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Evolution in the Sample Preparation for the Measurement of POPs in Biological Matrices

Evolution in the Sample Preparation for the Measurement of POPs in Biological Matrices. J.-F. Focant. MS Laboratory Organic and Biological Anal. Chem. Human Exposure?. Non-occupational exposure (adults) > 90% due to food Invasive unpopular human biomonitoring

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Evolution in the Sample Preparation for the Measurement of POPs in Biological Matrices

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  1. Evolution in the Sample Preparation for the Measurement of POPs in Biological Matrices J.-F. Focant MS Laboratory Organic and Biological Anal. Chem.

  2. Human Exposure? • Non-occupational exposure (adults) • > 90% due to food • Invasive unpopular human biomonitoring • analyses of foodstuffs (feed, …) • Analyticaly challenging…

  3. A ‘Good’ Kick… Coût : 400 106 € (0.21% PIB) 1 gouvernement Time axis Focant and De Pauw, Les Dioxines. La Recherche323 (1999) 84. Cost : 1 government and 1-2 billions €… 7 106 chickens & 50,000 pigs slaughtered

  4. EU Commission Strategy (food-feed) • Maximum levels set as ALARA • MRL strategy(SANCO/11248/2011 & 11515/2011) • Uniform sampling and analysis criteria • Comprehensive & reliable data Robust tools needed…

  5. Analytical Criteria • Commission Regulation 1883/2006 • Commission Regulation 152/2009 • EPA1613B • prEN16215 (feed) • PBMS (different modules) • Module B: Extraction • Module C: Clean-up Manual or automated

  6. Today’s Capacity • D+1 Fat matrices (regular input) • D+3 Feed matrices (regular input) • D+5 All matrices (irregular input)

  7. Automated Solution

  8. prEN16215 Module B: Extraction

  9. Parallel PLE Extraction, solventreduction and exchange

  10. Automated PLE 70-85 min. + 5-25 min wash time = 75-110 min cycle time

  11. Control software

  12. Traceability of Events P(psi) T(C) 1800 150 1500 125 Heat & Pressurize Cool & Depressurize 0 0 27 37 45 Time (min.) Pressure: Chan. 1 Chan. 2 Chan. 3 Temperature: Chan. 1 Chan. 2 Chan. 3

  13. 1-6 lines system

  14. Natural Feed QC

  15. Online Solvent Reduction • 6 lines system • N2 flow • T prog. • No water bath • Solvent exchange • Dustfilter in

  16. PLE Properties • Stand-alone automated parallel system • Up to 6 samples at a time (modular) • 1.8h / 6 samples (cycle time) • Wide bore plumbing (no pump cavitation) • PLE is an ‘old’ and proven concept • Robust and versatile (various cell sizes) • Easily usable under QA/QC requirements • Good throughput / cost effectiveness ratio

  17. prEN16215 Module C: Clean-up

  18. Parallel Clean-up and Fractionation

  19. 1) Hexane 90ml 2) 50:50 100ml Waste 3) Hexane 10ml PCBs Waste 4) Toluene Extract in hexane (20 ml) Silica Alumina PCDD/Fs & NO-PCBs Carbon

  20. Automated Clean-up 75 min. + 15 min wash time = 90 min cycle time

  21. Manual Smith et al. setup

  22. 1-6 lines system

  23. Previous generation Current generation

  24. Previous generation Current generation Previous generation Current generation

  25. Tracability by Lot # • Good stability • Good lot-to-lot reproducibility • ‘PCB-free’ , ‘PBDE-free’ columns…

  26. Natural Spray Dried Milk Experiment CR values 10.5±2.4 26.2±0.4 4.8±0.4 BCR-607 (n=3) (PCDD/Fs + cPCBs in ppt, other PCBs in ppb) RSDs < 20% Recovery rates inside EU Directive range

  27. QC Serum Samples (n=4) (PCDD/Fs + cPCBs in ppt, other PCBs in ppb) RSDs < 10% Recovery rates in the high 60% range

  28. Online Solvent Reduction • 100 mL Hx/DCM to 500 µL • 80 mL toluene to 500 µL • Nitrogen flow • 30°C, heating metal block

  29. Sample Clean-up Properties • Stand-alone automated parallel system • Up to 6 samples at a time (modular) • 1.5h / 6 samples (cycle time) • Disposable Si, Al, and C • 20 year old concept, many revisions since then • Robust and versatile (various column sizes) • Easily usable under QA/QC requirements • Good throughput / cost effectiveness ratio

  30. Global Solution

  31. The Integrated Approach 13C spiking Solvent exchange Lipid Determination Keeper Several fractions PTV-LVI PLE Keep it open SR-1 Clean-up & Fractionation SR-2 GC-MS

  32. Time Scale • Condition the clean-up system • Fill PLE cell • Heat and presurize • Cool, nitrogen purge to evaporator • Reduce volume (on the go) • Load on silica • Elute silica with hexane • Elute alumina with 50:50 (PCBs) • Back-elute carbon with toluene (D/Fs) 25 min 25 min per cycle 30 min 40 min Total time : 2 to 3h per sets of 6 samples in parallel

  33. Same-Day Testing Capability • Sample preparation for PLE 0.5 h • Parallel PLE (2 cycles) 1.5 h • First solvent reduction 0.5 h • Parallel Clean-up and fractionation 2 h • Second solvent reduction 1.5 h • Std addition and transfer to GC 0.1 h • PTVLVI-GC-IDHRMS 1 h • QA/QC check and reporting 0.5 h • TOTAL ~ 8 h

  34. The missing link (2009)... PLE-Vap-PrepLC-GCxGC-PTVLVI-IDEIHRMS

  35. The missing link (2012)... Std addition & injection on TriPlusTM Autosampler

  36. What Next for Tomorrow ? • Dioxin testing is getting faster and more reliable • Confirmatory approach status changed… • Confirmatory not too far from screening… • EU strategy to be revisited ? • Focus on ‘better’ use of CALUX

  37. Not to Forget… • Dioxin testing remains a task for chemists… • Keeping blank levels under control is crucial… • ‘Simplifying’ the MS side is one thing, keep • performing state-of-the-art sample preparation is • another one… • Fast and reliable does not mean trivial…

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