International Journal of Analytical Chemistry

Research Article

Optimization of Resolving Power, Fragmentation, and Mass Calibration in an Orbitrap Spectrometer for Analysis of 24 Pesticide Metabolites in Urine

Table 1

Pesticide metabolites: diagnostic and fragment ions used for analysis.


Class	Compound	Metabolite	Acronym	Elemental composition	Diagnostic ion	Exact mass m/z diagnostic ion (Da)	Fragment elemental composition	m/z fragment ion (Da)

Organophosphate insecticides	Chlorpyrifos, chlorpyrifos-methyl	3,5,6-Trichloro-2-pyridinol	TCPy	C₅H₂NOCl₃	[M-H]^-	195.91292	-	-
	Parathion, methyl parathion	p-nitrophenol	PNP	C₆H₅NO₃	[M-H]^-	138.01966	C₆H₄O₂	108.02167
	Pirimiphos-methyl	2-Diethylamino-6-methyl-6-hydroxypyrimidine	DEAMPY	C₉H₁₅N₃O	[M+H]⁺	182.12879	C₇H₁₂N₃O	154.09748
	Diazinon	2-Isopropyl-4-methyl-6-hydroxypyrimidine	IMPY	C₈H₁₂N₂O	[M+H]⁺	153.10224	C₄H₆NO	84.04439
	Coumaphos	3-Chloro-7-hydroxy-4-methylcoumarin	CMHC	C₁₀H₇ClO₃	[M-H]^-	209.00109	C₉H₅O₂	145.02841
	Fenitrothion	3-Methyl-4-nitrophenol	MNP	C₇H₇NO₃	[M-H]^-	152.03531	C₇H₆O₂	122.03733
	Dimethoate	Dimethoate	DIMET	C₅H₁₂NO₃PS₂	[M+H]⁺	230.00690	C₂H₆O₂PS	124.98206
	Omethoate	Omethoate	OMET	C₅H₁₂NO₄PS	[M+H]⁺	214.02974	C₄H₈O₄PS	182.98754
	Acephate	Acephate	AP	C₄H₁₀NO₃PS	[M+H]⁺	184.01917	C₂H₈O₃PS	142.99262
	Methamidophos	Methamidophos	MMP	C₂H₈NO₂PS	[M+H]⁺	142.00861	-	112.01577
	Chlorethoxyphos, chlorpyrifos coumaphos, diazinon, disulfoton, ethion, parathion, phorate, phosalone, sulfotep, terbufos, azinphos-methyl, dichlorvos, dicrotophos, dimethoate, fenitrothion, fenthion, malathion, methyl parathion, trichlorfon, chlorpyrifos-methyl, methidathion, mevinphos, oxydemeton-methyl, phosmet, pirimiphos-methyl, temephos, tetrachlorvinphos, isazofos-methyl, naled	Diethyl phosphate	DEP	C₄H₁₁O₄P	[M-H]^-	153.03221	C₂H₆O₄P	125.00092
		Diethyl thiophosphate	DETP	C₄H₁₁O₃PS	[M-H]^-	169.00937	C₂H₆O₃PS	140.97807
		Dimethyl thiophosphate	DMTP	C₂H₇O₃PS	[M-H]^-	140.97807	CH₃O₃PS	125.95460
		Dimethyl dithiophosphate	DMDTP	C₂H₇O₂PS₂	[M-H]^-	156.95523	CH₃O₂PS₂	141.93174

Phenoxy herbicides	2,4-Dichlorophenoxyacetic acid	2,4-Dichlorophenoxyacetic acid	2,4-D	C₈H₆O₃Cl₂	[M-H]^-	218.96212	C₆H₃OCl₂	160.95664
Phenoxy herbicides	2,4,5-Trichlorophenoxyacetic acid	2,4,5-Trichlorophenoxyacetic acid	2,4,5-T	C₈H₅O₃Cl₃	[M-H]^-	252.92315	C₆H₂OCl₃	194.91767

Chloroacetanilide herbicides	Atrazine	Atrazine mercapturate	ATZM	C₁₃H₂₂N₆O₃S	[M+H]⁺	343.15468	C₈H₁₆N₅S	214.11209
	Alachlor	Alachlor mercapturate	ALAM	C₁₉H₂₈N₂O₅S	[M+H]⁺	397.17916	C₅H₈N O₃	130.04987
	Metolachlor	Metolachlor mercapturate	METM	C₂₀H₃₀N₂O₅S	[M+H]⁺	411.19481	C₁₅H₂₄N O₂S	282.15223

Pyrethroid insecticides	Commercial Pyrethroids	3-Phenoxybenzoic acid	PBA	C₁₃H₁₀O₃	[M-H]^-	213.05571	C₁₂H₉O	169.06589
	Cyfluthrin	4-Fluoro-3-phenoxybenzoic acid	FPBA	C₁₃H₉FO₃	[M-H]^-	231.04629	C₁₂H₈OF	187.05647
	Permethrin, cypermethrin, cyfluthrin	cis-(2,2-Dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid	cis-DCCA	C₈H₁₀O₂Cl₂	[M-H]^-	206.99850	-	-
	Permethrin, cypermethrin, cyfluthrin	trans-(2,2-Dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid	trans-DCCA	C₈H₁₀O₂Cl₂	[M-H]^-	206.99850	-	-
	Deltamethrin	cis-(2,2-Dibromovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid	DBCA	C₈H₁₀O₂Br₂	[M-H]^-	294.89747	-	-

Internal Standards			PNP-D4	C₆HD₄NO₃	[M-H]^-	142.04477	-	-
			FPBA-13C6	¹³C₆C₇H₉FO₃	[M-H]^-	237.06642	-	-
			DCCA-13C2	¹³C₂C₆H₉DCl₂O₂	[M-H]^-	210.01149	-	-
			ATZM-13C3	₁₃C₃C₁₀H₂₂N₆O₃S	[M+H]⁺	346.16475	-	-
			2,4-D-D3	C₈H₃Cl₂O₃D₃	[M-H]^-	221.98095	-	-
			MMP-D6	C₂H₂NO₂PSD₆	[M+H]⁺	148.04627	-	-
			DIMET-D6	C₅H₆NO₃PS₂D₆	[M+H]⁺	236.04455	-	-
			DBP	C₈H₁₉O₄P	[M-H]^-	209.09481	-	-