虫螨腈及其代谢物溴代吡咯腈在芥菜上的残留行为与膳食风险评估

孙瑞卿; 王霞; 任鹏程; 金静; 李晋栋; 乔雄梧; 秦曙

doi:10.16801/j.issn.1008-7303.2022.0049

虫螨腈及其代谢物溴代吡咯腈在芥菜上的残留行为与膳食风险评估

doi: 10.16801/j.issn.1008-7303.2022.0049

1.
山西农业大学山西功能农产品检验检测中心，农业农村部农产品质量安全风险评估实验室 (太原)，太原 030031

基金项目: 农业行业标准制定和修订项目.

详细信息

作者简介:
孙瑞卿，sunruiqing001@163.com

通讯作者:
秦曙，qinshu55@126.com

中图分类号: TQ450.26；S482.3
计量
- 文章访问数: 101
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- 被引次数: 0
出版历程
- 收稿日期: 2021-11-19
- 录用日期: 2022-04-11
- 网络出版日期: 2022-05-26
- 刊出日期: 2022-06-10

Residue behavior and dietary risk assessment of chlorfenapyr and its metabolite tralopyril in mustard

1.
(Shanxi Center for Testing of Functional Agro-Products, Shanxi Agricultural University, Laboratory for Risk Assessment of Quality and Safety of Agro-Products (Taiyuan), Ministry of Aagriculture and Rural Affairs, Taiyuan 030031, China

Funds: Development and Revision of Agricultural Industry Standards.

摘要

摘要: 为评价虫螨腈及其代谢物溴代吡咯腈在芥菜中的残留行为与膳食摄入风险，在山西、北京、吉林、河南、安徽、贵州6地进行了规范残留试验，建立了快速、简便的检测芥菜中虫螨腈残留的气相色谱-串联质谱(GC-MS/MS)方法及检测芥菜中溴代吡咯腈残留的超高效液相色谱-串联质谱(UPLC-MS/MS)方法，研究了虫螨腈及溴代吡咯腈在芥菜中的最终残留和消解动态，并就两种农药对中国不同人群的长期及短期膳食摄入风险进行了评估。结果表明：在0.01~30 mg/kg添加水平范围内，虫螨腈及溴代吡咯腈的平均回收率分别在89%~105%和97%~104%之间，相对标准偏差 (RSD) 分别在2%~4%和1%~3%之间；两种化合物在芥菜叶和根中的检测方法定量限 (LOQ) 均为0.01 mg/kg。虫螨腈在芥菜叶中的消解动态符合一级反应动力学方程，消解半衰期为4.2~5.9 d；溴代吡咯腈的消解动态因拟合曲线符合性太差无法进行一级反应动力学方程拟合。100 g/L虫螨腈悬浮剂以推荐最高剂量(有效成分105 g/hm²)施药2次、施药间隔期5 d、采收间隔期14 d，膳食消费量为97.5%位点处，芥菜叶中虫螨腈残留对3~5岁儿童和普通人群长期膳食摄入风险的贡献率分别为0.49%和2.47%，说明通过芥菜摄入虫螨腈及其代谢物残留对人体产生的长期膳食摄入风险较小；而短期膳食摄入风险评估结果表明，芥菜叶中虫螨腈对中国1~6岁儿童和普通人群均存在不可接受的短期膳食摄入风险，且对1~6岁儿童的风险远高于对普通人群。选择不同施药方式下的最终残留量数据进行评估，将可能导致风险评估结果产生较大差异，施药剂量或施药次数的增加会大幅提高农药残留的短期膳食摄入风险，建议可通过延长采收间隔期的方法降低农药的短期膳食摄入风险水平。
- 虫螨腈 /
- 溴代吡咯腈 /
- 芥菜 /
- 代谢物 /
- 残留 /
- 膳食摄入风险评估
Abstract: In order to evaluate the residue behavior and dietary exposure risk of chlorfenapyr and its metabolite tralopyril applied to mustard, the supervised residual trial of chlorfenapyr in mustard were carried out in Shanxi, Beijing, Jilin, Henan, Anhui and Guizhou Provinces in China. A rapid and simple analytical method for determination of chlorfenapyr residues using GC-MS/MS and for tralopyril residues using UPLC-MS/MS in mustard was developed. The final residues and dissipation dynamics were studied, and the long-term and short-term dietary intake risks of the two pesticides to different Chinese populations were evaluated. The results showed that the average recoveries of chlorfenapyr and tralopyril in mustard samples at three spiked levels from 0.01 mg/kg to 30 mg/kg were 89%-105% and 97%-104%, with the relative standard deviation (RSD) ranged from 2% to 4% and 1% to 3%, respectively. The limits of quantification (LOQs) of the two analytes in mustard root and mustard leaf were all 0.01 mg/kg. The dissipation dynamics of chlorfenapyr in mustard leaves accorded with the first-order reaction kinetic equation, and the half-life was 4.2-5.9 days, while the dissipation dynamics of tralopyril could not be fitted with the first-order reaction kinetic equation. The suspension concentrate of chlorfenapyr was sprayed twice at a 5-days interval and a dosage of 105 g a.i./hm² with a pre-harvest sampling interval of 14 days. The long-term dietary intake risk assessment at 97.5% food consumption showed that the contribution rate of mustard leaf residues to the ADI for children aged 3-5 and for the general population was 0.49% and 2.47%, respectively. This indicated that the chronic dietary intake risk of chlorfenapyr and its metabolite through mustard was very low. However, the short-term dietary intake risk assessment showed that the chlorfenapyr in mustard leaves had an unacceptable acute dietary intake risk for both Chinese children aged 1-6 years and the general population. The risk of acute dietary intake for children aged 1-6 years was much higher than for the general population. Changing of the pesticide application methods will lead to differentiated risk assessment results. Increasing the application dose or application times will lead to a higher acute dietary intake risk. Therefore, it is suggested to reduce the level of acute dietary intake risk by prolonging of the pre-harvest interval.
- chlorfenapyr /
- tralopyril /
- mustard /
- metabolite /
- residue /
- dietary risk assessment

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图 1 虫螨腈母体在山西 (A) 和北京 (B) 两地芥菜叶中的消解曲线

Figure 1. Digestion curves of chlorfenapyr in mustard leaf in Shanxi (A) and Beijing (B)

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表 1 虫螨腈和溴代吡咯腈质谱参数

Table 1. MS parameters of chlorfenapyr and tralopyril

化合物 Compound	保留时间 Retention time/min	定性离子对Qualitative ion, m/z	定量离子对Quantitative ion, m/z	碰撞能量 Collision energy/eV	锥孔电压 Cone voltage/V
虫螨腈 chlorfenapyr	8.2	246.9/227.0	246.9/227.0	15	—
虫螨腈 chlorfenapyr	8.2	136.9/102.0	—	15	—
溴代吡咯腈 tralopyril	3.0	349.0/81.0	—	33	30
溴代吡咯腈 tralopyril	3.0	349.0/131.0	349.0/131.0	38	30

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表 2 虫螨腈和溴代吡咯腈在芥菜中的添加回收率和相对标准偏差

Table 2. The recoveries and RSD of chlorfenapyr and tralopyril in mustard

杀虫剂 Insecticide	基质 Matrix	标准曲线 Standard curves	添加水平 Spiked level/(mg/kg)	平均回收率 Average recovery/%	相对标准偏差 RSD/%
虫螨腈 chlorfenapyr	芥菜根 Mustard root	y = 538617x − 4344.5 R² = 0.9985	0.01	93	4
			0.1	102	2
			1	105	4
	芥菜叶 Mustard leaf	y = 808495x − 567.18 R² = 0.9998	0.01	98	3
			0.1	100	3
			30	89	4
溴代吡咯腈 tralopyril	芥菜根 Mustard root	y = 416666x + 2985.6 R² = 0.9975	0.01	97	2
			0.05	102	1
			0.1	97	1
	芥菜叶 Mustard leaf	y = 397554x + 3742.5R² = 0.9949	0.01	104	3
			0.1	103	2
			0.3	97	2

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表 3 芥菜中虫螨腈、溴代吡咯腈及虫螨腈总量(评估定义)的最终残留

Table 3. Final residues of chlorfenapyr, tralopyril and total chlorfenapyr (evaluation definition) in mustard

基质 Matrix	施药次数 Times of application	施药剂量 Dosage, a.i./(g/hm²)	采收间隔期 Interval to harvest/d	残留量 Residue/(mg/kg)
基质 Matrix	施药次数 Times of application	施药剂量 Dosage, a.i./(g/hm²)	采收间隔期 Interval to harvest/d	虫螨腈 chlorfenapyr	溴代吡咯腈 tralopyril	虫螨腈总量 (风险评估定义)Total chlorfenapyr (definition for risk assessment)
芥菜根 Mustard root	2	105	0	0.032~0.17	<0.010	0.032~0.17
			10	0.026~0.21	<0.010	0.026~0.21
			14	0.015~0.22	<0.010	0.015~0.22
			21	0.019~0.18	<0.010	0.019~0.18
	2	157.5	0	0.045~0.48	<0.010	0.045~0.48
			10	0.042~0.74	<0.010	0.042~0.74
			14	0.039~0.36	<0.010	0.039~0.36
			21	0.031~0.45	<0.010	0.031~0.45
	3	105	0	0.036~0.42	<0.010	0.036~0.42
			10	0.014~0.20	<0.010	0.014~0.20
			14	0.034~0.28	<0.010	0.034~0.28
			21	0.030~0.23	<0.010	0.030~0.23
	3	157.5	0	0.048~0.86	<0.010	0.048~0.86
			10	0.034~0.67	<0.010	0.034~0.67
			14	0.064~0.65	<0.010	0.064~0.65
			21	0.033~0.58	<0.010	0.033~0.58
芥菜叶 Mustard leaf	2	105	0	1.79~7.74	<0.010~0.15	2.14~8.50
			10	0.46~4.17	<0.010~0.17	0.46~5.63
			14	0.25~6.80	<0.010~0.12	0.25~7.97
			21	0.20~4.59	<0.010~0.066	0.20~5.25
	2	157.5	0	2.03~14.06	0.020~0.17	2.23~15.03
			10	0.23~10.50	<0.010~0.26	0.23~13.06
			14	0.24~8.40	<0.010~0.21	0.24~10.52
			21	0.14~2.04	<0.010~0.17	0.14~3.25
	3	105	0	1.15~12.06	0.035~0.13	1.66~12.99
			10	0.36~8.51	<0.010~0.22	0.36~10.35
			14	0.20~8.72	<0.010~0.19	0.20~10.58
			21	0.11~1.27	<0.010~0.086	0.11~1.94
	3	157.5	0	2.94~29.56	<0.010~0.16	2.94~29.95
			10	0.70~17.47	<0.010~0.38	0.70~21.07
			14	0.31~22.59	<0.010~0.34	0.31~25.98
			21	0.080~2.71	<0.010~0.22	0.080~4.87

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表 4 虫螨腈母体在芥菜叶中的消解参数

Table 4. Dissipation parameters for chlorfenapyr in the mustard leaf

农药 Pesticide	试验地点 Location	消解方程 Digestion equation	相关系数 r	半衰期 T_1/2/d	k/(d⁻¹)
虫螨腈 chlorfenapyr	山西 Shanxi	c_t = 5.316 8e^−0.118t	0.9445	5.9	0.118
虫螨腈 chlorfenapyr	北京 Beijing	c_t = 2.706 5e^−0.163t	0.9630	4.2	0.163

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表 5 芥菜叶中虫螨腈残留的长期膳食摄入风险评估结果^[19]

Table 5. The results of long-term dietary intake risk assessment of chlorfenapyr in mustard leaf^[19]

消费群体 Consumer group	膳食 50% 位点 50% food comsumption		膳食 95% 位点 95% food comsumption		膳食 97.5% 位点 97.5% food comsumption
消费群体 Consumer group	膳食消费量 Dietary consumption/(g/d)	RQ_c%	膳食消费量 Dietary consumption/(g/d)	RQ_c%	膳食消费量 Dietary consumption/(g/d)	RQ_c%
一般人群 General population	1.8939	0.12	6.25	0.40	7.6923	0.49
3~5 岁儿童 3-5 years children	3.3109	0.64	10.5556	2.03	12.8	2.47
注：膳食消费量/体重的计算单位：g/kg bw。 Note: Unit of measure for dietary consumption/ body weight: g/ kg bw.

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表 6 虫螨腈的短期膳食摄入风险评估结果

Table 6. The results of short-term dietary intake risk assessment of chlorfenapyr

情景 Scenario	施药次数Times of application	施药剂量Dosage/ (g/hm²)	采收间隔期Interval to harvest/d	芥菜叶中残留量 (总量计) Residue of mustard leaf (total)/(mg/kg)	STMR/ (mg/kg)	HR/ (mg/kg)	%ARfD
情景 Scenario	施药次数Times of application	施药剂量Dosage/ (g/hm²)	采收间隔期Interval to harvest/d	芥菜叶中残留量 (总量计) Residue of mustard leaf (total)/(mg/kg)	STMR/ (mg/kg)	HR/ (mg/kg)	1~6 岁儿童Aged1-6 children	普通人群General population
1	2	105	14	0.25，0.29，0.36，0.47，0.48，0.70，0.75，0.78，0.96，1.07，1.21，1.41，1.54，1.54，1.64，5.23，5.54，7.97	1.02	7.97	1299	521
2	2	157.5	14	0.24，0.28，0.55，0.97，0.99，1.03，1.10，1.31，1.47，1.91，2.54，2.79，2.80，3.65，4.06，8.25，8.90，10.52	1.69	10.52	1715	688
3	3	105	14	0.20，0.22，0.26，059，0.62，0.72，0.74，0.78，1.03，1.08，1.47，1.79，2.69，3.04，3.08，9.16，9.34，10.58	1.06	10.58	1725	692
4	2	105	21	0.20，0.22，0.22，0.33，0.35，0.41，0.44，0.54，0.56，0.64，0.66，0.73，0.75，0.84，1.06，3.77，3.81，5.25	0.60	5.25	856	343

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