纳米四氧化三铁在茶叶农药残留检测中的应用及方法优化

李捷; 张峰; 黄菁菁; 丁立平; 杨方; 姚清华

doi:10.19303/j.issn.1008-0384.2021.01.009

纳米四氧化三铁在茶叶农药残留检测中的应用及方法优化

doi: 10.19303/j.issn.1008-0384.2021.01.009

李捷^{1, 2,},
张峰²,
黄菁菁²,
丁立平²,
杨方^1, ,,
姚清华^3, ,

1.
福州海关技术中心，福建　福州　350001
2.
榕城海关综合技术服务中心，福建　福州　350300
3.
福建省农业科学院农业质量标准与检测技术研究所，福建　福州　350003

基金项目: 福建省自然科学基金面上项目（2017J01040）；国家质量基础的共性技术研究与应用专项（2017YFF0211304）

详细信息

作者简介:
李捷（1982−），男，高级工程师，研究方向：食品理化分析（E-mail：103727281@qq.com）

通讯作者:
杨方（1969−），女，博士，主任技师，研究方向：食品安全分析（E-mail：964890740@qq.com）

姚清华（1985−），男，副研究员，研究方向：农产品质量安全风险评估（E-mail：yaoyaoshuimu@qq.com）

中图分类号: O 652.63
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出版历程
- 收稿日期: 2020-08-09
- 修回日期: 2020-11-03
- 网络出版日期: 2021-02-08
- 刊出日期: 2021-01-31

Optimized Application of Fe₃O₄ Nanoparticles for Pesticide Detection in Tea

LI Jie^{1, 2
,},
ZHANG Feng²,
HUANG Jingjing²,
DING Liping²,
YANG Fang^{1
, ,},
YAO Qinghua^{3
, ,}

1.
Technical Centre of Fuzhou Customs District, Fuzhou, Fujian 　350001, China
2.
Technical Centre of Rongcheng Customs District, Fuzhou, Fujian 　350300, China
3.
Institute of Agricultural Quality Standards and Testing Technology Research, Fujian Academy of Agricultural Sciences, Fuzhou, Fujian 　350003, China

摘要

摘要: 目的建立高效液相色谱-串联质谱测定茶叶中7种农药的分析方法，提高检测效率、降低检测成本。方法以多菌灵、嘧霉胺、三环唑、吡虫啉、啶虫脒、灭多威、噻虫嗪等7种农药为目标物，纳米Fe₃O₄作为净化材料，考察其对茶叶中色素的去除效果，并进行方法评价。结果茶叶基质中纳米Fe₃O₄组的7种农药回收率明显高于石墨化碳黑（GCB）组，最佳用量为300 mg。通过Phenomenex Luna C8 (150 mm × 2.0 mm × 3.0 µm)色谱柱梯度洗脱，流动相A为含0.1 %甲酸和5 mmol·L⁻¹乙酸铵的水，B为乙腈，多反应监测模式（MRM）监测。在0 ～ 50 µg·L⁻¹方法线性良好，相关系数（R²）大于0.995；在5、10、50 ng·g⁻¹添加水平下回收率为71.6%～107.7 %，相对标准偏差（RSD）为3.95%～13.62 %，检出限为0.15～0.60 µg·kg⁻¹，定量限为0.5～2.0 µg·kg⁻¹。结论基于纳米Fe₃O₄建立了高效液相色谱-串联质谱测定茶叶中农药残留的分析方法，该方法稳定、可靠，有效提高了茶叶中农药残留检测的回收率，降低了检测成本。
- 茶叶 /
- 农药残留 /
- 纳米四氧化三铁 /
- 液相色谱-串联质谱
Abstract: Objective A newly modified analytical method for detecting pesticide residues in tea was developed to improve test efficiency and reduce cost. Method Fe₃O₄ nanoparticles were used to replace the conventional pigment-removing material prior to measurements on pesticide residues, including carbendazim, pyrimethanil, tricyclazol, imidachloprid, acetamiprid, methomyl, and thiamethoxam, in tea by liquid chromatography-tandem mass spectrometry. The methodology was evaluated according to its applicability and validated in a spiked residue test. Result The recovery rates on the 7 pesticides under the modified method using 300 mg Fe₃O₄ nanoparticles for pigment removal pretreatment were higher than graphitizing with carbon black (GCB). The pigment-removed tea extracts were separated with a Phenomenex Luna C8 (150 mm × 2.0 mm × 3.0 µm) by using 0.1 % formic acid and 5 mmol·L^-1 ammonium acetate as Phase A and acetonitrile as Phase B for the mobile phase prior to the tandem mass spectrometric analysis under the multiple reaction monitoring mode with external standards. A linearity on the measurements by the new method was achieved within the pesticide concentrations of 0-50 µg·L^-1 showing correlation coefficients (R²) greater than 0.995 for all 7 pesticides. On 5, 10, and 50 ng·g^-1 spiked pesticide samples, average recovery rates of the new method ranged from 71.6 % to 107.7 % with relative standard deviations of 3.95%-13.62 %. The limits of detection (LOD) on the pesticides by the method were between 0.15 µg·kg^-1 and 0.60 µg·kg^-1, and the limits of quantitation (LOQ) between 0.5 µg·kg^-1 and 2.0 µg·kg^-1. Conclusion The newly developed pesticide detection method was stable, repeatable, and accurate for the designed purpose.
- Tea /
- pesticide residues /
- Fe₃O₄ nanoparticles /
- liquid chromatography-tandem mass spectrometry

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图 1 提取液经不同材料净化后的色素变化

Figure 1. Variation on pigments in tea extracts after treatment of different pigment-removing materials

下载: 全尺寸图片幻灯片

图 2 不同净化材料对7种农药的回收率影响

注：A，吡虫啉；B，啶虫脒；C，多菌灵；D，灭多威；E，嘧霉胺；F，噻虫嗪；G，三环唑。

Figure 2. Recovery rate on 7 pesticides of newly developed method with pretreatment using different pigment-removing materials

Note: A: imidacloprid; B: acetamiprid; C: carbendazim; D: methomyl; E: pyrimethanil; F: thiamethoxam; G: tricyclazole. Same for Figs. 3 and 4.

下载: 全尺寸图片幻灯片

图 3 纳米Fe₃O₄用量的优化

注：A，吡虫啉；B，啶虫脒；C，多菌灵；D，灭多威；E，嘧霉胺；F，噻虫嗪；G，三环唑。

Figure 3. Optimization on Fe₃O₄ nanoparticle usage

Note: A, imidacloprid; B, acetamiprid; C, carbendazim; D, methomyl; E, pyrimethanil; F, thiamethoxam; G, tricyclazole.

下载: 全尺寸图片幻灯片

图 4 净化材料对茶叶中农药检测基质效应的影响

注：A，吡虫啉；B，啶虫脒；C，多菌灵；D，灭多威；E，嘧霉胺；F，噻虫嗪；G，三环唑。

Figure 4. Effect of pigment-removing materials on determination of 7 pesticides in tea

Note: A, imidacloprid; B, acetamiprid; C, carbendazim; D, methomyl; E, pyrimethanil; F, thiamethoxam; G, tricyclazole.

下载: 全尺寸图片幻灯片

图 5 50 µg·L⁻¹ 的7种农药的标准溶液的总离子流图

注：从左至右：峰1，多菌灵；峰2，噻虫嗪；峰3，灭多威；峰4，三环唑；峰5，啶虫脒；峰6，吡虫啉；峰7，嘧霉胺。

Figure 5. Total ion chromatograms on 50 μg·L⁻¹ solutions of 7 pesticides

Note: Left to right: Peak 1: carbendazim; Peak 2: thiamethoxam; Peak 3: methomyl; Peak 4: tricyclazole; Peak 5: acetamiprid; Peak 6: imidacloprid; Peak 7: pyrimethanil.

下载: 全尺寸图片幻灯片

表 1 7种农药的液相色谱质谱分析参数

Table 1. LC-MS/MS testing parameters for 7 pesticides

序号 No.	农药 Pesticide	保留时间 Retention time/min	离子碎片信息 Information of ion fragments/（m·z⁻¹）	碎裂电压 Fragmentor/V	碰撞电压 Collision energy/eV
A	吡虫啉 Imidacloprid	3.19	256＞209*, 256＞175	120	9, 12
B	啶虫脒 Acetamiprid	2.49	223.1＞125.8*, 223.1＞90	87	17, 36
C	多菌灵 Carbendazim	1.24	192＞160*, 192＞132	100	16, 33
D	灭多威 Methomyl	2.01	163＞88*, 163＞106	58	2, 5
E	嘧霉胺 Pyrimethanil	4.61	200＞107*, 200＞168	127	23, 30
F	噻虫嗪 Thiamethoxam	1.57	291.9＞210.9*, 291.9＞180.9	80	5, 18
G	三环唑 Tricyclazole	2.38	190＞162.9*, 190＞136	130	20, 30
注：* 为定量离子对。 Note: *is quantitative ion pairs.

下载: 导出CSV

表 2 方法的线性回归方程、相关系数、检出限和定量限

Table 2. Linear equations, R², LODs, and LOQs on detections of 7 pesticides by newly developed detection method

目标物 Component	回归方程 Regression equation	线性范围 Linear range/（µg·L⁻¹）	相关系数 R²	LOD /（µg·kg⁻¹）	LOQ /（µg·kg⁻¹）
多菌灵 Carbendazim	y=20760x+8436.7	0～50	0.9986	0.15	0.5
噻虫嗪 Thiamethoxam	y=2473.4x+1116.1	0～50	0.9989	0.3	1
灭多威 Methomyl	y=1918.8x+1382.8	0～50	0.9992	0.6	2
三环唑 Tricyclazole	y=14481x+6394.9	0～50	0.9992	0.15	0.5
啶虫脒 Acetamiprid	y=11083x-2560.6	0～50	0.9997	0.15	0.5
吡虫啉 Imidacloprid	y=1517.2x+571.3	0～50	0.9979	0.6	2
嘧霉胺 Pyrimethanil	y=3576.5x+3143.3	0～50	0.9987	0.3	1

下载: 导出CSV

表 3 7种农药的加标回收率及精密度（n=6）

Table 3. Recovery rates and RSDs on spiked pesticides of newly developed detection method (n=6)

目标物 Component	添加水平 Spiked levels/（ng·g⁻¹）	回收率 Recovery/%	相对标准偏差 RSD/%
多菌灵 Carbendazim	5, 10, 50	75.4, 71.6, 72.5	9.71, 6.69, 6.43
噻虫嗪 Thiamethoxam	5, 10, 50	94.5, 99.7, 104.0	10.75, 4.13, 5.79
灭多威 Methomyl	5, 10, 50	100.2, 102.8,107.7	8.65, 8.18, 6.10
三环唑 Tricyclazole	5, 10, 50	78.9, 74.1, 77.5	5.35, 8.13, 4.62
啶虫脒 Acetamiprid	5, 10, 50	104.6, 105.6, 102.3	6.17, 4.46, 3.95
吡虫啉 Imidacloprid	5, 10, 50	92.9, 94.8, 101.2	13.62, 8.58, 6.22
嘧霉胺 Pyrimethanil	5, 10, 50	100.8, 95.4, 98.6	7.97, 5.14, 5.03

下载: 导出CSV

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