Risk Assessment and Ranking of Pesticide Residues in Different Varieties of Xinjiang Red Jujube
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摘要: 为了评估新疆不同品种红枣中农药残留的危害，探明不同品种红枣（冬枣、灰枣和骏枣）中农药残留的高风险危害因子及其风险等级。利用液相色谱-质谱法和气相色谱-质谱法测定红枣中的93种农药，比较不同品种红枣的农药残留差异，并进行风险评估，对红枣中的农药残留风险和样品风险进行排序。85份红枣共检出农药16种，不同品种的红枣农药残留检出率和检出种类不同，冬枣的农药残留检出率93.33%、检出农药种类15种，明显高于灰枣和骏枣农药残留检出率和农药种类。红枣检出农药的慢性膳食摄入风险和急性膳食摄入风险远小于100%，风险在可接受范围。冬枣中高风险农药是甲氨基阿维菌素苯甲酸盐和中风险农药哒螨灵、联苯菊酯、辛硫磷、啶虫脒、甲氰菊酯。灰枣和骏枣中风险农药为：辛硫磷、丙溴磷和啶虫脒。冬枣样品中存在高风险和中等风险的样品，灰枣和骏枣样品为中风险和低风险样品。新疆红枣的质量安全状况整体良好，但冬枣农药残留风险整体偏高，应引起重视。Abstract: In order to evaluate the harm of pesticide residues and explore the high-risk hazard factors and risk levels in different varieties of Xinjiang red jujube (winter jujube, Hui jujube and Jun jujube), 93 pesticides were determined by liquid chromatography-mass spectrometry and gas chromatography-mass spectrometry. The differences of pesticide residues in different varieties of jujube were compared, and the risk of pesticide residues in jujube samples were evaluated and ranked. A total of 16 kinds of pesticides were detected in 85 red jujube samples. The detection rates and types of pesticide residues in different varieties of red jujube were different. The detection rates of pesticide residues in winter jujube were 93.33% and 15 kinds of pesticides were detected, which were significantly higher than those in Hui jujube and Jun jujube. The risk of chronic dietary intake and acute dietary intake of pesticides detected in jujube were far less than 100%, which was in an acceptable range. The high and medium risk pesticides in winter jujube were methamamectin benzoate, mite, biphenthrin, thiophosphate, acetamidine and permethrin. The medium risk pesticides in Hui jujube and Jun jujube were: phosphorus, propylene bromphosphorus and acetamidine. There were high risk and medium risk samples in the winter jujube samples, but the Hui jujube and Jun jujube samples were both medium risk and low risk samples. The quality and safety of jujube in Xinjiang is generally good, but the risk of pesticide residue in winter jujube is generally high, which should be paid attention to.
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Key words:
- Xinjiang red jujube /
- different varieties /
- pesticide residues /
- risk assessment /
- risk ranking
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图 1 检出不同农药种数的冬枣样品所占比例
Figure 1. The proportion of winter jujube samples with different kinds of pesticides detected
图 2 冬枣中检出率在10%以上的11种农药
Figure 2. Winter jujube detection rate in more than 10% of the 11 pesticides
图 3 检出不同农药种数的灰枣和骏枣样品所占比例
Figure 3. The proportion of Hui jujube and Jun jujube samples with different kinds of pesticides detected
表 1 红枣样品中待测农药信息
Table 1. Pesticide information tested in red jujube samples
检测方法 农药名称 数量（种） 液相色谱-质谱法 噻虫嗪，灭多威，除虫脲，虫螨腈，甲萘威，啶虫脒，辛硫磷，涕灭威，氯菊酯，甲氰菊酯，灭幼脲，3-羟基克百威，亚胺硫磷，醚菊酯，涕灭威砜，氰戊菊酯，氟甲腈，敌百虫，涕灭威亚砜，氟氰戊菊酯，氟胺氰菊酯，噻嗪酮，丁草胺，溴氰菊酯，乙酰甲胺磷，甲胺磷，吡虫啉，阿维菌素，氟虫腈砜，虫酰肼，氯虫苯甲酰胺，氟虫腈硫醚，甲氨基阿维菌素苯甲酸盐，吡唑醚菌酯，异菌脲，腈苯唑，氯苯嘧啶醇，烯酰吗啉，甲基硫菌磷，苯醚甲环唑，霜霉威，多菌灵，咪鲜胺，氯吡脲，克百威，毒死蜱，甲拌磷亚砜，丙溴磷，甲拌磷砜，甲基异柳磷 50 气相色谱-质谱法 乐果，三氯杀螨醇，异丙甲草胺，氯氟氰菊酯，六六六-δ，水胺硫磷，哒螨灵，马拉硫磷，氧乐果，甲拌磷，伏杀硫磷，六六六-γ，甲基对硫磷，3,5-二氯苯胺，氟氯氰菊酯，六六六-α，杀螟硫磷，六六六-β，氯氰菊酯，灭蝇胺，苯醚甲环唑，乙烯菌核利，丙环唑，五氯硝基苯，2,4,6-三氯苯酚，百菌清，醚菌酯，甲霜灵，戊唑醇，腈菌唑，二甲戊乐灵，多效唑，联苯菊酯，抗蚜威，对硫磷，氟虫腈，敌敌畏，异丙威，二嗪磷，三唑磷，三唑酮，三唑醇，腐霉利 43 合计 93 注：依据GB 23200.121-2021和GB 23200.113-2018的规定，93 种农药的定量限范围为0.002~0.01 mg/kg。 
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表 2 农药风险排序赋分标准
Table 2. Pesticide risk ranking and assigning criteria
指标 指标值 得分 指标值 得分 指标值 得分 指标值 得分 毒性得分 低毒 2 中毒 3 高毒 4 剧毒 5 毒效得分（mg·kg−1） >1×10−2 0 1×10−4~1×10−2 1 1×10−6~1×10−4 2 <1×10−6 3 膳食比例得分 <2.5 0 2.5~20 1 20~50 2 50~100 3 农药使用频率得分 <2.5 0 2.5~20 1 20~50 2 50~100 3 高暴露人群得分 无 0 不太可能 1 有可能 2 无相关数据 3 残留水平得分 未检出 1 <限量值 2 ≥限量值 3 ≥10倍限值 4
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表 3 冬枣质量安全状况
Table 3. Quality and safety status of winter jujube
名称 样品（个） 检出（个） 检出（%） 超标（个） 超标（%） 数量 30 28 93.33 0 0
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表 4 灰枣和骏枣质量安全状况
Table 4. Quality and safety status of Hui jujube and Jun jujube
名称 样品（个） 检出（个） 检出（%） 超标（个） 超标（%） 数量 55 16 29.09 0 0
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表 5 新疆红枣农药残留安全性评估
Table 5. Safety assessment of pesticide residues in Xinjiang red jujube
序号 农药名称 毒性 残留平均值（mg/kg） 最大残留值（mg/kg） ADI（mg/kg） %ADI（%） ARfD（mg/kg） %ARfD（%） 1 烯酰吗啉 低 0.0029 0.0760 0.20 0.0017 0.60 0.0705 2 辛硫磷 低 0.0003 0.0098 0.004 0.0087 − − 3 咪鲜胺 低 0.0109 0.4620 0.01 0.1309 0.10 2.5735 4 甲氨基阿维菌素苯甲酸盐 中 0.0007 0.0416 0.0005 0.1640 − − 5 吡虫啉 低 0.0053 0.1294 0.06 0.0106 0.40 0.1802 6 啶虫脒 中 0.0003 0.0191 0.07 0.0005 0.10 0.1067 7 多菌灵 低 0.0082 0.3361 0.03 0.0329 0.10 1.8721 8 醚菌酯 低 0.0003 0.0292 0.40 0.0001 − − 9 噻虫嗪 低 0.0041 0.0618 0.08 0.0061 1 0.0344 10 哒螨灵 中 0.0006 0.0261 0.01 0.0073 − − 11 多效唑 低 0.0025 0.1319 0.10 0.0030 − − 12 氟苯虫酰胺 低 0.0035 0.2111 0.02 0.0210 0.20 0.5879 13 联苯菊酯 中 0.0004 0.0094 0.01 0.0042 0.01 0.5211 14 虫螨腈 低 0.0027 0.0704 0.03 0.0108 0.03 1.3074 15 甲氰菊酯 中 0.0004 0.0350 0.03 0.0016 0.03 0.6491 16 丙溴磷 中 0.0001 0.0029 0.03 0.0002 1 0.0016 合计 − − − − − 0.4037 − 7.9047 注：“−”表示未检出。
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表 6 新疆冬枣农药残留得分及风险排序
Table 6. Score and risk ranking of pesticide residues in Xinjiang winter jujube
序号 农药名称 风险得分 排序 1 甲氨基阿维菌素苯甲酸盐 20.8 1 2 哒螨灵 16 2 3 联苯菊酯 15.4 3 4 辛硫磷 15.2 4 5 啶虫脒 15.1 5 6 甲氰菊酯 15.1 5 7 多菌灵 11.34 7 8 噻虫嗪 11.34 7 9 多效唑 11.34 7 10 氟苯虫酰胺 10.47 10 11 烯酰吗啉 10.40 11 12 咪鲜胺 10.40 11 13 虫螨腈 10.40 11 14 吡虫啉 10.27 14 15 醚菌酯 10.07 15
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表 7 新疆灰枣和骏枣农药残留得分及风险排序
Table 7. Score and risk ranking of pesticide residues in Xinjiang Hui jujube and Jun jujube
序号 农药名称 风险得分 排序 1 辛硫磷 15.22 1 2 丙溴磷 15.11 2 3 啶虫脒 15.05 3 4 多菌灵 10.36 4 5 吡虫啉 10.07 5 6 噻虫嗪 10.04 6
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表 8 灰枣和骏枣农药残留风险等级及指数划分
Table 8. Risk grades and index classification of pesticide residues in Hui jujube and Jun jujube
风险等级 风险指数划分 占比 风险指数（RI） 极低风险 RI<5 0% 低风险 15>RI≥5 94.55% 中等风险 20>RI≥15 5.45% 高风险 RI≥20 0%
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