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甲基硫菌灵及其代谢物多菌灵在猕猴桃上的残留及安全性评价

花匠小妙招
2026-05-10 13:05

摘要: 为了评估甲基硫菌灵在猕猴桃上使用的安全性，采用QuEChERS-超高效液相色谱-串联质谱分析方法，对甲基硫菌灵及其代谢物多菌灵在猕猴桃上的残留量进行了分析，明确了其消解规律及半衰期，通过进行膳食摄入风险评估，以推荐甲基硫菌灵在猕猴桃上的最大残留限量 (MRL)，并对其代谢物多菌灵的残留量进行了安全性评价。结果表明：在0.01、0.1和1.0 mg/kg 3个添加水平下，甲基硫菌灵的回收率为85%~102%，相对标准偏差 (RSD) 为1.0%~7.1%；多菌灵的回收率为86%~101%，RSD为2.1%~5.2%；两者的定量限均为0.01 mg/kg。甲基硫菌灵在猕猴桃上的消解符合一级反应动力学方程，半衰期为10.1~10.5 d，属易消解农药。70%甲基硫菌灵可湿性粉剂在猕猴桃上按照推荐剂量及1.5倍推荐剂量 (875和1 166.7 mg/kg) 分别施药3次和4次，推荐采收间隔期为21 d，膳食风险商为78.7%，推荐MRL值为5 mg/kg，该结果通常不会对一般人群健康产生不可接受的风险。依据GB 2763多菌灵在猕猴桃上的MRL值0.5 mg/kg，代谢物多菌灵存在较大的超标风险。建议有关部门制定甲基硫菌灵在猕猴桃上的MRL值，并重新评估多菌灵在猕猴桃上的MRL值。

Abstract: To evaluate the safety of thiophanate-methyl in kiwi fruit, the QuEChERS-ultra high performance liquid chromatography-tandem mass spectrometry (QuEChERS-UPLC-MS/MS) analysis method was used to analyze the residues of thiophanate-methyl and its metabolite carbendazim in kiwi fruit. The kinetic equation and half-life of thiophanate-methyl residues in kiwi fruit were calculated. The dietary intake risk assessment was conducted. The maximum residue limit (MRL) of thiophanate-methyl in kiwi fruit was recommended and the safety of its metabolite carbendazim was evaluated. The results showed that the recovery rates of thiophanate-methyl and carbendazim were 85%-102% and 86%-101%, respectively, and their relative standard deviations (RSD) were 1.0%-7.1% and 2.1%-5.2%, respectively, at the spiked levels of 0.01, 0.1 and 1.0 mg/kg. The limits of quantitation (LOQ) of two pesticides on kiwi fruit were both 0.01 mg/kg. The regulation of thiophanate-methyl residues in kiwi fruit conformed to the first-order reaction kinetic equation, with the half-life of 10.1-10.5 d. When the recommended dosage and 1.5 times of the recommended dosage (875 mg/kg, 1 166.7 mg/kg) of thiophanate-methyl (70% WP) were sprayed for 3-4 times and the harvest interval was 21 days, the dietary risk quotient (RQ) was calculated as 78.7%. The result was acceptable to the general population and a MRL valaue of 5 mg/kg was recommended. The metabolite carbendazim had a greater risk of exceeding the standard of 0.5 mg/kg according to GB 2763. The MRL valaue of thiophanate-methyl should be established in kiwi fruit, while the MRL value of carbendazim should be reevaluated.

表 1 甲基硫菌灵和多菌灵在猕猴桃中的添加回收率及相对标准偏差 (n = 5)

Table 1 Recoveries and RSDs of thiophanate-methyl and carbendazim in kiwi fruit(n = 5)

农药
Pesticide添加水平
Fortified level/(mg/kg)平均回收率
Average recovery/%相对标
准偏差
RSD/%甲基硫菌灵
thiophanate-methyl0.011027.00.1887.11851.0多菌灵
carbendazim0.011015.20.1922.11862.2

表 2 甲基硫菌灵在猕猴桃上的消解动态方程及半衰期 (2018年)

Table 2 The kinetic equation and half lives of thiophanate-methyl in kiwi fruit (Year 2018)

农药
Pesticide试验地点
Location一级动力学方程
First-order kinetic equation相关系数
r半衰期
Half-life/d药后 28 d消解率
Dissipation rate at 28 days
after spraying/%甲基硫菌灵
thiophanate-methyl山东 Shandongct = 1.63e−0.068 4t−0.969 710.186湖北 Hubeict = 2.74e−0.065 7t−0.947 510.594

表 3 甲基硫菌灵和多菌灵在猕猴桃中的最终残留量 (2018年) (n = 3)

Table 3 Terminal residues of thiophanate-methyl and carbendazim in kiwi fruit (Year 2018) (n = 3)

农药　　
Pesticide　　采收间隔期
PHI/d残留量 Residues/(mg/kg)山东
Shandong湖北
Hubei重庆
Chongqing安徽
Anhui陕西
Shaanxi山西
Shanxi多菌灵 carbendazim140.33~0.580.67~1.01−0.11~0.240.27~0.730.83~1.25210.19~0.550.15~0.480.29~0.450.07~0.180.36~0.540.82~1.32280.15~0.300.13~0.480.24~0.390.06~0.150.26~0.480.62~0.99甲基硫菌灵 thiophanate-methyl141.19~1.712.44~3.26−0.28~0.670.95~2.391.79~2.47210.41~0.950.50~2.131.64~2.620.16~0.371.28~2.001.58~2.49280.26~0.730.32~1.631.55~2.650.09~0.240.84~1.820.98~1.82注：− 表示数据缺失。Note: − indicated no data.

表 4 膳食风险评估

Table 4 Dietary risk assessment

食物种类
Food category膳食量[20]
Dietary intake[20]/kg参考限量[18]
MRL[18]/(mg/kg)限量来源　
Source　国家估算每日摄入量
NEDI/mg风险商
Risk quotient/%米及其制品 Rice and products0.239 92中国 China0.239 9面及其制品 Flour and products0.138 50.5中国 China0.069 25其他谷类 Other cereals0.023 30.5中国 China0.006 757薯类 Tubers0.049 50.6日本 Japan0.004 95深色蔬菜 Dark vegetables0.091 53中国 China0.274 5浅色蔬菜 Light vegetables0.183 73中国 China0.367 4水果 Fruits0.045 71.4残留中值 STMR0.070 378植物油 Plant oil0.032 70.2中国 China0.003 27糖、淀粉 Sugar and starch0.004 40.1中国 China0.000 88酱油 Soy sauce0.0090其他类小计 Others0.210 40合计 Total1.028 61.487 078.7 [1] 李华丽, 魏仲珊, 邓萍, 等. 猕猴桃的营养价值及其加工应用[J]. 湖南农业科学, 2019(1): 119-122.

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