The ability to quantify levels of target analytes in biological samples accurately and precisely, in biomonitoring, involves the use of highly sensitive and selective instrumentation such as tandem mass spectrometers and a thorough understanding of highly variable matrix effects. Typically, matrix effects are caused by co-eluting matrix components that alter the ionization of target analytes as well as the chromatographic response of target analytes, leading to reduced or increased sensitivity of the analysis. Thus, before the desired accuracy and precision standards of laboratory data are achieved, these effects must be characterized and controlled. Here we present our review and observations of matrix effects encountered during the validation and implementation of tandem mass spectrometry-based analytical methods. We also provide systematic, comprehensive laboratory strategies needed to control challenges posed by matrix effects in order to ensure delivery of the most accurate data for biomonitoring studies assessing exposure to environmental toxicants.

A laboratory experiment was developed to target analytical chemistry students and to teach them about insecticides in food, sample extraction, and cleanup. Micro concentrations (sub-μg/mL levels) of 12 insecticides spiked into apple juice samples are extracted using liquid−liquid extraction and cleaned up using either a primary−secondary amine (PSA) cartridge or a C 18 cartridge. Extracts are then separated by gas chromatography and analyzed with tandem mass spectrometry. The method has been successfully tested by three cohorts of quantitative analysis students to determine the concentration of the insecticides spiked at 50 ng/mL in apple juice. Students' average recoveries were between 78 and 121% using C 18 cartridges (n = 30). Using PSA cartridges, average recoveries were between 47 and 121% (n = 6). Overall, this laboratory experiment was successful in teaching analytical chemistry students about environmental exposure to insecticides and sample processing.

A solid phase extraction method was developed to isolate four insecticide degradates from baby food that were measured subsequently using high-performance liquid chromatography–tandem mass spectrometry. The degradates [parent insecticide] measured were malathion dicarboxylic acid [malathion], 3,5,6-trichloro-2-pyridinol [chlorpyrifos, chlorpyrifos methyl] (TCPy), cis/trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid [permethrin, cypermethrin, cyfluthrin], and 3-phenoxybenzoic acid [general pyrethroid]. All degradates produced recoveries between 80 and 120% except TCPy in fruit (122% recovery), and all relative standard deviations were <16%. Use of this method demonstrated that insecticide degradates were found in baby foods frequently purchased in the United States, supporting the need for this method. These data will assist in differentiating whether biomarker levels of insecticide metabolites are the result of exposures to the toxic insecticide or its preformed degradate.

This study was designed to observe the production of degradates of two organophosphorus insecticides and one pyrethroid insecticide in beverages. Purified water, white grape juice, apple juice, and red grape juice were fortified with 500 ng/g malathion, chlorpyrifos, and permethrin, and aliquots were extracted for malathion dicarboxylic acid (MDA), 3,5,6-trichloro-2-pyridinol (TCPy), and 3-phenoxybenzoic acid (3-PBA) several times over a 15 day period of being stored in the dark at 2.5 °C. Overall, first-order kinetics were observed for production of MDA, and statistically significant production of TCPy was also observed. Statistically significant production of 3-phenoxybenzoic acid was not observed. Results indicate that insecticides degrade in food and beverages, and this degradation may lead to preexisting insecticide metabolites in the beverages. Therefore, it is suggested that caution should be exercised when using urinary insecticide metabolites to assess exposure and risk.