PowerPoint PresentationFlavors and FragrancesHypothesisRelevanceAnalytical TechniquesHPLC-MS/MS AnalysisExperimentationSlide 8HPLC-MS/MS ConceptFigures of MeritSummaryAdditional ReferencesTransfer of pesticides from commodities to natural flavors and aroma chemicalsIan RonningenChem 4101December 9, 2011Flavors and Fragrances•Aroma chemicals are extracted from commodities through a number methods•Mechanical pressing•Solvent extraction•Distillation•Expression•These extracts are commonly concentrated and then sold as fragrances or flavorsAtrazine WarfarinDiazinonHypothesisExtraction processes commonly used to separate flavors and aroma chemicals from commodities also extract pesticides Extracted pesticides could make their way to consumers either through foods (flavors) or fragrances (aroma chemicals)Pesticides present have the potential to pose either a chronic or acute health risk1. Muzaurieta, Annie Bell. "Vitamin C Foods." The Daily Green. Web. 4 Dec. 20112. "OMG! Cookies." Poached Prose. Web. 04 Dec. 2011. <http://poachedprose.wordpress.com/2010/08/02/omg-cookies/>Orange, Source of Expressed orange oil(1)Potential Final Application (2)RelevanceTo gain a competitive advantage flavor houses are increasingly sourcing rare commodities which come from countries that generally have less regulation surrounding pesticidesCommodity testing is limited, and screens limited number of pesticides. Screening focus is towards pesticides used in the United States. If any pesticide ended up harming a consumer the producer of the food or fragrance would see massive economic backlash1. Borneo Rainforest - Borneo Malaysia." Online Travel Guides of Travel Destinations -. Destination 360.Borneo Rainforest(1)AlachorAnalytical TechniquesSeparationTechnique Positive NegativeHPLC High sample throughput, numerous separation mechanisms, large variety of samples analyzed, AOAC sample preparation (QueChers)High solvent costs, co-elution an issue, GC Moderate sample throughput, high resolution, numerous separation mechanismsDerivatization maybe required, sample preparation may be laborious, thermal degradation is possibleCE Good separation, resolution can be made high, small sample sizePoor selectivity for similar analytes, may require numerous separations of one sampleDetection MethodsMethod Positive NegativeMass Spectrometry (triple-quad)Established libraries, highly selective, sensitivity adequate for expected concentrationExpense, sensitivity may be low without concentration stepFlourescence High sensitivity Low selectivity, some compounds may need to be derivitized, no library availableHPLC-MS/MS Analysis•High sample throughput, automated, rapid analysis, ability to deal with complex matrices•Mass Spectrometer has high analytical selectivity•Established Mass Spectra Libraries simplifies data analysis•Many stationary phases available for wide application•C18 is a good starting point, Phenyl Hexyl also an option•Online SPE Also an option for higher sample throughputExperimentationIncoming CommoditiesWashingExtractionFinal ProductSample and analysisSample and analysisSample and analysisSample and analysisAddition of internal standards of phenolic butyl-parabensControl Experiments:•Sample organic or hydroponic commodities (for incoming and extraction, and final product)•Sample unused wash water"15 Eccentric Endangered Trees, Plants, and Flowers | WebEcoist." WebEcoist. Web. 07 Dec. 2011"Citrus Processing." Triowin. Web. 07 Dec. 2011HPLC-MS/MS Analysis1. Morphed, James, and Peter Hancock. “A RAPID METHOD FOR THE SCREENING AND CONFIRMATION OF OVER 400 PESTICIDE RESIDUES IN FOOD“ Waters Application Notes. Tech. Waters, 2008. Web. 1 Dec. 20112. AOAC Official Method 2007.01, Pesticide Residues in Foods by Acetonitrile Extraction and Partitioning withMagnesium Sulfate3. QuEChERS-A Mini-Multiresidue Method for the Analysis of Pesticide Residues in Low-Fat Products. ResTek Application Notes. SampleSample preparation and clean up Separation and characterization•Reference to established libraries•Unidentified peaks will be further investigatedRestek QuEChERS sSPE tubes are an AOAC Method for Prep.Available (1,2).Include:•C18, MGSO4, PSA, GCBHPLC-MS/MS ConceptHPLCSeparation of compounds from matrix based off interaction of compounds with stationary and mobile phasesMass SpectrometerIonization of analytes happens at the source, MS can either be used to scan or it can be operated in MS/MS utilizing collision cell and second quadrapole to analyze fragmentation patterns 1. “HPLC Separation Modes” Waters Application Notes, Waters Corporation. 2011.2. “Mass Spectrometry Introduction." Department of Chemistry , University of Pittsburgh. Diagram of Separation (1)Diagram of Triple-quad (2)Figures of Merit(1)Xu, Y. "Simultaneous Determination of Flonicamid and Its Metabolites in Vegetables Using QuEChERS and Reverse-Phase Liquid Chromatography Tandem Mass Spectrometry." Journal of chromatography. (2011). Figure LevelExpected analyte concentration after SPE1-500 ppmDesired Limit of detection* 10 ppbXevo TQD limit of detection (1) 0.2 ppbRequired Accuracy* 1-2 ppb*Figure and requirements depends on the analyte, since instrument response and level in extract is dependent on pesticideSummary•Sampling along the line of extraction of aroma chemical from commodities will allow investigation of safety of these products•HPLC-MS/MS Analysis allows for effective separation of pesticides from complex matrix and effective analysis of pesticides in natural flavors and fragrances extracted from commodities•Although added cost of a MS/MS instrument is high added selectivity and sensitivity justify costAdditional References•AOAC Official Method 2007.01, Pesticide Residues in Foods by Acetonitrile Extraction and Partitioning with Magnesium Sulfate.•Culliney, T W. "Pesticides and natural toxicants in foods." Agriculture, ecosystems & environment 41.3-4 (1992):297-320•Davies J, Barquet A, Vaclavek C, et al. Human Pesticide Poisonings by a Fat-Soluble Organophosphate Insecticide. Archives of Environmental Health. December 1975;30(12):608.•Picó, Y. "Environmental and food applications of LC–tandem mass spectrometry in pesticide‐residue analysis: An overview." Mass spectrometry reviews 23.1 (2003):45.•Reineccius, Gary. Flavor Chemistry and Technology. Boca Raton : Taylor & Francis, c2006.•Schreiber, A. "Application of spectral libraries for high-performance
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