基于UPLC-MS/MS的土壤中敌草隆残留检测技术

doi:10.16178/j.issn.0528-9017.20230070

摘要/Abstract

摘要：

为了提高土壤中敌草隆的萃取效率,更为精确地检测其残留量,采用加压溶剂萃取作为土壤中敌草隆的萃取方式,使用超高效液相色谱-三重四极杆串联质谱法对土壤中残留的敌草隆进行了检测,建立了一种土壤中敌草隆萃取和检测的新方法。试样经冷冻干燥处理后,将其研磨样装入加压溶剂萃取仪,使用2∶1的甲醇-二氯甲烷混合溶液作为萃取剂,萃取液经Carb/PSA石墨化炭黑/乙二胺-N-丙基固相萃取柱净化后,通过C18色谱柱进行分离,并以体积比为1∶9的甲醇-二氯甲烷混合溶剂进行梯度洗脱,质谱中选择电子轰击离子源和多反应监测模式。结果显示,敌草隆在20~500 μg·L^-1范围内具有良好的线性关系,相关系数为0.999 5,且目标峰分离效果较好;不同浓度下敌草隆的加标回收率为71.2%~90.3%,相对标准偏差为1.7%~9.4%,检出限为0.000 287 μg·g^-1。该方法有利于对土壤中敌草隆残留量大批量检测的操作,提高了目标物的萃取效率和检测效率,提高样品检测准确性。

关键词: 敌草隆, 加压溶剂萃取, 液质联用, 农药残留

Abstract:

In order to improve the extraction efficiency of diuron in soil and to detect its residues more accurately, pressurized solvent extraction was used as the extraction method for diuron in soil, and a new method for the extraction and detection of diuron in soil was established by using ultra performance liquid chromatography-triple quadrupole tandem mass spectrometry. The sample was freeze-dried and loaded into a pressurized solvent extractor, and a methanol-dichloromethane mixture was used as the extractant. The extract was cleaned up by a Carb/PSA graphitized carbon black/ethylenediamine-N-propyl solid phase extraction column, and then separated by a C18 column with a gradient elution of methanol-dichloromethane mixture at a volume ratio of 1∶9. The electron bombardment ion source and multiple reaction were selected in the mass spectrometry monitoring mode. The results showed that there was a good linear relationship within the range of 20-500 μg·L^-1 diuron, with a correlation coefficient of 0.999 5, and the target peak separation effect is good. The spiked recoveries of diuron were 71.2%-90.3%, the relative standard deviations were 1.7%-9.4%, and the detection limits were 0.000 287 0 μg·g^-1. This method is conducive to the operation of large-scale detection of diuron residues in soil, improving the extraction and detection efficiency of target substances, and improving the accuracy of sample detection.

Key words: diuron, pressurized solvent extraction, liquid mass spectrometry, pesticide residues

中图分类号:

S482.4

施超宇, 孙晓欣, 吴嵘, 杨勇, 王雪, 肖学喜. 基于UPLC-MS/MS的土壤中敌草隆残留检测技术[J]. 浙江农业科学, 2024, 65(1): 157-161.

SHI Chaoyu, SUN Xiaoxin, WU Rong, YANG Yong, WANG Xue, XIAO Xuexi. UPLC-MS/MS based technique for the detection of diuron residues in soil[J]. Journal of Zhejiang Agricultural Sciences, 2024, 65(1): 157-161.

图/表 6

参考文献 22

[1]	陈君杨, 牛航宇, 冯景伟, 等. 水中敌草隆去除技术研究进展[J]. 环境科学与技术, 2015, 38(S1): 181-185,197.
[2]	BERS K, LEROY B, BREUGELMANS P, et al. A novel hydrolase identified by genomic-proteomic analysis of phenylurea herbicide mineralization by Variovorax sp. Strain SRS16[J]. Applied and Environmental Microbiology, 2011, 77(24): 8754-8764.
[3]	MALATO S, BLANCO J, CÁCERES J, et al. Photocatalytic treatment of water-soluble pesticides by photo-Fenton and TiO₂ using solar energy[J]. Catalysis Today, 2002, 76(2/3/4): 209-220.
[4]	PANDEY S, SINGH D K. Soil dehydrogenase, phosphomonoesterase and arginine deaminase activities in an insecticide treated groundnut (Arachis hypogaea L.) field[J]. Chemosphere, 2006, 63(5): 869-880.
[5]	LAMOREE M H, SWART C P, VAN DER HORST A, et al. Determination of diuron and the antifouling paint biocide Irgarol 1051 in Dutch marinas and coastal waters[J]. Journal of Chromatography A, 2002, 970(1/2): 183-190.
[6]	OKAMURA H, AOYAMA I, ONO Y, et al. Antifouling herbicides in the coastal waters of western Japan[J]. Marine Pollution Bulletin, 2003, 47(1/2/3/4/5/6): 59-67.
[7]	OKAMURA H. Photodegradation of the antifouling compounds Irgarol 1051 and Diuron released from a commercial antifouling paint[J]. Chemosphere, 2002, 48(1): 43-50.
[8]	THOMAS K V, FILEMAN T W, READMAN J W, et al. Antifouling paint booster biocides in the UK coastal environment and potential risks of biological effects[J]. Marine Pollution Bulletin, 2001, 42(8): 677-688.
[9]	THOMAS K V, MCHUGH M, WALDOCK M. Antifouling paint booster biocides in UK coastal waters: inputs, occurrence and environmental fate[J]. Science of the Total Environment, 2002, 293(1/2/3): 117-127.
[10]	VERCRAENE-EAIRMAL M, LAUGA B, SAINT LAURENT S, et al. Diuron biotransformation and its effects on biofilm bacterial community structure[J]. Chemosphere, 2010, 81(7): 837-843.
[11]	GIACOMAZZI S, COCHET N. Environmental impact of diuron transformation: a review[J]. Chemosphere, 2004, 56(11): 1021-1032.
[12]	LEWIS R J. Sax's dangerous properties of industrial materials[M]. 8th ed. New York: Van Nostrand Reinhold, 1992.
[13]	RAGSDALE N N, MENZER R E. Carcinogenicity and pesticides: principles, issues, and relationships[M]. Washington, DC: American Chemical Society, 1989.
[14]	张素娣. 敌草隆的气相色谱分析[J]. 广西化工, 1998, 27 (4): 45-46, 54.
[15]	郭永泽, 张玉婷, 刘磊, 等. 棉籽中敌草隆及其代谢产物残留量的测定方法[J]. 天津农业科学, 2010, 16(3): 69-71.
[16]	冯凯, 段苏然, 商春锋. 气相色谱-质谱法测定灵芝9种农药残留含量[J]. 食品界, 2022(8): 99-101.
[17]	陈樱玉. 敌草隆的液相色谱分析[J]. 化工技术与开发, 2006, 35(6): 19-20.
[18]	寿林飞, 金铨, 徐静高, 等. 甘蔗及土壤中敌草隆残留的分析方法[J]. 浙江农业科学, 2007, 48(1): 82-83.
[19]	陈樱玉. 液相色谱法同时测定敌草隆和莠去津[J]. 安徽化工, 2007, 33(4): 61-62.
[20]	李军民, 黄化成, 裘立群. 色谱法测定肉及肉制品中敌草隆、绿麦隆、莠去津和西玛津残留量[J]. 色谱, 2004, 22(1): 88.
[21]	平立凤, 李振, 赵华, 等. 超高效液相色谱法测定甘蔗和土壤中敌草隆残留[J]. 分析科学学报, 2011, 27(2): 235-237.
[22]	毛慎, 朱雪婷, 刘克勤, 等. 基于纳米材料构建电化学传感器对水产品中敌草隆的检测[J]. 安徽农业科学, 2019, 47(18): 198-200, 217.

时间/min	流动相A/%	流动相B/%
0	90	10
5.00	40	60
10.00	40	60
10.01	90	10
13.00	停止	停止

时间/min	流动相A/%	流动相B/%
0	90	10
5.00	40	60
10.00	40	60
10.01	90	10
13.00	停止	停止

	测定含量/ (μg·g^-1)	平均值/ (μg·g^-1)	标准偏差/%	检出限/ (μg·g^-1)	定量限/ (μg·g^-1)
1	11.519	12.570	0.91	0.000 287	0.001 148
2	12.783
3	12.196
4	13.483
5	11.402
6	12.825
7	13.783

	测定含量/ (μg·g^-1)	平均值/ (μg·g^-1)	标准偏差/%	检出限/ (μg·g^-1)	定量限/ (μg·g^-1)
1	11.519	12.570	0.91	0.000 287	0.001 148
2	12.783
3	12.196
4	13.483
5	11.402
6	12.825
7	13.783

加标量/ ng	空白样序号	检测值/ μg	回收率/ %	平均回收率/%	相对标准偏差/%
40	1	35.1	87.8	79.2	7.1
	2	31.6	79.0
	3	30.4	76.0
	4	31.4	78.5
	5	28.5	71.2
	6	32.9	82.2
200	1	166.0	83.0	84.5	1.7
	2	170.0	85.0
	3	166.0	83.1
	4	169.0	84.4
	5	169.0	84.6
	6	174.0	86.8
400	1	361.0	90.3	80.5	9.4
	2	302.0	75.5
	3	340.0	85.0
	4	293.0	73.2
	5	345.0	86.1
	6	291.0	72.7