Enhanced Hydrocarbon Fingerprinting TCEQ Trade Fair May 2018
Enhanced Hydrocarbon Fingerprinting TCEQ Trade Fair May 2018 Kesavalu M. Bagawandoss, Ph. D. , J. D. Laboratory Director Copyright © © 2018 Test. America. All rights reserved.
Agenda • • • Introduction Why do we need Chemical Fingerprinting ? How do Products get into the Environment? What is necessary to perform Fingerprinting? Analytical Tiers Methods and Choices Matrices Factors Affecting Fingerprinting Techniques Laboratory Information (Data Presentation) Example Data Summary Copyright © 2018 Test. America. All rights reserved.
Introduction • • Types of Products Chemical Fingerprinting and Comparisons Hydrocarbon GW Plume Sources Multiple Sources State Agency Analytical Parameter Recommendations Combination of Methods Communication • Tiered Approach to Characterization Copyright © 2018 Test. America. All rights reserved.
Why do we need Chemical Fingerprinting? • Characterization of Product • Determination of Source • Multiple Sources? • Allocation of Liability Copyright © 2018 Test. America. All rights reserved.
How do Products get into the Environment? • • Spills Leaks Explosions Natural Seeps (6500 -7000 GPD)(NOAA, Lorenson et al. , 2011) Copyright © 2018 Test. America. All rights reserved.
What is necessary to perform Fingerprinting? • • Samples from Site Source Product or Products Historical Background All other Information MORE INFORMATION THE BETTER !!! Copyright © 2018 Test. America. All rights reserved.
Analytical Tiers • Tier I – GC/FID* • Tier II – GC/MS (SHC’s, PAH/APAH’s, BIOMARKERS, PIANO) • Tier III – CSIA (Carbon Stable Isotope Analysis) • *Fuels comparison • Whole Oil Analysis (GC/FID) P (Paraffins), I (Isoparaffins), A (Aromatics), N (Naphthenes), O (Olefins) Copyright © 2018 Test. America. All rights reserved.
Methods and Choices Volatiles (VOA) • GC/FID • GC/MS • SW 846 8015 Mod. • SW 846 8260 Mod. • SW 846 8270 D Mod. • ASTM D 7900 (Detailed Hydrocarbon Analysis (DHA)) • ASTM D 6730 Mod. (DHA Analysis) • ASTM D 8003 HPLIS (n-C 1 through n-C 24) • Organic Lead, Manganese Analysis • Sulfur Analysis (ASTM D 4294……. ) Copyright © 2018 Test. America. All rights reserved.
Methods and Choices Semi Volatiles (SVOA) • GC/FID • GC/MS • SW-846 8015 Mod • ASTM D 3328 • ASTM D 7363 • ASTM D 5739 • SW 846 8270 D Mod • SINTEF 2002 • Prep Methods • Cleanup Methods Quantitative method best approach Copyright © 2018 Test. America. All rights reserved.
Matrices • • • Pure Product NAPL (Nonaqueous Phase Liquids) Soils & Sediments Water Matrix Combinations Copyright © 2018 Test. America. All rights reserved.
Factors Affecting Fingerprinting • • Weathering Evaporation Water Washing Biodegradation Additives and Blending Crude Oil Genesis Petroleum Refining Mixing in the Environment Naturally Occurring Sources and Anthropogenic Sources Copyright © 2018 Test. America. All rights reserved.
Techniques • • Fingerprints Diagnostic ratios Models, Statistics, Chemo metrics Mapping and Visualization Copyright © 2018 Test. America. All rights reserved.
Data Presentation • • Quantitation Reports GC/FID traces Total Ion Chromatograms Weathering patterns Diagnostic ratios – Isoprenoids, PAH’s/APAH’s, Biomarkers Histograms – SHC’s, PAH’s/APAH’s, Biomarkers, Metals Determination of processes (Petrogenic, Pyrogenic, Biogenic) • Scatter Plots, Radar Plots (PIANO Components) • Principal Component Analysis (PCA) • Data Interpretation Reports Copyright © 2018 Test. America. All rights reserved.
Example Data – GC/FID Traces Copyright © 2018 Test. America. All rights reserved.
Example Data - Overlays Copyright © 2018 Test. America. All rights reserved.
Example Data – Weathering patterns Copyright © 2018 Test. America. All rights reserved.
Example Data – Weathering patterns Copyright © 2018 Test. America. All rights reserved.
Example Data - PIANO • PIANO - GC/MS 8260 (Paraffins, Isoparaffins, Aromatics) Copyright © 2018 Test. America. All rights reserved.
Example Data – PIANO • PIANO - GC/MS 8260 (Naphthenes & Olefins) Copyright © 2018 Test. America. All rights reserved.
Example Data – Diagnostic Ratios Isoprenoid Ratios • n-C 17/Pristane • n-C 18/Phytane • Pristane/Phytane • n-C 17/n-C 18 PAH’s C 2 DBT/C 2 PHE C 3 DBT/C 3 CHR Copyright © 2018 Test. America. All rights reserved.
Example Data – Diagnostic Ratios Copyright © 2018 Test. America. All rights reserved.
Example Data - Histograms Copyright © 2018 Test. America. All rights reserved.
Example Data - Histograms Copyright © 2018 Test. America. All rights reserved.
0 Fluorene C 1 -Fluorenes C 2 -Fluorenes C 3 -Fluorenes Naphthalene C 1 -Naphthalenes C 2 -Naphthalenes C 3 -Naphthalenes C 4 -Naphthalenes Phenanthrene/Anthracene C 1 -Phenanthrenes/Anthracenes C 2 -Phenanthrenes/Anthracenes C 3 -Phenanthrenes/Anthracenes C 4 -Phenanthrenes/Anthracenes Fluoranthene/Pyrene C 1 -Fluoranthenes/pyrene C 2 -Fluoranthenes/Pyrene C 3 -Fluoranthenes/Pyrene Chrysene C 1 -Chrysenes C 2 -Chrysenes C 3 -Chrysenes C 4 -Chrysenes Benzo(b)thiophene C 1 -Benzothiophenes C 2 -Benzothiophenes C 3 -Benzothiophenes C 4 -Benzothiophenes Dibenzothiophene C 1 -Dibenzothiophenes C 2 -Dibenzothiophenes C 3 -Dibenzothiophenes C 4 -Dibenzothiophenes Decahydronaphthalene (cis & trans) C 1 -Decalins C 2 -Decalins C 3 -Decalins C 4 -Decalins Example Data - Histograms Example PAH/APAH Histogram - Crude Oil (petrogenic signature) 600 500 400 300 200 100 Crude Copyright © 2018 Test. America. All rights reserved.
0 Fluorene C 1 -Fluorenes C 2 -Fluorenes C 3 -Fluorenes Naphthalene C 1 -Naphthalenes C 2 -Naphthalenes C 3 -Naphthalenes C 4 -Naphthalenes Phenanthrene/Anthracene C 1 -Phenanthrenes/Anthracenes C 2 -Phenanthrenes/Anthracenes C 3 -Phenanthrenes/Anthracenes C 4 -Phenanthrenes/Anthracenes Fluoranthene/Pyrene C 1 -Fluoranthenes/pyrene C 2 -Fluoranthenes/Pyrene C 3 -Fluoranthenes/Pyrene Chrysene C 1 -Chrysenes C 2 -Chrysenes C 3 -Chrysenes C 4 -Chrysenes Benzo(b)thiophene C 1 -Benzothiophenes C 2 -Benzothiophenes C 3 -Benzothiophenes C 4 -Benzothiophenes Dibenzothiophene C 1 -Dibenzothiophenes C 2 -Dibenzothiophenes C 3 -Dibenzothiophenes C 4 -Dibenzothiophenes Decahydronaphthalene (cis & trans) C 1 -Decalins C 2 -Decalins C 3 -Decalins C 4 -Decalins Example Data - Histograms Example PAH's/APAH's - Coal Tar (pyrogenic signature) 600 500 400 300 200 100 Coal Tar Copyright © 2018 Test. America. All rights reserved.
Example Data - Histograms Copyright © 2018 Test. America. All rights reserved.
Example Data - Histograms Copyright © 2018 Test. America. All rights reserved.
Example Data – Radar Plot Copyright © 2018 Test. America. All rights reserved.
Summary • • • Analysis is complicated Methods are standard with modifications Must understand the overall history Must know the site well and its documentation Multiple sources always a problem Source and Library of Components Necessary Multiple Paths for Data Interpretation consists of visual and quantitative techniques Cannot provide rush TATs like the traditional analyses Lots of Information Needed !!!!! Copyright © 2018 Test. America. All rights reserved.
References 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. SW 846 8015 SW 846 8260 SW 846 8270 mod. ASTM D 7900 ASTM D 6730 Mod ASTM D 3328 Oil Spill Environmental Forensics – Fingerprinting and Source Identification, Zhendi Wang and Scott A. Stout, 2007 Introduction to Environmental Forensics, 3 rd Edition, Brian L. Murphy and Robert D. Morrison, 2015. Kaplan Isaac R. (2003), “Age Dating of Environmental Organic Residues”, Environmental Forensics, 4: 2, 95 -141. Kaplan Isaac R. et. Al. , “Forensic Environmental Geochemistry: differentiation of fuel-types, their sources and release time”, Org. Geochem. Vol. 27, No. 5/6, 289 -317, 1997. Ioana Petrisor, Contaminant Source Tracking and Age-Dating, San Diego, CA, Feb. 28 -Mar 11, 2011. http: //www. rsc. org/images/Gil_Oudijk_tcm 18 -235152. pdf https: //books. google. com/books? id=CXUIKWXt. Vc 8 C&pg=PA 180&lpg=PA 180&dq=Star+diagrams+for+ PIANO+hydrocarbons&source=bl&ots=wmrm. GNEq 8 m&sig=t. Y 6 Syk. WAujs 9 nr 54 ea 7 h. P 03 m. FM 0&hl=en &sa=X&ved=0 ah. UKEwi 54 t. Hb 36 XXAh. US 3 YMKHcd. CBEo. Q 6 AEISDAG#v=onepage&q=Star%20 diagra ms%20 for%20 PIANO%20 hydrocarbons&f=false. Robert D. Morrison, Environmental Forensics – Principles & Applications, 2000. http: //www. triassictechnology. com/wp-content/uploads/2015/12/articles-Fingerprinting-and-age-datingof-gasoline-releases-A-case-study. pdf https: //www. google. com/search? q=Picture+of+a+GW+monitoring+well&safe=strict&tbm=isch&tbo=u&s Copyright © 2018 Test. America. All rights reserved. ource=univ&sa=X&ved=0 ah. UKEwj. Jr 4 z 3 -Kz. XAh. VD-m. MKHUXYD_o. Qs. AQIJQ&biw=1920&bih=1024
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