HPLC/fluorescence

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 this study, HPLC/fluorescence was compared with HPLC/ESI-MS and HPLC/ESI-MS/MS. A summary of the procedure is described as follows. The sample was prepared using the method of Luke et al.f and the sample was then cleaned up using a 1-g aminopropyl SPE cartridge. The sample was loaded on to the... 

In this study, the preliminary findings showed that the HPLC/fluorescence data were in agreement for all 12 carbamates with HPLC/ESI-MS/MS for most of the nine fruits and vegetables at the 1.0 ng g fortification level. The recoveries were generally within 70-120% however, at the 1.0 ng g level in each commodity, HPLC/ESI-MS (single-stage MS) had difficulty with interferences for three out of the 12 carbamate pesticides (aldicarb sulfoxide, aldicarb sulfone, and 3-hydroxycarbofuran), which made quantification impossible for these three compounds. 

There were also problems with interferences using HPLC/fluorescence with carrots and grapefruit juice for most of the carbamates at the 1 ngg level. For example,... 

Figure 6 HPLC/fluorescence of grapefruit juice control...

Reversed-phase HPLC followed by post-column derivatization and subsequent fluorescence detection is the most common technique for quantitative determination of oxime carbamate insecticides in biological and environmental samples. However, for fast, sensitive, and specific analysis of biological and environmental samples, detection by MS and MS/MS is preferred over fluorescence detection. Thus, descriptions and recommendations for establishing and optimizing HPLC fluorescence, HPLC/ MS, and HPLC/MS/MS analyses are discussed first. This is followed by specific rationales for methods and descriptions of the recommended residue methods that are applicable to most oxime carbamates in plant, animal tissue, soil, and water matrices. 

Table 2 HPLC/fluorescence analysis of methomyl in crops (Multi-residue Method 2)...

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