PesticideScreener. Innovation with Integrity

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1 PesticideScreener A complete multi-residue solution for pesticide screening using high resolution full scan accurate mass data Innovation with Integrity LC-MS

2 The Challenge of Ever Increasing Number of Targets Pesticides have become a ubiquitous element in our food production cycle. As a consequence, their residues in consumers products must be suitably controlled. Accurate and reliable screening for the presence of pesticides in food is therefore a critical analytical task. However, this task is far from simple. The increasing number of target compounds with ever-lower detection thresholds poses special analytical challenges, with hundreds of different pesticide targets assessed during the analysis of each food sample coming from a vast variety of different food products. A Ready-To-Go Solution in Your Hands Bruker s PesticideScreener delivers a comprehensive screening solution for pesticides and plant metabolites in food. Market-leading Q-TOF mass spectrometry technology is combined with a high-quality compound database and a rigorously tested method, ready developed using SANCO guidelines. Identification of compounds is based on combined scoring of mass accuracy, isotopic patterns and retention times and, optionally, MS/MS qualifier ion fragment data. The powerful package enables confident and comprehensive multitarget analysis of pesticides in food in a single LC-MS run.

3 Our Workflow Solution Sample Pesticides QuECHERS extract food, feed, water LC-QTOF-MS U-HPLC + maxis impact Sub-ppb sensitivity Full sensivity resolution 1- mda hrxic true isotope pattern Multi-target screening application s/w One shot qual/quant analysis with no method development Processing: TargetAnalysis High Quality Pesticide Database In-silico retrospective analysis of new targets Identification Confirmation Quantitation Reporting maxis impact delivering wide dynamic range for quantitation of screening results: example calibration curve for methomyl Complete solution consisting of U-HPLC & QTOF hardware, applications software, ultra-stable LC-MS methods for the entire workflow. Plus high-quality multi-target screening database.

4 Automation & High-Quality Database Ready-to-go, no method development required At the heart of Bruker s Pesticide Screener is a high-quality database of more than 7 target pesticides. Far more than a list of compounds Retention times for the matched UHPLC method Adduct information Isomer information Fragment ions on MS data level Isotopic confirmation Qualifier ions for confirmation in broad band MS/MS mode For definitive analyte detection Processing is completely automated with TargetAnalysis Level of confidence Results Overview Detailed report on bbcid qualifier ions 3 Data are screened and scored against the database information for at-a-glance confidence Use qualifier ions (and their intensity ratios) from broad band MS/MS for enhanced confirmation (++++) Enables fast and reliable identification of target compounds at ppb levels, with very low false positive rates even in complex matrices Get quantitative results via integrated link to quantitation software Perform in-silico retrospective analysis of new targets at a click of a mouse

5 x Amitrole Methamidophos Time [min] Methomyl Fragm 88 Oxamyl Fragm 7 Oxamyl Fragm Methomyl Monocrotophos 9 Fragm 17 Carbendazim Aldicarb Fragm 116 Thiabendazole Carbaryl Fragm 145 Carbofuran Pirimicarb Metalaxyl Phosmet Fragm 16 Azoxystrobin Acetamiprid Quinoxyphen Thiacloprid Triazophos Spinosad A Indoxacarb (Spinosyn A) Monocrotophos Dimethoate Carbofuran Fragm 165 Bifenthrin (NH4) Methomyl Fragm 16 Linuron Tebufenozide Kresoxim-methyl Fragm 97 Imidacloprid Monocrotophos Fragm 98 Butocarboxim Aldicarb Fragm Fragm Penconazole Prochloraz Cyhalothrin. lambda- (NH4) Omethoate Imazalil Methoxyfenozide Fragm 313 Profenophos Tebuconazole Carbaryl Phosmet Fludioxonil (NH4) Difenoconazole Peak 1 Boscalid Azinphos-methyl Fragm 13 EPN Propargite Chlorpyriphos Fragm 31 Monocrotophos Fragm 193 Carbendazim Fragm 16 Azinphos-methyl Fragm Dimethomorph Methoxyfenozide 16 Peak Dimethoate Fragm 199 Kresoxim-methyl Tolyfluanid Tolyfluanid Fragm 137 Indoxacarb 6 (Na) Dimethomorph Chlorpropham Peak Fenhexamid Myclobutanil Fragm 17 Ethion Fragm 199 Triadimenol 1 Tebufenozide Spinosad A (Spinosyn A) Fragm 544 II Fragm 7 Etofenprox Fragm 359 Tolyfluanid (NH4) Pendimethalin Chlorantraniliprole Oxamyl (NH4) Tolyfluanid Fragm 38 Spinosad D Pendimethalin Cypermethrin Fragm 1 II (NH4) Azinphos-methyl Azoxystrobin (Guthion) Fragm 37 Omethoate Fragm Oxamyl 183Monocrotophos (NH4) Triadimenol I Fragm 7 Butocarboxim Aldicarb (NH4) Carbaryl (NH4) Triadimenol II Prochloraz Fragm 38 Cyhalothrin. Cypermethrin AvermectinB1a lambda- (Na) III (NH4) (Abamectin) (NH4) Phosmet (NH4) Chlorpropham Kresoxim-methyl (NH4) Chlorpyriphos-methyl Spinosad D (Fragm 558) Fludioxonil Triadimenol II (Na) Spinosyn B or K (last of 3-4 peaks) Propargite Cypermethrin AvermectinB1a II (Na) III (Na) (Abamectin) (Na) Pyrimethanil Cyprodinil Diazinon Pyraclostrobin Trifloxystrobin Pyriproxyfen Propargite (NH4) Ethion Etofenprox (NH4) Time [min] High Precision Data Means Ultimate Selectivity hrxic = High-resolution extracted ion chromatogram / XIC of the mass +/- mda BPC Carbofuran Fragm 165 Linuron Imazalil Methoxyfenozide Fragm 313 x Carbaryl Carbaryl (NH4) Phosmet Fludioxonil (NH4) Boscalid Azinphos-methyl Fragm 13 Azinphos-methyl Fragm Dimethomorph Methoxyfenozide 16 Peak Dimethomorph Chlorpropham Peak 1 Fragm 17 Chlorantraniliprole Azinphos-methyl Azoxystrobin (Guthion) Fragm 37 Phosmet (NH4) Fludioxonil hrxic 8 x MS, min #53-536, found: Phosmet (C 11 H 1 N 1 O 4 P 1 S, , [ [M+H]+: ]) phosmet, experimental, full scan Phosmet(C ₁H₁₂N₁O₄P₁S₂, , err[mda]: -.15, msigma: 9.1) theoretical m/z 41. +MS, min #53-536, found: Phosmet (C 11 H 1 N 1 O 4 P 1 S, , [ [M+H]+: ]) Phosmet(C ₁H₁₂N₁O₄P₁S₂, , err[mda]: -.15, msigma: 9.1) ID by mass accuracy/isotope pattern m/z High-resolution extracted ion chromatograms are used to pull components out of complex matrix backgrounds. Interrogating the compound database, accurate-mass and isotopic fits are calculated and checked automatically, along with retention times and, where necessary, fragment ions. This combination of data definitively confirms the presence of target pesticides.

6 Result confirmation by parallel detection of diagnostic ions The impact of knowing compound behavior Proof of identity, detection of adducts and fragments for unambiguous identifications x CVUA_-5_1ppm_RA1_1_17.d Aldicarb same sum formula, almost coeluting, no M + H detectable Butocarboxim: m/z 75: C 3 H 7 S 4 Butocarboxim [M+NH 4 ] Time [min] Aldicarb: m/z 89: C 4 H 9 S Only a screening database with knowledge about fragmentation behaviour yields to correct identifications. Reconfirmation: detection of adducts and fragments for enhanced confidence in findings x Methiocarb Fragm Halofenozide Fragm 75 7 Promecarb Fragm CVUA_-5_1ppm_RA1_1_17.d Fenobucarb 1 Fenobucarb Fragm 15 Fenobucarb Fragm 95 Fenobucarb Fragm Fenobucarb (NH4) 19 Methiocarb/Mercaptodimethur 3 Promecarb 36 Halofenozide Fragm 15 8 Promecarb Fragm Halofenozide (Na) 5 Halofenozide 6 Fludioxonil Fragm 9 Fludioxonil (NH4) Methiocarb (NH4) Fludioxonil Time [min] In this example, the identification of Fenobucarb is re-confirmed by the presence of 4 diagnostic ions (3 fragment ions, NH4-adduct).

7 Azoxystrobin 44 1ppb_bbCID_Orange_ul_RB4_1_853.d Time [min] +MS, found: Azoxystrobin (C H 17 N 3 O 5, , [ [M+H]+: ]) Why Use bbcid Fragment Ions? What is bbcid? Alternative acquisition of full scan data with/without fragmentation. Example of interference in Orange, spiked 1 ppb x1 6 Azoxystrobin BPC XIC@ m/z43 In this spectrum, an interference peak m/z 43 is masking azoxystrobin m/z 44 But, the CID method generates fragments in parallel Each individual fragment is identified by accurate mass, isotope pattern and intensity ratio x azoxystrobin, experimental, full scan ! Reference: SANCO/1495/11: Method validation and quality control procedures for pesticide residues analysis in food and feed: Where an ion chromatogram shows evidence of significant chromatographic interference, it must not be relied upon to quantify or identify residues.. x bbcid MS, 5.eV (.5), (-1.4), : points : 3 bbcid So, azoxystrobin is still definitively identified The database contains qualifier ions for species which may require extra information (-1.4), %I (.5), %I m/z and m/z are qualifier ions. Brackets represent relative intensity range. Highlest level of confidence: ID by mass accuracty, isotopic pattern and adduct information Confirmation by diagnostic ions and bbcid Very low false positive rates

8 Bruker Daltonics is continually improving its products and reserves the right to change specifications without notice. BDAL 9-1, #7316 maxis impact: Highest Performance Benchtop Q-TOF One, no compromise mode: Resolution and speed simultaneously for coupling to high-res LC Full Sensitivity Resolution (FSR) One shot method Excellent sensitivity, high dynamic range True Isotope Pattern (TIP): For ultimate confidence in the molecular formula Extracted ion chromatograms (hrxic) +/- 1 mda Resolution (FWHM) Maximum Speed (spectra/second) MS and MS/MS Accuracy/ppm maxis impact 4, 5.8 True Isotope Pattern confidence PesticideScreener Solution: Ultimate robustness of LC methods System-to-system reproducibility <.1 min RT Ultimate confidence in results Ready-to-go with methods and high quality database For research use only. Not for use in diagnostic procedures. Bruker Daltonik GmbH Bremen Germany Phone +49 ()41-5- Fax +49 () sales@bdal.de Bruker Daltonics Inc. Billerica, MA USA Fremont, CA USA Phone +1 (978) Phone +1 (51) Fax +1 (978) Fax +1 (51) ms-sales@bdal.com ms-sales@bdal.com