在线固相萃取/净化-高效液相色谱-串联质谱法同时测定番茄、大米和圆白菜中8种氨基甲酸酯类农药残留

doi:10.3724/SP.J.1123.2021.01028

摘要/Abstract

摘要：

建立了在线固相萃取/净化-高效液相色谱-串联质谱(online SPE-HPLC-MS/MS)同时测定番茄、大米和圆白菜中8种氨基甲酸酯类农药的分析方法。将番茄5.0 g(不加水)、圆白菜和大米各2.0 g(各加3 mL水),以1000 r/min旋涡1 min,加入2 g氯化钠和10 mL 0.5%(v/v)甲酸乙腈溶液,旋涡均匀后离心,上清液氮吹后用10%(v/v)乙腈水溶液复溶,复溶液使用CAPCELL PAK C₁₈净化柱(50 mm×2.0 mm, 15 μm)进行在线净化,当流动相0.1%(v/v)甲酸水溶液和乙腈的体积比分别为90∶10和35∶65时,可实现氨基甲酸酯农药的吸附和洗脱。以ACQUITY UPLC CSH C₁₈色谱柱(100 mm×2.1 mm, 1.7 μm)为分析柱,实现8种氨基甲酸酯类农药的分离,以0.1%(v/v)甲酸水溶液和乙腈为流动相进行梯度洗脱,在12.0 min内即可完成分析。在优化条件下,8种氨基甲酸酯类农药在各自线性范围内线性良好,相关系数均大于0.995, LOD和LOQ分别为0.01~0.3 ng/mL和0.05~1.0 ng/mL;在3个加标水平下,8种氨基甲酸酯类农药的加标回收率为73.76%~112.32%,相对标准偏差为1.28%~13.14%(n=6)。通过在线净化的方式,大大提高了前处理效率,只需12 min即可完成净化上样,不需氮吹复溶等步骤,提高了处理效率。该法回收率高,重复性好,具有准确、快速、灵敏、环保等优点,可用于植物性食品中8种氨基甲酸酯类农药的检测。

关键词: 高效液相色谱-串联质谱, 在线固相萃取, 氨基甲酸酯类农药残留, 植物性食品

Abstract:

Carbamate pesticides are a class of synthetic pesticides having wide antimicrobial spectrum, good insecticidal efficacy, and a short residual period. These pesticides are used in agriculture, forestry, and animal husbandry. Their widespread use in the last two decades has led to the existence of drug residues in the environment, which are transferred to food, thereby raising concerns regarding the potential threat to human health. Rapid and accurate detection of carbamate pesticide residues in food is of great significance for food safety, and this requires pretreatment to purify the target components and maximize the accuracy and precision of the analysis. A rapid and accurate analytical method based on online solid phase extraction/purification-high performance liquid chromatography-tandem mass spectrometry (online SPE-HPLC-MS/MS) was established for the determination of eight carbamate pesticides in tomato, rice, and cabbage. About 5.0 g of tomato (without water), 2.0 g of cabbage, and 2.0 g of rice (mixed with 3 mL of water) were vortexed at 1000 r/min for 1 min. After adding 2 g of sodium chloride and 10 mL of acetonitrile containing 0.5% (v/v) formic acid, the samples were extracted and centrifuged. The supernatants were combined after the samples were extracted again. The reconstituted solutions were then purified on a CAPCELL PAK C₁₈ column (50 mm×2.0 mm, 15 μm). When the volume ratio of 0.1% (v/v) formic acid aqueous solution and acetonitrile (used as the mobile phases) was 90∶10 and 35∶65, the eight carbamate pesticides could be completely adsorbed and eluted. The carbamate pesticides were separated on an ACQUITY UPLC CSH C₁₈ column (100 mm×2.1 mm, 1.7 μm) under gradient elution and analyzed in the multiple reaction monitoring (MRM) mode with positive electrospray ionization (ESI⁺). Under the optimum conditions, the calibration curves of the eight carbamate pesticide residues showed good linearity (r>0.995) within their respective linear ranges. The limits of quantification (LOQs) and limits of detection (LODs) were in the range of 0.05-1.0 ng/mL (S/N=10) and 0.01-0.3 ng/mL (S/N=3). The recoveries were in the range of 73.76%-112.32% at three spiked levels (2, 10, and 20 ng/mL), with relative standard deviations of 1.28%-13.14% (n=6). The online purification method showed better enrichment and purification ability for the target substances than did the offline purification method and greatly improved the pretreatment efficiency. The loading and purification could be completed within 12 min. The developed method has the advantages of high recovery rate, good reproducibility, accuracy, rapidness, sensitivity, and environment friendliness. It can be used for the determination of the eight carbamate pesticides in plant foods, such as tomato, rice, and cabbage.

Key words: high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), online solid phase extraction, carbamate pesticide residues, plant foods

中图分类号:

O658

刘欣, 孙秀兰, 曹进. 在线固相萃取/净化-高效液相色谱-串联质谱法同时测定番茄、大米和圆白菜中8种氨基甲酸酯类农药残留[J]. 色谱, 2021, 39(12): 1324-1330.

LIU Xin, SUN Xiulan, CAO Jin. Simultaneous determination of eight carbamate pesticide residues in tomato, rice, and cabbage by online solid phase extraction/purification-high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2021, 39(12): 1324-1330.

Compound	Retention time/min	Parent ion (m/z)	Daughter ion (m/z)	DP/ V	CE/ eV
Methomyl	3.78	163.1	106.1	85	18
			88.1^*	85	18
Pirimicarb	3.90	239.1	182.2^*	85	20
			72.2	85	20
Metolcarb	5.74	166.1	109.1^*	85	15
			94.0	85	40
Propoxur	5.98	210.3	168.1	90	8
			111.2^*	80	22
Carbaryl	6.14	202.2	145.1^*	85	25
			127.1	85	38
Isoprocarb	6.33	194.3	137.2	50	15
			95.2^*	85	20
Methiocarb	6.54	226.1	169.2	80	15
			121.2^*	80	25
Fenobucarb	6.55	208.1	152.1	80	8
			95.0^*	85	25

Compound	Retention time/min	Parent ion (m/z)	Daughter ion (m/z)	DP/ V	CE/ eV
Methomyl	3.78	163.1	106.1	85	18
			88.1^*	85	18
Pirimicarb	3.90	239.1	182.2^*	85	20
			72.2	85	20
Metolcarb	5.74	166.1	109.1^*	85	15
			94.0	85	40
Propoxur	5.98	210.3	168.1	90	8
			111.2^*	80	22
Carbaryl	6.14	202.2	145.1^*	85	25
			127.1	85	38
Isoprocarb	6.33	194.3	137.2	50	15
			95.2^*	85	20
Methiocarb	6.54	226.1	169.2	80	15
			121.2^*	80	25
Fenobucarb	6.55	208.1	152.1	80	8
			95.0^*	85	25

Compound	Linear equation	Linear range/(ng/mL)	r	LOD/(ng/mL)	LOQ/(ng/mL)
Methomyl	y=1.08×10⁴x+2.51×10³	0.5-50	0.9953	0.05	0.15
Pirimicarb	y=3.64×10⁵x+5.03×10³	0.1-100	0.9951	0.01	0.05
Metolcarb	y=3.63×10⁴x+4.15×10²	0.1-100	0.9991	0.04	0.10
Propoxur	y=2.60×10⁴x+4.76×10³	0.5-100	0.9970	0.05	0.15
Carbaryl	y=9.40×10³x+1.87×10³	1.0-100	0.9992	0.30	1.0
Isoprocarb	y=1.17×10⁵x+1.11×10⁴	0.1-100	0.9984	0.03	0.10
Methiocarb	y=9.29×10⁴x+3.03×10³	0.5-100	0.9970	0.05	0.20
Fenobucarb	y=1.74×10⁵x+1.64×10⁴	0.5-100	0.9979	0.06	0.20

Compound	Linear equation	Linear range/(ng/mL)	r	LOD/(ng/mL)	LOQ/(ng/mL)
Methomyl	y=1.08×10⁴x+2.51×10³	0.5-50	0.9953	0.05	0.15
Pirimicarb	y=3.64×10⁵x+5.03×10³	0.1-100	0.9951	0.01	0.05
Metolcarb	y=3.63×10⁴x+4.15×10²	0.1-100	0.9991	0.04	0.10
Propoxur	y=2.60×10⁴x+4.76×10³	0.5-100	0.9970	0.05	0.15
Carbaryl	y=9.40×10³x+1.87×10³	1.0-100	0.9992	0.30	1.0
Isoprocarb	y=1.17×10⁵x+1.11×10⁴	0.1-100	0.9984	0.03	0.10
Methiocarb	y=9.29×10⁴x+3.03×10³	0.5-100	0.9970	0.05	0.20
Fenobucarb	y=1.74×10⁵x+1.64×10⁴	0.5-100	0.9979	0.06	0.20

Compound	Spiked level/ (ng/mL)	Tomato		Rice		Cabbage
Compound	Spiked level/ (ng/mL)	Recovery/%	RSD/%	Recovery/%	RSD/%	Recovery/%	RSD/%
Methomyl	2	80.40	5.88	106.81	3.58	108.59	5.11
	10	86.07	5.77	94.41	8.92	93.79	11.92
	20	75.98	8.65	85.87	10.55	75.32	6.51
Pirimicarb	2	80.03	4.37	102.35	1.79	107.36	8.59
	10	84.36	2.42	97.79	7.82	100.06	4.34
	20	83.19	4.47	111.76	4.67	88.67	6.18
Metolcarb	2	95.84	3.89	92.38	1.28	101.92	2.27
	10	94.50	2.31	101.28	11.95	95.33	2.64
	20	88.50	3.51	97.35	2.96	85.97	3.56
Propoxur	2	77.37	9.99	82.49	4.56	101.33	8.19
	10	78.89	5.60	96.52	7.05	94.95	6.06
	20	111.62	4.98	90.41	7.26	84.01	13.14
Carbaryl	2	74.98	8.13	87.72	7.00	86.09	5.19
	10	82.35	3.84	94.04	6.80	89.69	9.74
	20	73.76	9.05	92.17	3.21	81.22	7.60
Isoprocarb	2	112.32	3.94	86.96	3.13	105.35	3.90
	10	103.45	1.41	82.35	4.59	109.01	4.73
	20	92.81	2.54	89.34	2.92	101.06	3.11
Methiocarb	2	82.65	4.36	82.77	3.24	97.41	2.45
	10	84.61	1.92	91.08	7.81	84.50	5.45
	20	75.35	3.51	82.61	4.68	93.92	5.50
Fenobucarb	2	94.84	2.94	100.63	1.91	101.28	3.57
	10	97.10	2.24	103.01	2.99	98.58	5.23
	20	91.03	3.71	95.72	2.71	97.01	4.65

在线固相萃取/净化-高效液相色谱-串联质谱法同时测定番茄、大米和圆白菜中8种氨基甲酸酯类农药残留

Simultaneous determination of eight carbamate pesticide residues in tomato, rice, and cabbage by online solid phase extraction/purification-high performance liquid chromatography-tandem mass spectrometry

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Metrics

Step	Time/min	φ(A)/%	φ(B)/%	Position	Function
1	0.5	90	10	A	injection
2	0.5	90	10	B	loading
3	3.0	90	10	B	rinse
4	2.0	35	65	B	elution
5	2.0	10	90	B	elution
6	2.0	90	10	A	balance

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