Multi-Residue Method for Determination of Thirty-Five Pesticides, Pharmaceuticals and Personal Care Products in Water Using Ionic Liquid-Dispersive Liquid-Liquid Microextraction Combined with Liquid Chromatography-Tandem Mass Spectrometry

Marube, Liziane C.; Caldas, Sergiane S.; Santos, Elisane O. dos; Michaelsen, Andressa; Primel, Ednei G.

doi:10.21577/0103-5053.20170234

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Articles • J. Braz. Chem. Soc. 29 (6) • June 2018 • https://doi.org/10.21577/0103-5053.20170234 copy

Multi-Residue Method for Determination of Thirty-Five Pesticides, Pharmaceuticals and Personal Care Products in Water Using Ionic Liquid-Dispersive Liquid-Liquid Microextraction Combined with Liquid Chromatography-Tandem Mass Spectrometry

Authorship SCIMAGO INSTITUTIONS RANKINGS

Ionic liquid-dispersive liquid-liquid microextraction (IL-DLLME) was used for the determination of different chemical classes of analytes for the first time. Limits of quantification (LOQs) ranged from 0.5 to 2.5 µg L^-1, and the linearity ranged from the LOQ of each compound to 50 µg L^-1. Recoveries ranged from 70 to 120% for the compounds, with relative standard deviations less than 18%. The proposed method demonstrates for the first time that sample preparation by IL-DLLME and determination by liquid chromatography-tandem mass spectrometry (LC-MS/MS) can be used successfully for the simultaneous extraction of 19 kinds of pesticides and 16 PPCPs from water samples. In addition, to eliminate the environmental risk of waste solvent disposal, this technique uses a low-toxicity extraction solvent. Finally, the analytical method proposed was applied successfully in analysis in surface water samples.

Keywords:
IL-DLLME; water; pesticides; PPCPs; LC-MS/MS

Analyte	Linear range / (µg L^-1)	Analytical curves in the solvent	r	Analytical curves in the extract	r	ME / %
PPCP
Amitriptyline	2.5-50	y = 105817x - 246.59	0.9996	y = 86525x - 1008.1	0.9997	-18
Albendazole	2.5-50	y = 533150x + 6761.3	0.9981	y = 155409x - 2618.4	0.9993	-70
Bisphenol-A	2.5-50	y = 1448.3x + 74.866	0.9939	y = 1315.4x + 27.958	0.9988	-9
Carbamazepine	0.5-50	y = 284148x + 3244.7	0.9993	y = 228100x - 1040.7	0.9991	-19
Diltiazem hydrochloride	2.5-50	y = 217669x + 1652.5	0.9984	y = 155905x - 4527.9	0.9951	-27
Furosemide	2.5-50	y = 31920x + 159.1	0.9997	y = 26058x - 611.77	0.9953	-18
Gemfibrozil	2.5-50	y = 21093x + 544.79	0.9988	y = 19173x - 155.03	0.9996	-9
Glibenclamide	2.5-50	y = 47900x + 556.34	0.9996	y = 41530x - 765.79	0.9993	-13
Haloperidol	2.5-50	y = 555340x + 14865	0.9944	y = 435016x - 2921.4	0.9965	-21
Mebendazole	0.5-50	y = 295820x + 2374.8	0.999	y = 248359x - 1939.5	0.9995	-16
Miconazole	0.5-50	y = 150768x - 761.35	0.9994	y = 147611x - 2460.8	0.9989	-2
Nifedipine	2.5-50	y = 35851x - 875.21	0.9965	y = 35768x - 1456.7	0.9917	-2
Nimesulide	2.5-50	y = 62516x + 5188	0.9904	y = 63877x + 1214.8	0.9919	-2
Propylparaben	0.5-50	y = 37044x + 1353.2	0.9931	y = 30325x + 505.83	0.9971	-18
Triclocarban	2.5-50	y = 105111x + 4158.3	0.9981	y = 99013x - 1463.3	0.998	-5
Triclosan	2.5-50	y = 1514.9x + 3.5007	0.9946	y = 1085.4x - 13.272	0.9997	-28
Pesticide
Azoxystrobin	0.5-50	y = 349993x + 1509.3	0.9995	y = 221454x - 5334.5	0.9967	-36
Carbofuran	0.5-50	y = 284094x + 4283.7	0.9986	y = 169818x + 11.22	0.9999	-40
Cyproconazole	0.5-50	y = 115826x + 106.26	0.998	y = 94030x - 325.98	0.9997	-18
Clomazone	0.5-50	y = 449535x + 8023.8	0.9986	y = 344387x - 1801.7	0.9994	-23
Dichloran	2.5-50	y = 1977x + 55.354	0.9987	y = 1496.8x - 16.029	0.9995	-22
Difenoconazole	2.5-50	y = 303289x + 6291.5	0.9995	y = 265085x - 4726.5	0.999	-12
Diuron	0.5-50	y = 44133x + 744.64	0.9972	y = 33791x + 41.586	0.9997	-23
Epoxyconazole	0.5-50	y = 241974x + 2509.5	0.9992	y = 201343x - 2119.8	0.9992	-16
Fenoxaprop-p-ethyl	2.5-50	y = 83721x + 2605.3	0.9994	y = 75106x - 1385.1	0.9979	-10
Fipronil	0.5-50	y = 183647x + 2696.3	0.9954	y = 150456x - 864.97	0.9996	-18
Iprodione	0.5-50	y = 47045x + 706.21	0.9986	y = 36848x - 490.24	0.9993	-21
Irgarol	2.5-50	y = 1 × 10⁶x + 3167.9	0.9987	y = 852511x - 23118	0.9979	-14
Malathion	2.5-50	y = 228987x + 4467.7	0.9972	y = 197237x - 2374.1	0.9914	-13
Penoxsulam	2.5-50	y = 10583x + 597.99	0.9901	y = 7582.9x - 72.213	0.9999	-28
Pyraclostrobin	2.5-50	y = 111679x + 1530.2	0.9996	y = 91457x - 1483.5	0.9975	-18
Propanil	2.5-50	y = 81483x + 5243.3	0.994	y = 72974x - 1866	0.9958	-10
Propiconazole	2.5-50	y = 130660x + 1830	0.9999	y = 108460x - 876.93	0.9999	-16
Tebuconazole	2.5-50	y = 125507x + 2530.7	0.9989	y = 101851x - 281.53	0.9989	-18
Trifloxystrobin	2.5-50	y = 161855x + 3533.2	0.9989	y = 144828x - 2072.4	0.9964	-10

Analyte	LOD / (µg L^-1)	LOQ / (µg L^-1)	Repeatability (R ± RSD) / %			Intermediate precision (R ± RSD) / %
Analyte	LOD / (µg L^-1)	LOQ / (µg L^-1)	LOQ	5LOQ	10LOQ	LOQ	5LOQ	10LOQ
PPCP
Amitriptyline	0.8	2.5	95 ± 6	70 ± 10	75 ± 5	81 ± 8	73 ± 7	71 ± 4
Albendazole	0.8	2.5	80 ± 5	116 ± 7	120 ± 1	75 ± 8	80 ± 6	76 ± 5
Bisphenol-A	0.8	2.5	98 ± 7	75 ± 8	72 ± 9	76 ± 10	70 ± 6	72 ± 9
Carbamazepine	0.1	0.5	115 ± 2	113 ± 11	70 ± 7	102 ± 5	95 ± 3	80 ± 9
Diltiazem hydrochloride	0.8	2.5	80 ± 7	76 ± 4	85 ± 15	72 ± 13	82 ± 9	76 ± 6
Furosemide	0.8	2.5	120 ± 7	109 ± 6	113 ± 8	82 ± 7	75 ± 9	98 ± 11
Gemfibrozil	0.8	2.5	100 ± 8	80 ± 1	97 ± 2	76 ± 3	79 ± 6	74 ± 7
Glibenclamide	0.8	2.5	84 ± 2	80 ± 5	70 ± 8	120 ± 2	87 ± 7	74 ± 8
Haloperidol	0.8	2.5	120 ± 3	100 ± 6	120 ± 10	95 ± 4	80 ± 6	75 ± 9
Mebendazole	0.1	0.5	120 ± 7	100 ± 8	100 ± 5	120 ± 9	105 ± 5	105 ± 7
Miconazole	0.1	0.5	100 ± 15	120 ± 5	100 ± 13	100 ± 9	120 ± 5	100 ± 9
Nifedipine	0.8	2.5	120 ± 9	110 ± 8	80 ± 5	110 ± 6	120 ± 9	110 ± 6
Nimesulide	0.8	2.5	100 ± 7	105 ± 9	80 ± 9	80 ± 7	85 ± 6	90 ± 4
Propylparaben	0.1	0.5	105 ± 14	73 ± 10	80 ± 7	110 ± 10	105 ± 5	80 ± 7
Triclocarban	0.8	2.5	80 ± 2	120 ± 6	97 ± 5	90 ± 8	110 ± 9	85 ± 5
Triclosan	0.8	2.5	118 ± 2	120 ± 8	100 ± 2	120 ± 10	105 ± 9	107 ± 15
Pesticide
Azoxystrobin	0.1	0.5	100 ± 9	120 ± 8	100 ± 3	70 ± 11	80 ± 8	70 ± 6
Carbofuran	0.1	0.5	80 ± 6	75 ± 9	90 ± 8	120 ± 10	85 ± 3	80 ± 9
Cyproconazole	0.1	0.5	80 ± 6	75 ± 9	90 ± 8	120 ± 10	85 ± 4	80 ± 11
Clomazone	0.1	0.5	97 ± 8	120 ± 4	100 ± 3	90 ± 6	98 ± 3	76 ± 5
Dichloran	0.8	2.5	100 ± 7	80 ± 5	72 ± 3	100 ± 4	80 ± 8	120 ± 9
Difenoconazole	0.8	2.5	100 ± 10	120 ± 15	80 ± 16	99 ± 15	120 ± 8	100 ± 16
Diuron	0.1	0.5	80 ± 14	85 ± 10	70 ± 9	82 ± 17	90 ± 5	92 ± 9
Epoxyconazole	0.1	0.5	100 ± 13	120 ± 12	100 ± 18	90 ± 13	95 ± 8	85 ± 9
Fenoxaprop-p-ethyl	0.8	2.5	100 ± 8	90 ± 11	91 ± 5	95 ± 10	90 ± 6	80 ± 7
Fipronil	0.1	0.5	70 ± 14	70 ± 5	90 ± 10	85 ± 5	70 ± 5	100 ± 6
Iprodione	0.1	0.5	100 ± 2	120 ± 6	97 ± 8	100 ± 4	120 ± 10	98 ± 8
Irgarol	0.8	2.5	70 ± 16	80 ± 10	93 ± 4	70 ± 3	90 ± 6	100 ± 10
Malathion	0.8	2.5	120 ± 10	104 ± 15	120 ± 9	90 ± 12	75 ± 10	80 ± 9
Penoxsulam	0.8	2.5	70 ± 3	110 ± 5	120 ± 15	76 ± 18	113 ± 15	120 ± 10
Pyraclostrobin	0.8	2.5	100 ± 7	120 ± 10	95 ± 6	120 ± 10	85 ± 15	100 ± 12
Propanil	0.8	2.5	120 ± 13	80 ± 7	79 ± 10	118 ± 10	88 ± 9	78 ± 10
Propiconazole	0.8	2.5	120 ± 16	116 ± 12	110 ± 9	116 ± 14	108 ± 7	96 ± 10
Tebuconazole	0.8	2.5	106 ± 12	72 ± 14	74 ± 10	110 ± 12	90 ± 9	84 ± 12
Trifloxystrobin	0.8	2.5	82 ± 8	100 ± 11	105 ± 5	80 ± 10	107 ± 8	85 ± 7
Diuron-d₆	0.8	0.5	70 ± 4
Carbofuran-d₃	0.8	0.5	100 ± 3

Extraction technique	Analyte	Sample volume	Extraction solvent (volume)	Extraction time	Centrifuged time / min	Accuracy / %	Precision / %	LOQ range / (µg L^-1)	Reference
IL-TC-DLLME^a a temperature-controlled ionic liquid dispersive liquid-liquid microextraction;	2 pesticides	10 mL rainwater, groundwater and river water	[C₆MIM][PF₆] (50 µL)	heating at 80 ºC for 30 min	20 min	88-103	< 3	0.2-0.3	¹⁸18 Zhou, Q.; Bai, H.; Xie, G.; Xiao, J.; J. Chromatogr. A 2008, 1188, 148.
IL-DLLME^b b ionic liquid dispersive liquid-liquid microextraction;	4 pesticides	5 mL tap, lake and fountain waters	[C₆MIM][PF₆] (40 µL)		10 min at 4000 rpm	82-106	< 10.7	1.7-4.2	⁵²52 Liu, Y.; Zhao, E.; Zhu, W.; Gao, H.; Zhou, Z.; J. Chromatogr. A 2009, 1216, 885.
IL-TC-DLLME^a a temperature-controlled ionic liquid dispersive liquid-liquid microextraction;	1 pesticide and 3 metabolites	10 mL surface water sample	C₆MIM][PF₆] (50 µL)	heating at 75 ºC for 30 min, ice‑water bath for 2 min	15 min at 4000 rpm	97-106	< 7	0.2-0.4	⁵³53 Bai, H.; Zhou, Q.; Xie, G.; Xiao, J.; Anal. Chim. Acta 2009, 651, 64.
IL-USA-DLLME^c c ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction. LOQ: limit of quantification; PPCPs: pharmaceuticals and personal care products.	4 solar filters	10 mL pool water, tap and 1 river water	[HMIM][FAP] (20 µL)	17 min of total extraction time, used an ultrasound bath and methanol		71-118	< 6.3	0.6-15	⁵⁰50 Zhang, Y.; Lee, H. K.; Anal. Chim. Acta 2012, 750, 120.
IL-DLLME^b b ionic liquid dispersive liquid-liquid microextraction;	8 antibiotics	10 mL groundwater samples	[C₈MIM] [PF₆] (52 µL)		10 min at 4000 rpm	85-107	< 9.3	0.003-0.05	⁵⁴54 Vázquez, M. P.; Vázquez, P. P.; Galera, M. M.; García, M. G.; Anal. Chim. Acta 2012, 748, 20.
IL-TC-DLLME^a a temperature-controlled ionic liquid dispersive liquid-liquid microextraction;	3 pesticides	10 mL rainwater and underground	[C₈MIM][PF₆] (55 µL)	30 min over heating at 90 ºC	20 min at 4000 rpm	83-118	< 11	0.0015-2.64	⁵⁵55 Zhou, Q.-X.; Gao, Y.-Y.; Chin. Chem. Lett. 2014, 25, 745.
IL-DLLME^b b ionic liquid dispersive liquid-liquid microextraction;	35 pesticides and PPCPs	10 mL surface sample pH 4	[C₆MIM][PF₆] (100 µL)		10 min at 4000 rpm	70-120	≤ 18	0.5-2.5	this work

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