PesticideScreener. Innovation with Integrity. Comprehensive Pesticide Screening and Quantitation UHR-TOF MS

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1 PesticideScreener Comprehensive Pesticide Screening and Quantitation Innovation with Integrity UHR-TOF MS

2 The Challenge of Comprehensive Pesticide Residue Analysis The use of pesticides to reduce crop damage and increase horticultural productivity has been implemented on a global scale for many decades. Due to their toxicity, the potential migration of these chemicals into the human food and water supply chains presents considerable health concerns for the population at large. Therefore the maximum residue level (MRL) permitted for pesticides in food, feedstuffs and water are strictly controlled by local and international regulatory bodies. One of the most important aspects in reducing pesticide exposure is to monitor their levels in food and the environment. However, with increasing demands for lower detection thresholds to cover hundreds of pesticides originating from numerous sample types, accurate and reliable pesticide screening is a critical and complex analytical task. The Bruker PesticideScreener is a powerful liquid chromatography-mass spectrometry solution developed to meet these challenging demands. The solution intelligently exploits high resolution, accurate mass measurements, enabling you to spend less time on method development and more time confidently screening, confirming and quantifying pesticides. A ready to go solution...in your hands Semiquant The choice is yours!

3 The Power of Accurate Mass for Screening and Quantitation The Bruker PesticideScreener is based on industry leading Liquid Chromatography - Quadrupole Time of Flight (LC-QTOF) accurate mass technology. The use of accurate mass for trace pesticide residue screening has significant throughput and cost-saving benefits as it potentially allows for an unlimited number of pesticides to be analyzed in a single run without the need to use expensive standards for every compound. Sample Fruit / vegetable: QuEChERS Water: SPE, LLE or direct injection LC-QTOF UHPLC + Bruker QTOF Chromatographic separation with accurate mass bbcid data acquisition Identification Confirmation Report Exact Mass Pesticide Database containing multiple qualifier ions per pesticide and retention time information TASQ TM Screening and Quantitation software The Bruker PesticideScreener: Screen, confirm and quantify hundreds of pesticides in 20 minutes Add or remove compounds from the database to meet the changing needs of your laboratory. Fig.1: PesticideScreener complete solution consisting of UHPLC and QTOF hardware, TASQ applications software, accurate mass pesticide database and a verified analysis protocol for the entire workflow.

4 Broadband CID (bbcid) Data Acquisition Measurement of the precursor accurate mass and retention time alone can lead to a high number of false positive results, particularly with complex matrices such as QuEChERS extractions. However by including diagnostic qualifier ion (QI) information as a mandatory requirement in the confirmation criteria, false positive detections are practically eliminated, delivering maximum confidence in your screening result. Accurate mass measurement Confidence in ID Precursor ion monoisotopic mass (M+H) or adduct e.g. (M+Na) Retention time (R t ) First isotope (M+1) Qualifier Ions (QI s) Possible detection, with very low confidence in ID Plausible ID Tentative ID High Confidence ID Cumulative Increase in Confidence Fig.2: Illustrating the accumulation of retention time and qualifier ion information to reduce false positive detections The Bruker PesticideScreener continuously generates fragment ions using broadband Collision Induced Dissociation (bbcid). During the complete screening process, the QTOF mass spectrometer rapidly and continuously cycles between low collision energy (TOF-MS) and elevated collision energy (bbcid) MS/MS, resulting in the seamless collection of accurate mass precursor and fragment ion data in a single analysis. The ability of the PesticideScreener to detect all of the ions, all of the time in full scan MS and MS/MS modes without compromising sensitivity or resolution, results in a dataset that is complete and unrestricted. The diagnostic Qualifier Ions (QI s) can then be used as a part of an enhanced pesticide confirmation criterion to eliminate false positive findings as well as delivering unambiguous ID s for closely eluting similar pesticides (see figures 2-6).

5 Eliminate False Positive Findings and Achieve Unambiguous ID s At the heart of the PesticideScreener solution lies the accurate mass pesticide database. In addition to monoisotopic precursor ion masses and retention time data, the database also contains diagnostic QI information, comprising of accurate mass bbcid fragments and in source fragment ions as well as adduct and isomer information (see figure 3). The PesticideScreener retention time tolerances can be independently adjusted by the user for each pesticide The analyst can assign any ion(s) as mandatory to meet confirmation/ exclusion criteria Tolerances for EIC width, intensity / area threshold, isotopic fit etc. can be adjusted by the user for each ion of every pesticide Multiple qualifier ions (QI s) can be specified for every pesticide PesticideScreener accurate mass database includes bbcid fragment ions, adducts, isomer and retention time information. Fig.3 Snapshot of the PesticideScreener accurate mass and retention time database The detection of diagnostic QI s can be specified as a mandatory requirement as part of the confirmation criteria. Figure 4 shows how unique mandatory QI s enable two closely eluting isomeric pesticides (terbutryn and prometryn) to be clearly distinguished from each other. Prometryn and terbutryn pesticides C 10 H 19 N 5 S: R t ~10 seconds Fig.4: High resolution XIC traces for qualifier ions unambiguously differentiate isomeric pesticides prometryn and terbutryn

6 Intelligent Data Review Data processing for screening and quantitation is powered by TASQ (Target Analysis for Screening and Quantitation) software. TASQ intelligently uses the diagnostic QI s to reduce false positive detections, bringing a new level of confidence to screening workflows (see figures 5 and 6). Color coded screening results are easily reviewed in either a sample centric or analyte centric fashion as desired by the analyst. Once reviewed, qualitative and quantitative sample reports are then easily generated. Top pane: Screening result table for an orange QuEChERS extract showing positive pesticide identifications highlighted in green Lower left pane: Overlaid confirmatory qualifier ion traces for carbendazim Lower right pane: Fit of experimental isotopic pattern against the theoretical isotopic pattern for carbendazim Fig.5: Example of TASQ screening results with confirmatory qualifier ion and isotopic pattern information TASQ enables the analyst to specify multiple QI s in the PesticideScreener data processing step. Figure 6 shows the clear and unambiguous positive ID of prometryn and terbutryn pesticides summarized by the color coded MRSQ column of the results table. Despite excellent agreement of the measured mass accuracy (<1ppm), retention time and isotopic pattern fit (m-sigma) scores, with the Pesticide- Screener database, the two pesticides are indistinguishable at the MS1 level After application of the diagnostic, qualifier ion confirmation criteria, the pesticides are clearly distinguished from each other Fig.6: PesticideScreener diagnostic QI screening result for closely eluting isomeric pesticides

7 Quantitation Over a Wide Dynamic Range If calibration standards are incorporated into the experiment, then a combined screening and quantitation experiment is realised without the need for a second sample injection. PesticideScreener, also supports semiquantitative workflows by exploiting single point and multi-point legacy calibrations functions to deliver new levels of productivity to your laboratory. Carbendazim in Orange Carbendazim 192 M+nH 193 M+nH bbcd QI Quantifier and qualifier hrxic traces for carbendazim in orange at 10 ppb. The presence of the confirmatory QI within the ion ratio limits provides additional confidence in the quantitative result Fig.7: Quantitation carbendazim in orange QuEChERS extracts using TASQ software. Linearity of calibration curve ,000ng/ml, R

8 Bruker Daltonics is continually improving its products and reserves the right to change specifications without notice. BDAL , PesticideScreener Applications Kit The PesticideScreener applications kit enables you to readily deploy routine pesticide screening and quantitation. Included within the applications kit are the analytical and guard columns, a test mix, accurate mass pesticide database and all the necessary chromatographic and mass spectrometric parameters that are needed to perform the screening workflow. The PesticideScreener is a ready to go solution, requiring no method development, delivering maximum productivity to your laboratory in the shortest possible time. Bruker PesticideScreener: Maximize your laboratory throughput; Spend less time on method development and more time producing high quality data For research use only. Not for use in diagnostic procedures. Bruker Daltonik GmbH Bremen Germany Phone +49 (0) Fax +49 (0) Bruker Daltonics Inc. Billerica, MA USA Phone +1 (978) Fax +1 (978)

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