THE CHEMISTRY IN THE HUMAN HEALTH RISK ASSESSMENT DUE PESTICIDES EXPOSURE

Medeiros, Jéssyca Ferreira de; Acayaba, Raphael D’Anna; Montagner, Cassiana Carolina

doi:10.21577/0100-4042.20170699

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Revisão • Quím. Nova 44 (5) • May 2021 • https://doi.org/10.21577/0100-4042.20170699 copy

THE CHEMISTRY IN THE HUMAN HEALTH RISK ASSESSMENT DUE PESTICIDES EXPOSURE

Authorship SCIMAGO INSTITUTIONS RANKINGS

Pesticides are widely used worldwide in urban and rural environments. Since most pesticides are not selective for target species the concern about possible impacts on human health has increased for the workers exposed to these substances (occupational exposure) and for the general population (environmental exposure). Epidemiological studies, in vivo and in vitro have associated several diseases with pesticide exposure, such as cancer, diabetes, Parkinson’s, and others. Therefore, chemistry plays an important role in evaluation of external (food and drinking water) and internal (human biomonitoring) exposure to pesticides through of analytical methodologies, for instance, chromatography coupled with mass spectrometry, proving to be an important complement in the evaluation of risks of pesticides in human health.

Keywords:
pesticides; human health; internal and external exposure; analytical methods

Pesticidas	Preparo de amostra	Análise instrumental	LD	LQ	Referência
Difenoconazol, epoxiconazol, tebuconazol, atrazina, azoxistrobina, piraclostrobina, picoxistrobina, trifloxistrobina, profenofós, fipronil	SPE	LC-MS/MS	1-50 ng L^-1	1-180 ng L^-1	101
2,4-D, diazinon, malation, pirimifós-metil, fenepropimorfo	LLE	LC-MS/MS	0,3-15,0 ng L^-1	1,0-50,0 ng L^-1	94
Atrazina, desetil-atrazina	SPE online	UHPLC-MS/MS	2-6 ng L^-1		102
Endosulfan, hexaclorohexano	DLLE	GC-MS	1,0-2,4 μg L^-1		111
Atrazina	SPE	LC-MS/MS	1 ng L^-1	2 ng L^-1	100
Clorpirifós, diclorvos, triclorfom, trifluralina, propanil, diuron, endosulfan alpha, endosulfan beta, endosulfan sulfato, lindane	DLLME	GC-MS/MS	1,2-55 μg L^-1	3,1-77 μg L^-1	112
α-HCH, β-HCH, γ-HCH, δ-HCH, p,p’-DDE, p,p’-DDD, o,p’-DDT, p,p’-DDT	SPE	GC-MS	1,95-9,38 ng L^-1		113
Tiametoxame, atrazina, deisopropil-atrazina, desetil-atrazina, clotianidina, imidacloprido, acetamiprido, tiaclopride, simazina, ametrina, isoproturon, diuron, prometrina, terbutrina, propazina, metiocarbe, terbutilazina, cybutryne, clorfenvinfos, clorpirifós, pentaclorofenol, metaflumizona	SPE online	LC-MS/MS	0,15-10,0 ng L^-1		114
Isoprocarbe, fenobucarbe, pirimicarbe, carbofurano, tiabendazol, carbendazim, metalaxil, imidacloprido, acetamiprido, boscalida, metolacloro, tiametoxame, dimetoato, isocarbofos, diniconazol, miclobutanil, epoxicolazol, triadimentol, propiconazole, hexaconazol, tebuconazol, paclobutrazol, buprofezina, ametrina, azoxistrobina, dimetomorfo, pirimetanil, isoprotiolano	SPE	UPLC-MS/MS	0,01-2,00 ng L^-1	0,02-5,00 ng L^-1	115
Alaclor, aldrin, atrazina, carbofurano, clordano, clorpirifós, dieldrin, endrin, 4,4'-DDD, 4,4'-DDE, a-endosulfan, β-endosulfan, endosulfan sulfato, lindane, metolacloro, molinate, paration metil, pendimetalina, permetrina, profenofos, tebuconazol, terbufos, trifluralina	SPME	GC-ECD GC-MS	0,006-5,454 μg L^-1	0,02-18,00 μg L^-1	116
Azoxistrobina, buprofezina, clorantraniliprol, difenoconazol, fipronil, imidacloprida, isoprotiolano, propiconazol, pimetrozina, triciclazol, trifloxistrobina, pretilacloro, tebuconazol	SPE	UHPLC-MS/MS	0,2-5,0 ng L¹>	1-25 ng L¹	117
Acetocloro, alacloro, amitrole, atrazina, carbendazim, triadimefon, penconazol, propiconazol, carbaril, carbofurano	SPE	UHPLC-MS/MS	0,01-0,64 ng L^-1	0,03-2,13 ng L^-1	118
Ametrina, atrazina, azoxistrobina, carbendazim, diuron, hexazinona, imazaquin, imazetapir, imidacloprida, propiconazol, tebuconazol, tebutiuron	SPE	LC-MS/MS	0,003-0,010 μg L^-1	0,01-0,10 μg L^-1	119
Carbendazim, simazina, carbofurano, atrazina, diuron, 2,4-D, 2,4,5-T, tebuconazol, paration-metil, metolacloro, 4,4’-DDD, 4,4’-DDE	DPX	HPLC-DAD	0,04-0,69 μg L^-1	0,14-2,30 μg L^-1	120
Ametrina, atrazina, azoxistrobina, carbendazim, carbofurano, clomazona, clorpirifós, diuron, hexazinona, imidacloprida, malation, simazina, tebuconazol, tebutiuron	SPE	LC-MS/MS	1-33 ng L^-1	4-99 ng L^-1	109
3- hidroxicarbofurano, azinfos-metil, chorpirifós	SPE	LC-MS/MS	0,005-0,200 μg L^-1	0,01-0,5 μg L^-1	121
Atrazina, azoxistrobina, bentazone, carbendazim, carbofurano, ciproconazol, clomazona, diuron, difenoconazol, epoxiconazol, fipronil, imazapic, imazetapir, iprodiona, irgarol, pirazosulfuron-etil, propanil, quinclorac, simazina, tebuconazol, trifloxistrobina	SPE	LC-MS/MS		0,8-80 ng L^-1	110
Difenoconazol, epoxiconazol, tebuconazol, atrazina, azoxistrobina, picoxistrobina, piraclostrobina, trifloxistrobina, chlorpirifós, profenofós, fipronil, carbendazim	SPE	LC-MS/MS		0,2-18,0 ng L^-1	122
Lindane, DDT, metoxicloro, acefato, diazinon, fenitrotion, simazina, atrazina, alfa-cipermetrina, deltametrina	SPE	GC-ECD	0,01-2,00 μg L^-1		123
Ametrina, asulam, atrazina, carbofuran, clorpirifós, clopiralide, DEET, DEA, DIA, diazinon, diclorvos, diuron, flumeturon, hexazinona, imazetapir, imidacloprida, metolacloro, metribuzin, picloram, metsulfurom-metil, prometrina, propiconazol, propoxur, simazina, tebutiuron, terbutilazina, terbutilazina- desetil, bromoxinil, mecoprop	Injeção direta SPE	LC-MS/MS		0,1-1,0 μg L^-1	124
Metiocarbe, oxadiazon, imidacloprida, tiacloprido, tiametoxame, clotianidina, acetamiprido, triallate	SPE	LC-MS/MS	0,1-1,4 ng L^-1	0,3-4,8 ng L^-1	125
Clopiralide, diuron, florasulam, CGA 282149, CGA 322704, CGA 353968, CGA 355190, NOA 404617, NOA 407475, 2,4-D, 2,4,5-T, 2,6- ácido difluorobenzoico, bentazone, dicamba, diclorprop, dimetomorfo, flumetsulame, imidacloprida, linuron, MCPA, mecoprop, penconazol, tiametoxame	SPE online	LC-MS/MS	1,2-18,0 ng L^-1		126
ametrina, atrazina, cianazina, prometrina, propazina, simazina, simetrin, terbutilazina, terbutrina	SPE	HPLC-DAD	0,010-0,023 μg L^-1		127

Matriz	Analitos	Preparo de amostra	Análise instrumental	LD	LQ	Referência
Frutas e suco de frutas	Diazinon, malation, imidacloprida, triadimefon	LLE	LC-MS/MS	0,3-30 μg L^-1		128
Maça, uva e suco de cereja	Diazinon, clorpirifós, fosalona, ametreina, propazine, simazina, penconazol, hexazonazol, diniconazol, difenoconazol, tebuconazol	LLE	GC-FID GC-MS	0,34-5 μg L^-1	1-16 μg L^-1	130
Suco de laranja	Acefato, carbendazim, acetamiprido, imidacloprida, metrifonato, ametrina, bromacila, carbofuran, tiofanato-metílico, diuron, pirimifos-metila, tebuconazol, diflubenzuron, malation, diazion, difenoconazole, clorpirifós, abamectina	LLE	LC-ESI-MS/MS	0,003-0,33 mg L^-1	0,01-1,11 mg L^-1	129
Óleo de soja	95 pesticidas	LLE	GC-MS		0,004-0,05 mg kg^-1	131
Alface, brócolis, mostarda, espinafre, couve-flor, salsão e repolho	α-HCH, β-HCH, γ-HCH, clorpirifós, DDD, DDE, diazinon, dimetoato, DDT, endosulfan, fenvelerato, malation, paration metil, permetrina, paration etil	SPE	GC-ECD	0,02-4,5 ng g^-1	0,2-45 ng g^-1	132
Suco de pera	α-HCH, β-HCH, γ-HCH, δ-HCH, p,p’-DDE, p,p’-DDD, o,p’-DDT, p,p’-DDT	SPE	GC-MS/MS	0,39-0,7 ng L^-1	1,45-2 ng L^-1	133
Repolho, couve-flor, goiaba, quiabo, berinjela, cebola, maçã, banana, uva, laranja, romã	60 pesticidas	SPE	UHPLC-TOF/MS	0,3-3,8 μg kg^-1	0,8-11,8 μg kg^-1	134
Tomate	Metolcarb, carbofurano, isoprocarbe, metiocarbe	SPE	HPLC-DAD	0,58-2,06 ng g^-1		135
Ervas medicinais	135 pesticidas	SPE QuEChERS	LC-MS/MS		1-5 ng g^-1	140
Folhas de alcachofra	98 pesticidas	QuEChERS	GC-MS LC-MS/MS	0,003-0,025 mg kg^-1		136
Alface	Acefato, carbaril, carbendazim, metamidofós, metomil, procloraz, tebuconazol, azoxistrobina, clotianidina, difenoconazol, fenamidone, imidaclopida, iprodiona, malation, tiaclopride, tiametoxame	QuEChERS	LC-MS/MS		5-3200 μg kg^-1	137
Tomate	57 pesticidas	QuEChERS	LC-ESI-MS/MS	0,0005-0,02 mg kg^-1	0,002-0,07 mg kg ^-1	138
Alho-poró, alface	70 pesticidas	QuEChERS	LC-MS/MS	0,1-2,4 μg kg^-1	0,3-7,9 μg kg^-1	139
Pepino, pera, repolho	Bifentrin, fenpropatrina, cialotrina, permetrina, ciflutrina, flucitrinato, fenvalerato, deltametrina	SPME	GC-μECD	0,1-0,5 ng g^-1	0,3-1,7 ng g^-1	142
Pera, uva e berinjela	Diazinon, paration, fentiona, clorpirifós	SPME	GC-IMS	0,05-0,3 μg Kg^-1		143
Suco de fruta	Clorpirifós, penconazol, procimidona, bromopropilato, lambda-cialotrina	SPME	GC-ECD	0,002-0,667 ng mL^-1		144
Chá	Forato, diazinon, tolclofos-metil, malation, fentiona, quinalfós, fenamifós	SDME	GC-MS	0,4-1,7 μg Kg^-1	1,1-5,6 μg Kg^-1	145
Mel	HCB, diazinon, lindane, clorpirifós-metil, clorpirifós-etil, procimidona, captan, a-endosulfan, β-endosunfan, endosunfan sulfato, bromopropilato, fosalona, fenarimol, coumafós	SDME	GC-MS	0,01-3,75 μg Kg^-1		146
Vegetais	Demeton-s-metil, forato, diazinon, tolclofos-metil, malation, fentiona, quinalfós, fenamifós	CFME	GC-MS	0,59-1,57 μg Kg^-1	1,96-5,23 μg Kg^-1	147
Alface	Procimidona, iprodiona	SLE	GC-ECD	0,4-37 μg Kg^-1		148

Matriz	Pesticidas	Preparo de amostra	Análise instrumental	LD	LQ	Referência
Urina	Glifosato e AMPA	SPE com ponta de pipeta	LC-HRMS	1-3 μg L^-1	2,5-6 μg L^-1	193
Urina	Imidacloprida e ácido 6-cloronicotínico	SPE	LC-MS/MS	0,009-0,011 μg L^-1	0,029-0,038 μg L^-1	177
Urina	Metabólitos de organofosforados (TCPY, IMPY, PNP, CMHC, DEAMPY) e de piretróides (3-PBA, 4-F-3-PBA, cis/trans-DCCA)	Cromatografia de fluxo turbulento	LC- HRMS		1-10 μg L^-1	198
Urina	Metabólitos de organofosforados (DAPs, TCPY, PNP, MDA, CMHC, IMPY, DEAMPY) e de piretróides (3-PBA, 4-F-3-PBA)	SPE	UHPLC-MS/MS	14-69 μg L^-1		196
Urina	Glifosato	SPE	LC-MS/MS		0,5 μg L^-1	175
Sangue	Carbofurano, terbufos, carbaril, metiocarbe, pirimicarb	SPE dispersiva	PTV-LVI-GC/MS		0,02-0,03 mg L^-1	214
Sangue	α-HCH, β-HCH, γ-HCH, DDE	SPE online	LVI-GC-HRMS		0,007-0,017 μg L^-1	200
Sangue	Amitraz e seus metabolitos (DMPF, DMF, DMA)	SPE	LC-MS/MS	0,5 μg L^-1	2 μg L^-1	215
Sangue do cordão umbilical	Cipermetrina e clorpirifós	SPE online	LC-MS/MS	0,01-0,05 μg L^-1		197
Sérum	α-HCH, β-HCH, γ-HCH, δ-HCH, 4,4’-DDD, DDE, DDT, aldrin, heptacloro, heptacloro epóxido, α-endosulfan, β-endosulfan, sulfato endosulfan, HCB, atrazina	SPME	GC-MS	0,22-5,41 μg L^-1	1,57-10,09 μg L^-1	204
Plasma	HCB, trans-clordano, cis-clordano, trans- nonacloro, p,p'-DDE	SPE	GC-HRMS	5,9-89,1 μg L^-1		216
Cabelo	Acetoclor, α-clordano, γ-clordano, nonacloro, oxiclordano, clorpirifós-etil, clorpirifós-metil, λ-cialotrina, α-cipermetrina, β-cipermetrina, deltametrina, diazinon, dieldrin, α-endosulfan, heptacloro epóxido A, heptacloro epóxido B, metoxicloro, p,p'-DDE, p,p'-DDT, o,p'-DDT, p,p'-DDD, acetamiprido, atrazina, DIA, DEA, carbofurano, imidacloprida, linuron	QuEChERS	GC-MS UHPLC-MS/MS	0,18-86,6 μg g^-1	0,6-288,5 μg g^-1	207
Cabelo	Dimetomorfo, penconazol, ciazofamida, fenamidona, quinoxifena, clorpirifós, ciprodinil, metrafenona, boscalid, pirimetanil, tebuconazol, azoxistrobina, fenhexamida, imidacloprida, carbendazim, imazalil, tiabendazol, piraclostrobina, difenoconazol, metolaclor, tiaclopride, dimetenamida, fluopirame, procloraz, cialotrina (lambda), propamocarb, cloridazon	SLE	LC-MS/MS	0,5-15 μg g^-1		45
Cabelo	Aldrin, cis-clordano, trans-clordano, p,p'- DDD, o,p'-DDD, p,p'- DDE, o,p'-DDE, p,p'- DDT, o,p'-DDT, dieldrin, endosulfan I, endosulfan II, endrin, heptacloro, heptacloro epóxido A, heptacloro epóxido B, hexaclorobenzeno, α-HCH, β-HCH, γ-HCH, δ-HCH, metoxicloro, isodrin, oxiclordano, mirex	SLE	GC-MS		0,7-33 pg g^-1	217
Cabelo	Penconazol e tebuconazol	SLE	LC-MS/MS		1 μg g^-1	218
Urina e cabelo	Metabólitos de organofosforados (DMP, DEP, DETP, DEDTP)	SPE SLE	UHPLC-MS/MS GC-MS	0,5-1 μg L^-1 3-6 pg g^-1		187
Mecônio	Malation, diazinon, clorpirifós, cipermetrina, ciflutrina, deltametrina, propoxur, mancozeb, isoproturon, MCPA e os metabólitos DMP, DMTP, DMDTP, DMDTP, DEP, DETP, DCCA, EU, ETU, desmetil isoproturon	SLE	LC-MS/MS	0,07-66,7 ng g^-1	0,2-200 ng g^-1	186
Mecônio	Clordano, clorpirifós, DDT, diazinon, lindane, malation, paration, pentaclorofenol	SLE	GC-MS	0,186-6,616 mg L^-1		219
Mecônio	Clorpirifós, DETP, diazinon, DEP, malation, DMP, propoxur, ETU, isoproturon, desmetil isoproturon, MCPA	SLE	LC-MS/MS	0,1-1 ng g^-1		220
Leite materno	o,p'-DDE, p,p'-DDE, o,p'-DDD, p,p'-DDD, o,p'-DDT, p,p'-DDT, α-HCH, β-HCH, γ-HCH, δ-HCH, oxiclordano, trans-clordano, trans-nonaclordano, cis-nonaclordano, HCB, heptacloro, heptacloro epóxido, mirex	SPE	GC-HRMS	0,0004-0,0010 ng g^-1	0,10-0.25 ng g^-1	221
Leite materno	α-HCH, β-HCH, γ-HCH, δ-HCH, ε-HCH, 4,4’-DDT, 2,4’-DDT, 4,4’-DDD, 2,4’-DDD, 4,4’-DDE, 2,4’-DDE, trans-clordano, cis-clordano, oxy-clordano, heptacloro, cis- heptaclorepóxido, trans- heptaclorepóxido, aldrin, dieldrin, endrin, endosulfan-I, endosulfan-II, metoxicloro, mirex, pentaclorobenzeno, hexaclorobenzeno, pentacloroanisol, octacloroestireno	LLE	GC-HRMS	1-31 pg g^-1		190
Leite materno	α-HCH, β-HCH, γ-HCH, δ-HCH, heptacloro, α-clordano, γ-clordano, 4,4’-DDT, 4,4’-DDE, 4,4’-DDD	LLE	GC-ECD	8 ng g^-1	17 ng g^-1	²²²222 Rojas-Squella, X.; Santos, L.; Baumann, W.; Landaeta, D.; Jaimes, A.; Correa, J. C.; Sarmiento, O. L.; Ramos-Bonilla, J. P.; Chemosphere 2013, 91, 733.

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