A rapid screening method for pesticides has been developed to promote more efficient processing of produce entering the United States. Foam swabs were used to recover a multiclass mixture of 132 pesticides from the surfaces of grapes, apples, and oranges. The swabs were analyzed using direct analysis in real time (DART) ionization coupled with a high-resolution Exactive Orbitrap™ mass spectrometer. By using a DART helium temperature gradient from 100-350°C over 3 min, a minimal separation of analytes based on volatility differences was achieved. This, combined with the Exactive's mass resolution of 100,00, allowed the chromatographic step, along with the typical compositing and extraction steps associated with gas chromatography/mass spectrometry (GC/MS) or liquid chromatography/mass spectrometry (LC/MS) approaches, to be eliminated. Detection of 86% of the analytes present was consistently achieved at levels of 2 ng/g (per each apple or orange) and 10 ng/g (per grape). A resolution study was conducted with four pairs of isobaric compounds analyzed at a mass resolution of 100 000. Baseline separation was achieved with analyte ions differing in mass by 25 ppm and analyte ions with a mass difference of 10 ppm were partially resolved. In addition, field samples that had undergone traditional sample preparation using QuEChERS (quick, easy, cheap, rugged, and safe) were analyzed using both LC/MS and DART-MS and the results from the two techniques were found to be comparable in terms of identification of the pesticides present. The use of swabs greatly increased sample throughput by reducing sample preparation and analysis time.

A rapid screening method for pesticides has been developed to streamline the processing of produce entering the United States. Foam swabs were used to recover multi-class mixtures of 240, 140, 132 and 60 pesticides from the surfaces of apples, kiwis, peaches and tomatoes. The mixtures were selected to span a large range of chemical classes, polarities, solubilities and sizes to provide a broad look at how this technique will perform for a variety of analytes. The swabs were analysed using direct analysis in real-time (DART) ionisation coupled with a high-resolution Exactive Orbitrap™ mass spectrometer. This study expands the types of commodities analysed using this method and explores the feasibility of compositing multiple units of produce per batch to analyse a representative sample. It was established that whilst smooth-skinned produce, such as apples, maintained a high detection rate for the pesticide mixtures even when ten apples are swabbed with one foam disk, commodities with rougher surfaces, such as peaches, suffered a decrease in detection rate when ten peaches are swabbed with one foam disk. In order to maintain some consistency across the sample preparation process, a composite size of three units was selected. The varying topography of the commodities necessitated minor modifications to the method; for example, analysis of kiwi required that the hair on the surface be shaved prior to swabbing to achieve good recovery. Additionally, the effect of storage conditions on detection rate was analysed by spiking the surface of tomatoes at levels of 5 and 10 ng g(-1) for each pesticide, storing them under refrigeration and ambient conditions for 3 and 8 days, and then analysing the surface using this method. After 8 days of storage under both conditions more than 80% of the pesticides in the mixture were detected. Also, analysis of the multi-class mixtures was performed in both positive- and negative-ion mode and many classes were detected in both modes. Some classes, such thiocarbamates, phenylamides and organochlorine pesticides, were only observed in the positive-ion mode, whilst benzoylphenylurea pesticides were only detected in the negative-ion mode.

U.S. food imports have been increasing steadily for decades, intensifying the need for a rapid and sensitive screening technique. A method has been developed that uses foam disks to sample the surface of incoming produce. This work provides complimentary information to the extensive amount of published pesticide fragmentation data collected using LCMS systems (Sack et al. Journal of Agricultural and Food Chemistry, 59, 6383-6411, 2011; Mol et al. Analytical and Bioanalytical Chemistry, 403, 2891-2908, 2012). The disks are directly analyzed using transmission-mode direct analysis in real time (DART) ambient pressure desorption ionization coupled to a high resolution accurate mass-mass spectrometer (HRAM-MS). In order to provide more certainty in the identification of the pesticides detected, a library of accurate mass fragments and isotopes of the protonated parent molecular ion (the [M+H]⁺) has been developed. The HRAM-MS is equipped with a quadrupole mass filter, providing the capability of "data-dependent" fragmentation, as opposed to "all -ion" fragmentation (where all of the ions enter a collision chamber and are fragmented at once). A temperature gradient for the DART helium stream and multiple collision energies were employed to detect and fragment 164 pesticides of varying chemical classes, sizes, and polarities. The accurate mass information of precursor ([M+H]⁺ ion) and fragment ions is essential in correctly identifying chemical contaminants on the surface of imported produce. Additionally, the inclusion of isotopes of the [M+H]⁺ in the database adds another metric to the confirmation process. The fragmentation data were collected using a Q-Exactive mass spectrometer and were added to a database used to process data collected with an Exactive mass spectrometer, an instrument that is more readily available for this screening application. The commodities investigated range from smooth-skinned produce such as apples to rougher surfaces like broccoli. The minimal sample preparation and absence of chromatography has shortened the analysis time to about 15 min per sample, and the simplicity and robustness of the technique make it ideal for rapid screening.