APCI carbamates

For the analysis of 10 carbamates in fruits and vegetables a comparison of ESI and APCI-LC-MS switching from positive to negative ionisation was performed (cf APCI carbamates). APCI was more efficient than ESI. Detection Umits were equivalent to 0.002-0.033 mg per kg of crop [358]. Nevertheless, DiCorcia applied ESI-LC-MS(-I-) to analyse 12 N-methylcarbamate insecticides in 10 types of fruits... 

Electrospray ionization (ESI) and APCI are the two popular API techniques that will be discussed here. The applications to the analysis of pesticides that will be discussed include imidazolinone herbicides, phenoxy acid herbicides, and A-methyl carbamate insecticides. Matrix effects with respect to quantitation also will be discussed. Eor the... 

In addition to HPLC/fluorescence, there are references to the use of both APCI and/or ESI with HPLC/MS for the determination of A/-methyl carbamate insecticides in a variety of matrices." Ongoing studies at the US EPA for the determination of /V-methyl carbamate insecticides in nine fmits and vegetables at the 1.0 ngg level are described below. The fruits and vegetables investigated were cranberries, peaches, blueberries, kiwi, carrots, tomatoes, potatoes, lettuce, and grapefmit juice. The purpose of including an account of this work is to illustrate why HPLC/MS/MS is the method of choice for residue work at the 1.0 ng g level, especially for difficult matrices. 

In the case of carbamate insecticides, both ESI and APCI can be used. However, in this study, the sensitivity of APCI was 3-5-fold less than that of ESI. In this case, the Z-spray configuration was used with APCI, which gives a lower efficiency of ions reaching the mass analyzer than is achieved with other instrumental configurations. 

APCI can help to reduce matrix effects when analyzing for carbamate insecticides. Eor example, when analyzing for methiocarb in citrus products, the apparent recoveries were in the region of 50% with ESI. However, on changing to APCI, the apparent recoveries were increased to 110%. This is an example where APCI can be an alternative API method if matrix effects are a problem with ESI. It is important to note that the analyte must show sufficient sensitivity to both API techniques. 

Currently, HPLC/fiuorescence is still the most common technique for the determination of residues of oxime carbamates. With the introduction of ESI and APCI MS interfaces, HPLC/MS analysis for oxime carbamates in various sample matrices has become widespread. However, for a rapid, sensitive, and specific analysis of biological and environmental samples, HPLC/MS/MS is preferred to HPLC/MS and HPLC/fiuorescence. With time, improved and affordable triple-quadrupole mass spectrometers will be available in more analytical laboratories. With stricter regulatory requirements, e.g., highly specific and conclusive methods with lower LOQ, HPLC/MS/MS will be a method of choice for oxime carbamates and their metabolites. 

In APCI mass spectra of carbamates, fragment ions are observed, which are most likely due to thermal decomposition in the heated nebulizer interface and snbseqnent ionization of the thermal decomposition products [11, 14, 20-23]. For example, base peaks were observed at m/z 163 for oxamyl, due to the loss of methyl isocyanate, at m/z 168 for propoxur, dne to the loss of propylene, and at m/z 157 for aldicarb, due to the loss of HjS. The APCI mass spectra of aldicaib and two of its metabolites, aldicarb sulfoxide and aldicarb snlfone, showed significant fragmentation. Major fragments for aldicarb were dne to the loss of carbamic acid (to m/z 116) and due to charge retention at [CH3-S-C(CH3)2]. For aldicarb sulfoxide and aldicarb sulfone, the loss of carbamic acid resnlted in the base peaks of the spectra (at m/z 132 and 148, respectively). 

S. Kawasaki, F. Nagumo, H. Ueda, Y. Tajima, M. Sano, J. Tadano, Simple, rapid and simultaneous measurement of eight different types of carbamate pesticides in serum usingLC-APCI-MS, J. Chromatogr., 620 (1993) 61. 

The LC/MS positive-ion mode analysis of grape carbamates reported in Fig. 9.11 (carbaryl, carbofuran, diethofencarb, ethiofencarb, fenobu-carb, fenoxycarb, isoprocarb, methiocarb, metholcarb, oxamyl, pirimi-carb, propoxur, and thiobencarb) was performed by matrix solid-phase dispersion (MSPD) extraction using either atmospheric pressure-chemical ionization (APCI) or electrospray ionization (ESI) (Fernandez et al., 2000). 

Figure 9.11. Carbamates determined by LC-atmospheric pressure chemical ionization (APCI) or electrospray (ES) in positive-ion mode (Fern ndez et al., 2000). (24) car-bofuran, (25) ethiofencarb, (26) methiocarb, (27) fenobucarb, (28) isoprocarb, (29) fenoxycarb, (30) diethofencarb, (31) metholcarb, (32) propoxur, (33) pirimicarb, (34) oxamyl, (35) thiobencarb. Structure of carbaryl is reported in Fig. 9.1.

The contamination of fruits and vegetables with pesticides became a problem with the increased application of pesticides because of an intensified agriculture. So the comparison of APCI and ESI-LC-MS for the determination of 10 pesticides of carbamate type (pirimicarb, carbofuran, 3-hydroxycarbofuran, aldicarb, and its metabolites, the sulfoxide and the sulfone), besides others in fruits, met the... 

Carbamates. A fast, sensitive and selective method for the concentration and analysis of 9 N-methylcarbamate pesticides was reported by Volmer et al. [507]. Three different SPME fibres combined with short-column ESI-LC-MS(-i-) and MS/MS were applied. The detection limits observed were 0.3-1.9 pg Signal intensities increasing by a factor of 2-7 were observed [508] using non-volatile buffers in the separation process prior to ESI-MS. After EC removal of the non-volatile buffers was essential. The results obtained by ESI and APCI-LC-MS and MS/MS for the analysis of the eight N-methylcarbamate pesticides and their degradation products were compared with results obtain with the application of TSP or PBI (cf. 15.3.3.1 TSP, carbamates) [108]. ESI-LC-MS and TSP-LC-MS were used for quantitative determination of 10 different carbamate pesticides which showed a broad variety in polarity. ESI-SIM detection limits were typically 10-60 pg which was 10-150 times better than using TSP-MS (cf. 15.3.3.1 TSP, carbamates) [509]. Interfacing a commercial ESI source to an ITMS allowed the determination of carbamates as well as triazines and azo dyes. Identification could be performed either by IT-MS/MS or by ESI-CID [424]. 

Liquid chromatography-mass spectrometry The initial attempts to couple LC with MS lacked important attributes for trace analysis sensitivity, robustness, and reliable quantitation. Moreover, the cost of the early LC-MS instruments was prohibitive for most laboratories. The revolutionary introduction of atmospheric pressure ionization (API) techniques, mainly electrospray (ESI) and atmospheric pressure chemical ionization (APCI), resulted in greater applicability of LC-MS and manufacture of more reliable, affordable, and user-friendly instruments. Thus, LC-MS is now becoming an indispensable part of the analytical strategy in many routine laboratories, enabling direct, selective, and sensitive multiclass, multiresidue analysis of more polar, low volatile, and/or thermolabile pesticides, such as carbamates, phenylureas, sulfonylureas, imidazoles, triazoles, imidazolinones, chlorophenoxy acids, and many others. 

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