Selected ion monitoring (SIM) or selected reaction monitoring (SRM) transitions for organophosphorus pesticides (OPs) by GC-EI-MS or GC-EI-MS/MS methods.
Abstract
This chapter reviews the selection of chromatography-mass spectrometry methods for the analysis of organophosphorus pesticides, pyrethroid insecticides, carbamates, and phenylureas. Options with different GC-MS, GC-MS/MS, and LC-MS/MS methods will be discussed for inclusion of the targeted pesticides. In addition, methods for the analysis of metabolites of these chemical classes of pesticides are investigated, including the feasibility of simultaneous analysis with parent pesticides. In some cases, a targeted approach is required for the analyses of metabolites. These methods apply to a wide variety of sample matrices including environmental (air, water, and soil), food (fruits, vegetation, or food products), and biological samples (urine and blood). The focus of the chapter is on MS detection approaches with consideration of the chromatographic separation conditions as required. A short discussion of multiresidue analysis methods and/or where feasible, other chemical classes or selected pesticides from these chemical classes can be analyzed in existing methods is included.
Keywords
- gas chromatography-mass spectrometry (GC-MS)
- gas chromatography-tandem mass spectrometry (GC-MS/MS)
- liquid chromatography-tandem mass spectrometry (LC-MS/MS)
- carbamates
- organophosphorus pesticides (OPs)
- phenylureas
- pyrethroids
- metabolites
- degradation products
1. Introduction
Organophosphorus pesticides, pyrethroids, carbamates, and phenylureas remain important chemical classes of pesticides that require chemical analysis by gas chromatography-mass spectrometry (GC-MS), gas chromatography-tandem mass spectrometry (GC-MS/MS), or liquid chromatography-tandem mass spectrometry (LC-MS/MS) methods. The most diverse range of chromatography-mass spectrometry methods is available for these chemical classes of pesticides with method selection often based upon sensitivity and selectivity needs (see Figure 1). The chapter will discuss selection of methods for chemical analysis for each of these chemical classes of pesticides along with the feasibility of separate or simultaneous analysis of metabolites and degradation products of these parent pesticides. The focus of this chapter is on the chromatography-mass spectrometry aspects of the methods. Extraction and clean-up or pre-concentration procedures for the target analytes from sample matrices will also influence the magnitude of matrix enhancement or suppression in the MS detection and column choice (or separation conditions used) to minimize the influence of matrix peaks. Further discussion on sample preparation procedures has been recently reviewed [1, 2].
2. Organophosphorus pesticides and their degradation products or metabolites
Organophosphorus pesticides (OPs) include both organophosphates ((RO)3PO) and organothio phosphates ((R1O)3PS, R(R1O)2PS, RS(R1O)2PS with OR1 typically methoxy or ethoxy group) as shown in Figure 1. Common organophosphates analyzed include bromofenvinphos, chlorfenvinphos, dichlorvos, mevinphos, and tetrachlorvinphos [3–6]. The majority of OPs analyzed (see Table 1) are organothiophosphates including aliphatic organothiophosphates (chlormephos, demephion-O and S, disulfoton, ethion, ethoprofos, malathion, phorate, and sulfotep) [3–10], aliphatic amide organothiophosphates (dimethoate, o-methoate) [4, 6, 9, 10], heterocyclic organothiophosphates (coumaphos, azinphos-methyl, azinphos-ethyl, phosmet, pyrazophos, chlorpyrifos-methyl, chlorpyrifos-ethyl, diazinon, pirimiphos) [3–10], phenyl organothiophosphates (bromophos-methyl, bromophos-ethyl, carbophenothion, dichlofenthion, fenchlorphos, fenitrothion, fenthion, parathion-methyl, parathion-ethyl, prothiofos, sulprofos) [3, 5–9] and phosphonothioates (fonofos, trichloronat, cyanofenphos, leptophos, fenamiphos, and acephate) [3, 4, 6, 7].
OP | Molecular formula | SIM | Ref. | SRM | Ref. |
---|---|---|---|---|---|
Acephate | 136 | [10] | 136→42, 136→94 | [3] | |
Aspon | 211, 253 | [1] | 378→210, 378→115 | [7] | |
Azinphos-methyl | 160→105, 160→132 | [3] | |||
132→104 | [6] | ||||
Azinphos-ethyl | 160→105, 160→132 | [3] | |||
132→04 | [6] | ||||
Bromfenvinphos-methyl | 295→295 | [5] | |||
Bromfenvinphos-ethyl | 267→159 | [5] | |||
Bromophos-ethyl | 359→303, 359→331 | [3, 6] | |||
359→303 | [5] | ||||
Bromophos-methyl | 331→286, 331→316 | [3, 6] | |||
331→331 | [5] | ||||
Carbofenothion | 157, 342 | [1] | 342→157, 342→143 | [7] | |
Chlormefos | 234→121, 234→154 | [3] | |||
243→121 | [5] | ||||
235→171, 235→199 | [6] | ||||
Chlorphenvinphos | 267→159, 323→267 | [3] | |||
323→267 | [5] | ||||
267→159 | [6] | ||||
Chlorpyrifos-methyl | 286, 125 | [1] | 321→268, 321→208 | [7] | |
286 | [10] | 286→136, 286→241 | [3] | ||
286, 288, 125 | [17] | 286→93 | [5] | ||
286→208, 286→286 | [6] | ||||
Chlorpyrifos-ethyl | 97, 197 | [1] | 349→208, 349→40 | [7] | |
199 | [10] | 314→258, 314→286 | [3, 6] | ||
97, 197 | [11] | 314→258 | [5] | ||
Coumaphos | 362 | [10] | |||
Cyanofenphos | 185→157, 157→110 | [3] | |||
157→139, 157→110 | [6] | ||||
Demeton-o | 88, 60 | [11] | |||
Diazinon | 137, 179 | [1] | 304→179, 304→137 | [7] | |
304 | [10] | 304→137, 304→179 | [3] | ||
137, 304 | [11] | 304→179 | [5, 6] | ||
287, 302, 288 | [17] | ||||
Diazinon-d10 | 314 | [1] | 314→185 | [7] | |
Dichlofenthion | 223, 97 | [1] | 314→223, 319→81 | [7] | |
279→222, 279→251 | [3] | ||||
279→223 | [5] | ||||
279→223, 279→251 | [6] | ||||
Dichlorvos | 185 | [10] | 185→93 | [5] | |
221→141, 221→145 | [6] | ||||
Dimethoate | 125 | [10] | 230→199 | [6] | |
87, 125 | [11] | ||||
87, 93, 125 | [17] | ||||
Disulfoton | 88, 60 | [11] | 274→88 | [5] | |
Dyfonate | 109, 137 | [1] | 246→137, 246→109 | [7] | |
Ethion | 231, 97 | [1] | 384→231, 384→203 | [7] | |
231, 384 | [11] | 231→175, 231→203 | [3] | ||
Ethoprophos | 158→97, 158→114 | [3] | |||
158→97 | [5] | ||||
243→131, 243→173 | [6] | ||||
Fenamiphos | 303→154, 303→180 | [3] | |||
Fenchlorphos | 125, 287 | [1] | 320→285, 320→204 | [7] | |
285→270 | [5] | ||||
Fenitrothion | 277, 125 | [1] | 277→260, 277→109 | [7] | |
109, 125 | [11] | 260→109, 260→125 | [3] | ||
277→260 | [5] | ||||
260→125 | [6] | ||||
Fenthion | 278, 125 | [11] | 278→125, 278→245 | [3] | |
278→109 | [5] | ||||
278→135 | [6] | ||||
Fonophos | 246→109, 246→137 | [3] | |||
246→137, 246→109 | [6] | ||||
Leptophos | 171, 377 | [1] | |||
Malathion | 173, 125 | [1] | 173→ 99 | [5] | |
173, 125, 93 | [17] | 173→127 | [6] | ||
93, 125 | [11] | ||||
o-methoate | 156 | [10] | |||
Mevinphos | 192 | [10] | 192→127, 192→164 | [3] | |
192→127 | [5] | ||||
193→127 | [3] | ||||
Parathion ethyl | 97, 291 | [1] | 291→109, 291→137 | [12] | |
291, 109 | [11] | 291→91, 291→109 | [8] | ||
291→109 | [3] | ||||
291→263, 291→143 | [18] | ||||
Parathion methyl | 109, 125 | [11] | 263→79, 263→109 | [8] | |
263→109 | [3] | ||||
263→136, 263→246 | [18] | ||||
Phorate | 121, 75 | [1] | 260→75, 263→231 | [12] | |
231→129 | [3] | ||||
Phosmet | 160 | [10] | 160→77 | [3] | |
Pirimiphos-ethyl | 333→163, 333→168 | [3] | |||
316→166 | [5] | ||||
318→182, 318→166, 318→246 | [6] | ||||
Pirimiphos-methyl | 290→125, 290→151 | [3] | |||
290→125 | [5] | ||||
290→151 | [6] | ||||
Prothiofos | 309→221, 309→239 | [3] | |||
162→63 | [5] | ||||
309→239, 309→281 | [6] | ||||
Pyrazophos | 265→138, 265→210 | [3] | |||
221→93 | [5] | ||||
265→210 | [6] | ||||
Quinalphos | 298→156, 298→190 | [3] | |||
146→91 | [5] | ||||
146→118 | [11] | ||||
Sulfoprofos | 140, 322 | [1] | 322→156, 322→97 | [7] | |
322→156, 322→139 | [3] | ||||
Sulfotep | 322, 202 | [1] | 322→202, 322→146 | [7] | |
322, 97 | [11] | 322→146, 322→266 | [3] | ||
322→146 | [5] | ||||
Tetrachlorvinphos | 329→109 | [3, 5] | |||
331→109 | [6] | ||||
Tokuthion | 113, 267 | [1] | 344→328, 344→73 | [7] | |
Tolclophos methyl | 265→220, 265→250 | [3] | |||
265→250 | [5] | ||||
265→220, 265→215 | [6] | ||||
Tributylphosphorotrithioite | 169, 57 | [1] | 314→115, 314→113 | [7] | |
Trichloronate | 109, 297 | [1] |
OPs are both GC-MS and LC-MS/MS amenable and the choice often depends upon instrument availability, what other pesticide chemical classes are analyzed for and whether there is a need to also analyze degradation products or metabolites of OPs [9, 12, 13]. In general, a greater diversity of OPs has been analyzed simultaneously by GC-MS or GC-MS/MS methods as compared to LC-MS/MS. For analysis of OPs by GC-MS methods, electron impact ionization (EI) remains the most widely used due to its ease of operation and ability to provide spectral library matches (see Table 1) [3–10]. Other pesticide classes that are most frequently analyzed with OPs by GC-MS include OCs, pyrethroids, and a few selected azole fungicides, strobilurin fungicides and carbamates [3, 5, 7, 9, 14].
Selection ion monitoring (SIM) with EI does not always meet sensitivity or selectivity needs or provide information on the molecular weight for some OPs due to the high amount of fragmentation in the EI source. OPs are prone to fragmentation in the EI source such that the molecular ion is often too low in abundance to monitor such that fragment ions are used for quantitation and confirmation analysis [3–7, 9, 10]. Positive or negative chemical ionization may be selected to obtain molecular weight confirmation, however, even with negative chemical ionization (NCI) significant amount of fragmentation of OPs may occur in the ion source although typically few fragment ions are observed in NCI as compared to EI [7, 10]. Electron capture in NCI can occur by dissociate electron capture and the structure of the OP may lead to more stable negatively charged fragment ions than the molecular ion. PCI is generally not selected for quantitative analysis as it does not provide significant improvements in selectivity over EI, while NCI is used for OPs, organochlorines (OCs), and pyrethroids when additional sensitivity or selectivity is required [7, 10]. OPs, organochlorines, and pyrethroids that contain halogen atoms or nitro groups often have lower detection limits with NCI than EI. For example, diazinon and malathion (see structures in Figure 2) have better sensitivity with GC-EI-MS than GC-NCI-MS, while chlorpyrifos-ethyl (chlorinated) and parathion-ethyl (contains a nitro group) have good sensitivity with GC-NCI-MS [7]. The 37Cl or 81Br isotopes of the molecular ion or fragment ions can be used for confirmation analysis with GC-EI-MS such as for chlorpyrifos methyl (
Most halogenated OPs observed better sensitivity with GC-NCI-MS than GC-EI-MS or GC-EI-MS/MS [7]. To provide additional selectivity, GC-EI-MS/MS has been used; however, when the molecular ion is selected as the precursor ion for collision-induced dissociation (CID), the sensitivity is lower than when NCI in SIM mode is used [7]. If the OR1 group is an ethoxy group, CID of the molecular ion may lead to loss of ethene (C2H4) from the ethoxy group and if the OP is halogenated, the loss of halogen radical (e.g., Cl radical) is also frequently observed [6]. For example, the SRM 349→286 of chlorpyrifos corresponds to CID of the molecular ion (M+•) to form fragment ion F+ (Cl2NC4HOPS(OC2H5)(OH)+) as a result of loss of C2H2 from an ethoxy group and Cl radical from the aromatic R group. Phorate observes loss of ethyl from the aliphatic R group (SRM: 260→231) to form (+SCH2SPS(OC2H5)2) [5, 7]. As phorate has an aliphatic R group, fragmentation within the R group can result in a stable fragment ion CH3CH2SCH2+ at
To improve the sensitivity of GC-EI-MS/MS, the precursor ion can be selected as an abundant fragment ion rather than the molecular ion (see Table 1). For bromophos-methyl (monoisotopic mass 364) and bromophos-ethyl (monoisotopic mass 392), the fragment ions at
Metabolite or degradation product analysis has become of increasing importance for biological monitoring studies (urine or blood) and environmental studies (atmosphere or surface water) [8, 14, 16–21]. Organophosphorus pesticides can be grouped into organophosphates and organothiophosphates with different R-group substituents. Alkylphosphates (dimethylphosphate and diethylphosphate) and alkylthiophosphates (dimethylthiophosphate, dimethylethylthiophosphate, dimethyldithiophosphate, and dimethyldithiophosphates) are formed from metabolism of OPs. They can be analyzed by GC-MS methods following a derivatization step with N-(
OP degradation product, derivatization agent | Parent | SIM | Ref | SRM | Ref |
---|---|---|---|---|---|
Diazinon oxon (oxadiazinon) | diazinon | 175→112, 258→112 | [7] | ||
Dibutylphosphate, PFBBr (IS) | OP | 335, 279 | [12, 13, 20] | 209→79NCI | [14] |
2,4-Dichlorophenol, MTBSTFA | dichlofenthion | 219, 221 | [8] | ||
2,5-Dichlorophenol, MTBSTFA | p-dichlorobenzene | 221, 219 | [8] | ||
Diethyldithiophosphate, PFBBr | OP | 366, 185 | [18] | 185→111, 185→157NCI | [14] |
Diethyldithiophosphate, CIP | OP | 366, 185, 157 | [12, 13, 20] | 263→153, 265→153PCI | [16, 17] |
Diethylphosphate, MTBSTFA | OP | 211, 155 | [8] | 153→79, 153→125 | [14] |
Diethylphosphate, PFBBr | OP | 258, 334 | [18] | 231→127, 233→127PCI | [16, 17] |
Diethylphosphate, CIP | OP | 334, 278, 258 | [12, 13, 20] | ||
Diethylthiophosphate, MTBSTFA | OP | 227, 199 | [8] | 169→95, 169→141NCI | [14] |
Diethylthiophosphate, PFBBr | OP | 350, 274 | [18] | 247→191, 249→191PCI | [16, 17] |
Diethylthiophosphate, CIP | OP | 350, 274, 169 | [12, 13, 20] | ||
Diisopropylphosphate (IS), MTBSTFA | OP | 155, 239 | [8] | ||
Dimethyldithiophosphate, PFBBr | OP | 338, 157 | [12, 13, 20] | 157→112, 157→142NCI | [14] |
Dimethyldithiophophate, CIP | OP | 235→125, 235→125PCI | [16, 17] | ||
Dimethylphosphate, MTBSTFA | OP | 183, 153 | [18] | 125→63, 125→79NCI | [14] |
Dimethylphosphate, PFBBr | OP | 306, 110 | [18] | 203→127, 205→127PCI | [16, 17] |
Dimethylphosphate, CIP | OP | 306, 307, 194 | [12, 13, 20] | ||
Dimethylthiophosphate, MTBSTFA | OP | 199, 169 | [8] | 141→126, 141→96NCI | [14] |
Dimethylthiophosphate, PFBBr | OP | 322, 211, 110 | [12, 13, 20] | 219→143, 221→143PCI | [16, 17] |
Dimethylthiophosphate, CIP | OP | ||||
Fenamiphos sulfone | fenamiphos | 292→213, 320→292 | [3] | ||
Fenamiphos sulfoxide | fenamiphos | 304→122, 304→196 | [3] | ||
2-Isopropyl-6-methyl-4-pyrimidinol, MTBSTFA | diazinon | 209, 210 | [19] | ||
3-Methyl-4-(methylthio)phenol, MTBSTFA | fenthion | 268, 196 | [14] | ||
6-Methyl-2-(1-methylethyl)4(1H)-pyrimidinone | diazinon | 137, 152, 124 | [19] | ||
3-Methyl-4-nitrophenol, MTBSTFA | fenitrothion | 267, 210 | [8] | 152→122, 152→107NCI | [14] |
3-Methyl-4-nitrophenol, PFBBr | fenitrothion | ||||
3,5,6-Trichloro-2-pyridinol, MTBSTFA | chlorpyrifos | 254, 258 | [8] | 196→35, 198→35NCI | [14] |
3,5,6-Trichloro-2-pyridinol, PFBBr | chlorpyrifos | 256, 254, 258 | [21] | ||
Paraoxon methyl | parathion methyl | 230→106, 230→136 | [3] | ||
Phosmet oxon | phosmet | 160→77, 160→133 | [3] |
The analysis of OPs by LC-ESI+-MS/MS has grown [11, 22–39]. OPs that are amenable to electrospray ionization often have lower detection limits than with GC-MS methods particularly for those OPs most widely studied, including azinphos-methyl, chlorpyrifos, diazinon, and malathion [7, 8, 11]. Since electrospray ionization is a much softer ionization process than EI, the protonated molecular ion can be selected as the precursor ion for LC-ESI+-MS/MS and generally two fragments of significant abundance are observed such that two SRM transitions are available for quantitative and confirmation analysis (see Table 3). Organochlorines have poor sensitivity with LC-ESI+-MS/MS such that GC-MS methods are selected over LC-ESI+-MS/MS if organochlorines (OCs) are targeted along with OPs in a multiclass method (see Figure 1). However, LC-ESI+-MS/MS is also more amenable to a wider range of other pesticides included in multiclass methods, including azole fungicides, carbamates, phenylureas, and strobilurin fungicides (see Figure 1). Either chemical class-specific or multiclass separations can be achieved on reversed-phase stationary phases including C8, C12, C18, C6phenyl. OPs, OPoxons, OPsulfoxides, and OPsulfones observed better sensitivity with methanol rather than acetonitrile as the organic modifier in the mobile phase. Generally, ammonium acetate or ammonium formate is selected as an additive and pending the target list of OPs and their degradation products, 0.1% formic acid may also be added to the mobile phase to improve sensitivity. Only a few OP sulfones, sulfoxides, and oxons have been analyzed by GC-EI-MS/MS methods (Table 2) often due to the poor sensitivity, poor peak shapes, or poor chromatographic separation of these analytes due to their more polar nature such that LC-ESI+-MS/MS are preferred (see Table 4) [4, 6, 11, 19, 22–41].
OP | Organic modifier, additives in MP; column | SRM (quantitative, confirmation) | Ref |
---|---|---|---|
Acephate | MeOH, 10mM CH3COONH4; XTerra MS C18 | 182 | [25] |
MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 184→113, 184→95 | [35] | |
ACN, 0.1% HCOOH; C18 | 184→143 | [4] | |
Azamethiphos | MeOH, 5 mM HCOONH4; XDB-C18 | 325→183, 325→139 | [23] |
Azinphos-ethyl | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 346→160, 346→132 | [11] |
Azinphos-methyl | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 318→160, 318→132 | [11] |
ACN, 0.1% HCOOH; C18 | 318→125, 318→132 | [28] | |
MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 318→160, 318→132 | [35] | |
MeOH, 5 mM HCOONH4; ODS-4 | 318→132, 318→160 | [37] | |
Chlorpyrifos-ethyl | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 352→97, 352→125 | [11] |
MeOH, 5 mM HCOONH4; XDB-C18 | 352→200, 352→97 | [23] | |
ACN, 0.1% HCOOH; C18 | 352→97, 352→200 | [28] | |
ACN, 20 mM CH3COOH (pH 6.45-7.45); mixed mode RP/WAX | 352→200, 352→115 | [24] | |
ACN, 0.025% HCOOH; Zorbax Extended C8 | 352→200 | [29] | |
ACN, 0.1% HCOOH; C18 | 350→198, 350→125, 352→200, 352→125 | [30] | |
ACN, 0.025% HCOOH; XDB-C8 | 352→200 | [32] | |
MeOH, 0.1% CH3COOH; XSELECT™ CSH™C18 | 350→198, 352→200 | [33] | |
MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 350→198, 350→97 | [35] | |
MeOH, 20 mM CH3COONH4; C18 | 350→198, 350→294 | [36] | |
MeOH, 5 mM HCOONH4; ODS-4 | 350→198, 350→97 | [37] | |
MeOH, 2 mM CH3COONH4; C18 | 350→198, 352→200 | [38] | |
ACN, 20 mM CH3COONH4, RP18 | 350→125, 352→198 | [39] | |
ACN, 0.1% HCOOH; C18 | 352→198 | [4] | |
Chlorpyrifos-methyl | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 322→125, 324→125 | [4] |
MeOH, 5 mM HCOONH4; XDB-C18 | 322→125, 322→290 | [26] | |
MeOH, 0.1% CH3COOH; XSELECT™ CSH™C18 | 322→125, 324→125 | [36] | |
MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 322→125, 322→290 | [38] | |
MeOH, 5 mM HCOONH4; ODS-4 | 322→125, 322→290 | [40] | |
ACN, 0.1% HCOOH; C18 | 322→290 | [4] | |
Coumaphos | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 363→227, 363→307 | [6] |
MeOH, 0.1% HCOOH; Acquity UPLC™BEH C18 | 363→303, 363→289 | [6] | |
MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 363→227, 363→307 | [35] | |
Cyanophos | MeOH, 10mM CH3COONH4; XTerra MS C18 | 228 | [25] |
Demeton-S-methyl | MeOH, 0.1% HCOOH; Acquity UPLC™BEH C18 | 231→89, 231→61 | [6] |
MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 231→89, 231→61 | [35] | |
Diazinon | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 305→169, 305→153 | [11] |
MeOH, 5 mM HCOONH4; XDB-C18 | 305→169, 305→153 | [23] | |
MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 305→169, 305→97 | [35] | |
MeOH, 5 mM HCOONH4; ODS-4 | 305→169, 305→153 | [37] | |
MeOH, 2 mM CH3COONH4; C18 | 305→169, 305→153 | [38] | |
ACN, 20 mM CH3COONH4, RP18 | 305→169, 305→153 | [39] | |
ACN, 0.1% HCOOH; C18 | 322→290 | [4] | |
ACN, 0.1% HCOOH; XDB-C18 | 305.103, 277.077, 249.047, 169.077, 153.102* | [22] | |
MeOH, 0.1 % HCOOH; X-Terra C18 | 305.1089→169.0799, 305.1089→153.1028* | [27] | |
Diazinon-d10 (IS) | MeOH, 0.1% HCOOH and 2 Mm CH3COONH4; C6phenyl | 315→170, 315→154 | [11] |
Dichlorvos | MeOH, 5 mM HCOONH4; XDB-C18 | 221→109, 221→127 | [23] |
MeOH, 5 mM HCOONH4; ODS-4 | 221→109, 221→127 | [37] | |
MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 221→127, 221→109 | [35] | |
ACN, 0.1% HCOOH; C18 | 221→127 | [4] | |
Dichlorvinphos | MeOH, 0.1% HCOOH; Acquity UPLC™BEH C18 | 238→112, 238→193 | [6] |
Dicrotophos | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 238→112, 238→127 | [35] |
Dimethoate | MeOH, 0.1% HCOOH and 2 Mm CH3COONH4; C6phenyl | 230→199, 230→125 | [11] |
MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 230→199, 230→125 | [35] | |
MeOH, 5 mM HCOONH4; ODS-4 | 230→199, 230→125 | [37] | |
MeOH, 2 mM CH3COONH4; C18 | 230→125, 230→143 | [38] | |
ACN, 0.1% HCOOH; C18 | 221→127 | [4] | |
Disulfoton | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 275→89, 275→61 | [35] |
Ethion | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 385→199, 385→171 | [35] |
Ethoprofos | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 243→131, 243→97 | [35] |
MeOH, 5 mM HCOONH4; ODS-4 | 243→97, 243→131 | [37] | |
Fenamiphos | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 304→217, 304→202 | [35] |
Fenchlorphos | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 321→125, 321→109 | [11] |
Fenitrothion | MeOH, 10mM CH3COONH4; XTerra MS C18 | 262 | [25] |
MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 278→125, 278→109 | [35] | |
Fensulfothion | MeOH, 0.1% HCOOH; Acquity UPLC™BEH C18 | 309→281, 309→157 | [6] |
Fenthion | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 279→169, 279→247 | [35] |
MeOH, 5 mM HCOONH4; ODS-4 | 279→169, 279→247 | [37] | |
MeOH, 2 mM CH3COONH4; C18 | 279→169, 279→105 | [38] | |
Malathion | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 331→127, 331→285 | [11] |
MeOH, 10mM CH3COONH4; XTerra MS C18 | 315 | [25] | |
MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 331→127, 331→99 | [35] | |
MeOH, 5 mM HCOONH4; ODS-4 | 331→127, 331→99 | [37] | |
ACN, 20 mM CH3COONH4, RP18 | 331→127, 331→285 | [39] | |
Mevinphos | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 225→127, 225→193 | [35] |
Methamidophos | MeOH, 5 mM HCOONH4; XDB-C18 | 142→94, 142→125 | [23] |
Monocrotophos | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 224→127, 224→98 | [35] |
MeOH, 5 mM HCOONH4; ODS-4 | 331→127, 331→99 | [37] | |
Naled | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 398→127, 398→109 | [35] |
Parathion-ethyl | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 292→236, 292→97 | [35] |
Parathion-methyl | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 264→125, 264→232 | [35] |
MeOH, 5 mM HCOONH4; ODS-4 | 264→125, 264→109 | [37] | |
Phorate | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 261→75, 261→47 | [11] |
MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 261→75, 261→171 | [35] | |
Phosmet | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 318→160, 318→133 | [35] |
Pirimiphos methyl | MeOH, 5 mM HCOONH4; XDB-C18 | 306→164, 306→108 | [23] |
MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 306→164, 306→108 | [35] | |
MeOH, 5 mM HCOONH4; ODS-4 | 306→164, 306→108 | [37] | |
Prothiophos | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 345→241,345→133 | [35] |
MeOH, 5 mM HCOONH4; ODS-4 | 345→241,345→133 | [37] | |
Pyrazophos | MeOH, 5 mM HCOONH4; ODS-4 | 374→222, 374→194 | [37] |
Quinalphos | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 299→163, 299→147 | [35] |
Tebufos | MeOH, 0.1% HCOOH; Acquity UPLC™BEH C18 | 289→103, 289→57 | [6]* |
289→57, 289→103 | [35] | ||
Temephos | ACN, CH3COONH4; C18 | 484, 523 | [26] |
Tetrachlorvinphos | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 367→127, 367→241 | [35] |
Triazophos | MeOH, 0.1% HCOOH; Acquity UPLC™BEH C18 | 314→162, 314→119 | [6] |
314→162, 314→119 | [35] | ||
Trichlorfon | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 274→109, 274→221 | [35] |
MeOH, 5 mM HCOONH4; ODS-4 | 257→109, 257→221 | [37] |
An additional reason why LC-ESI+-MS/MS is chosen over GC-MS methods for OPs is the ability to analyze OPs and OP sulfones, sulfoxides, and oxons simultaneously with often comparable sensitivities to their parent OPs [6, 11, 26, 28, 29, 32, 35]. Molecular weight confirmation is available as the protonated molecular ion is high in abundance and generally selected for the precursor ion for LC-MS/MS (Table 3). Similar to the OPs, mobile phase containing methanol (and gradient elution) is often preferred for optimal sensitivity of OP degradation products. However, when OPs (or their degradation products) are included in multiclass methods, acetonitrile may be selected due to the sensitivity needs of other target chemical classes of pesticides and to reduce run times. Other degradation products including hydroxyl degrades of OPs and IMP can also be analyzed in positive ion mode by LC-ESI+(or APCI+)-MS/MS or LC-QTOF [11, 22, 27, 33, 40, 42].
Alkylphosphates and alkylthiophosphates can also be analyzed by LC-MS/MS but to achieve the required sensitivity LC-ESI--MS/MS is selected such that they are typically analyzed in a separate method from OPs (see Table 4) [11, 24, 27, 31, 33, 34, 39]. To provide the best sensitivity, acetonitrile rather than methanol is selected as the organic modifier in the mobile phase with either acetic or formic acid as a mobile phase additive. Chlorpyrifos degradation product 3,5,6-trichloro-2-pyridinol has been widely studied and can be included in LC-ESI+-MS/MS methods with approximately a 50 times higher detection limit than OPoxons [11]. LC-ESI--MS/MS has also been widely used, however, collision-induced dissociation only produces the Cl- fragment ion such that it is more common to monitor the 35Cl and 37Cl isotopes peaks of the deprotonated molecular ion at 196→196 or 198→198 if included in SRM methods when concentrations are lower [23, 29, 30, 32, 40, 41].
OP | Parent | Organic modifier, additives; column | SRM (quantitative, confirmation) | Ref |
---|---|---|---|---|
Azinphos methyl oxon | Azinphos methyl | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 302→160, 302→132 | [11] |
ACN, 0.1% HCOOH; C18 | 302→132, 302→245 | [28] | ||
Chlorpyrifos-methyl oxon | Chlorpyrifos-methyl | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 308→109, 306→109 | [11] |
Chlorpyrifos-ethyl oxon | Chlorpyrifos-ethyl | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 336→280, 336→200 | [11] |
ACN, 0.1% HCOOH; C18 | 336→280, 336→308 | [28] | ||
ACN, 0.025% HCOOH; Zorbax Extended C8 | 336→280 | [29] | ||
ACN, 0.025% HCOOH; XDB-C8 | 336→280 | [32] | ||
Coumaphos oxon | coumaphos | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 347→291, 347→211 | [11] |
Demeton-S-methyl sulfone | Demeton-S-methyl | MeOH, 0.1% HCOOH; Acquity UPLC™BEH C18 | 263→169, 263→121 | [6] |
MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 263→169, 263→108 | [35] | ||
Dibutylphosphate (IS) | ACN, 20 mM CH3COOH (pH 6.45-7.45); mixed mode RP/WAX | 209→79, 209→153ESI- | [24] | |
Diethyl phosphate | OP | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 155→99, 155→127 | [11] |
ACN, 20 mM CH3COOH (pH 6.45-7.45); mixed mode RP/WAX | 153→79, 153→125ESI- | [24] | ||
ACN, 0.1% HCOOH; MAXRP, RP12 | 153→125, 153→79ESI- | [31] | ||
ACN, 1 mM tetrabutylammonium acetate; C18 | 153→79, 153→125, 153→63ESI- | [34] | ||
MeOH, 0.1% HCOOH; X-Terra C18 | 153.0317→125.0004, 153.0317→78.9585ESI-* | [27] | ||
MeOH, 0.1% CH3COOH; XSELECT™ CSH™C18 | 153→79, 153→125ESI- | [33] | ||
Diethyldithiophosphate | OP | ACN, 1 mM tetrabutylammonium acetate; C18 | 185→111ESI- | [31] |
ACN, 20 mM CH3COONH4, RP18 | 155→127, 155→99 | [39] | ||
Diethylthiophosphate | OP | ACN, 20 mM CH3COOH (pH 6.45-7.45); RP/WAX | 169→95, 169→141ESI- | [24] |
ACN, 1 mM tetrabutylammonium acetate; C18 | 169→97, 169→141ESI- | [31] | ||
MeOH, 0.1% CH3COOH; XSELECT™ CSH™C18 | 169→95, 169→141ESI- | [33] | ||
ACN, 0.1% HCOOH; MAXRP, C-12 | 169→95, 169→141, 169→63ESI- | [34] | ||
MeOH, 0.1% HCOOH; X-Terra C18 | 169.0977→140.9775, 169.0977→94.9357ESI-* | [27] | ||
ACN, 20 mM CH3COONH4, RP18 | 171→143, 171→115 | [39] | ||
Dimethylphosphate | OP | ACN, 1 mM tetrabutylammonium acetate; C18 | 125→63, 125→79ESI- | [31] |
MeOH, 0.1% CH3COOH; XSELECT™ CSH™C18 | 125→79, 125→63ESI- | [33] | ||
ACN, 20 mM CH3COONH4, RP18 | 127→109, 129→95 | [39] | ||
Dimethylthiophoshate | OP | ACN, 1 mM tetrabutylammonium acetate; C18 | 141→126, 141→95ESI- | [31] |
MeOH, 0.1% CH3COOH; XSELECT™ CSH™C18 | 141→79, 141→63, 141→95ESI- | [33] | ||
ACN, 20 mM CH3COONH4, RP18 | 143→125, 143→111 | [39] | ||
dimethyldithiophosphate | OP | ACN, 20 mM CH3COONH4, RP18 | 157→142, 157→112 | [39] |
Diazinon-oxon | diazinon | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 289→153, 289→93 | [11] |
MeOH, 0.1% HCOOH; X-Terra C18 | 289.1317→153.1028, 289.1317→261.1004* | [27] | ||
Disulfoton sulfone | disulfoton | MeOH, 0.1% HCOOH; Acquity UPLC™BEH C18 | 307→97, 307→153 | [6] |
MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 307→153, 307→171 | [35] | ||
Disulfoton sulfoxide | disulfoton | MeOH, 0.1% HCOOH; Acquity UPLC™BEH C18 | 291→185, 291→97 | [6] |
MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 291→213, 291→185 | [35] | ||
Fenamiphos sulfone | fenamiphos | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 336→266, 336→308 | [35] |
Fenamiphos sulfoxide | fenamiphos | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 320→171, 320→251 | [35] |
Fenchlorphos oxon | fenchlorphos | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 307→109, 305→109 | [11] |
Fenthion sulfone | fenthion | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 311→125, 311→279 | [35] |
Fenthion sulfoxide | fenthion | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 295→280, 295→127 | [35] |
5-hydroxydiazinon | diazinon | MeOH, 0.1% HCOOH; X-Terra C18 | 321.1038→293.0725, 321.1038→185.0749* | [27] |
319.0882→291.0568, 319.0882→229.0412ESI-* | ||||
7(1-hydroxy isopropyl diazinon | diazinon | MeOH, 0.1% HCOOH; X-Terra C18 | 321.1038→303.0932, 321.1038→275.0619* | [27] |
4(1-hydroxyisopropyl diazoxon | diazinon | MeOH, 0.1% HCOOH; X-Terra C18 | 305.1266→287.1161, 305.1266→277.0953* | [27] |
2-(1-hydroxy-1-methylethyl)-6-methyl-4(1H)-pyrimidinone | diazinon | MeOH, 0.1% HCOOH; Zorbax SB-CN | 169→84 | [19] |
2-isopropyl-6-methyl-4-pyrimidinol | diazinon | ACN, 0.1% HCOOH; XDB-C18 | 153.1022, 84.0444, 70.0651* | [22] |
MeOH, 0.1% HCOOH; X-Terra C18 | 153.1028→137.0715, 153.1028→84.0575*, 151.0872→135.0558, 151.0872→123.0558ESI-* | [27] | ||
isomalathion | malathion | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 331→99, 331→127 | [11] |
2-isopropyl-6-methyl-4-pyrimidinol (IMP) | diazinon | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 153→84, 153→70 | [11] |
MeOH, 0.1% CH3COOH; XSELECT™ CSH™C18 | 153→84, 153→70 | [33] | ||
MeOH, 1% CH3COOH; C18 | 153→84, 153→70 | [40] | ||
ACN, 0.1% HCOOH; XDB-C18 | 153.1022, 84.0444, 70.0651* | [22] | ||
Malathion monocarboxylic acid | malathion | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 303→127, 303→99 | [11] |
MeOH, 0.1% CH3COOH; XSELECT™ CSH™C18 | 301→142, 301→157 | [33] | ||
301→126, 301→141 | ||||
Malathion dicarboxylic acid | malathion | MeOH, 0.1% CH3COOH; XSELECT™ CSH™C18 | 273→141, 273→157 | [33] |
Malathion-oxon | malathion | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 315→127, 315→99 | [11] |
o-methoate | dimethoate | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 214→183, 214→125 | [11] |
MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 214→125, 214→109 | [35] | ||
MeOH, 5 mM HCOONH4; ODS-4 | 214→125, 214→183 | [37] | ||
214→183 | [4] | |||
6-methyl-2-(1-methylethyl)4(1H)-pyrimidinone | diazinon | MeOH, 0.1% HCOOH; Zorbax SB-CN | 153→84 | [19] |
3-methyl4-nitrophenol | fenitrothion | MeOH, 10mM CH3COONH4; XTerra MS C18 | 152 | [25] |
Parathion methyl oxon | Parathion methyl | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 248→202, 248→109 | [35] |
Phorate oxon | phorate | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 245→75, 245→47 | [11] |
Phorate sulfone | phorate | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 293→171, 293→97 | [35] |
Phorate sulfoxide | phorate | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 277→199, 277→143 | [35] |
3,5,6-trichloro-2-pyridinol | chlorpyrifos | MeOH, 0.1% HCOOH and 2 mM CH3COONH4; C6phenyl | 198→107, 198→134 | [11] |
ACN, 0.1% CH3COOH; XDB-C18 | 198→198, 196→196ESI- | [23] | ||
ACN, 20 mM CH3COOH (pH 6.45-7.45); RP/WAX | 196→35, 198→35ESI- | [24] | ||
ACN, 0.025% HCOOH; Zorbax Extended C8 | 198ESI- | [29] | ||
ACN, 0.1% HCOOH; C18 | 196→196, 198→198, 200→200ESI- | [30] | ||
ACN, 0.025% HCOOH; XDB-C8 | 198→198 | [32] | ||
MeOH, 0.1% CH3COOH; XSELECT™ CSH™C18 | 198→37, 198→35, 196→35 ESI- | [33] | ||
ACN, 0.1% HCOOH; MAXRP, RP12 | 196→35, 198→37, 198→35, ESI- | [34] | ||
MeOH, 1% CH3COOH; C18 | 196→196, 198→198ESI- | [40] | ||
MeOH, 1% CH3COOH; PhenylC6 | 196→196, 198→198ESI- | [41] | ||
Temephos oxon | temephos | ACN, CH3COONH4; C18 | 468 | [26] |
Temephos sulfoxide | temephos | ACN, CH3COONH4; C18 | 482, 483, 500, 523 | [26] |
Terbufos sulfone | terbufos | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 321→115, 321→171 | [35] |
Terbufos sulfoxide | terbufos | MeOH, 5 mM CH3COONH4; MAX RP, C-12 | 305→131, 305→159 | [35] |
3. Carbamates and phenylureas
LC-ESI+-MS/MS can be used for the simultaneous analysis of carbamates (general structure R1OCONR2R3), phenylureas, and selected degradation products (see Table 5 for target list). Few carbamates are still analyzed directly by GC-EI-MS or GC-EI-MS/MS in multiclass methods (primarily carbaryl, carbofuran, carbosulfan, EPTC, isoprocarb, pirimicarb) [3, 9, 42, 43]. To improve sensitivity and extend the range of carbamates amenable to GC-EI-MS methods derivatized prior to analysis with 9-xanthydol, trimethylphenylammonium hydroxide and trimethylsulfonium hydroxide or sodium hydride has been used [43–45]. Metabolites of carbofuran and carbaryl have been analyzed after derivatization using trifluoroacetic acid with trimethylamine to produce volatile derivatives that can be analyzed by GC-EI-MS [46]. Photodegradation products (phenols and para-hydroxybenzamides) of carbamates were analyzed directly by GC-EI-MS/MS method [47].
LC-ESI+-MS/MS is more frequently chosen than GC-MS methods for the analysis of carbamates and phenylureas in chemical class-specific or multiclass methods [39, 48–58]. OPs, carbamates, and phenylureas have a wide range of polarities so they can elute over similar time periods when typical reversed-phase stationary phases are used; however, in general, phenylureas elute later than carbamates and within the time range for OPs and pyrethroid insecticides.
For LC-ESI+-MS/MS the precursor ion is generally selected as the protonated molecular ion [M+H]+ (see Table 6). Both methanol and acetonitrile have been used as the organic modifier in the mobile phase for the separation of carbamates and when both chemical classes are analyzed together; however, acetonitrile provides the best overall sensitivity. Sodium adducts of carbamates can also be observed with ESI+ and have been attributed to impurities in methanolic mobile phases or sodium from metal tubing [51]. Both 0.1% formic acid and 5 mM ammonium acetate should be added to the mobile phase to improve sensitivity and to provide for ammonium adduct [M+NH4]+ formation for aldicarb, methiocarb sulfone, and oxamyl (see Table 6) [51, 53]. Ammonium acetate can also improve the peak shapes observed in the separation. Aldicarb sulfone and methiocarb sulfone observed both the protonated molecular ion and ammonium adduct under these conditions [53]. The addition of ammonium acetate to the mobile phase also minimizes sodium adduct formation which was observed in this work and others for aldicarb, aldicarb sulfone, aldicarb sulfoxide, 3-hydroxycarbofuran, siduron, and diuron [51]. The common, group-specific fragmentation pathway for
Atmospheric pressure chemical ionization in positive and negative modes (APCI+ or APCI-) can give similar range of sensitivity and structural information as ESI+ and can provide added selectivity for the LC-MS/MS analysis of carbamates [51]. Sodium adducts of the molecular ion do not form with APCI+ and sensitivity is better in positive ion mode than in negative ion mode, partially due to greater fragmentation with to [M-CONHCH3]− in the APCI− ion source [52, 59]. LC-APCI+-MS has also been found to be more sensitive for some phenylureas [60].
Compound (molecular weight) | Transitions | Cone voltage (V) | Collision energy (eV) | Ratio SRM1/SRM2 areas ± RSD | Retention time (min) |
---|---|---|---|---|---|
Aldicarb (190.27) | 10 | 15 | 2.66 ± 12.5% | 12.46 | |
208→116 | 10 | 15 | |||
Aldicarb sulfone (222.26) | 15 | 10 | 2.83 ± 35.9% | 4.60 | |
240→86 | 15 | 20 | |||
Aldicarb sulfoxide (206.26) | 15 | 15 | 1.13 ± 17.7% | 3.29 | |
207→132 | 10 | 5 | |||
Aminocarb (208.26) | 20 | 15 | 1.39 ± 4.72% | 2.85 | |
209→137 | 20 | 20 | |||
Carbaryl (201.22) | 22 | 10 | 3.32 ± 14.2% | 16.35 | |
202→127 | 20 | 25 | |||
Carbofuran (221.25) | 20 | 20 | 2.73 ± 34.5% | 15.27 | |
222→165 | 20 | 20 | |||
Carboxin (235.31) | 25 | 15 | 3.08 ± 11.3% | 16.35 | |
236→86 | 20 | 25 | |||
EPTC (189.32) | 20 | 10 | 1.70 ± 20.5% | 19.99 | |
190→86 | 20 | 10 | |||
3-Hydroxycarbofuran (237.25) | 20 | 10 | 3.03 ± 10.6% | 8.92 | |
238→220 | 20 | 10 | |||
Methiocarb (225.31) | 15 | 20 | 1.40 ± 11.4% | 18.31 | |
226→169 | 15 | 10 | |||
Methiocarb sulfone (257.31) | 15 | 20 | 1.01 ± 2.10% | 12.61 | |
258→122 | 25 | 15 | |||
Methiocarb sulfoxide (241.31) | 20 | 25 | 1.24 ± 9.46% | 9.35 | |
242→170 | 20 | 25 | |||
Methomyl (162.21) | 10 | 10 | 1.63 ± 4.24% | 5.48 | |
163→106 | 10 | 10 | |||
Methomyl-oxime (105.16) | 15 | 10 | 1.00 ± 7.02% | 3.23 | |
106→106 | 20 | 0.010 | |||
Oxamyl (219.36) | 20 | 10 | 2.45 ± 35.9% | 4.66 | |
237→90 | 20 | 10 | |||
Oxamyl-oxime (162.21) | 15 | 10 | 7.03 ± 27.7% | 2.68 | |
163→90 | 15 | 20 | |||
Pirimicarb (238.29) | 25 | 20 | 2.51 ± 7.80% | 8.35 | |
239→182 | 30 | 15 | |||
Propamocarb HCl (224.73) | 30 | 10 | 7.49 ± 21.4% | 2.90 | |
189→74 | 35 | 15 | |||
Thiodicarb (354.47) | 15 | 10 | 2.06 ± 29.5% | 15.63 | |
355→108 | 15 | 15 | |||
Diuron (233.10) | 25 | 15 | 1.98 ± 23.1% | 16.83 | |
235→72 | 25 | 15 | |||
Linuron (249.09) | 15 | 20 | 2.20 ± 30.5% | 18.68 | |
251→184 | 20 | 15 | |||
Neburon (275.18) | 30 | 15 | 4.86 ± 15.0% | 20.27 | |
276→114 | 35 | 15 | |||
Siduron (232.32) | 30 | 20 | 1.12 ± 6.70% | 18.22 | |
233→137 | 30 | 17 | |||
EPTC-d14 (203.4) | 20 | 20 | N/A | 19.99 | |
Diuron-d6 (239.13) | 20 | 20 | N/A | 16.83 |
Some of the main degradation products analyzed by LC-ESI+-MS/MS are shown in Table 6 and include carbamate sulfone or sulfoxides and hydroxyl derivative. Metabolites of carbofuran and carbosulfan have also been analyzed using LC-turboIonSpray-MS/MS, LC-APCI+-MS and LC-QqTOF-MS/MS [61–66]. Other degradation products identified include 3-ketocarbofuran, 3-hydroxy-7-phenolcarbofuran, 3-keto-7-phenolcarbofuran, 7-phenolcarbofuran, and dibutyl amine.
LC-APCI +-MS and LC-atmospheric pressure photoionization (APPI+)-MS have also been used to analyze these metabolites as well as sulfoxides and sulfones of carbamates with the protonated molecular ion, ammonium adduct, and [M+H-CH3NCO]+ observed in the ion source [67–69].
4. Pyrethroid insecticides and their metabolites
Figure 3 shows the structures of the pyrethroid insecticides. They have been routinely analyzed with GC-EI/MS, GC-EI-MS/MS, or GC-NCI-MS methods (see Table 7) [3, 5, 6, 9, 10, 14, 42, 70–81]. For the diverse range of pyrethroids these methods are preferred over LC-MS/MS methods. Pyrethroid insecticides are also often analyzed simultaneously with OCs and OPs (either EI or NCI) and generally elute latter in the separation than OCs and OPs. Detection limits with GC-EI-MS for pyrethroids are often more than sufficient for routine analysis in the μg/L range [10].
Analyte | SIM or SRM ( | Ref |
---|---|---|
Allethrin C19H26O3 | 123, 136, 202 | [70] |
167, 68NCI, CH4 | This work | |
Bifenthrin C22H22ClF3O2 | 181, 165 | [5, 6] |
181, 105 | [9] | |
181→ 115, 181→165 | [3] | |
181, 165, 166 | [79, 10] | |
181→166, 181→165 | [76] | |
205, 241NCI, CH4 | [77], this work | |
386, 387, 388NCI, CH4 | [10] | |
Cyfluthrin (4 peaks) C22H18Cl2FNO3 | 163, 226 | [70] |
163, 127 | [5] | |
206, 150 | [6] | |
163→127, 226→206 | [3] | |
207, 209NCI, CH4 or NH3 | This work | |
λ-Cyhalothrin C23H19ClF3NO3 | 209, 181 | [70] |
181, 127 | [5] | |
181, 152 | [6] | |
205→121, 241→205 | [76] | |
197→141, 197→161 | [14] | |
181→127, 197→161 | [3] | |
181→152, 197→141, 197→161 | [80] | |
205, 241NCI, NH3 or CH4 | [77], this work | |
Cypermethrin (4 peaks) C22H19Cl2NO3 | 163, 181 | [70] |
181, 163, 209 | [79] | |
181, 127 | [5] | |
163, 127 | [6] | |
91, 163, 181 | [42] | |
163, 165, 181 | [10] | |
207, 171NCI, NH3 | [77] | |
207, 209NCI, CH4 | This work | |
207, 209, 171 | [10] | |
207→35, 209→35 | [14] | |
163→127, 181→127 | [3] | |
163→127, 165→127, 165→129 | [80] | |
Deltamethrin (2 peaks) | 253, 255 | [70] |
C22H19Br2NO3 | 253, 172 | [14] |
93, 181, 253 | [42] | |
253, 172+174 | [6] | |
181, 253, 163, 165 | [81] | |
181, 253, 251 | [10] | |
172→93, 253→93 | [3] | |
253→172, 253→174 | [80] | |
79, 137NCI, NH3 | [77] | |
79,81NCI, CH4 | This work | |
297, 299, 79NCI, CH4 | [10] | |
Esfenvalerate (2 peaks) C25H22ClNO3 | 419, 167, 181 | [70] |
211, 167NCI | [77] | |
211, 213NCI | This work | |
225→119, 225→147 | [3] | |
Fenpropathrin C22H23NO3 | 181, 265 | [70] |
141NCI | [77], this work | |
Fenvalerate (2 peaks) C22H22ClNO3 | 167, 125 | [5] |
109, 127, 244 | [42] | |
211, 167NCI | [77] | |
211→167, 213→169 | [14] | |
225→119, 225→147 | [3] | |
167→125, 125→89, 125→99 | [80] | |
τ-fluvalinate C26H22ClF3N2O3 | 250, 55 | [5] |
250, 206, 252 | [79] | |
250, 200+214 | [6] | |
294, 258NCI | [77] | |
294, 296NCI | This work | |
250→55, 250→200 | [3] | |
Flucythrinate (2 peaks) C26H23F2NO4 | 199, 157 | [5] |
Imiprothrin | 123, 318, 151 | [70] |
Cis/trans-permethrin (2 peaks) C21H20Cl2O3 | 183, 165 | [6, 70, 78] |
183, 163 | [5, 9] | |
207, 171NCI | [77] | |
207, 209NCI | This work | |
207→35, 209→35 | [14] | |
163→127, 183→128 | [3] | |
163→127, 165→127 | [80] | |
165→129 | ||
Phenothrin C23H26O3 | 183, 163 | [70] |
331, 167NCI | [77] | |
Prallethrin C19H24O3 | 123, 300 | [70] |
167, 132, 168 | This work | |
Resmethrin (two peak) C22H26O3 | 171, 123, 338 | [70] |
337, 167NCI | [77] | |
Tefluthrin C17H14ClF7O2 | 205, 241NCI | This work |
Tetramethrin (two peak) C19H25NO4 | 164, 123 | [70] |
164, 107 | [5] | |
349, 167NCI | [77] | |
Tralomethrin C22H19Br4NO3 | 181, 253, 163, 165 | [81] |
79, 137NCI | [77] | |
Transfluthrin C15H12Cl2F4O2 | 163→121, 163→117 | [3] |
CA (diazomethane) | 182, 167, 123 | [70] |
CA (PFBBr) | 295→79, 297→79 | [14] |
DBCA(diazomethane) | 231, 233 | [70] |
DBCA (PFBBr) | 312, 253, 231 | [71] |
DBCA (PFBBr) | 295→79, 297→79 | [14] |
DBCA (MTBSTA) | 355, 353, 357, 172 | [73, 75] |
DBCA (HFIP) | 369 | [74] |
DCCA (diazomethane) | 187, 189, 163 | [70] |
DCCA (PFBBr) | 222, 187, 163 | [71] |
DCCA (PFBBr) | 207→35, 209→35 | [14] |
DCCA (MTBSTA) | 265, 267 | [72, 75] |
DCCA (MTBSTA) | 265, 267, 128, 307 | [73] |
DCCA (HFIP) | 323 | [74] |
3PBA (diazomethane) | 197, 228 | [70] |
3PBA (PFBBr) | 228, 197 | [71] |
3PBA (MTBSTFA) | 271, 227, 197 | [73, 75] |
3PBA (HFIP) | 364 | [74] |
4F3PBA (diazomethane) | 246, 215 | [70] |
4F3PBA (PFBBr) | 246, 215 | [71] |
4F3BA (MTBSTFA) | 289, 245, 214 | [73, 75] |
FBAc(TMSI-TMCS) | 251, 252 | [72] |
MCA(TMSI-TMCS) | 211, 212 | [72] |
CH3FBAc(TMSI-TMCS) | 265, 266 | [72] |
FB-Al (TMSI-TMCS) | 237, 238 | [72] |
CH3-FB-Al (TMSI-TMCS) | 251, 252 | [72] |
CH3OCH2-FB-Al | 281, 282 | [72] |
HOCH2-FB-Al | 339, 340 | [72] |
Negative chemical ionization can provide higher MS selectivity for halogenated pyrethroids compared to GC-EI-MS [7, 10]. Some studies have shown that ammonia, rather than methane, as the reagent gas yields lower detection limits for pyrethroids analyzed by GC-NCI-MS [74], however, methane is still preferred for analysis of OCs and OPs [7, 10]. Pyrethroids also easily fragment in the EI source such that the molecular ion has low abundance and fragment ions are selected for quantitation and confirmation as shown in Table 7. For GC-EI-MS/MS the precursor ion is selected as a fragment ion in order to obtain sufficient sensitivity and used over GC-EI-MS when added selectivity is required for more difficult sample matrices.
Metabolites of pyrethroids include the following: 3-(2,2-dimethylvinyl)-2,2-dimethylcyclopropane-1-carboxylic acid, CA (metabolite of allethrin, imiprothrin, phenothrin, prallethrin, resmethrin, and tetramethrin); 4-fluoro-3-phenoxybenzoic acid, 4-fluoro-3-phenoxybenzoic acid, 4FPBA (metabolite of cyfluthrin), cis- and trans-2,2-dichlorvinyl-2,2-dimethylcyclopropane-1-carboxylic acid, DCCA (metabolite of cyfluthrin, cypermethrin, and permethrin); and 3-phenoxybenzoic acid, 3-PBA (metabolite of cyhalothrin, cypermethrin, deltamethrin, esfenvalerate, fenpropathrin, phenothrin, and permethrin), cis-2,2-dibromovinyl-2,2-dimethyl-2,2-dimethylcyclopropane-1-carboxylic acid, DBCA (metabolite of deltamethrin). Additionally, both carboxylic acid and alcoholic derivatives can form fluoro-containing pyrethroids including the following: 2,3,5,6-tetrafluorobenzyl alcohol (FB-Al) and 2,3,5,6-tetraflurobenzoic acid (FB-Ac) (metabolites of transfluthrin); 2,3,5,6-tetrafluorobenzoic acid (CH3-FB-Ac) and 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol (CH3-FB-Al) (metabolites of profluthrin); 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol (CH3OCH2-FB-Al) (metabolite of metofluthrin); and 4-hydroxymethyl-2,3,5,6-tetrafluorobenzyl alcohol (HOCH2-FB-Al) (metabolite of metofluthrin and profluthrin) [72]. Most studies include cis/trans-DCCA, DBCA, 4F3PBA, and 3PBA in their analysis of metabolites of pyrethroids (see Table 7). Analysis of metabolites by GC-EI-MS requires derivatization of the metabolites prior to analysis with pentafluorobenzyl bromide (PFBBr), tert-butyldimethylsilyl-N-methyltrifluoroacetamide (MTMSTFA). or 1,1,1,3,3,3-hexafluoroisopropanol (HFIP), and N-trimethlsilylimidazole (TMSI)-trimethylchlorosilane (TMCS) for alcoholic metabolites [14, 70–75]. GC-EI-MS/MS has not been widely used for analysis of the metabolites. Derivatization extends the range of metabolites that are amenable to GC-EI-MS above those commonly analyzed by LC-MS/MS. Some metabolites of pyrethroids including DBCA, DCCA, 4FPBA, and 3PBA can be analyzed by LC-ESI--MS/MS (see Table 8) [33, 41, 82–84]. Pyrethroids that ionize in an electrospray ion source are more sensitive in positive ion mode with the ammonium adduct formed such that ammonium acetate at ~5 mM should be added to the mobile phase. For those pyrethroids that are more sensitive with LC-ESI--MS/MS (cyfluthrin and cyhalothrin), the deprotonated molecular ion forms in the ion source. The metabolites form the deprotonated molecular ion in the ESI ion source. In general, only a few pyrethroids have been included in LC-ESI+-MS/MS multiclass methods.
Analyte (monoisotopic mass) | SIM or SRM ( | Reference |
---|---|---|
Bifenthrin (422.1) | 440→182 | [82] |
Cyfluthrin (433.1) | 451→191, 451→434 | [39] |
435→191, 435→127 | [84] | |
432→405 | [82] | |
Cyhalothrin (449.1) | 448.2→402.8ESI- | [82] |
Cypermethrin (415.1) | 433→191, 433→416 | [35, 39, 84] |
433→191 | [82] | |
Deltamethrin (502.0) | 523→506, 523→281 | [39] |
506→281, 506→253 | [84] | |
521→279 | [82] | |
Permethrin (390.1) | 408→355, 408→183 | [84] |
408→183 | [82] | |
Esfenvalerate (419) | 437→167 | [82] |
DBCA | 343→81, 297→81ESI- | [83] |
295→79ESI- | [82] | |
299→299 | [84] | |
DCCA | 207→207, 209→209ESI- | [41, 84] |
207→207, 207→35ESI- | [39] | |
207→35, 209→35, 209→37ESI- | [33] | |
209→37, 207→35ESI- | [83] | |
207→35ESI- | [82] | |
4-FPBA | 231→93, 231→65ESI- | [83] |
231→93ESI- | [82] | |
3-PBA | 213→93, 213→169ESI- | [33, 41] |
213→93, 213→65ESI- | [83] | |
213→93ESI- | [82] |
5. Other considerations
Generally, there is a larger diversity of azole fungicides and strobilurin fungicides that can be analyzed with LC-ESI+-MS/MS methods as compared to those amenable to GC-MS methods [76, 79, 80, 85, 86]. For pesticides that are halogenated, GC-NCI-MS should be considered as an option to improve the sensitivity or selectivity of the analysis. Dissociative electron capture is often observed in negative chemical ionization for OPs, OCs, pyrethroids, azole fungicides, and strobilurin fungicides. GC-EI-MS/MS methods may also provide added selectivity; however, as many pesticides from these chemical classes fragment easily in an EI ion source, the precursor ion may need to be selected as a fragment ion which is capable of undergoing further collision-induced dissociation to achieve the required sensitivity. OP metabolites (OP oxons, sulfones, sulfoxides, and selected others) can be analyzed by LC-ESI+-MS/MS, while alkylphosphates or alkylthiophosphates should be analyzed by LC-ESI --MS/MS or following derivatization by GC-MS. Pyrethroid metabolites are still commonly analyzed following derivatization with GC-EI-MS methods with a small selection of common pyrethroid metabolites also frequently analyzed by LC-MS/MS.
6. Conclusions
A larger number of OPs including organophosphates and organothiophosphates have been analyzed by GC-MS or GC-MS/MS methods as compared to LC-ESI+-MS/MS. GC-EI-MS or GC-EI-MS/MS is most commonly selected for analysis of OPs, and GC-EI-MS provides excellent confirmation of identity of the OP through spectral library matches. When added selectivity is required, such as when matrix remains after sample clean-up, analysis of OPs by GC-NCI-MS or GC-EI-MS/MS should be selected. GC-NCI-MS analysis of halogenated (or nitro substituted) OPs generally provides better sensitivity than GC-EI-MS/MS, particularly when the precursor ion selected for CID is the molecular ion. Although NCI is a softer ionization process than EI, fragment ions are still often observed as a result of dissociative electron capture. Sensitivity of GC-EI-MS/MS can be improved by selection of an abundant fragment ion for the precursor ion rather than the molecular ion which may be too low in abundance. The number of applications using LC-ESI+-MS/MS for the analysis of OPs has increased in the past ten years and for those OPs that can be ionized efficiently by ESI, the sensitivity may be better than with GC-MS methods (particularly for OPs that elute later in the GC separations). Another advantage of LC-ESI+-MS/MS is that it is feasible to analyze OP degradation products (OP oxons, OP sulfones, or OP sulfoxides) simultaneously with parent OPs. Derivatization of alkylphosphates and alkylthiophosphates metabolites of OPs is required to achieve the desired sensitivity when analyzed by GC-MS or GC-MS/MS methods. Alkylphosphate metabolites can also be analyzed by LC-ESI--MS/MS.
Pyrethroids can be analyzed simultaneously with OCs and OPs using GC-EI-MS or GC-EI-MS/MS. A number of pyrethroids are halogenated and consequently they can be analyzed by GC-NCI-MS for added selectivity and sensitivity. Metabolites of pyrethroids are derivatized prior to the analysis by GC-EI-MS or GC-EI-MS/MS and this approach remains the method of choice for their analysis. Analysis of pyrethroids by LC-MS/MS is more limited; however, metabolites of pyrethroids can be analyzed using LC-ESI--MS/MS.
Carbamates and phenylureas are commonly analyzed by LC-ESI+-MS/MS. Selected carbamates can be analyzed by GC-MS methods, but a derivatization step is required prior to analysis. The main degradation products of carbamates including carbamate sulfone or sulfoxides can be analyzed by LC-ESI+-MS/MS simultaneously with carbamates and phenylureas. APCI and APPI in positive ion mode have also been used to ionize metabolites of carbamates to achieve better sensitivity than ESI. APCI+ is also not prone to sodium adduct formation. Mobile phase additives used for the LC-ESI+-MS/MS separation of both OPs, carbamates and phenylureas include 0.1% formic acid and 5 mM ammonium acetate. Better sensitivity for OPs is obtained when methanol is used as the organic modifier for gradient elution, while acetonitrile is more commonly used for the separation of carbamates to obtain optimal sensitivity. Carbamates are prone to adduct formation (reduce sensitivity) in mobile phases containing methanol, and ammonium formate or ammonium acetate is generally used to reduce sodium adduct formation. Other pesticides that can be analyzed by LC-ESI+-MS/MS include azole fungicides, neonicotinoid insecticides, and strobilurin fungicides. Pending the target list of pesticides, it is feasible to obtain simultaneous analysis of all these chemical classes; however, if optimal sensitivity is required then class-specific methods will achieve better results.
Acknowledgments
This work was financially supported by the Natural Sciences and Engineering Research Council (NSERC) of Canada and additional instrument support from Canadian Foundation for Innovation.
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