基于QuEChERS-GC/MS法对土壤和甜菜中精异丙甲草胺的残留降解动态测定

doi:10.6048/j.issn.1001-4330.2023.03.022

摘要/Abstract

摘要：

【目的】研究精异丙甲草胺在甜菜及种植土壤中的残留降解动态。【方法】采用QuEChERS-GC/MS法,分析不同深度土壤和甜菜中施用的不同浓度的精异丙甲草胺。【结果】精异丙甲草胺在0.01~1.0 mg/L浓度范围内呈良好线性,相关系数为0.999 4,所建立的最小检出限为0.001 mg/kg;平均回收率在84.81%~110.45%,相对标准偏差(RSD,n=3)在1.36%~9.0%。1 296、1 944、3 888 g.a.i/hm²的精异丙甲草胺在0~5、5~10、10~15 cm的土壤以及甜菜中的降解遵循一级动力学方程,不同深度土壤中的残留量随浓度的增加而增加,随时间的延长而降低,不同施用浓度在不同深度土壤中的半衰期为9.12~17.77 d。施用浓度越高,降解速度越慢。在甜菜中的残留量和降解速率都低于土壤,半衰期较土壤中略高,3个浓度在甜菜中的半衰期分别为19.25、26.65和32.85 d。【结论】施用1 296和1 944 g.a.i/hm²的精异丙甲草胺,收获期在土壤和甜菜中的降解率均能达到90%;施用超剂量3 888 g.a.i/hm²的精异丙甲草胺在收获期的降解率会低于80%,精异丙甲草胺在土壤和甜菜中较易降解,属于易降解农药。

关键词: 精异丙甲草胺; 土壤; 甜菜; QuEChERS-GC/MS; 降解动态

Abstract:

【Objective】 This project aims to clarify the residual degradation dynamics of metolachlor in sugar beet and planting soil.【Method】 QuEChERS-GC/MS method was used to study the effects of different concentrations of S-Metolachor in different soil depths and sugarbeet.【Results】 The results showed that the S-Metolachorresidue was linear in the concentration range of 0.01-1.0 mg/L with a correlation coefficient of 0.999 4.The minimum detection limit was 0.001 mg/kg; the average recovery was 84.81-110.45%, relative standard deviation (RSD, n=3) was between 1.36% and 9.0%.The degradation of S-Metolachorresidue in 0-5, 5-10, 10-15 cm soil and sugar beet in 1,296, 1,944, 3,888 g.a.i/hm², following the first-order kinetic equation.The residue in different depth soil increased with the increase of concentration, and decreased with the extension of time.The half-life of different application concentration in different depth soil was 9.12-17.77 d.The higher the application concentration, the slower the degradation rate.The residual amount and degradation rate in sugar beet were lower than that in soil, and the half-life was slightly higher than that in soil.The half-lives of three concentrations in sugar beet were 19.25 d, 26.65 d and 32.85 d, respectively.【Conclusion】 The degradation rate of S-Metolachlor in soil and sugar beet can reach 90% when 1,296 g.a.i/hm² and 1,944 g.a.i/hm² are applied, and is lower than 80% when the dosage of S-Metolachlor is 3,888 g.a.i/hm².From the perspective of degradation rate, S-Metolachlor is easy to degrade in soil and sugar beet, which belongs a kind of degradable pesticide.

Key words: S-Metolachor; soil; sugar beet; QuEChERS-GC/MS; degradation dynamics

中图分类号:

S566.3

程文亮, 宋文钰, 王浩东, 许同心, 吴彩兰, 王春娟, 杨德松. 基于QuEChERS-GC/MS法对土壤和甜菜中精异丙甲草胺的残留降解动态测定[J]. 新疆农业科学, 2023, 60(3): 706-714.

CHENG Wenliang, SONG Wenyu, WANG Haodong, XU Tongxin, WU Cailan, WANG Chunjuan, YANG Desong. Determination of Residual Degradation of S-Metolachor Residue in Soil and Sugar Beet by QuEChERS-GC/MS[J]. Xinjiang Agricultural Sciences, 2023, 60(3): 706-714.

图/表 9

参考文献 20

[1]	王荣华, 王维成, 刘珣. 等. 关于新疆甜菜产业发展的调研报告[J]. 中国糖料, 2014,(4): 86-89.
	WANG Ronghua, WANG Weicheng, LIU Yu, et al. Research Report on the development of beet industry in Xinjiang[J]. Sugar Crops of China, 2014,(4): 86-89.
[2]	李蔚农, 姜莉, 董戈. 我国甜菜生产中除草剂应用现状及发展前景[J]. 中国糖料, 2014,(4): 83-85,96.
	LI Weinong, JIANG Li, DONG Ge. Application status and development prospect of herbicides in beet production in China[J]. Sugar Crops of China, 2014,(4): 83-85,96.
[3]	朱诗禹, 崔娟, 徐伟. 等. 精异丙甲草胺苗前封闭处理对大豆苗期生长及其生理生化指标的影响[J]. 植物保护学报, 2016, 43(4): 677-682.
	ZHU Shiyu, CUI Juan, XU Wei, et al. Effects of the treatment with S-Metolachor before seedling emergence on the soybean growth and physiological and biochemical indexes[J]. Journal of Plant Protection, 2016, 43(4): 677-682.
[4]	景闻华. 除草剂精异丙甲草胺的合成工艺研究[D]. 杭州: 浙江工业大学, 2017.
	JING Wenhua. Study on the synthesis of herbicide product S-Metolachor[D]. Hangzhou: Zhejiang University of Technology, 2017.
[5]	Rangani G, Noguera M, Salas P.R, et al. Mechanism of Resistance to S-metolachlor in Palmer amaranth[J]. Frontiers in Plant Science, 2021.
[6]	龙水亮, 吴晓峰, 雷干农. 等. 烟·硝·莠去津-精异丙甲草胺组合防除春玉米杂草效果与安全性[J]. 湖北农业科学, 2020, 59(14): 80-84,124.
	LONG Shuiliang, WU Xiaofeng, LEI Gannong, et al. Effect and safety of nicosulfuron·mesotrione·atrazine and S-Metolachor in controlling spring corn weeds[J]. Hubei Agricultural Sciences, 2020, 59(14): 80-84,124.
[7]	王建平, 刘小民, 许贤, 等. 52%精异丙甲草胺·丙炔氟草胺悬乳剂防治花生田一年生杂草的效果及其安全性评价[J]. 杂草学报, 2020, 38(4): 44-48.
	WANG Jianping, LIU Xiaomin, XU Xian, et al. Seectivity Assessment and Efficacy of S-Metolachor Flumioxazin 52% SC for Annuaul Weed Control in Peanuts[J]. Journal of Weed Science, 2020, 38(4): 44-48.
[8]	Nader S, Christy S, Todd C, et al. Tolerance of Black Beans (Phaseolus vulgaris) to Soil Applications of S-Metolachlor and Imazethapyr1[J]. Weed Technology, 2004, 18(1).
[9]	李春花, 黄金亮, 王艳青. 等. 精异丙甲草胺不同剂量和苦荞不同种植密度的除草和产量效应[J]. 杂草学报, 2019, 37(4): 37-44.
	LI Chunhua, HUANG Jinliang, WANG Yanqing, et al. Effects of S-MetolachorDosage and Planting Density on Weeding andd Yield of Fagopyrum tataricum[J]. Journal of Weed Science, 2019, 37(4): 37-44.
[10]	刘洋. 精异丙甲草胺的发展现状及未来趋势评述[J]. 农药市场信息, 2017,(6): 27-29.
	LIU Yang. Development status and future trend of S-Metolachor[J]. Pesticide Market Information, 2017,(6): 27-29.
[11]	Kabler A K, Chen S. Determination of the 1’S and 1’R diastereomers of metolachlor and S-metolachlor in water by chiral liquid chromatography-mass spectrometry/mass spectrometry (LC/MS/MS)[J]. Journal of Agricultural and Food Chemistry, 2006, 54(17): 6153-6160. PMID
[12]	宋国春, 于建垒, 李瑞娟. 等. 精异丙甲草胺在花生和土壤中的残留[J]. 农药, 2008,(8): 598-600.
	SONG Guochun, YU Jianlei, LI Ruijuan, et al. Residue Dynamics of S-Metolachor in Peanut and Soil[J]. Agrochemicals, 2008,(8): 598-600.
[13]	周芹, 吴玉梅, 许庆轩. 超高效液相色谱-串联质谱法测定甜菜中除草剂残留含量[J]. 中国农学通报, 2017, 33(36): 152-156. DOI
	ZHOU Qin, WU Yumei, XU Qingxuan. Determination of Herbicide Residue in Sugarbeet by Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry[J]. Chinese Agricultural Science Bulletin, 2017, 33(36): 152-156.
[14]	舒梅, 冯绍卫, 岩吞. 等. 农药降解及其影响因素研究进展[J]. 农家参谋, 2018,(4): 74-75,53.
	SHU Mei, FENG Shaowei, YAN Tun, et al. Research progress on pesticide degradation and its influencing factors[J]. The Farmers Consultant, 2018,(4): 74-75,53.
[15]	侯少锋, 李荣玉, 尹显慧. 等. 精异丙甲草胺胁迫下烟草根际土壤微生物的动态响应及其降解[J]. 江苏农业科学, 2016, 44(6): 493-495.
	HOU Shaofeng, LI Rongyu, YIN Xianhui, et al. Dynamic response and degradation of tobacco rhizosphere soil microorganisms under S-Metolachor stress[J]. Jiangsu Agricultural Sciences, 2016, 44(6): 493-495.
[16]	O'CONNELL P-J, HARMS C-T, JRF A. Metolachlor, S-metolachlor and their role within sustainable weed-management.[J]. Crop Protection, 1998, 17(3): 207-212. DOI URL
[17]	张玉婷, 郭永泽, 刘磊. 等. 精异丙甲草胺在大豆及土壤中的残留动态[J]. 农药, 2008,(2): 130-131,139.
	ZHANG Yuting, GUO Yongze, LIU Lei, et al. Residue dynamics of S-Metolachor in soybean and soil[J]. Agrochemicals, 2008,(2): 130-131,139.
[18]	王岩, 孟宪杰. 精异丙甲草胺在甜菜和土壤中的残留动态[J]. 中国糖料, 2010,(3): 20-21,23.
	WANG Yan, MENG Xianjie. Residue Dynamics of S-Metolachor in Sugarbeet and Soil[J]. Sugar Crops of China, 2010,(3): 20-21,23.
[19]	方旭元, 夏高峰, 石巧巧. 等. QuEChERS-GC-MS法检测当归中9种除草剂残留[J]. 华南农业大学学报, 2017, 38(6): 79-83.
	FANG Xuyuan, XIA Gaofeng, SHI Qiaoqiao, et al. Determination of 9 herbicide residues in Angelica sinensis by QuEChERS GC-MS[J]. Journal of South China Agricultural University, 2017, 38(6): 79-83.
[20]	谭华东, 张汇杰, 武春媛. 超声辅助提取-QuEChERS/GC-MS法快速测定土壤中六六六和滴滴涕[J]. 分析试验室, 2019, 38(11): 1303-1308.
	TAN Huadong, ZHANG Huijie, WU Chunyuan. Rapid determination of hexachlorcyclohexane and dichlorodiphenyltrichloroethane in soil using ultrasound-assisted QuEChERS/GC-MS[J]. Chinese Journal of Analysis Laboratory, 2019, 38(11): 1303-1308.

样品 Sam- ple	添加水平 Addition level (μg/mL)	回收率 Recovery (%)			平均回收率 Average recovery (%)	相对标准偏差 Relative standard deviation (%)
土壤 Soil	0.10	77.93	87.95	88.56	84.81	7.04
	0.50	82.20	88.03	90.62	86.95	4.96
	1.00	92.42	95.38	98.42	95.41	3.14
甜菜 Sugar beet	0.10	99.48	101.52	98.95	99.98	1.36
	0.50	120.51	110.21	100.64	110.45	9.00
	1.00	102.50	99.84	100.03	100.79	1.47

样品 Sam- ple	添加水平 Addition level (μg/mL)	回收率 Recovery (%)			平均回收率 Average recovery (%)	相对标准偏差 Relative standard deviation (%)
土壤 Soil	0.10	77.93	87.95	88.56	84.81	7.04
	0.50	82.20	88.03	90.62	86.95	4.96
	1.00	92.42	95.38	98.42	95.41	3.14
甜菜 Sugar beet	0.10	99.48	101.52	98.95	99.98	1.36
	0.50	120.51	110.21	100.64	110.45	9.00
	1.00	102.50	99.84	100.03	100.79	1.47

深度 Depth (cm)	浓度 Concentration (g.a.i/hm²)	消解方程 Digestion equation	K	R²	半衰期 Half-life (d)
0~5	1 296	Y=3.869 e^-0^.⁰⁶⁵^t	0.065	0.891 3	10.66
	1 988	Y=4.821 e^-0^.⁰⁵⁹^t	0.059	0.900 5	11.75
	3 888	Y=7.283 e^-0^.⁰⁶⁴^t	0.064	0.970 5	10.83
5~10	1 296	Y=0.797 e^-0^.⁰⁵⁷^t	0.057	0.965 9	12.16
	1 988	Y=1.661 e^-0^.⁰⁴³^t	0.043	0.966 4	16.12
	3 888	Y=6.254 e^-0^.⁰⁷⁶^t	0.076	0.956 1	9.12
10~15	1 296	Y=0.491 e^-0^.⁰⁶¹^t	0.061	0.978 7	11.36
	1 988	Y=0.991 e^-0^.⁰³⁹^t	0.039	0.943 0	17.77
	3 888	Y=0.706 e^-0^.⁰⁵³^t	0.053	0.985 3	13.08

深度 Depth (cm)	浓度 Concentration (g.a.i/hm²)	消解方程 Digestion equation	K	R²	半衰期 Half-life (d)
0~5	1 296	Y=3.869 e^-0^.⁰⁶⁵^t	0.065	0.891 3	10.66
	1 988	Y=4.821 e^-0^.⁰⁵⁹^t	0.059	0.900 5	11.75
	3 888	Y=7.283 e^-0^.⁰⁶⁴^t	0.064	0.970 5	10.83
5~10	1 296	Y=0.797 e^-0^.⁰⁵⁷^t	0.057	0.965 9	12.16
	1 988	Y=1.661 e^-0^.⁰⁴³^t	0.043	0.966 4	16.12
	3 888	Y=6.254 e^-0^.⁰⁷⁶^t	0.076	0.956 1	9.12
10~15	1 296	Y=0.491 e^-0^.⁰⁶¹^t	0.061	0.978 7	11.36
	1 988	Y=0.991 e^-0^.⁰³⁹^t	0.039	0.943 0	17.77
	3 888	Y=0.706 e^-0^.⁰⁵³^t	0.053	0.985 3	13.08

时间 Time	消解率 Digestion rate	深度 Depth 0~5 (cm)			深度 Depth 5~10 (cm)			深度 Depth 10~15 (cm)
		浓度 Concentration (g.a.i/hm²)
		1 296	1 944	3 888	1 296	1 944	3 888	1 296	1 944	3 888
施药后1 d 1 d after application	w/(mg/kg)	5.00	6.40	8.75	0.56	0.75	6.56	0.26	0.31	0.32
施药后7 d 7 d after application	w/(mg/kg)	3.31	4.15	5.01	0.79	0.98	7.74	0.41	0.36	0.42
施药后7 d 7 d after application	消解率(%)	33.60	35.11	42.79	-	-	-	-	-	-
施药后14 d 14 d after application	w/(mg/kg)	2.15	2.89	3.24	0.54	0.75	3.86	0.26	0.53	0.72
施药后14 d 14 d after application	消解率(%)	56.94	54.87	63.03	4.10	0.53	41.10	-	-	-
施药后21 d 21 d after application	w/(mg/kg)	1.07	1.34	2.06	0.27	0.74	2.55	0.25	0.41	0.50
施药后21 d 21 d after application	消解率(%)	78.68	79.01	76.43	51.52	1.33	61.19	2.70	-	-
施药后30 d 30 d after application	w/(mg/kg)	0.44	0.67	1.04	0.25	0.47	1.04	0.17	0.24	0.28
施药后30 d 30 d after application	消解率(%)	91.31	89.46	88.07	55.79	37.33	84.19	32.82	20.92	14.81
施药后45 d 45 d after application	w/(mg/kg)	0.09	0.12	0.23	0.16	0.29	0.33	0.09	0.23	0.25
施药后45 d 45 d after application	消解率(%)	98.22	98.15	97.40	71.84	61.33	95.00	66.02	23.53	22.84
施药后60 d 60 d after application	w/(mg/kg)	0.03	0.08	0.19	0.09	0.212	0.20	0.03	0.13	0.15
施药后60 d 60 d after application	消解率(%)	99.41	98.74	98.65	83.96	71.73	96.94	90.35	56.21	53.09
施药后90 d 90 d after application	w/(mg/kg)	0.03	0.06	0.11	0.02	0.02	0.09	0.01	0.02	0.07
施药后90 d 90 d after application	消解率(%)	99.33	99.13	98.76	96.43	97.07	98.60	94.98	92.81	79.63