Determination of 20 organochlorine and pyrethroid pesticides residues in water by dispersive liquid-liquid microextraction

doi:10.16178/j.issn.0528-9017.20221190

Abstract

Abstract:

In this study, a method for the determination of 20 organochlorine and pyrethroid pesticide residues in drinking water was established by dispersive liquid-liquid microextraction (DLLME). The influencing factors related to DLLME extraction were optimized by expanding the extraction of pesticide residues in water by expanding dispersive liquid-liquid microextraction: 0.4 mL of chloroform and 4 mL of acetonitrile were used as extractants and dispersants for 40 mL of water samples, extracted and centrifuged and dried with nitrogen, and 100 μL of n-hexane solvent was replaced by gas chromatography electron capture detector (GC-ECD) for detection. The results showed that the linearity of 20 organochlorine and pyrethroid pesticides in water was good in the concentration range of 0.002-0.10 μg·mL^-1 and 0.01-0.20 μg·mL^-1, respectively, the correlation coefficient was 0.998, and the detection limit of the method was 0.001-0.002 μg·L^-1, the enrichment folds of the method were 168-206, the recoveries of the high, medium and low concentrations were 83.30%-116.70%, and the relative standard deviation (RSD) was 0.84%-9.87%. The established method was used to test 135 rural drinking water samples, and the results were below the limit values. This method has high sensitivity, accuracy, good stability, and is more operable in batch analysis, and is suitable for the qualitative and quantitative analysis of organochlorine and pyrethroid in drinking water.

Key words: drinking water, dispersive liquid-liquid microextraction, organochlorine, pyrethroids

CLC Number:

Hongfei RUI, Jun WU, Shuwen LUO, Xiaojie OUYANG, Xiaoying LIU, Fenghua WU. Determination of 20 organochlorine and pyrethroid pesticides residues in water by dispersive liquid-liquid microextraction[J]. Journal of Zhejiang Agricultural Sciences, 2024, 65(2): 469-474.

Figures/Tables 5

References 18

[1]	DAI G H, LIU X H, LIANG G, et al. Evaluating the sediment-water exchange of hexachlorocyclohexanes (HCHs) in a major lake in North China[J]. Environmental Science Processes & Impacts, 2013, 15(2): 423-432.
[2]	LOHMANN R, BREIVIK K, DACHS J, et al. Global fate of POPs: current and future research directions[J]. Environmental Pollution, 2007, 150(1): 150-165.
[3]	李炳华, 任仲宇, 陈鸿汉, 等. 太湖流域某农业区浅层地下水有机氯农药残留特征初探[J]. 农业环境科学学报, 2007, 26(5): 1714-1718.
[4]	姜珊, 孙丙华, 徐彪, 等. 巢湖主要湖口水体和表层沉积物中有机氯农药的残留特征及风险评价[J]. 环境化学, 2016, 35(6): 1228-1236.
[5]	何健, 豆叶枝, 李菊颖, 等. 气相色谱-质谱法测定水-沉积物系统中13种拟除虫菊酯类农药[J]. 农药学学报, 2021, 23(4): 732-738.
[6]	许梓红, 罗林, 陈子键, 等. 拟除虫菊酯类农药及其代谢物免疫检测技术研究进展[J]. 食品与发酵工业, 2022, 48(8): 320-328.
[7]	陈兴连, 邵金良, 方海仙, 等. 气相色谱法同时快速测定茶饮料及其制品中17种有机氯、拟除虫菊酯农药残留[J]. 食品安全质量检测学报, 2018, 9(6): 1275-1283.
[8]	符靖雯, 林玉婵, 黄梅花, 等. QuEChERS萃取结合GC-ECD测定甜玉米中多种有机氯及拟除虫菊酯类农药残留[J]. 理化检验-化学分册, 2017, 53(9): 1036-1041.
[9]	陈波, 吴卫东, 卞学海, 等. QuEChERS-分散液液微萃取-气相色谱串联质谱技术检测果蔬中31种农药残留[J]. 中国卫生检验杂志, 2019, 29(17): 2060-2067.
[10]	崔淑敏. 分散液液微萃取—气相色谱联用在有机物残留分析中的应用研究[D]. 金华: 浙江师范大学, 2013.
[11]	王娜, 王海娇, 李丽君. 液液萃取处理样品-气相色谱法测定水中22种有机氯农药[J]. 理化检验-化学分册, 2010, 46(12): 1453-1455, 1464.
[12]	闻亚. 分散液液微萃取技术在挥发性有机物及有机氯农残分析中的应用[D]. 杭州: 浙江工业大学, 2014.
[13]	李晓晶, 陈安, 黄聪, 等. 分散液液微萃取-气相色谱法快速测定水中23种有机磷农药[J]. 分析测试学报, 2011, 30(3): 326-329.
[14]	FARAJZADEH M A, DJOZAN, KHORRAM P. Development of a new dispersive liquid-liquid microextraction method in a narrow-bore tube for preconcentration of triazole pesticides from aqueous samples[J]. Analytica Chimica Acta, 2012, 713: 70-78.
[15]	夏英, 张澜, 赵尔成, 等. 分散固相萃取/分散液液微萃取-气相色谱法测定甘蓝中的拟除虫菊酯类农药残留[J]. 分析测试学报, 2014, 33(2): 192-196.
[16]	王宇, 朱成华, 邹晓莉, 等. 溶剂去乳化-悬浮固化分散液液微萃取-气相色谱-质谱联用测定水中的有机氯农药[J]. 色谱, 2013, 31(11): 1076-1080.
[17]	陈潇, 李妍, 王宇, 等. 轻质萃取剂-溶剂去乳化分散液相微萃取-气相色谱质谱法测定水样中有机氯农药[J]. 现代预防医学, 2015, 42(4): 701-704.
[18]	李妃, 陶建斌, 柯志恒, 等. 气相色谱法测定洞头海域海水中16种有机氯农药残留量[J]. 中国卫生检验杂志, 2021, 31(17): 2060-2063.

化合物	回归曲线	线性范围/ (μg·mL^-1)	相关系数	检出限/ (μg·L^-1)	定量限/ (μg·L^-1)	富集因子
α-666	y=2 927 590x+1 460.95	0.002~0.10	0.998 4	0.001	0.003	185
六氯苯	y=3 651 300x+8 233.88	0.002~0.10	0.998 8	0.002	0.006	174
β-666	y=1 965 890x+3 234.78	0.002~0.10	0.999 4	0.002	0.006	199
γ-666	y=2 895 010x+2 269.34	0.002~0.10	0.998 9	0.001	0.003	174
δ-666	y=2 431 250x+1 733.91	0.002~0.10	0.998 8	0.002	0.006	199
七氯	y=2 548 640x+5 439.60	0.002~0.10	0.998 5	0.002	0.006	178
环氧七氯	y=2 878 940x+4 311.96	0.002~0.10	0.998 1	0.001	0.003	190
硫丹	y=2 591 738x+4 493.59	0.002~0.10	0.998 5	0.002	0.006	193
p,p'-DDE	y=2 578 520x+3 112.97	0.002~0.10	0.998 8	0.001	0.003	194
p,p'-DDT	y=1 007 050x-1 074.68	0.002~0.10	0.999 2	0.002	0.006	168
o,p'-DDT	y=1 083 010x+1 468.31	0.002~0.10	0.998 5	0.002	0.006	206
p,p'-DDD	y=2 409 190x+4 229.25	0.002~0.10	0.998 4	0.002	0.006	198
三氯杀螨醇	y=501 875x+1 882.17	0.01~0.20	0.999 1	0.002	0.006	190
联苯菊酯	y=513 181x+1 512.27	0.01~0.20	0.999 1	0.002	0.006	179
甲氰菊酯	y=488 092x+1 414.65	0.01~0.20	0.999 2	0.002	0.006	178
氯氟氰菊酯	y=799 326x+169.177	0.01~0.20	0.999 5	0.002	0.006	184
氟氯氰菊酯	y=626 925x+526.21	0.01~0.20	0.999 8	0.002	0.006	181
氯氰菊酯	y=664 906x+139.92	0.01~0.20	0.999 5	0.002	0.006	180
氰戊菊酯	y=637 025x+275.37	0.01~0.20	0.999 4	0.002	0.006	176
溴氰菊酯	y=529 423x+860.07	0.01~0.20	0.999 8	0.002	0.006	178

化合物	回归曲线	线性范围/ (μg·mL^-1)	相关系数	检出限/ (μg·L^-1)	定量限/ (μg·L^-1)	富集因子
α-666	y=2 927 590x+1 460.95	0.002~0.10	0.998 4	0.001	0.003	185
六氯苯	y=3 651 300x+8 233.88	0.002~0.10	0.998 8	0.002	0.006	174
β-666	y=1 965 890x+3 234.78	0.002~0.10	0.999 4	0.002	0.006	199
γ-666	y=2 895 010x+2 269.34	0.002~0.10	0.998 9	0.001	0.003	174
δ-666	y=2 431 250x+1 733.91	0.002~0.10	0.998 8	0.002	0.006	199
七氯	y=2 548 640x+5 439.60	0.002~0.10	0.998 5	0.002	0.006	178
环氧七氯	y=2 878 940x+4 311.96	0.002~0.10	0.998 1	0.001	0.003	190
硫丹	y=2 591 738x+4 493.59	0.002~0.10	0.998 5	0.002	0.006	193
p,p'-DDE	y=2 578 520x+3 112.97	0.002~0.10	0.998 8	0.001	0.003	194
p,p'-DDT	y=1 007 050x-1 074.68	0.002~0.10	0.999 2	0.002	0.006	168
o,p'-DDT	y=1 083 010x+1 468.31	0.002~0.10	0.998 5	0.002	0.006	206
p,p'-DDD	y=2 409 190x+4 229.25	0.002~0.10	0.998 4	0.002	0.006	198
三氯杀螨醇	y=501 875x+1 882.17	0.01~0.20	0.999 1	0.002	0.006	190
联苯菊酯	y=513 181x+1 512.27	0.01~0.20	0.999 1	0.002	0.006	179
甲氰菊酯	y=488 092x+1 414.65	0.01~0.20	0.999 2	0.002	0.006	178
氯氟氰菊酯	y=799 326x+169.177	0.01~0.20	0.999 5	0.002	0.006	184
氟氯氰菊酯	y=626 925x+526.21	0.01~0.20	0.999 8	0.002	0.006	181
氯氰菊酯	y=664 906x+139.92	0.01~0.20	0.999 5	0.002	0.006	180
氰戊菊酯	y=637 025x+275.37	0.01~0.20	0.999 4	0.002	0.006	176
溴氰菊酯	y=529 423x+860.07	0.01~0.20	0.999 8	0.002	0.006	178

化合物	加标0.025 μg·L^-1		加标0.05 μg·L^-1		加标0.25 μg·L^-1
化合物	回收率	RSD	回收率	RSD	回收率	RSD
α-六六六	113.30	7.87	91.70	4.89	85.80	5.73
六氯苯	96.70	6.34	91.70	2.10	85.00	9.06
β-六六六	106.70	8.05	108.30	7.89	98.30	2.09
γ-六六六	100.90	5.45	83.30	8.97	90.00	5.65
δ-六六六	113.30	6.63	101.50	8.95	98.30	5.85
七氯	88.25	3.52	97.56	5.55	94.32	3.54
环氧七氯	113.30	5.62	91.70	8.58	94.20	8.07
硫丹	95.00	3.08	116.70	9.75	91.70	1.50
p,p'-DDE	106.70	6.73	101.00	7.98	97.50	4.66
p,p'-DDD	86.70	1.24	91.70	9.56	85.80	8.41
o,p'-DDT	106.70	5.32	115.20	4.35	103.30	6.45
p,p'-DDT	110.00	9.87	101.40	0.84	100.80	2.61
三氯杀螨醇	108.20	3.55	95.20	3.52	95.30	3.85
联苯菊酯	89.20	6.58	98.20	2.58	94.20	3.88
甲氰菊酯	95.30	4.25	94.50	3.51	91.20	5.01
氯氟氰菊酯	96.30	5.21	99.60	4.25	94.20	4.32
氟氯氰菊酯	92.20	1.36	95.20	3.33	98.10	3.33
氯氰菊酯	94.10	6.32	93.10	1.58	96.20	4.12
氰戊菊酯	89.30	4.52	94.30	4.20	93.20	3.65
溴氰菊酯	90.20	5.32	94.20	3.33	96.20	2.54

化合物	加标0.025 μg·L^-1		加标0.05 μg·L^-1		加标0.25 μg·L^-1
化合物	回收率	RSD	回收率	RSD	回收率	RSD
α-六六六	113.30	7.87	91.70	4.89	85.80	5.73
六氯苯	96.70	6.34	91.70	2.10	85.00	9.06
β-六六六	106.70	8.05	108.30	7.89	98.30	2.09
γ-六六六	100.90	5.45	83.30	8.97	90.00	5.65
δ-六六六	113.30	6.63	101.50	8.95	98.30	5.85
七氯	88.25	3.52	97.56	5.55	94.32	3.54
环氧七氯	113.30	5.62	91.70	8.58	94.20	8.07
硫丹	95.00	3.08	116.70	9.75	91.70	1.50
p,p'-DDE	106.70	6.73	101.00	7.98	97.50	4.66
p,p'-DDD	86.70	1.24	91.70	9.56	85.80	8.41
o,p'-DDT	106.70	5.32	115.20	4.35	103.30	6.45
p,p'-DDT	110.00	9.87	101.40	0.84	100.80	2.61
三氯杀螨醇	108.20	3.55	95.20	3.52	95.30	3.85
联苯菊酯	89.20	6.58	98.20	2.58	94.20	3.88
甲氰菊酯	95.30	4.25	94.50	3.51	91.20	5.01
氯氟氰菊酯	96.30	5.21	99.60	4.25	94.20	4.32
氟氯氰菊酯	92.20	1.36	95.20	3.33	98.10	3.33
氯氰菊酯	94.10	6.32	93.10	1.58	96.20	4.12
氰戊菊酯	89.30	4.52	94.30	4.20	93.20	3.65
溴氰菊酯	90.20	5.32	94.20	3.33	96.20	2.54