QuEChERS-高效液相色谱-串联质谱法同时测定豆芽中40种植物生长调节剂、杀菌剂、杀虫剂和抗生素类药物残留

doi:10.3724/SP.J.1123.2021.12028

色谱 ›› 2022, Vol. 40 ›› Issue (9): 843-853.DOI: 10.3724/SP.J.1123.2021.12028

QuEChERS-高效液相色谱-串联质谱法同时测定豆芽中40种植物生长调节剂、杀菌剂、杀虫剂和抗生素类药物残留

冯军军¹, 姜海云², 王静³, 景正义¹, 张帆¹, 谭天宇¹, 贺锋¹, 江利华¹, 李海芹¹, 常世敏¹, 李腾飞¹^,^*()

1.河北工程大学生命科学与食品工程学院, 河北邯郸 056038
2.邯郸市食品药品检验中心, 河北邯郸 056004
3.河北工程大学材料科学与工程学院, 河北邯郸 056038

收稿日期:2021-12-28 出版日期:2022-09-08 发布日期:2022-09-26
通讯作者: 李腾飞
基金资助:
河北省自然科学基金项目(C2019402379);河北省教育厅科学研究计划项目(QN2018159);邯郸市科学技术研究与发展计划项目(21422903298)

Simultaneous determination of 40 plant growth regulators, fungicides, insecticides, and antibiotics in bean sprouts by QuEChERS-high performance liquid chromatography-tandem mass spectrometry

FENG Junjun¹, JIANG Haiyun², WANG Jing³, JING Zhengyi¹, ZHANG Fan¹, TAN Tianyu¹, HE Feng¹, JIANG Lihua¹, LI Haiqin¹, CHANG Shimin¹, LI Tengfei¹^,^*()

1. College of Life Science and Food Engineering, Hebei University of Engineering, Handan 056038, China
2. Food and Drug Inspection Center of Handan City, Handan 056004, China
3. College of Materials Science and Engineering, Hebei University of Engineering, Handan 056038, China

Received:2021-12-28 Online:2022-09-08 Published:2022-09-26
Contact: LI Tengfei
Supported by:
Hebei Provincial Natural Science Foundation(C2019402379);Scientific Research Program of Education Department of Hebei Province(QN2018159);Handan Science and Technology Research and Development Program(21422903298)

摘要/Abstract

摘要：

研究从豆芽质量安全监管的实际需求出发,建立了QuEChERS-高效液相色谱-串联质谱同时测定豆芽中植物生长调节剂、杀菌剂、杀虫剂和抗生素类等40种药物残留的方法。首先通过参数优化确定最佳质谱条件,然后比较不同提取溶剂(甲醇、乙腈、0.1%氨水乙腈、1%乙酸乙腈)、提取方法(超声、振荡)以及乙二胺-N-丙基硅烷化硅胶(PSA)、C₁₈净化剂添加量时40种药物的回收率,确定最优前处理过程。样品用10 mL 1%乙酸乙腈提取两次,超声波辅助提取,100 mg C₁₈为净化剂。选用Waters ACQUITY UPLC BEH C₁₈色谱柱(100 mm×2.1 mm, 1.7 μm)进行分离,甲醇和0.01%甲酸水为流动相梯度洗脱,多反应监测(MRM)模式进行质谱监测,基质匹配外标法定量。结果表明,40种药物可在15 min内完成色谱分离,在2~200 μg/L的线性范围内均呈现出良好的线性关系,相关系数(r²)均大于0.99,检出限(LOD)和定量限(LOQ)分别为0.1~3 μg/kg和0.3~9 μg/kg。以阴性豆芽为基质,分别在5、10、50 μg/kg 3个水平下进行加标回收试验,40种药物的平均回收率为78.5%~115.3%,相对标准偏差(RSD)为1.3%~9.7%(n=6)。将该方法用于分析邯郸本地豆芽中40种药物的污染状况,结果显示4-氯苯氧乙酸、6-苄基腺嘌呤、多菌灵、2,4-二氯苯氧乙酸(2,4-D)、赤霉素和恩诺沙星检出率较高,分别为28.6%、19.0%、9.5%、9.5%、4.8%和4.8%,含量范围为37.5~352.4、32.4~273.1、28.8~38.7、16.1~20.2、19.9和13.6 μg/kg。研究建立的方法简单、快速,灵敏度高,适用于大批量豆芽中40种药物的快速准确测定。

关键词: QuEChERS, 高效液相色谱-串联质谱, 植物生长调节剂, 杀菌剂, 杀虫剂, 抗生素, 豆芽

Abstract:

Chromatography combined with mass spectrometry is the most commonly used detection technology, and it offers the advantages of high sensitivity and high selectivity. The quick, easy, inexpensive, effective, rugged, and safe (QuEChERS) method is low-cost, effective, and time efficient. The application of the QuEChERS has now been extended to the analysis of contaminants in food samples. The aim of the study was to identify different concentration levels of multiple harmful drug residues in bean sprouts. In this study, QuEChERS coupled with high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was established for the simultaneous determination of 40 plant growth regulators, fungicides, insecticides, and antibiotics in bean sprouts. In the HPLC-MS/MS experiment, gibberellic acid, 4-fluorophenoxyacetic acid, chloramphenicol, N6-(δ2-isopentenyl)-adenine, 6-benzylaminopurine, 4-chlorophenoxyacetic acid, and 2,4-dichlorophenoxyacetic acid (2,4-D) were analyzed by MS/MS with negative electrospray ionization (ESI^-). The other 33 target analytes (chlormequat, ronidazole, metronidazole, pymetrozine, dimetridazole, methomyl, carbendazim, enoxacin, levofloxacin, pefloxacin mesylate, norfloxacin, ciprofloxacin, enrofloxacin, thiabendazole, lomefloxacin, chlorpyrifos, sarafloxacin, imidacloprid, etc.) were analyzed by MS/MS with positive electrospray ionization (ESI⁺). Sensitive MS conditions were realized by optimizing the instrumental parameters such as the desolvent temperature, collision energy, spraying needle position, precursor ions, and product ions. Then, the optimal pretreatment method was determined by comparing the recovery rates of the 40 drugs obtained with different extraction solvents (methanol, acetonitrile, acetonitrile containing 0.1% ammonia, acetonitrile with 1% acetic acid), different extraction methods (ultrasonic extraction, shaking extraction), and purification with primary secondary amine (PSA) and C₁₈. In this study, the bean sprouts samples were extracted twice by 10 mL acetonitrile with 1% acetic acid, and extracted under ultrasonic conditions. Then, the extracting solution was only cleaned with 100 mg C₁₈. The chromatographic separation of the 40 compounds was accomplished on a Waters ACQUITY UPLC BEH C₁₈ column (100 mm×2.1 mm, 1.7 μm) with gradient elution. Methanol and 0.01% formic acid aqueous solution were used as the mobile phases. The 40 compounds were analyzed in the multiple reaction monitoring (MRM) mode. The matrix matching external standard method was used for quantitative determination. The results showed that the 40 compounds could be analyzed within 15 min. Under the optimized conditions, the calibration curves showed good linearities for the 40 compounds, and the coefficients of determination (r²) were greater than 0.99 in the range of 2-200 μg/L. The limits of detection (LODs) and limits of quantification (LOQs) were in the range of 0.1-3 μg/kg and 0.3-9 μg/kg, respectively. Using negative bean sprouts as the substrates, the recovery tests were carried out at three spiked levels of 5, 10, and 50 μg/kg. The average recoveries of the 40 drugs were 78.5% to 115.3%, and the corresponding relative standard deviations (RSDs) were 1.3% to 9.7% (n=6). This method was successfully applied to the analysis of the 40 drug residues in 21 batches of local bean sprouts in Handan city. The results revealed the presence of extensive drug residues in the bean sprouts. The 26 batches were detected to varying degrees, among which 4-chlorophenoxyacetic acid, carbendazim, 6-benzyladenine, 2,4-D, enrofloxacin, and metronidazole were detected at high rates. The detection rates of 4-chlorophenoxyacetic acid, 6-benzyladenine, carbendazim, 2,4-D, gibberellic acid, and enrofloxacin were 28.6%, 19.0%, 9.5%, 9.5%, 4.8%, and 4.8%, respectively. The contents ranged from 37.5-352.4, 32.4-273.1, 28.8-38.7, 316.1-20.2, 19.9 and 13.6 μg/kg, respectively. Given its advantages of simplicity, rapidness, and high sensitivity, the developed method can be used for the rapid and accurate determination of trace levels of the 40 drug residues in large quantities of bean sprouts.

Key words: QuEChERS, high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), plant growth regulators, fungicides, insecticide, antibiotics, bean sprout

中图分类号:

O658

冯军军, 姜海云, 王静, 景正义, 张帆, 谭天宇, 贺锋, 江利华, 李海芹, 常世敏, 李腾飞. QuEChERS-高效液相色谱-串联质谱法同时测定豆芽中40种植物生长调节剂、杀菌剂、杀虫剂和抗生素类药物残留[J]. 色谱, 2022, 40(9): 843-853.

FENG Junjun, JIANG Haiyun, WANG Jing, JING Zhengyi, ZHANG Fan, TAN Tianyu, HE Feng, JIANG Lihua, LI Haiqin, CHANG Shimin, LI Tengfei. Simultaneous determination of 40 plant growth regulators, fungicides, insecticides, and antibiotics in bean sprouts by QuEChERS-high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2022, 40(9): 843-853.

图/表 7

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No.	Compound	Retention time/min	Ionization mode	Precursor ion (m/z)	Product ions (m/z)	Collision energies/eV
1	chlormequat (矮壮素)	1.066	ESI⁺	122.10	58.10^*, 63.10	-31, -24
2	ronidazole (洛硝哒唑)	3.903	ESI⁺	201.00	139.70^*, 54.60	-10, -15
3	metronidazole (甲硝唑)	3.999	ESI⁺	172.00	81.80^*, 127.70	-25, -15
4	pymetrozine (吡蚜酮)	4.192	ESI⁺	408.10	105.05^*, 68.10	-39, -30
5	dimetridazole (二甲硝咪唑)	5.211	ESI⁺	142.10	96.05^*, 81.10	-16, -27
6	methomyl (灭多威)	6.850	ESI⁺	163.05	88.00^*, 106.05	-11, -13
7	carbendazim (多菌灵)	6.959	ESI⁺	192.05	160.05^*, 32.05	-17, -30
8	levofloxacin (氧氟沙星)	7.261	ESI⁺	362.10	318.20^*, 61.10	-20, -30
9	enoxacin (依诺沙星)	7.272	ESI⁺	340.20	303.10^*, 203.85	-20, -48
10	pefloxacin mesylate (培氟沙星)	7.301	ESI⁺	334.00	290.10^*, 16.10	-20, -20
11	norfloxacin (诺氟沙星)	7.384	ESI⁺	320.00	302.00^*, 76.00	-20, -17
12	ciprofloxacin (环丙沙星)	7.537	ESI⁺	332.20	314.05^*, 31.00	-24, -41
13	enrofloxacin (恩诺沙星)	7.672	ESI⁺	360.20	316.10^*, 42.15	-22, -25
14	thiabendazole (噻菌灵)	7.749	ESI⁺	202.00	175.05^*, 31.10	-24, -33
15	lomefloxacin (洛美沙星)	7.749	ESI⁺	352.00	265.00^*, 80.10	-25, -20
16	chlorpyrifos (毒死蜱)	7.768	ESI⁺	351.90	265.05^*, 37.05	-30, -39
17	sarafloxacin (沙拉沙星)	8.048	ESI⁺	385.90	367.95^*, 98.90	-25, -20
18	imidacloprid (吡虫啉)	8.172	ESI⁺	256.05	175.10^*, 09.05	-17, -14
19	sparfloxacin (司帕沙星)	8.480	ESI⁺	393.00	349.00^*, 92.00	-40, -20
20	acetamiprid (啶虫脒)	8.682	ESI⁺	223.10	126.05^*, 56.05	-22, -15
21	gibberellic acid (赤霉素)	8.744	ESI^-	345.40	143.20^*, 39.50	32, 16
22	4-fluorophenoxyacetic acid (4-氟苯氧乙酸)	8.941	ESI^-	169.20	111.00^*, 95.00	16, 18
23	chloramphenicol (氯霉素)	9.144	ESI^-	340.00	152.10^*, 57.10	17, 11
24	3-indolylacetic acid (吲哚乙酸)	9.230	ESI⁺	176.10	129.80^*, 03.10	-18, -16
25	N6-(δ2-isopentenyl)-adenine (异戊烯腺嘌呤)	9.434	ESI^-	202.30	133.00^*, 34.15	22, 17
26	6-benzylaminopurine (6-苄基腺嘌呤)	9.487	ESI^-	224.00	133.00^*, 06.00	40, 34
27	4-chlorophenoxyacetic acid (4-氯苯氧乙酸)	10.040	ESI^-	185.00	127.10^*, 29.00	15, 14
28	thidiazuron (噻苯隆)	10.056	ESI⁺	240.20	102.00^*, 28.00	-16, -17
29	3-indolebutyric acid (吲哚丁酸)	10.229	ESI⁺	204.20	186.20^*, 29.90	-10, -28
30	atrazine (莠去津)	10.556	ESI⁺	406.10	174.05^*, 96.05	-17, -25
31	forchlorfenuron (氯吡脲)	10.595	ESI⁺	248.05	129.05^*, 93.05	-17, -34
32	metalaxyl-M (精甲霜灵)	10.614	ESI⁺	280.10	220.15^*, 48.10	-13, -10
33	metalaxyl (甲霜灵)	10.619	ESI⁺	280.10	220.15^*, 92.15	-13, -18
34	2,4-dichlorophenoxyacetic acid (2,4-滴)	10.669	ESI^-	409.00	160.85^*, 25.00	14, 29
35	azoxystrobin (嘧菌酯)	10.826	ESI⁺	404.10	372.05^*, 29.00	-14, -31
36	paclobutrazol (多效唑)	11.064	ESI⁺	294.10	70.05^*, 125.05	-40, -40
37	triazophos (三唑磷)	11.152	ESI⁺	314.05	162.15^*, 19.15	-19, -35
38	isazophos (氯唑磷)	11.161	ESI⁺	314.10	162.10^*, 20.10	-16, -27
39	flusilazole (氟硅唑)	11.394	ESI⁺	316.10	247.10^*, 65.10	-18, -29
40	pyraclostrobin (吡唑醚菌酯)	11.635	ESI⁺	388.10	194.05^*, 63.05	-30, -32

No.	Compound	Retention time/min	Ionization mode	Precursor ion (m/z)	Product ions (m/z)	Collision energies/eV
1	chlormequat (矮壮素)	1.066	ESI⁺	122.10	58.10^*, 63.10	-31, -24
2	ronidazole (洛硝哒唑)	3.903	ESI⁺	201.00	139.70^*, 54.60	-10, -15
3	metronidazole (甲硝唑)	3.999	ESI⁺	172.00	81.80^*, 127.70	-25, -15
4	pymetrozine (吡蚜酮)	4.192	ESI⁺	408.10	105.05^*, 68.10	-39, -30
5	dimetridazole (二甲硝咪唑)	5.211	ESI⁺	142.10	96.05^*, 81.10	-16, -27
6	methomyl (灭多威)	6.850	ESI⁺	163.05	88.00^*, 106.05	-11, -13
7	carbendazim (多菌灵)	6.959	ESI⁺	192.05	160.05^*, 32.05	-17, -30
8	levofloxacin (氧氟沙星)	7.261	ESI⁺	362.10	318.20^*, 61.10	-20, -30
9	enoxacin (依诺沙星)	7.272	ESI⁺	340.20	303.10^*, 203.85	-20, -48
10	pefloxacin mesylate (培氟沙星)	7.301	ESI⁺	334.00	290.10^*, 16.10	-20, -20
11	norfloxacin (诺氟沙星)	7.384	ESI⁺	320.00	302.00^*, 76.00	-20, -17
12	ciprofloxacin (环丙沙星)	7.537	ESI⁺	332.20	314.05^*, 31.00	-24, -41
13	enrofloxacin (恩诺沙星)	7.672	ESI⁺	360.20	316.10^*, 42.15	-22, -25
14	thiabendazole (噻菌灵)	7.749	ESI⁺	202.00	175.05^*, 31.10	-24, -33
15	lomefloxacin (洛美沙星)	7.749	ESI⁺	352.00	265.00^*, 80.10	-25, -20
16	chlorpyrifos (毒死蜱)	7.768	ESI⁺	351.90	265.05^*, 37.05	-30, -39
17	sarafloxacin (沙拉沙星)	8.048	ESI⁺	385.90	367.95^*, 98.90	-25, -20
18	imidacloprid (吡虫啉)	8.172	ESI⁺	256.05	175.10^*, 09.05	-17, -14
19	sparfloxacin (司帕沙星)	8.480	ESI⁺	393.00	349.00^*, 92.00	-40, -20
20	acetamiprid (啶虫脒)	8.682	ESI⁺	223.10	126.05^*, 56.05	-22, -15
21	gibberellic acid (赤霉素)	8.744	ESI^-	345.40	143.20^*, 39.50	32, 16
22	4-fluorophenoxyacetic acid (4-氟苯氧乙酸)	8.941	ESI^-	169.20	111.00^*, 95.00	16, 18
23	chloramphenicol (氯霉素)	9.144	ESI^-	340.00	152.10^*, 57.10	17, 11
24	3-indolylacetic acid (吲哚乙酸)	9.230	ESI⁺	176.10	129.80^*, 03.10	-18, -16
25	N6-(δ2-isopentenyl)-adenine (异戊烯腺嘌呤)	9.434	ESI^-	202.30	133.00^*, 34.15	22, 17
26	6-benzylaminopurine (6-苄基腺嘌呤)	9.487	ESI^-	224.00	133.00^*, 06.00	40, 34
27	4-chlorophenoxyacetic acid (4-氯苯氧乙酸)	10.040	ESI^-	185.00	127.10^*, 29.00	15, 14
28	thidiazuron (噻苯隆)	10.056	ESI⁺	240.20	102.00^*, 28.00	-16, -17
29	3-indolebutyric acid (吲哚丁酸)	10.229	ESI⁺	204.20	186.20^*, 29.90	-10, -28
30	atrazine (莠去津)	10.556	ESI⁺	406.10	174.05^*, 96.05	-17, -25
31	forchlorfenuron (氯吡脲)	10.595	ESI⁺	248.05	129.05^*, 93.05	-17, -34
32	metalaxyl-M (精甲霜灵)	10.614	ESI⁺	280.10	220.15^*, 48.10	-13, -10
33	metalaxyl (甲霜灵)	10.619	ESI⁺	280.10	220.15^*, 92.15	-13, -18
34	2,4-dichlorophenoxyacetic acid (2,4-滴)	10.669	ESI^-	409.00	160.85^*, 25.00	14, 29
35	azoxystrobin (嘧菌酯)	10.826	ESI⁺	404.10	372.05^*, 29.00	-14, -31
36	paclobutrazol (多效唑)	11.064	ESI⁺	294.10	70.05^*, 125.05	-40, -40
37	triazophos (三唑磷)	11.152	ESI⁺	314.05	162.15^*, 19.15	-19, -35
38	isazophos (氯唑磷)	11.161	ESI⁺	314.10	162.10^*, 20.10	-16, -27
39	flusilazole (氟硅唑)	11.394	ESI⁺	316.10	247.10^*, 65.10	-18, -29
40	pyraclostrobin (吡唑醚菌酯)	11.635	ESI⁺	388.10	194.05^*, 63.05	-30, -32

Compound	Linear equation	Linear range/(μg/L)	r²	LOD/(μg/kg)	LOQ/(μg/kg)
Chlormequat	y=1.27×10³x-5.36×10²	2-200	0.9966	1.5	4.5
Ronidazole	y=1.82×10⁴x-9.28×10³	2-200	0.9987	0.1	0.3
Metronidazole	y=1.28×10⁴x+4.55×10³	2-200	0.9998	0.5	1.5
Pymetrozine	y=2.98×10⁴x-1.13×10⁵	2-200	0.9929	0.5	1.5
Dimetridazole	y=3.14×10⁴x-1.22×10⁴	2-200	0.9997	0.2	0.6
Methomyl	y=1.43×10⁴x-3.36×10⁴	2-200	0.9914	0.2	0.6
Carbendazim	y=5.18×10⁴x+3.92×10⁴	2-200	0.9998	0.2	0.6
Enoxacin	y=2.01×10⁴x-1.33×10⁴	2-200	0.9919	1.0	3.0
Levofloxacin	y=2.07×10⁴x-6.38×10⁴	2-200	0.9939	1.0	3.0
pefloxacin mesylate	y=1.07×10⁴x-2.77×10⁴	2-200	0.9959	1.0	3.0
Norfloxacin	y=2.86×10⁴x-1.09×10⁴	2-200	0.9977	0.5	1.5
Ciprofloxacin	y=1.01×10⁴x+1.21×10⁴	2-200	0.9939	1.0	3.0
Enrofloxacin	y=1.45×10⁴x-6.98×10⁴	2-200	0.9932	1.0	3.0
Thiabendazole	y=1.26×10⁴x-1.20×10⁴	2-200	0.9976	0.5	1.5
Lomefloxacin	y=3.72×10⁴x-1.31×10³	2-200	0.9917	0.5	1.5
Chlorpyrifos	y=2.17×10⁴x-4.32×10⁴	2-200	0.9903	0.5	1.5
Sarafloxacin	y=2.25×10⁴x-7.64×10⁴	2-200	0.9953	0.5	1.5
Imidacloprid	y=3.84×10³x-1.55×10⁴	2-200	0.9908	1.0	3.0
Sparfloxacin	y=9.99×10³x-4.35×10⁴	2-200	0.9906	0.5	1.5
Acetamiprid	y=1.18×10⁴x-1.79×10⁴	2-200	0.9948	0.5	1.5
Gibberellic acid	y=5.95×10⁴x-2.08×10³	2-200	0.9914	3.0	9.0
4-Fluorophenoxyacetic acid	y=6.08×10³x-3.00×10³	2-200	0.9989	1.5	4.5
Chloramphenicol	y=8.61×10²x+1.86×10³	2-200	0.9970	3.0	9.0
3-Indolylacetic acid	y=7.02×10³x+1.76×10³	2-200	0.9961	2.0	6.0
N6-(δ2-Isopentenyl)-adenine	y=3.27×10²x-3.65×10²	2-200	0.9967	3.0	9.0
6-Benzylaminopurine	y=3.97×10²x-2.74×10³	2-200	0.9945	3.0	9.0
4-Chlorophenoxyacetic acid	y=2.78×10³x-2.33×10³	2-200	0.9995	3.0	9.0
Thidiazuron	y=5.69×10⁴x-2.10×10⁴	2-200	0.9996	0.5	1.5
3-Indolebutyric acid	y=4.55×10³x-4.29×10³	2-200	0.9967	2.0	6.0
Atrazine	y=2.23×10⁴x-7.41×10⁴	2-200	0.9956	0.2	0.6
Compound	Linear equation	Linear range/(μg/L)	r²	LOD/(μg/kg)	LOQ/(μg/kg)
Forchlorfenuron	y=1.83×10⁵x-3.65×10⁵	2-200	0.9977	0.1	0.3
Metalaxyl-M	y=4.74×10⁴x+1.29×10⁵	2-200	0.9981	0.2	0.6
Metalaxyl	y=2.84×10⁴x+9.92×10⁴	2-200	0.9966	0.2	0.6
2,4-Dichlorophenoxyacetic acid	y=8.84×10³x-3.59×10³	2-200	0.9995	2.0	6.0
Azoxystrobin	y=5.32×10⁴x+1.19×10⁴	2-200	0.9992	0.2	0.6
Paclobutrazol	y=2.02×10⁵x-3.79×10²	2-200	0.9986	0.1	0.3
Triazophos	y=6.95×10⁴x+1.02×10⁵	2-200	0.9983	0.1	0.3
Isazophos	y=6.66×10⁴x+1.08×10⁵	2-200	0.9966	0.1	0.3
Flusilazole	y=3.28×10⁴x-2.57×10⁴	2-200	0.9994	1.0	3.0
Pyraclostrobin	y=8.67×10⁴x+5.62×10⁵	2-200	0.9979	0.5	1.5

Compound	Linear equation	Linear range/(μg/L)	r²	LOD/(μg/kg)	LOQ/(μg/kg)
Chlormequat	y=1.27×10³x-5.36×10²	2-200	0.9966	1.5	4.5
Ronidazole	y=1.82×10⁴x-9.28×10³	2-200	0.9987	0.1	0.3
Metronidazole	y=1.28×10⁴x+4.55×10³	2-200	0.9998	0.5	1.5
Pymetrozine	y=2.98×10⁴x-1.13×10⁵	2-200	0.9929	0.5	1.5
Dimetridazole	y=3.14×10⁴x-1.22×10⁴	2-200	0.9997	0.2	0.6
Methomyl	y=1.43×10⁴x-3.36×10⁴	2-200	0.9914	0.2	0.6
Carbendazim	y=5.18×10⁴x+3.92×10⁴	2-200	0.9998	0.2	0.6
Enoxacin	y=2.01×10⁴x-1.33×10⁴	2-200	0.9919	1.0	3.0
Levofloxacin	y=2.07×10⁴x-6.38×10⁴	2-200	0.9939	1.0	3.0
pefloxacin mesylate	y=1.07×10⁴x-2.77×10⁴	2-200	0.9959	1.0	3.0
Norfloxacin	y=2.86×10⁴x-1.09×10⁴	2-200	0.9977	0.5	1.5
Ciprofloxacin	y=1.01×10⁴x+1.21×10⁴	2-200	0.9939	1.0	3.0
Enrofloxacin	y=1.45×10⁴x-6.98×10⁴	2-200	0.9932	1.0	3.0
Thiabendazole	y=1.26×10⁴x-1.20×10⁴	2-200	0.9976	0.5	1.5
Lomefloxacin	y=3.72×10⁴x-1.31×10³	2-200	0.9917	0.5	1.5
Chlorpyrifos	y=2.17×10⁴x-4.32×10⁴	2-200	0.9903	0.5	1.5
Sarafloxacin	y=2.25×10⁴x-7.64×10⁴	2-200	0.9953	0.5	1.5
Imidacloprid	y=3.84×10³x-1.55×10⁴	2-200	0.9908	1.0	3.0
Sparfloxacin	y=9.99×10³x-4.35×10⁴	2-200	0.9906	0.5	1.5
Acetamiprid	y=1.18×10⁴x-1.79×10⁴	2-200	0.9948	0.5	1.5
Gibberellic acid	y=5.95×10⁴x-2.08×10³	2-200	0.9914	3.0	9.0
4-Fluorophenoxyacetic acid	y=6.08×10³x-3.00×10³	2-200	0.9989	1.5	4.5
Chloramphenicol	y=8.61×10²x+1.86×10³	2-200	0.9970	3.0	9.0
3-Indolylacetic acid	y=7.02×10³x+1.76×10³	2-200	0.9961	2.0	6.0
N6-(δ2-Isopentenyl)-adenine	y=3.27×10²x-3.65×10²	2-200	0.9967	3.0	9.0
6-Benzylaminopurine	y=3.97×10²x-2.74×10³	2-200	0.9945	3.0	9.0
4-Chlorophenoxyacetic acid	y=2.78×10³x-2.33×10³	2-200	0.9995	3.0	9.0
Thidiazuron	y=5.69×10⁴x-2.10×10⁴	2-200	0.9996	0.5	1.5
3-Indolebutyric acid	y=4.55×10³x-4.29×10³	2-200	0.9967	2.0	6.0
Atrazine	y=2.23×10⁴x-7.41×10⁴	2-200	0.9956	0.2	0.6
Compound	Linear equation	Linear range/(μg/L)	r²	LOD/(μg/kg)	LOQ/(μg/kg)
Forchlorfenuron	y=1.83×10⁵x-3.65×10⁵	2-200	0.9977	0.1	0.3
Metalaxyl-M	y=4.74×10⁴x+1.29×10⁵	2-200	0.9981	0.2	0.6
Metalaxyl	y=2.84×10⁴x+9.92×10⁴	2-200	0.9966	0.2	0.6
2,4-Dichlorophenoxyacetic acid	y=8.84×10³x-3.59×10³	2-200	0.9995	2.0	6.0
Azoxystrobin	y=5.32×10⁴x+1.19×10⁴	2-200	0.9992	0.2	0.6
Paclobutrazol	y=2.02×10⁵x-3.79×10²	2-200	0.9986	0.1	0.3
Triazophos	y=6.95×10⁴x+1.02×10⁵	2-200	0.9983	0.1	0.3
Isazophos	y=6.66×10⁴x+1.08×10⁵	2-200	0.9966	0.1	0.3
Flusilazole	y=3.28×10⁴x-2.57×10⁴	2-200	0.9994	1.0	3.0
Pyraclostrobin	y=8.67×10⁴x+5.62×10⁵	2-200	0.9979	0.5	1.5

Compound	5 μg/kg		10 μg/kg		50 μg/kg
Compound	Recovery/%	RSD/%	Recovery/%	RSD/%	Recovery/%	RSD/%
Chlormequat	83.4	6.9	86.1	5.2	93.6	2.8
Ronidazole	111.2	4.3	93.2	2.4	96.2	3.7
Metronidazole	88.2	5.3	85.7	6.5	91.0	5.7
Pymetrozine	102.4	6.9	82.1	5.1	84.5	6.5
Dimetridazole	108.4	2.1	89.6	3.9	92.6	2.2
Methomyl	82.7	8.7	89.4	4.9	85.4	5.1
Carbendazim	84.3	7.5	97.6	4.7	94.1	8.0
Enoxacin	82.6	1.8	95.6	3.0	101.7	4.5
Levofloxacin	102.1	7.6	106.5	7.1	93.0	5.4
pefloxacin mesylate	90.3	7.1	101.5	5.9	92.8	4.1
Norfloxacin	84.2	5.9	86.7	4.6	88.6	4.7
Ciprofloxacin	99.5	8.3	102.2	7.2	96.4	4.3
Enrofloxacin	104.7	5.3	100.9	4.2	101.6	3.8
Thiabendazole	85.4	9.0	82.9	6.3	82.6	4.4
Lomefloxacin	97.9	6.2	105.5	6.1	99.2	2.9
Chlorpyrifos	112.6	9.7	113.1	6.3	107.4	4.1
Sarafloxacin	108.4	4.4	105.2	3.9	102.6	3.7
Imidacloprid	80.0	7.6	84.4	6.2	85.1	5.9
Sparfloxacin	106.6	5.3	98.4	3.6	102.5	5.4
Acetamiprid	105.3	3.8	111.6	3.2	115.3	4.2
Gibberellic acid	77.4	8.2	81.6	1.7	82.1	5.7
4-Fluorophenoxyacetic acid	98.6	7.2	93.6	4.8	91.9	3.3
Chloramphenicol	78.8	4.0	85.8	5.1	85.4	5.9
3-Indolylacetic acid	89.9	3.1	86.5	3.4	97.7	6.3
N6-(δ2-Isopentenyl)-adenine	92.3	1.6	87.2	6.2	96.8	4.0
6-Benzylaminopurine	102.4	6.4	94.3	5.9	95.6	5.2
4-Chlorophenoxyacetic acid	111.3	8.9	108.4	5.3	106.8	5.7
Thidiazuron	94.7	1.9	95.5	4.6	92.7	2.4
3-Indolebutyric acid	78.5	6.2	90.3	3.6	86.4	3.5
Atrazine	94.6	3.8	89.0	6.4	86.9	4.6
Compound	5 μg/kg		10 μg/kg		50 μg/kg
Compound	Recovery/%	RSD/%	Recovery/%	RSD/%	Recovery/%	RSD/%
Forchlorfenuron	103.4	5.3	108.2	4.2	105.7	2.7
Metalaxyl-M	112.4	4.7	98.8	2.7	106.4	4.6
Metalaxyl	97.4	3.0	108.5	1.7	102.1	3.2
2,4-Dichlorophenoxyacetic acid	85.5	8.3	83.2	8.0	87.5	6.6
Azoxystrobin	91.6	3.4	87.3	5.7	84.2	5.9
Paclobutrazol	112.6	2.2	103.5	6.1	107.6	3.6
Triazophos	82.1	9.1	84.3	7.4	88.6	5.5
Isazophos	91.6	5.5	83.6	3.8	84.3	1.9
Flusilazole	82.1	2.1	88.3	4.4	85.7	1.3
Pyraclostrobin	116.4	5.9	107.2	4.6	108.7	4.8

QuEChERS-高效液相色谱-串联质谱法同时测定豆芽中40种植物生长调节剂、杀菌剂、杀虫剂和抗生素类药物残留

Simultaneous determination of 40 plant growth regulators, fungicides, insecticides, and antibiotics in bean sprouts by QuEChERS-high performance liquid chromatography-tandem mass spectrometry

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Metrics

Compound	Contents/(μg/kg)
Compound	This method	Standard method
4-Chlorophenoxyacetic acid	37.5-52.4	34.2-343.5
6-Benzylaminopurine	32.4-273.1	29.3-279.4
Carbendazim	28.8-38.7	-
2,4-Dichlorophenoxyacetic acid	16.1-20.2	14.1-18.3
Gibberellic acid	19.9	22.1
Enrofloxacin	13.6	15.3

Compound	LODs/(μg/kg)
Compound	Reference	This work
Chlormequat	5^[33]	0.2
Carbendazim	45^[22]	0.2
Ronidazole	0.4^[37]	0.1
Dimethylnidazole	0.5^[10]	0.2
Carbendazim	3.7^[27]	0.2
Enoxacin	2^[35]	1.0
Levofloxacin	2^[20]	1.0
pefloxacin mesylate	2^[35]	1.0
Norfloxacin	64^[22]	0.5
Ciprofloxacin	2^[35]	1.0
Enrofloxacin	2^[20]	1.0
Thiabendazole	2.1^[27]	0.5
Lomefloxacin	2^[35]	0.5
Sarafloxacin	2^[35]	0.5
Sparfloxacin	2^[35]	0.5
Gibberellic acid	6.0^[21]	3.0
4-Fluorophenoxyacetic acid	10^[36]	1.5
Chloramphenicol	10^[9]	2.0
3-Indolylacetic acid	72^[22]	3.0
N6-(δ2-Isopentenyl)-adenine	10^[36]	3.0
6-Benzylaminopurine	3.8^[12]	3.0
4-Chlorophenoxyacetic acid	5^[34]	3.0
Thidiazuron	10^[36]	0.2
3-Indolebutyric acid	10^[36]	2.0
Atrazine	1^[33]	0.2
Forchlorfenuron	0.26^[13]	0.1
2,4-Dichlorophenoxyacetic acid	1^[33]	2.0
Paclobutrazol	0.6^[21]	0.1

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