHADO I, GEREZ N, PISTON M, et al. Determination of pesticide residues in globe artichoke leaves and fruits by GC-MS and LC-MS/MS using the same QuEChERS procedure[J]. Food Chem, 2017,227:227-236.
[19] CALDAS S S, ROMBALDI C, DE J L, et al. Multi-residue method for determination of 58 pesticides, pharmaceuticals and personal care products in water using solvent demulsification dispersive liquid-liquid microextraction combined with liquid chromatography-tandem mass spectrometry[J]. Food Chem, 2016,146:676-688.
[2] TAMPOURIS S,PAPASSIOPI N.PASPALIARIS I. Removal of contaminant metals from finegrained soil using agglomeration chloride solutions and pile leaching techniques[J]. J Hazard Mater,2001, 84 (2): 297-319.
[3] 中华人民共和国国家卫生健康委员会.生活饮用水卫生标准:GB 5749—2006[S].北京:中国标准出版社,2006.
[4] 黄亮,刘芯成,朱萌萌,等.气相色谱-串联质谱法测定灌溉水中二甲四氯异辛酯的残留量[J].浙江农业科学,2017,58(3):504-507.
[5] 任琳,秦忠雪,朱婧,等. 固相萃取-气相色谱-串联质谱法测定水中16种有机磷和有机氯农药残留[J]. 中国卫生检验杂志, 2017,27(10): 1396-1399.
[6] 华勃,陈小辉,蚁焕钿.固相萃取-气相色谱法测定生活饮用水中的有机磷农药[J].环境科学, 2010,23(2): 62-67.
[7] 邵阳,杨国胜,韩深,等.加速溶剂萃取-硅胶萃取净化-气相色谱/质谱法检测地表水中有机氯农药和多氯联苯[J].分析化学, 2016,44(5): 698-706.
[8] 滕瑞菊,王欢,王雪梅,等.超声辅助分散液液微萃取-高效液相色谱法快速测定水中的6种农药[J].分析化学, 2017,45(2):275-281.
[9] 罗晓飞,杨元,孙成均. 固相膜萃取-毛细管气相色谱法同时测定粮食中45种有机磷农药残留[J].四川大学学报(医学版), 2012,43(1):108-112.
[10] US Environmental Protection Agency. EPA Method 525.2. Determination of organic compounds in drinking water by liquid solid extraction and capillary column gas chromatography/mass spectrometry [S]. Cincinnati, OH: USEPA, 1994.
[11] 廖和菁,胡礼渊,刘瑞芳,等.气相色谱法测定坚果中8种拟除虫菊酯农药残留[J].分析测试学报,2017,36(5):669-673.
[12] NAKSEN W, PRAPAMONTOL T, MANGKLABRUKS A, et al. A single method for detecting 11 organophosphate pesticides in human plasma and breastmilk using GC-FPD[J]. J Chromatogr B, 2016,1025:92-104.
[13] REJCZA T, TUZIMSKI T. QuEChERS-based extraction with dispersive solid phase extraction clean-up using PSA and ZrO2 -based sorbents for determination of pesticides in bovine milk samples by HPLC-DAD[J]. Food Chem, 2017,217:225-233.
[14] 李亚珍,李兆乾,朱华玲,等.磁性石墨烯固相萃取-毛细管电泳联用测定水样中三嗪类农药残留[J].分析化学, 2015,43(15):1182-1187.
[15] 杭莉,杨华梅.超高效液相色谱-串联质谱法同时测定地表水中13种氨基甲酸酯类农药残留[J].江苏预防医学, 2017,28(1):25-28.
[16] 段辉,周密,姜波,等. 疏水性聚合树脂吸附-气相色谱质谱法快速测定地表水农药残留[J].化学工程师, 2016, 245(2):33-38.
[17] SHANSIPUR M, YAZDANFAR N, GHAMBARIAN M. Combination of solid-phase extraction with dispersive liquid-liquid microextraction followed by GC-MS for determination of pesticide residues from water, milk, honey and fruit juice[J]. Food Chem, 2016,204:289-297.
[18] MACHADO I, GEREZ N, PISTON M, et al. Determination of pesticide residues in globe artichoke leaves and fruits by GC-MS and LC-MS/MS using the same QuEChERS procedure[J]. Food Chem, 2017,227:227-236.
[19] CALDAS S S, ROMBALDI C, DE J L, et al. Multi-residue method for determination of 58 pesticides, pharmaceuticals and personal care products in water using solvent demulsification dispersive liquid-liquid microextraction combined with liquid chromatography-tandem mass spectrometry[J]. Food Chem, 2016,146:676-688.