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Chemistry Matters Dioxin2016 Analytical Summary

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Final day of the Dioxin 2016 conference in Florence, Italy, Dr. Court Sandau presented a summary of the analytical talks and posters presented at the Dioxin conference this year. Discussed the biggest highlights on PFAs, PBDEs, the history of Dioxin analysis and his impressions of where biomonitoring is going.

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Chemistry Matters Dioxin2016 Analytical Summary

  1. 1. © 2016 Chemistry Ma2ers Inc. 1 Dioxin 2016 – Florence, Italy Making chemistry data meaningful New Methods and Perspec=ve of Analysis Court Sandau, PhD Donald G. Pa2erson Jr., PhD2 September 2, 2016 Dioxin 2016, Florence, Italy
  2. 2. © 2016 Chemistry Ma2ers Inc. Looking for Inspira=on 2 Dioxin 2016 – Florence, Italy
  3. 3. © 2016 Chemistry Ma2ers Inc. 3 Quote for the day A people without the knowledge of their past history, origin and culture is like a tree without roots. – Marcus Garvey Dioxin 2016 – Florence, Italy
  4. 4. © 2016 Chemistry Ma2ers Inc. History is Important 4 Clement R et al., Analytical Chemistry, 1991, 63, 1130A–1139A. 1971 1988 Dioxin 2016 – Florence, Italy
  5. 5. © 2016 Chemistry Ma2ers Inc. Analy=cal Chemistry of the Time (1960s) 5 •  GC-ECD (only seeing electronega@ve compounds) and GC-FID very common •  Mass spectrometry s@ll quite specialized (but needed for iden@fica@on) •  Most analy@cal standards not made yet, need to be synthesized •  Packed GC columns provided very limited resolving power •  No personal computers or google searches •  Literature search began in library, with paper journals and took days/weeks Dioxin 2016 – Florence, Italy
  6. 6. © 2016 Chemistry Ma2ers Inc. PCB Metabolites Discovered 6 •  A decade later (1976), Dr. Soren Jensen s@ll analyzing PCBs in biota •  Le the laboratory in a hurry one evening •  Data was collec@ng on a Bal@c Seal sample •  A group of peaks elu@ng late from the GC- ECD •  Chemically synthesized standards to confirm iden@fica@on •  Iden@fied new compound group - metabolites of PCBs –  methylsulfonyl-PCBs –  Opened new research into the field of POP metabolites •  Comparing PCBs to metabolites, need as many PCBs as possible measured in the samples Jensen , Ambio 1976 Vol. 5, No. 5/6, 257-260 Swedish Environmental Protection Agency, Persistent Organic Pollutants, 1998, pp. 152. Dioxin 2016 – Florence, Italy
  7. 7. © 2016 Chemistry Ma2ers Inc. •  Chromatogram of early dioxin analysis of Agent Orange •  Inves@gators began by iden@fying all congeners for chlorinated dioxins and furans in the chromatograms –  210 congeners exist •  Using mass spectrometry and glass packed columns •  Synthesized compounds for posi@ve iden@fica@on 7 Rappe C et al., Chemosphere, 1978, 5, 431–438. Dioxin 2016 – Florence, Italy Rappe C, Gara A, Buser H.R, Chemosphere, 1978, 12, 981 – 991. Early Inves=ga=ons in Dioxin Contamina=on in Agent Orange and Chlorinated Phenols
  8. 8. © 2016 Chemistry Ma2ers Inc. DIOXIN-2016 Analy=cal Techniques GCxGC-TOFMS “Simpler” GCxGC-MS/MS Convergence Chromatography Timed-Cryogenic Zone Compression HRMS NCI-GC-HRMS LC-MS/MS APGC-MS/MS Bio-Assays GC-MS/MS “FASTER” GCxGC-QMS GCxGC-HRTOFMS No Targeted Analysis Parallel Dual-Column GCxGC-TOFMS LC-APCI-MS/MS Dioxin 2016 – Florence, Italy Supercri=cal Fluid DP-APCI/APPI-HRTOF-MS HRGC-HRMS 8
  9. 9. © 2016 Chemistry Ma2ers Inc. Analy=cal Content at Dioxin2016 9 •  118 talks and posters covered analytical subject matter •  21% of all posters/talks Dioxin 2016 – Florence, Italy
  10. 10. © 2016 Chemistry Ma2ers Inc. Some of the Highlights 10 Dioxin 2016 – Florence, Italy
  11. 11. © 2016 Chemistry Ma2ers Inc. Bioanaly=cal Developments •  CALUX Bioassay becomes more sensi@ve •  4x increase in response 11 Dioxin 2016 – Florence, Italy
  12. 12. © 2016 Chemistry Ma2ers Inc. Finding the Best Method for PFAs 12 Dioxin 2016 – Florence, Italy
  13. 13. © 2016 Chemistry Ma2ers Inc. Upda=ng Methods/Instrumenta=on 13 Dioxin 2016 – Florence, Italy •  Using nitrogen carrier gas and atmospheric pressure ioniza@on –  Measuring PBDEs
  14. 14. © 2016 Chemistry Ma2ers Inc. Revised MDL Study, Manuscript in preparation Dioxin 2016 – Florence, Italy 14 Comparing Instrumenta=on
  15. 15. © 2016 Chemistry Ma2ers Inc. Firefighter helmet wipes •  Model the direct exposure of firefighters to contact with PXDD/F compounds Anal. Chem., (2015) 87 (20), 10368-77 Dioxin 2016 – Florence, Italy 15
  16. 16. © 2016 Chemistry Ma2ers Inc. Interlaboratory Studies 16 Histogram 2,3,4,7,8-PeCDF Sugar Beat Pulp Results - 2,3,4,7,8-PeCDF Reported results: 87 Report results > LOQ: 86 Robust mean: 0.88 ng/kg (CV: 30%) Median: 0.89 ng/kg Modes: 0.81 ng/kg, 1.03 ng/kg Contribution to WHO-PCDD/F-TEQ: ca. 50 % Dioxin 2016 – Florence, Italy
  17. 17. © 2016 Chemistry Ma2ers Inc. c:Xcalibur...cdx_240315cdx_240315-16 3/25/2015 1:34:24 AM Zuckerrübenschnitzel-sugar beet pulp_t 150141982-001 RT: 19.31 - 21.21 19.4 19.5 19.6 19.7 19.8 19.9 20.0 20.1 20.2 20.3 20.4 20.5 20.6 20.7 20.8 20.9 21.0 21.1 21.2 Time (min) 0 20 40 60 80 100 0 20 40 60 80 100 0 20 40 60 80 100 RelativeAbundance 0 20 40 60 80 100 RT: 19.46 AA: 727412 RT: 20.94 AA: 584377 RT: 19.52 AA: 580258 RT: 20.44 AA: 389185 RT: 19.94 AA: 256338 RT: 21.01 AA: 251896RT: 20.26 AA: 169059 RT: 20.03 AA: 182541 RT: 20.12 AA: 90417 RT: 19.82 AA: 83916 RT: 19.66 AA: 53010 RT: 20.59 AA: 31000 RT: 19.46 AA: 455035 RT: 20.93 AA: 360979 RT: 19.52 AA: 352698 RT: 20.44 AA: 238310 RT: 19.93 AA: 161784 RT: 21.01 AA: 155133RT: 20.26 AA: 106435 RT: 20.03 AA: 106185 RT: 20.11 AA: 57517 RT: 19.82 AA: 50238 RT: 19.66 AA: 31708 RT: 20.59 AA: 18870 RT: 21.15 AA: 755 RT: 21.01 AA: 181912 RT: 20.25 AA: 53012 RT: 20.44 AA: 1830 RT: 20.93 AA: 862 RT: 21.15 AA: 441 RT: 19.93 AA: 340 RT: 19.52 AA: 422 RT: 19.39 AA: 284 RT: 21.01 AA: 113616 RT: 20.24 AA: 30769 RT: 20.46 AA: 431 RT: 20.88 AA: 507 RT: 20.41 AA: 276 RT: 20.59 AA: 283 RT: 20.01 AA: 252 RT: 19.95 AA: 170 RT: 19.47 AA: 98.68 NL: 1.77E5 m/z= 339.8595- 339.8601 MS ICIS cdx_24031 5-16 NL: 1.09E5 m/z= 341.8566- 341.8572 MS ICIS cdx_24031 5-16 NL: 5.86E4 m/z= 351.8996- 351.9004 MS ICIS cdx_24031 5-16 NL: 3.33E4 m/z= 353.8966- 353.8974 MS ICIS cdx_24031 5-16 It S=ll Comes Down to Chromatography 2,3,4,7,8-PeCDF DB-5 MS (Agilent) c:Xcalibur...cdx_200215cdx_200215-31 3/4/2015 8:28:08 PM 1 Animal Feed 1501-AFB-74.1_t AFB-74.1 RT: 26.77 - 34.51 40 60 80 100 0 20 40 60 80 100 0 20 40 60 80 100 RelativeAbundance 0 20 40 60 80 100 RT: 28.17 AA: 28645 RT: 33.31 AA: 28793RT: 27.44 AA: 33942 RT: 28.66 AA: 24124 RT: 30.64 AA: 16621 RT: 27.75 AA: 13713 RT: 30.59 AA: 6037 RT: 27.22 AA: 6541 RT: 30.00 AA: 4640 RT: 31.59 AA: 3998 RT: 33.74 AA: 3370 RT: 31.19 AA: 2599 RT: 33.53 AA: 441 RT: 28.17 AA: 18462 RT: 33.31 AA: 18170RT: 27.45 AA: 21557 RT: 28.66 AA: 15302 RT: 30.64 AA: 10406 RT: 27.75 AA: 8864 RT: 30.59 AA: 3999 RT: 27.23 AA: 4251 RT: 30.00 AA: 2758 RT: 31.59 AA: 2671 RT: 33.75 AA: 1359 RT: 31.19 AA: 1785 RT: 33.55 AA: 250 RT: 30.74 AA: 164 RT: 33.29 AA: 34396 RT: 27.41 AA: 7541 RT: 28.02 AA: 287 RT: 33.40 AA: 124 RT: 32.78 AA: 124 RT: 28.65 AA: 237 RT: 32.99 AA: 105 RT: 33.27 AA: 21044 RT: 27.42 NL: 5.58E3 m/z= 339.8595- 339.8601 MS ICIS cdx_20021 5-31 NL: 3.69E3 m/z= 341.8566- 341.8572 MS ICIS cdx_20021 5-31 NL: 6.28E3 m/z= 351.8996- 351.9004 MS ICIS cdx_20021 5-31 NL: 3.57E3 m/z= 353.8966- 353.8974 MS ICIS cdx_20021 5-31 Rtx-2330 (Restek) •  Values from ‘expert’ labs similar to other labs, therefore even experienced labs were not getting the identification correct. •  Analysts need to know their chromatograms. •  High TEQ, makes this compound important for studies. 2,3,4,7,8-PeCDF Dioxin 2016 – Florence, Italy 17
  18. 18. © 2016 Chemistry Ma2ers Inc. Comprehensive Analysis + Metabolomics 18 •  209 PCB Analysis (159 unique peaks w/ co-elutions) •  Surprising congeners in samples •  Need to measure all potential compounds Dioxin 2016 – Florence, Italy
  19. 19. © 2016 Chemistry Ma2ers Inc. Non-Targeted Analysis – Data Issues 19 Dioxin 2016 – Florence, Italy
  20. 20. © 2016 Chemistry Ma2ers Inc. Where are We Going? 20 Multi-residue extraction method Acidic, Basic and Neutral compounds Non-targeted/Ultra Trace Quantitation or Semi-Quantitation Multiple Methods? Gene Array/Gene Expression Quantitative Biomarker/Metabolites Dioxin 2016 – Florence, Italy Large Data Sets Data Handling/Storage Statistical Interpretation
  21. 21. © 2016 Chemistry Ma2ers Inc. Big Data is Coming – Are you Ready? 21 http://itknowledgeexchange.techtarget.com/IT-watch-blog/files/2013/05/shutterstock_134968730.jpg Dioxin 2016 – Florence, Italy
  22. 22. © 2016 Chemistry Ma2ers Inc. Thank you for your attention Contact Info: Chemistry Matters Inc. Court Sandau Cell: 403.669.8566 Email: csandau@chemistry-matters.com URL: chemistry-matters.com Visit my website and sign up for email for automatic receipt of my blogs! Twitter: @Chem_Matters Slideshare: www.slideshare.net/csandau 22 www.chemistry-mabers.com

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