Research Progress of Neonicotinoid Pesticides Certified Reference
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摘要: 新烟碱类农药已成为世界上使用最广泛的杀虫剂,具有高效、广谱、低毒和高选择性的特点。但该类农药可通过饮水、食物和呼吸等方式对人的神经系统、生殖系统等造成潜在的危害。新烟碱类农药有证标准物质是确保新烟碱类农药定量检测结果准确、可比、可溯源的化学砝码。对国内外新烟碱类农药有证标准物质的种类、样品制备和定值技术进行了全面的总结。国内新烟碱类农药有证标准物质以纯度和溶液为主,成份量基本都是啶虫脒和吡虫啉,基体标准物质非常缺乏;纯度标准物质通常采用提纯市售原料的方法制备,并使用质量平衡法、差示扫描量热法等进行定值。国际上新烟碱类农药有证标准物质以基体为主,含有多种特性量;采用向空白样本或者阳性样本添加预期浓度目标分析物的方式制备基体样品,并使用液相色谱同位素稀释质谱法等进行定值。我国新烟碱类农药有证标准物质在种类和结构上发展不平衡。因此,我国应加速开发多组分、多量值的新烟碱类农药基体标准物质,完善量值溯源体系,满足海量检测的需求。Abstract: Neonicotinoid pesticides, characterized by high efficiency, broad-spectrum application, low toxicity, and remarkable selectivity, are now the most widely used insecticides worldwide. Nonetheless, these pesticides pose potential risks to the human nervous and reproductive systems through exposure via drinking water, food, and inhalation. This paper comprehensively summarizes the types, sample preparation techniques, and value assignment methodologies for certified reference materials (CRMs) of neonicotinoid pesticides, crucial for ensuring accurate, comparable, and traceable quantitative detection results. In China, CRMs primarily consist of purity and solution reference materials, chiefly incorporating acetamiprid and imidacloprid. However, there is a significant shortage of matrix reference materials. Purity CRMs are typically prepared by purifying commercially available materials, and their values are primarily assigned using mass balance methods and differential scanning calorimetry. Conversely, international institutes have developed a plethora of matrix CRMs for neonicotinoid pesticides, containing various analytes. These matrix samples are prepared by spiking blank or positive samples with the expected concentration of analytes and are subsequently quantified using liquid chromatography isotope dilution mass spectrometry (LC-ID-MS). The development of neonicotinoid pesticide CRMs in China lacks balance both in type and structure. Hence, the development of multi-component and multi-level matrix CRMs for neonicotinoid pesticides needs to be accelerated to improve the quantitative traceability system and meet the growing demand for extensive testing.
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Key words:
- metrology /
- nicotinoids /
- pesticides /
- certified reference materials /
- value assignment /
- liquid chromatography
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表 1 检测食品中新烟碱类农药的国家标准
Table 1. National standards for neonicotinoid pesticides detection in food
目标物 标准号 名称 检测方法 吡虫啉 GB 23200.121 食品安全国家标准 植物源性食品中331种农药及其代谢物残留量的测定 液相色谱-质谱联用法 GB/T 20769 水果和蔬菜中450种农药及相关化学品残留量的测定 液相色谱-串联质谱法 GB/T 20770 粮谷中486种农药及相关化学品残留量的测定 液相色谱-串联质谱法 GB/T 23379 水果、蔬菜及茶叶中吡虫啉残留的测定 高效液相色谱法 啶虫脒 GB 23200.121 食品安全国家标准 植物源性食品中331种农药及其代谢物残留量的测定 液相色谱-质谱联用法 GB/T 20769 水果和蔬菜中450种农药及相关化学品残留量的测定 液相色谱-串联质谱法 GB/T 20770 粮谷中486种农药及相关化学品残留量的测定 液相色谱-串联质谱法 GB/T 20772 动物肌肉中461种农药及相关化学品残留量的测定 液相色谱-串联质谱法 GB/T 23584 水果、蔬菜中啶虫脒残留量的测定 液相色谱-串联质谱法 呋虫胺 GB 23200.51 食品安全国家标准 食品中呋虫胺残留量的测定 液相色谱-质谱/质谱法 GB 23200.121 食品安全国家标准 植物源性食品中331种农药及其代谢物残留量的测定 液相色谱-质谱联用法 GB 23200.37 食品安全国家标准 食品中烯啶虫胺、呋虫胺等20种农药残留量的测定 液相色谱-质谱/质谱法 GB/T 20769 水果和蔬菜中450种农药及相关化学品残留量的测定 液相色谱-串联质谱法 GB/T 20770 粮谷中486种农药及相关化学品残留量的测定 液相色谱-串联质谱法 噻虫胺 GB 23200.39 食品安全国家标准 食品中噻虫嗪及其代谢物噻虫胺残留量的测定 液相色谱-质谱/质谱法 GB 23200.121 食品安全国家标准 植物源性食品中331种农药及其代谢物残留量的测定 液相色谱-质谱联用法 GB/T 20769 水果和蔬菜中450种农药及相关化学品残留量的测定 液相色谱-串联质谱法 GB/T 20770 粮谷中486种农药及相关化学品残留量的测定 液相色谱-串联质谱法 噻虫啉 GB 23200.13 食品安全国家标准 茶叶中448种农药及相关化学品残留量的测定 液相色谱-质谱法 GB 23200.121 食品安全国家标准 植物源性食品中331种农药及其代谢物残留量的测定 液相色谱-质谱联用法 GB/T 20769 水果和蔬菜中450种农药及相关化学品残留量的测定 液相色谱-串联质谱法 GB/T 20770 粮谷中486种农药及相关化学品残留量的测定 液相色谱-串联质谱法 噻虫嗪 GB 23200.8 食品安全国家标准 水果和蔬菜中500种农药及相关化学品残留量的测定 气相色谱-质谱法 GB 23200.9 食品安全国家标准 粮谷中475种农药及相关化学品残留量的测定 气相色谱-质谱法 GB 23200.11 食品安全国家标准 桑枝、金银花、枸杞子和荷叶中413种农药及相关化学品残留量的测定 液相色谱-质谱法 噻虫嗪 GB 23200.39 食品安全国家标准 食品中噻虫嗪及其代谢物噻虫胺残留量的测定 液相色谱-质谱/质谱法 GB 23200.121 食品安全国家标准 植物源性食品中331种农药及其代谢物残留量的测定 液相色谱-质谱联用法 GB/T 20769 水果和蔬菜中450种农药及相关化学品残留量的测定 液相色谱-串联质谱法 GB/T 20770 粮谷中486种农药及相关化学品残留量的测定 液相色谱-串联质谱法 烯啶虫胺 GB 23200.13 食品安全国家标准 茶叶中448种农药及相关化学品残留量的测定 液相色谱-质谱法 GB 23200.37 食品安全国家标准 食品中烯啶虫胺、呋虫胺等20种农药残留量的测定 液相色谱-质谱/质谱法 GB/T 20769 水果和蔬菜中450种农药及相关化学品残留量的测定 液相色谱-串联质谱法 GB/T 20770 粮谷中486种农药及相关化学品残留量的测定 液相色谱-串联质谱法 表 2 新烟碱类农药基体标准物质信息
Table 2. Information on matrix reference materials for neonicotinoid pesticides
机构 编号 基体 量值及不确定度 KRISS 108-05-006 泡菜 啶虫脒(0.096 ± 0.004)mg/kg 吡虫啉(0.110 ± 0.004)mg/kg KRISS 108-05-013 泡菜 吡虫啉(0.860 ± 0.020)mg/kg 噻虫胺(0.524 ± 0.012)mg/kg 噻虫嗪(0.787 ± 0.014)mg/kg JRC ERM-BC403 黄瓜 啶虫脒(0.064 ± 0.004)mg/kg(k=2) 吡虫啉(0.627 ± 0.026)mg/kg(k=2) JRC ERM-BC700 大豆 吡虫啉(0.075 ± 0.009)mg/kg(k=2) JRC ERM-BC706 小麦面粉 吡虫啉(0.044 ± 0.007)mg/kg(k=2) NMIJ 7408-a 人工尿液 啶虫脒(1.38 ± 0.27)μg/kg(k=2) 噻虫胺(1.34 ± 0.31)μg/kg(k=2) 噻虫啉(0.19 ± 0.06)μg/kg(k=2) 噻虫嗪(1.32 ± 0.46)μg/kg(k=2) -
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