Validation of a LC-MS/MS Multiresidue Methodology Based on a QuEChERS Approach for the Determination of Fluoroquinolones, Sulfonamides and Trimethoprim in Poultry and Porcine Kidney According to the Normative Instruction 24/2009-MAPA

Rocha, Diego G.; Santos, Flavio A.; Gomes, Aline A.; Faria, Adriana F.

doi:10.5935/0103-5053.20160147

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Articles • J. Braz. Chem. Soc. 28 (1) • Jan 2017 • https://doi.org/10.5935/0103-5053.20160147 copy

Validation of a LC-MS/MS Multiresidue Methodology Based on a QuEChERS Approach for the Determination of Fluoroquinolones, Sulfonamides and Trimethoprim in Poultry and Porcine Kidney According to the Normative Instruction 24/2009-MAPA

Authorship SCIMAGO INSTITUTIONS RANKINGS

This work involved the validation of a multiresidue method according to the Normative Instruction 24/2009-MAPA for determining 25 analytes, among fluoroquinolones, sulfonamides and trimethoprim in samples of poultry and porcine kidney. The extraction procedure was based on a QuEChERS approach. A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed using the selected reaction monitoring mode (SRM) and ESI⁺ ionization. All of the validated figures of merit were evaluated as satisfactory. Accuracy was assessed by recovery studies, varying from 82.7 to 115.5% for porcine kidney and from 91.5 to 110.4% for poultry kidney. Relative standard deviations were lower than 25.5% for porcine kidney, and 29.8% for poultry kidney. Decision limits (CCα) comprised values from 10.37 to 3298.43 µg kg^-1 for porcine kidney and 10.08 to 3176.59 µg kg^-1 for poultry kidney. Detection capabilities (CCβ) varied from 10.73 to 3396.86 µg kg^-1 for porcine kidney and 10.67 to 3253.19 µg kg^-1 for poultry kidney. The developed method has been successfully employed in the routine analysis of incurred samples.

Keywords:
mass spectrometry; chromatography; sample preparation

	Intercept	Slope	R²	t-value	RSD_intra-day / %	RSD_inter-day / %
Ciprofloxacin	−0.005	0.001	0.929	7.24	4.25	8.3
Danofloxacin	0.032	0.006	0.953	9.00	5.25	15.2
Dapsone	0.002	0.008	0.918	4.62	1.30	25.5
Difloxacin	0.040	0.028	0.983	15.38	9.81	13.8
Enrofloxacin	0.018	0.020	0.966	10.67	6.65	12.5
Flumequine	1.110	0.059	0.961	9.91	12.00	9.0
Marbofloxacin	0.016	0.022	0.987	17.66	1.52	19.4
Nalidixic acid	0.001	0.135	0.995	28.03	1.16	15.3
Norfloxacina	0.002	0.013	0.979	13.76	1.51	24.4
Ofloxacin	0.005	0.063	0.974	12.20	1.36	18.7
Oxolinic acid	−0.094	0.105	0.974	12.34	4.13	14.2
Pipemidic acid	0.001	0.022	0.959	9.70	1.53	20.6
Sarafloxacin	0.004	0.024	0.962	10.02	1.45	20.6
Sulfaclorpiridazine	0.003	0.017	0.920	4.57	1.95	9.2
Sulfadiazine	0.001	0.009	0.986	11.94	2.60	9.7
Sulfadimethoxine	0.021	0.038	0.960	6.65	2.35	12.0
Sulfadoxine	0.007	0.047	0.978	7.65	2.58	9.9
Sulfamerazine	0.002	0.015	0.980	14.09	2.20	6.8
Sulfamethazine	0.002	0.014	0.986	11.62	2.37	10.3
Sulfamethoxazole	0.003	0.015	0.932	5.13	2.17	11.2
Sulfamethoxypyridazine	0.003	0.022	0.992	15.94	1.95	8.0
Sulfaquinoxaline	0.028	0.015	0.966	7.49	3.23	14.9
Sulfathiazole	0.005	0.005	0.972	8.22	2.30	13.1
Sulfisoxazole	0.001	0.004	0.924	4.83	3.18	10.6
Trimethoprim	0.001	0.008	0.984	2.81	2.67	15.1

Analyte	Porcine kidney Recovery / %			Poultry kidney Recovery / %
Analyte	0.5 RL	1.0 RL	1.25 RL	0.5 RL	1.0 RL	1.25 RL
Ciprofloxacin	84.6	82.7	90.4	98.7	110.4	102.3
Danofloxacin	94.7	96.1	102.8	95.6	110.0	109.5
Dapsone	89.7	95.3	96.4	90.4	95.0	101.9
Difloxacin	90.5	92.9	105.7	92.6	100.6	108.9
Enrofloxacin	95.9	102.0	104.8	102.6	109.3	110.1
Flumequine	83.0	84.7	92.7	99.7	97.4	95.4
Marbofloxacin	110.3	109.0	102.1	96.5	109.7	102.6
Nalidixic acid	88.2	95.9	90.6	91.7	104.5	98.5
Norfloxacina	97.1	105.7	101.5	98.2	97.8	102.3
Ofloxacin	92.3	97.2	101.9	92.9	91.5	102.4
Oxolinic acid	89.3	99.6	105.6	101.1	107.1	93.5
Pipemidic acid	101.7	115.5	91.9	93.2	101.7	95.5
Sarafloxacin	97.6	101.2	105.8	92.2	106.3	105.4
Sulfaclorpiridazine	105.1	99.6	96.4	107.2	103.1	102.0
Sulfadiazine	105.5	101.1	98.7	107.6	103.6	102.7
Sulfadimethoxine	106.6	101.0	98.6	109.1	106.9	107.8
Sulfadoxine	108.6	101.5	96.2	109.6	104.7	101.5
Sulfamerazine	105.6	100.2	97.9	108.7	102.0	101.8
Sulfamethazine	106.8	101.1	100.3	109.4	103.8	102.5
Sulfamethoxazole	107.1	102.0	104.6	107.5	106.3	101.9
Sulfamethoxypyridazine	106.3	100.5	99.6	107.1	103.5	102.4
Sulfaquinoxaline	107.3	94.3	96.5	102.3	93.4	98.8
Sulfathiazole	109.4	102.8	101.5	104.1	102.5	106.6
Sulfisoxazole	107.2	102.4	103.8	106.2	107.5	108.1
Trimethoprim	102.2	99.9	93.1	92.3	96.6	89.2

Analyte	RL / (μg kg^-1)	Porcine kidney		Poultry kidney
Analyte	RL / (μg kg^-1)	CCα / (μg kg^-1)	CCβ / (μg kg^-1)	CCα / (μg kg^-1)	CCβ / (μg kg^-1)
Ciprofloxacin	300	333.91	352.82	327.80	355.59
Danofloxacin	400	445.27	470.54	444.11	488.21
Dapsone	10	10.37	10.73	10.08	10.67
Difloxacin	600	704.69	789.38	662.47	684.95
Enrofloxacin	300	322.54	345.07	337.26	374.52
Flumequine	3000	3298.43	3396.86	3176.59	3253.19
Marbofloxacin	10	13.78	17.56	12.03	14.07
Nalidixic acid	10	12.40	14.8	11.22	12.44
Norfloxacin	10	14.05	15.11	11.12	12.25
Ofloxacin	10	13.05	16.10	12.23	14.54
Oxolinic acid	150	183.50	191.00	168.89	187.78
Pipemidic acid	10	13.86	17.72	11.42	12.84
Sarafloxacin	80	83.45	86.91	81.18	82.36
Sulfaclorpiridazine	100	106.61	113.22	103.89	107.78
Sulfadiazine	100	102.04	104.07	102.84	105.67
Sulfadimethoxine	100	103.83	107.66	103.48	106.96
Sulfadoxine	100	103.64	107.27	104.93	109.86
Sulfamethazine	100	102.06	104.11	103.86	107.73
Sulfamethoxazole	100	105.77	111.53	105.15	110.29
Sulfamethoxypyridazine	100	101.08	102.17	101.20	102.41
Sulfamiderazine	100	101.38	102.77	101.37	102.74
Sulfathiazole	100	103.13	106.25	103.13	106.26
Sulfisoxazole	100	106.21	112.42	106.43	112.86
Sulphaquinoxaline	100	100.93	101.85	101.15	102.30
Trimethoprim	50	55.59	61.17	52.60	55.20

Analyte	RL / (µg kg^-1)	Uncertainty / %
Analyte	RL / (µg kg^-1)	Porcine kidney	Poultry kidney
Ciprofloxacin	300	18.03	38.69
Danofloxacin	400	11.13	20.25
Dapsone	10	37.80	34.80
Difloxacin	600	10.28	10.10
Enrofloxacin	300	17.07	30.53
Flumequine	3000	4.50	5.06
Marbofloxacine	10	52.20	28.10
Nalidixic acid	10	61.90	40.40
Norfloxacin	10	56.80	21.80
Ofloxacin	10	56.60	70.30
Oxolinic acid	150	26.03	43.00
Pipemidic acid	10	83.70	32.60
Sarafloxacin	80	9.26	2.95
Sulfaclorpiridazine	100	11.27	7.83
Sulfadiazine	100	13.44	15.41
Sulfadimethoxine	100	20.38	11.21
Sulfadoxine	100	14.02	12.99
Sulfamerazine	100	10.29	9.54
Sulfamethazine	100	12.20	11.00
Sulfamethoxazole	100	13.62	12.53
Sulfamethoxipiridazine	100	11.13	7.53
Sulfaquinoxaline	100	24.58	23.07
Sulfathiazole	100	22.27	10.66
Sulfisoxazole	100	17.26	18.99
Trimethoprim	50	22.50	26.38

Analyte	Precursor ion	Product ion	Ion ratio / %	DP / V	CE / V	RT / min
Ciprofloxacin	332.0	314.0 231.0	90.4	60	40 35	5.60
Ciprofloxacin D8 (IS)	340.2	296.3 249.0	72.1	65	22 33	6.39
Danofloxacin	358.3	82.1 255.0	26.6	130	50 33	6.76
Dapsone	249.2	108.0 156.0	133.4	96	19	8.83
Difloxacin	400.1	356.0 299.3	112.4	21	29 37	7.65
Enrofloxacin	360.2	316.2 245.2	172.1	51	37 40	7.01
Flumequine	262.3	244.2 202.3	82.3	126	21 43	10.54
Marbofloxacin	363.0	72.0 320.0	28.7	40	32 28	5.89
Nalidixic acid	233.2	215.2 187.0	140.0	31	21 35	10.47
Norfloxacin	320.2	276.3 233.2	85.8	51	25 33	6.20
Ofloxacin	362.4	261.0 318.0	79.3	60	33 23	6.32
Oxolinic acid	262.1	244.2 216.0	23.2	66	23 39	9.41
Pipemidic acid	304.0	217.0 189.0	29.4	120	25 35	4.68
Sarafloxacin	386.2	342.1 299.0	123.0	21	29 37	7.58
Sulfaclorpiridazine	285.2	156.0 92.1	53.8	26	23 33	8.82
Sulfadiazine	251.0	156.2 92.1	105.1	46	17 31	6.21
Sulfadimethoxine	311.2	156.0 245.5	8.0	106	31 23	9.84
Sulfadoxine	310.9	153.3 92.1	70.6	21	23 43	9.00
Sulfamerazine	265.1	92.0 156.1	101.0	66	37 25	7.20
Sulfamethazine	279.0	124.0 186.0	52.3	51	29	7.92
Sulfamethoxazole	254.1	108.0 92.0	123.6	60	35	9.23
Sulfamethoxypyridazine	281.0	156.0 126.0	34.9	86	25	8.01
Sulfapyridine (IS)	250.0	156.1 184.3	63.7	41	23 25	6.70
Sulfaquinoxaline	301.0	156.0 118.1	6.9	106	23 39	9.72
Sulfathiazole	256.1	156.0 92.3	72.9	31	21 37	6.40
Sulfisoxazole	268.5	113.2 156.3	91.0	41	21	9.40
Trimethoprim	291.5	123.1 230.1	106.0	21	37 39	5.82

Analyte	Intercept	Slope	R²	t-value	RSD_intra-day / %
Ciprofloxacin	0.009	0.014	0.971	11.56	5.3
Danofloxacin	0.017	0.029	0.944	8.18	6.3
Dapsone	0.001	0.007	0.983	3.96	29.8
Difloxacin	0.027	0.021	0.994	25.08	6.6
Enrofloxacin	0.003	0.017	0.977	12.92	7.0
Flumequine	1.479	0.051	0.994	24.95	5.9
Marbofloxacin	0.001	0.031	0.997	36.01	11.5
Nalidixic acid	0.000	0.153	0.994	25.88	7.2
Norfloxacina	−0.002	0.012	0.981	14.28	7.0
Ofloxacin	0.015	0.042	0.951	8.79	15.3
Oxolinic acid	0.013	0.126	0.991	20.71	7.1
Pipemidic acid	0.000	0.008	0.998	46.33	9.0
Sarafloxacin	0.006	0.015	0.990	19.83	6.2
Sulfaclorpiridazine	0.005	0.022	0.978	9.45	10.3
Sulfadiazine	0.001	0.009	0.986	12.03	10.0
Sulfadimethoxine	0.030	0.045	0.977	9.06	9.7
Sulfadoxine	0.008	0.053	0.971	8.07	9.9
Sulfamerazine	0.003	0.016	0.984	14.55	6.4
Sulfamethazine	0.003	0.013	0.980	9.76	12.6
Sulfamethoxazole	0.005	0.019	0.970	8.03	11.8
Sulfamethoxypyridazine	0.004	0.022	0.992	15.8	7.1
Sulfaquinoxaline	0.014	0.017	0.988	12.54	17.8
Sulfathiazole	0.008	0.014	0.979	9.59	12.9
Sulfisoxazole	0.001	0.005	0.957	6.57	10.3
Trimethoprim	0.002	0.011	0.969	7.81	19.2

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