Validation and application of a method for determination of multi-class pesticides in muscle chicken breast fillets using QuEChERS extraction and GC/MS

Fig. 1.

List of pesticide residues and definitions, chemical classification and action (25), retention time, quantifier and qualifier ions, calibration curves, correlation coefficients and linearity (range 5–50 μg/kg)

Analyte	Chemical class	Pesticide action	Retention time, min	Quantifier trace	Qualifier ion, 1 > 2 > 3	Calibration curve	R2
Dichlorvos	Organophosphate	IN	5.58	109	185 >79 >187	y=3.233x + 16.244	0.998759
Acephate	Organophosphate	IN	7.47	136	94 >42 >95	y=0.611x − 55.278	0.994125
Propoxur	Carbamate	IN	9.96	110	152 >57 >111	y=0.516x − 0.659	0.999237
Ethoprophos	Organophosphate	IN, NE	10.41	158	97 >126 >139	y=0.678x−10.689	0.997375
α-HCH	Organochlorine	IN	11.74	181	183 > 219>217	y=0.821x + 0.192	0.997180
Dimethoate	Organophosphate	IN	12.34	87	93 > 125 >143	y=1.450x − 46.247	0.995620
Carbofuran	Carbamate	IN, NE, AC	12.59	164	149 >131 >123	y=1.376x − 23.924	0.999150
β-HCH	Organochlorine	IN	13.09	219	181 >183 >217	y=1.303x + 8.942	0.996873
Lindan	Organochlorine	IN	13.14	181	183 >219 >111	y=1.206x + 13.008	0.998267
Diazinon	Organophosphate	IN	13.78	179	137 >152 >199	y=0.739x − 4.005	0.999704
δ-HCH	Organochlorine	IN	14.65	181	219 >183 >217	y=0.603x + 1.174	0.997564
Methyl parathion	Organophosphate	IN	16.28	263	109 >125 >79	y=0.613x − 18.484	0.998040
Spiroxamine I	Morpholine	FU	16.33	100	101 >126 >198	y=0.134x + 1.758	0.997711
Heptachlor	Organochlorine	IN	16.49	100	270 >272 >274	y=0.694x + 14.471	0.994716
Carbaryl	Carbamate	IN, PG	16.66	144	115 >116 >145	y=1.701x − 60.691	0.990595
Metalaxyl	Phenylamide	FU	16.77	206	45 >160 >249	y=1.444x − 18.488	0.998995
Aldrin	Organochlorine	IN	18.45	100	101 >126 >198	y=0.948x + 12.281	0.996261
Malathion	Organophosphate	IN	18.26	173	127 >125 >93	y=0.898x − 21.530	0.999616
Spiroxamine II	Morpholine	FU	18.23	263	66 >265 >261	y=0.705x − 10.898	0.999415
Chlorpyrifos	Organophosphate	IN	18.46	197	199 >314 >97	y=0.908x − 16.933	0.998991
Heptachlor epoxide (trans, isomer A)	Organochlorine	IN	20.70	351	353 >355 >357	y=0.344x + 2.547	0.991486
Fipronil	Aminopyrazole carbonitrile	IN	21.13	367	369 >213 >351	y=0.437x − 17.073	0.997170
trans Chlordane	Organochlorine	IN	21.79	373	375 >377 >371	y=0.462x − 2.332	0.998275
Prallethrin cis	Pyrethroid	IN	22.17	123	105 >81 >134	y=0.350x − 15.113	0.993093
Prallethrin trans	Pyrethroid	IN	22.24	123	81 >105 >77	y=0.416x − 20.457	0.998616
Paclobutrazol	Triazole	PG	22.40	236	125 >238 >167	y=0.761x − 44.487	0.993356
α-Endosulfan	Organochlorine	IN	22.43	241	195 >239 >238	y=0.213x + 0.518	0.996908
cis Chlordane	Organochlorine	IN	22.47	373	375 >377 >371	y=0.473x − 6.305	0.996973
Imazalil	Imidazole	FU	23.40	41	215 >173 >217	y=0.665x − 10.165	0.994770
Fludioxonil	Phenylpyrrole	FU	23.85	248	127 >154 >182	y=0.517x − 23.688	0.993647
Dieldrin	Organochlorine	IN	23.72	79	263 >277 >279	y=1.184x + 0.013	0.999207
p, p′-DDE	Organochlorine metabolite	IN	23.77	246	318 >316 >248	y=1.613x − 67.643	0.999926
Kresoxim methyl	Strobilurin	FU	24.36	116	206 >131 >132	y=1.645x − 28.114	0.998792
Chlorfenapyr	Halogenated pyrrole	IN	24.68	59	247 >249 >408	y=0.478x + 2.522	0.999517
Endrin	Organochlorine	IN	24.60	263	317 >265 >245	y=0.479x − 1.059	0.991602
Beta Endosulfan	Organochlorine	IN	25.09	195	237 >207 >241	y=0.572x − 0.110	0.998883
p, p′-DDD	Organochlorine metabolite	IN	25.49	235	237 >165 >236	y=1.940x − 14.977	0.998987
Endosulfan sulphate	Organochlorine metabolite	IN	26.53	272	274 >229 >237	y=0.263x − 4.496	0.998369
Propiconazole I	Triazole	FU	26.60	69	173 >259 >175	y=0.743x − 10.101	0.998569
Trifloxystrobin	Strobilurin	FU	26.73	116	131 >59 >172	y=1.265x − 37.722	0.998671
Propiconazole II	Triazole	FU	26.79	173	69 >259 >175	y=1.098x − 14.776	0.998890
p, p′-DDT	Organochlorine metabolite	IN	26.77	235	237 >165 >236	y=1.313x − 25.359	0.999525
Tebuconazole	Triazole	FU	27.28	125	250 >70 >83	y=1.104x − 33.413	0.999160
Spiromesifen	Spirocyclic tetronic acid	IN	27.83	272	99 > 273 > 254	y=0.266x − 5.603	0.992335
Endrin ketone	Organochlorine metabolite	IN	28.00	317	67 >315 >319	y=0.262x + 0.423	0.999700
Phosmet	Organophosphate	IN	28.24	160	161 >77 >93	y=3.378x − 136.602	0.992964
Bifenthrin	Pyrethroid	IN	28.43	181	165 >166 >182	y=3.946x − 43.476	0.999588
Fenoxycarb	Carbamate	IN	28.56	255	186 >77 >185	y=0.641x − 11.790	0.990529
Methoxychlor	Organochlorine	IN	28.60	113	152 >227 >228	y=2.679x − 69.052	0.999788
Etoxazole	Diphenyloxazole	AC	28.64	141	204 >300 >359	y=0.268x + 0.366	0.999849
Permethrin I	Pyrethroid	IN	31.04	183	163 >165 >184	y=2.405x + 0.438	0.999773
Pyridaben	Pyridazinone	IN, AC	31.24	147	117 >148 >132	y=3.412x − 41.245	0.998908
Permethrin II	Pyrethroid	IN	31.23	183	163 >165 >184	y=2.228x − 12.107	0.999740
Cyfluthrin I	Pyrethroid	IN	31.84	163	206 >165 >226	y=0.175x + 0.333	0.999504
Cyfluthrin II	Pyrethroid	IN	31.99	163	206 >165 >226	y=0.222x + 2.497	0.994932
Cyfluthrin III	Pyrethroid	IN	32.06	163	206 >165 >226	y=0.246x − 6.336	0.998605
Cyfluthrin IV	Pyrethroid	IN	32.13	163	206 >165 >226	y=0.124x + 4.731	0.995465
Cypermethrin I	Pyrethroid	IN	32.31	181	163 >165 >209	y=0.182x + 1.980	0.998705
Cypermethrin II	Pyrethroid	IN	32.45	181	163 >165 >209	y=0.250x − 1.053	0.995146
Cypermethrin III	Pyrethroid	IN	32.54	181	163 >165 >209	y=0.139x − 0.982	0.994351
Cypermethrin IV	Pyrethroid	IN	32.63	181	163 >165 >209	y=0.147x − 1.307	0.999349
Boscalid	Carboxamide/anilide	FU	32.40	140	342 >344 >142	y=2.222x − 23.456	0.997997
Etofenprox	Pyrethroid	IN	32.75	163	164 >135 >107	y=4.654x + 51.022	0.999801
Azoxystrobin	Strobilurin	FU	35.68	344	388 >345 >372	y=0.956x − 3.589	0.999298

Pesticides detected and their concentrations in chicken breast fillets

Sample	Number of samples, pesticide <LOQ	Number of samples, pesticide, >LOQ	Cypermethrin (sum of isomers – μg/kg)	Endosulfan sulphate, (μg/kg)	Permethrin, (sum of isomers) μg/kg	Alpha endosulfan, μg/kg	p,p′-DDT, μg/kg
Domestic chicken fillets	37	3	<LOQ–11.5	<LOQ–4.9	<LOQ–15.2	<LOQ -5.4	<LOQ
Imported chicken fillets	39	1	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ–6.0
Organic domestic chicken fillets	20	0	<LOQ	<LOQ	<LOQ	<LOQ	<LOQ
Calculated value using Cf	/	/	11.5	4.7	15.2	5.4	6.0
MRL (sum)	/	/	100	50	50	50	1000

Recovery, relative standard deviation (RSD), limit of detection (LOD) and limit of quantification (LOQ) for determination of multi-class pesticides

No.	Pesticide	Recovery (RSD), % (n = 6) 5 μg/kg	Recovery (RSD), % (n = 6) 10 μg/kg	Recovery (RSD), % (n = 6) 20 μg/kg	LOD (n = 6) μg/kg	LOQ (n = 6) μg/kg
1	Acephate	72.8 (9.2)	71.8 (9.1)	84.2 (14.9)	1.1	3.6
2	Aldrin	75.2 (11.2)	78.2 (10.0)	105.2 (9.8)	1.3	4.2
3	α-Endosulfan	83.2 (6.5)	79.4 (7.0)	84.0 (9.8)	1.2	4.0
4	α-HCH	81.2 (6.1)	79.6 (9.4)	77.4 (6.3)	1.4	4.5
5	Azoxystrobin	100.5 (3.6)	103 (13.3)	82.1 (10.2)	1.0	3.3
6	β-Endosulfan	88.2 (4.2)	87.6 (13.3)	82.1 (10.2)	1.2	4.1
7	β-HCH	102.4 (11.3)	114.2 (14.4)	110.0 (14.8)	1.2	4.0
8	Bifenthrin	92.3 (8.2)	94.8 (10.9)	80.8 (11.3)	1.2	3.9
9	Boscalid	102.3 (4.6)	109.0 (10.9)	95.6 (10.7)	1.1	3.7
10	Carbaryl	102.4 (3.8)	95.6 (8.9)	106.2 (16.2)	1.5	4.9
11	Carbofuran	86.9 (11.9)	83.8 (13.6)	84.0 (10.1)	1.4	4.8
12	Chlorfenapyr	79.5 (5.2)	71.2 (11.7)	82.4 (12.6)	1.6	5.2
13	Chlorpyrifos	99.4 (3.2)	97.0 (6.1)	84.6 (12.0)	1.4	4.5
14	cis-Chlordane	90.7 (6.3)	90.8 (12.7)	92.0 (14.2)	1.4	4.5
15	Cyfluthrin (sum)	112.5 (7.2)	114.1 (12.9)	117.2 (7.8)	0.9	3.1
16	Cypermethrin (sum)	99.5 (3.5)	110.0 (9.6)	84.4 (15.5)	1.2	4.0
17	δ-HCH	93.4 (9.2)	89.8 (10.3)	110.2 (11.7)	1.1	3.7
18	Diazinon	99.9 (8.1)	96.3 (11.4)	105.8 (1.7)	1.4	4.6
19	Dichlorvos	83.2 (12.4)	82.2 (14.9)	83.2 (12.7)	1.5	4.9
20	Dieldrin	105.6 (4.5)	107.2 (6.2)	113.0 (14.3)	0.9	3.1
21	Dimethoate	111.1 (4.3)	112.2 (7.2)	112.6 (4.5)	1.0	3.2
22	Endosulfan sulphate	98.5 (5.8)	114.4 (4.1)	102.2 (8.3)	0.9	3.1
23	Endrin	87.8 (8.2)	82.8 (13.6)	73.6 (7.5)	1.0	3.5
24	Endrin ketone	82.5 (3.6)	81.0 (13.8)	101.6 (2.9)	1.0	3.4
25	Etofenprox	99.9 (11.6)	102.0 (18.9)	95.5 (13.2)	1.0	3.5
26	Ethoprophos	94.6 (5.7)	104.0 (7.8)	87.8 (14.3)	1.4	4.8
27	Etoxazole	111.6 (14.2)	118.8 (12.5)	113.0 (12.5)	1.4	4.7
28	Fenoxycarb	89.2 (7.8)	77.2 (13.5)	81.8 (17.8)	1.4	4.5
29	Fipronil	106.3 (12.4)	104.6 (17.4)	86.8 (17.9)	0.9	3.0
30	Fipronil sulfone	103.1 (3.5)	102.1 (6.3)	109.4 (4.9)	0.9	3.0
31	Fludioxonil	86.3 (4.9)	89.4 (4.6)	80.0 (18.1)	1.2	4.0
32	Heptachlor	85.4 (4.1)	80.2 (4.1)	86.0 (8.5)	1.2	4.0
33	Heptachlor epoxide (trans-, isomer A)	98.7 (4.4)	89.6 (11.8)	99.8 (15.2)	1.4	4.8
34	Imazalil	99.8 (12.3)	97.4 (16.6)	102 (18.0)	0.9	3.1
35	Kresoxim methyl	94.4 (2.9)	89.2 (7.8)	98.0 (3.6)	1.0	3.4
36	Lindane	79.3 (6.1)	77.4 (7.7)	75.4 (15.1)	1.2	4.0
37	Malathion	84.6 (6.9)	79.4 (15.4)	76.2 (8.1)	1.4	4.6
38	Metalaxyl	90.2 (4.3)	90.8 (11.5)	106.0 (7.6)	1.4	4.6
39	Methyl parathion	84.1 (6.7)	83.8 (13.8)	84.5 (6.1)	1.4	4.6
40	Metoxychlor	74.7 (4.2)	74.8 (6.8)	101.2 (16.7)	0.9	3.1
41	o,p′-DDT	92.6 (3.9)	95.6 (3.3)	97.9 (3.7)	1.2	4.0
42	p,p′-DDD (TDE)	100.1 (2.9)	89.4 (7.0)	101.2 (16.7)	1.2	4.0
43	p,p′-DDE	94.1 (1.6)	93.5 (3.5)	95.8 (11.8)	1.0	3.5
44	p,p′-DDT	94.2 (3.0)	84.8 (12.1)	101.0 (13.5)	1.0	3.5
45	Paclobutrazol	87.7 (3.5)	79.8 (5.7)	88.0 (13.7)	1.4	4.6
46	Permethrin (sum)	86.6 (8.9)	83.8 (14.8)	102.2 (8.4)	1.0	3.5
47	Phosmet	103.1 (2.9)	95.2 (14.1)	106.6 (10.6)	1.5	4.9
48	Prallethrin (sum)	98.5 (5.5)	102.4 (17.8)	92.6 (5.7)	1.0	3.3
49	Propiconazole (sum)	101.4 (11.3)	96.0 (10.6)	104.8 (14.4)	1.4	4.6
50	Propoxur	75.3 (3.1)	87.4 (10.9)	75.2 (9.7)	1.2	4.0
51	Pyridaben	110.3 (3.3)	114.0 (8.1)	85.4 (12.3)	1.4	4.8
52	Spiromesifen	89.9 (9.9)	81.6 (14.1)	90.8 (10.0)	1.2	4.0
53	Spiroxamine (sum)	113.4 (14.7)	118.8 (10.8)	105.4 (9.9)	1.4	4.6
54	Tebuconazole	94.2 (7.1)	110.6 (6.4)	71.2 (11.1)	1.2	4.0
55	trans-Chlordane	91.2 (4.6)	86.0 (10.3)	107.8 (17.2)	1.4	4.6
56	Trifloxystrobin	104.2 (2.9)	107.0 (15.1)	87.2 (3.0)	1.2	4.0