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HRMS Analysis of PAH and Alkylated PAH

HRMS Analysis of PAH and Alkylated PAH. Dave Hope, Pacific Rim Laboratories Inc. PAH Structure . Fused aromatic rings 2-ring Naphthalene 3-ring Acenaphthene Acenaphthylene Fluorene Phenanthrene Anthracene 4-ring Fluoranthene Pyrene Benz(a)anthracene Chrysene

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HRMS Analysis of PAH and Alkylated PAH

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  1. HRMS Analysis of PAH and Alkylated PAH Dave Hope, Pacific Rim Laboratories Inc

  2. PAH Structure Fused aromatic rings 2-ring Naphthalene 3-ring Acenaphthene Acenaphthylene Fluorene Phenanthrene Anthracene 4-ring Fluoranthene Pyrene Benz(a)anthracene Chrysene 5-ring Benzofluoranthene Benzo(a)pyrene Dibenz(ah)anthracene 6-ring Indenopyrene Benzo(ghi)perylene

  3. Methods of Analysis • GC/FID – requires good clean-up, DLs in ppm range • LC with UV and fluorescence detectors • GC/MS – most common approach • EPA 8270, 625, 525 (full scan methods) • Selected ion monitoring with good clean-up DLs of 1 ppb (soil) 10 ng/L water • Surrogates added, however quantitation is by Internal Standard

  4. Why PAH by HRGC/HRMS? • Commercial labs run routine PAH at “high: levels • Regulation in soil are ppm level • Lowest regulation in water is 10 pg/L • 2005 fire in commercial freezer potentially contaminated tons of fish stored there in • Needed to develop a method for detecting PAH in tissue at 0.1-0.3 ppb (ug/kg)

  5. What standards to use? • EPA methods use Internal Standard • Choices were deuterated PAH or 13C-PAH • Deuterated PAH • more economical • subject to loss of deuterium (d-10 Fluorene) • Elute 2-4 seconds prior to native PAH • 13C-PAH • Very stable • Elute at same RT as native

  6. ES-4087 US EPA 16 PAH Cocktail (13C, 99%)(Cambrige Isotope Labs) Chrysene (13C6, 99%) Dibenz[a,h]anthracene (13C6, 99%) Fluoranthene (13C6, 99%) Fluorene (13C6, 99%) Indeno[1,2,3-cd]pyrene (13C6, 99%) Naphthalene (13C6, 99%) Phenanthrene (13C6, 99%) Pyrene (13C6, 99%) • Acenaphthene (13C6, 99%) • Acenaphthylene (13C6, 99%) • Anthracene (13C6, 99%) • Benz[a]anthracene (13C6, 99%) • Benzo[b]fluoranthene (13C6, 99%) • Benzo[k]fluoranthene (13C6, 99%) • Benzo[g,h,i]perylene (13C12, 99%) • Benzo[a]pyrene (13C4, 99%)

  7. Sensitivity not an issue – 3 pg injected (13C-PAH @ 100 pg)

  8. MDL Water 12 real world samples unfortified pH 10 50 ng of 13C-PAH Liquid/liquid extraction with DCM Final volume 1 mL

  9. Blank Issues

  10. Limitations - background 3 solvent blanks -external standard 500 uL DCM with 25 ng 13C-PAH 500 uL DCM with 25 ng 13C-PAH Plus 25 ng of recovery standard (2-Me Naph d10, Terphenyl d14, Perlylene d12) All standards are >99% To get lower detection limits use smaller amounts of 13C-PAH (i.e. 5 ng)

  11. PAH in Tissue 10 g of homogenized tissue Fortify with 50 ng of 13C-PAH 10 g of NaOH 100 mL of Methanol Reflux for one hour and add 50 mL of water

  12. Effect of pH on 100 ng/L spike (50 ng/L 13C-PAH

  13. Soap! • Keep adding water until emulsions disappear (3 – 6 Litres) • Column on silica gel • Final volume 1 mL

  14. MDL Tissue 8 – 10 g sole filets spiked at 0.5 ng/g

  15. Alkylated PAH • 5 point calibration • 16 native PAH @ 3-300 ng/mL • 16 13C-PAH constant at 50 ng/mL • Single point calibration for alkylated PAH • Resolution 3000 • Single point cali for alkylated PAH • C1-C4 Naphthalene, Dibenzothiophene, Phenanthrene/Anthracene • C1-2 Flan/Pyrene, BaA/Chrysene, Bflan/Benzopyrene • Alkylated Standards obtained from Chiron (www.chiron.no) • Phenomenex SVOC column (30 m)

  16. Naphthalene Dibenzthiophene BaA/Chrys Phen/Anth Flan/Pyrene Bflan/BPyrene

  17. Naphthalene Alberta Crude Oil Me-Naphthalene C2-Naphthalene C3-Naphthalene C4-Naphthalene

  18. Alberta Crude Oil Phenanthrene/Anthracene Me Phen/Anth C2-Phen/Anth C3-Phen/Anth C4-Phen/Anth

  19. Dibenzthiophene Alberta Crude Oil BaA/Chrysene Flan/Pyrene BFlan/BPyrene

  20. Tissue Sample 10 g Naphthalene Me Naph C2 Naph C3 Naph C4 Naph

  21. Tissue Sample 10 g Phen/Anth Dibenzthiophene

  22. Tissue Sample 10 g BaA/Chrys Bflan/Benzopyrenes

  23. Crab meat near oil spill

  24. Alkylated PAH

  25. Thank you Thank You Great Barrier Reef August 2012 Napoleon Wrasse

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