Evaluation of analyte protectants to improve gas chromatographic analysis of pesticides

A common problem in gas chromatography (GC) applications is the analyte losses and/or peak tailing due to undesired interactions with active sites in the inlet and column. Analytes that give poor peak shapes or degrade have higher detection limits, are more difficult to identify and integrate, and are more prone to interferences than stable analytes that give narrow peaks. For susceptible analytes, significant peak quality improvements are obtained when matrix components are present because they fill active sites, thus reducing analyte interactions. This phenomenon is called "matrix-induced chromatographic response enhancement." Several approaches have been proposed to minimize peak distortion phenomena and compensate for matrix-induced effects, which is especially important for accurate quantitation, but each approach has serious limitations for routine multi-pesticide analysis. In this study, we demonstrate the feasibility of using "analyte protectants" to provide a more convenient and effective solution to the problem than other approaches developed thus far. The protecting agents are added to extracts and matrix-free standards alike to provide the chromatographic enhancement effect even for the most susceptible analytes in a very dirty GC system. In this study, we evaluated 93 different compounds to find the most suitable ones for improving chromatographic quality of the signal. Because hydrogen bonding has been shown to be an important factor in analyte interactions with active sites, we mainly focused on additives with strong hydrogen bonding capabilities. Dramatic peak enhancements were achieved using compounds containing multiple hydroxy groups, such as sugars and sugar derivatives, and gulonolactone appears to be the most effective protecting agent for the most pesticides that we tested. The benefits of using analyte protectants versus alternative procedures for overcoming matrix-induced effects in quantitation include: (a) simpler procedure; (b) easier integration of peaks; (c) lower detection limits; (d) better quantitation; (e) less maintenance of the GC inlet; and (e) lower cost. However, long-term influences on the performance of the chromatographic system have yet to be established.