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PAHs are families, not
orphans
Interpretation of PAH data from an
inland water body
Presented by: Phil Richards, PhD, PChem
at Watertech 2014, Banff, Alberta
Click here for related case study
So, there is an oil release into a
water body…
• Highly variable conditions – flow rate,
turbidity
• Large contact area with shoreline
• Backwater pooling
• Vegetation contact
• Suspended solids / dissolved organics
• Eventually deposition
Evaporation, Biodegradation (food source), Photolysis
Watertech 2014 - © Chemistry Matters Inc. 2014
Primary remediation efforts and monitoring
Trapping and collecting
•Booms, sponges, hydrovac.
Impacted area
•Aerial recon
Health guidelines
•Water sampling
So, there is an oil release into a
water body…
Watertech 2014 - © Chemistry Matters Inc. 2014
• What next…?
Long Term Monitoring
Watertech 2014 - © Chemistry Matters Inc. 2014
• Water via SPMDs
Very low solubility, very low concentrations,
affected by very small effects
• Fish
Biological processes impact PAH concentrations
in tissue
• Sediment
PAH reservoir
Still need upstream controls (PAHs are
ubiquitous)
Why Sediment?
Watertech 2014 - © Chemistry Matters Inc. 2014
Lifespan of chemical
residues after a spill
Days Weeks Months Years
BTEX
Alkanes
Biomarkers
PAHs
Watertech 2014 - © Chemistry Matters Inc. 2014
Residue after a spill
Days Weeks Months Years
BTEX
Alkanes
Biomarkers
PAHs
Watertech 2014 - © Chemistry Matters Inc. 2014
Analysis for PAHs
Parent PAHs
17 CCME
Naphthalene
Watertech 2014 - © Chemistry Matters Inc. 2014
Analysis for PAHs
Parent PAHs
17 CCME
Extended PAHs
50+
Naphthalene
C1-Naphthalenes
C2-Naphthalenes
C3-Naphthalenes
… …
…
Watertech 2014 - © Chemistry Matters Inc. 2014
vs.
Interpretation of Parent
PAHs Data
Watertech 2014 - © Chemistry Matters Inc. 2014
Interpretation of Extended
PAHs Data
Watertech 2014 - © Chemistry Matters Inc. 2014
Environmental Forensics
Interpretation of Extended
PAHs Data
Watertech 2014 - © Chemistry Matters Inc. 2014
Environmental Forensics
Fingerprint
Diagnostic
Ratios
Statistical
Analysis
Visual comparison of PAH
data
Relative concentration of
key PAHs
Comprehensive analysis of
all PAH data
Watertech 2014 - © Chemistry Matters Inc. 2014
PAH Fingerprints
Visual comparisons
•PAH groups
•Types of oils and refined products.
• light crude, heavy crude, gasoline,
diesel…
•Nature of background
Watertech 2014 - © Chemistry Matters Inc. 2014
Visit one of our past blogs on a natural PAH, called retene:
http://chemistry-matters.com/aha-moment-environmental-forensics/
Parent PAH Fingerprint
Watertech 2014 - © Chemistry Matters Inc. 2014
Extended PAH Fingerprint
Watertech 2014 - © Chemistry Matters Inc. 2014
Diagnostic Ratios
The relative concentration of specific
PAHs can be indicative of a potential
source.
Often, dibenzothiophene (DBT) is a
good indicator for crude products, and
the ratio of alkylated DBTs with alkylated
phenanthrenes (Phen) is a powerful
diagnostic tool.
Watertech 2014 - © Chemistry Matters Inc. 2014
Double Ratio Plot
Watertech 2014 - © Chemistry Matters Inc. 2014
Double Ratio Plot
Watertech 2014 - © Chemistry Matters Inc. 2014
Double Ratio Plot
Watertech 2014 - © Chemistry Matters Inc. 2014
Better interpretation?
Diagnostic ratios are indicators for 2 chemicals,
and a double ratio plot is good for 4 chemicals.
But, we can do better… we can develop
analysis to consider variability within all
chemicals –
Principle Components Analysis (PCA)
Watertech 2014 - © Chemistry Matters Inc. 2014
Statistical tool that considers all variability
within our PAH dataset.
PCA takes the concentrations of all of our
PAHs and presents an output that
represent the major differences within all
of that data.
Principle Components Analysis
Watertech 2014 - © Chemistry Matters Inc. 2014
Principle Components Analysis
Watertech 2014 - © Chemistry Matters Inc. 2014
Principle Components Analysis
Watertech 2014 - © Chemistry Matters Inc. 2014
PAHs from release
PAHs not from release
Principle Components Analysis
Watertech 2014 - © Chemistry Matters Inc. 2014
Summary
• PAHs are the focus of monitoring
post-spill
• Extended PAH analysis provides
much more information
• Fingerprinting
• Diagnostic Ratios
• Statistics
Watertech 2014 - © Chemistry Matters Inc. 2014
For more information on PAHs and PAH fingerprinting visit our
website on PAHs:
http://chemistry-matters.com/chemicals/polycyclic-aromatic-hydrocarbons-pah/
Questions?
Contact Info:
Chemistry Matters Inc.
Court Sandau
Twitter: @Chem_Matters
Slideshare: www.slideshare.net/csandau
Watertech 2014 - © Chemistry Matters Inc. 2014
Please visit our website for related information, case studies
and blogs. www.chemistry-matters.com

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PAHs_are_families_Watertech2014

  • 1. PAHs are families, not orphans Interpretation of PAH data from an inland water body Presented by: Phil Richards, PhD, PChem at Watertech 2014, Banff, Alberta Click here for related case study
  • 2. So, there is an oil release into a water body… • Highly variable conditions – flow rate, turbidity • Large contact area with shoreline • Backwater pooling • Vegetation contact • Suspended solids / dissolved organics • Eventually deposition Evaporation, Biodegradation (food source), Photolysis Watertech 2014 - © Chemistry Matters Inc. 2014
  • 3. Primary remediation efforts and monitoring Trapping and collecting •Booms, sponges, hydrovac. Impacted area •Aerial recon Health guidelines •Water sampling So, there is an oil release into a water body… Watertech 2014 - © Chemistry Matters Inc. 2014
  • 4. • What next…? Long Term Monitoring Watertech 2014 - © Chemistry Matters Inc. 2014
  • 5. • Water via SPMDs Very low solubility, very low concentrations, affected by very small effects • Fish Biological processes impact PAH concentrations in tissue • Sediment PAH reservoir Still need upstream controls (PAHs are ubiquitous) Why Sediment? Watertech 2014 - © Chemistry Matters Inc. 2014
  • 6. Lifespan of chemical residues after a spill Days Weeks Months Years BTEX Alkanes Biomarkers PAHs Watertech 2014 - © Chemistry Matters Inc. 2014
  • 7. Residue after a spill Days Weeks Months Years BTEX Alkanes Biomarkers PAHs Watertech 2014 - © Chemistry Matters Inc. 2014
  • 8. Analysis for PAHs Parent PAHs 17 CCME Naphthalene Watertech 2014 - © Chemistry Matters Inc. 2014
  • 9. Analysis for PAHs Parent PAHs 17 CCME Extended PAHs 50+ Naphthalene C1-Naphthalenes C2-Naphthalenes C3-Naphthalenes … … … Watertech 2014 - © Chemistry Matters Inc. 2014 vs.
  • 10. Interpretation of Parent PAHs Data Watertech 2014 - © Chemistry Matters Inc. 2014
  • 11. Interpretation of Extended PAHs Data Watertech 2014 - © Chemistry Matters Inc. 2014
  • 12. Environmental Forensics Interpretation of Extended PAHs Data Watertech 2014 - © Chemistry Matters Inc. 2014
  • 13. Environmental Forensics Fingerprint Diagnostic Ratios Statistical Analysis Visual comparison of PAH data Relative concentration of key PAHs Comprehensive analysis of all PAH data Watertech 2014 - © Chemistry Matters Inc. 2014
  • 14. PAH Fingerprints Visual comparisons •PAH groups •Types of oils and refined products. • light crude, heavy crude, gasoline, diesel… •Nature of background Watertech 2014 - © Chemistry Matters Inc. 2014 Visit one of our past blogs on a natural PAH, called retene: http://chemistry-matters.com/aha-moment-environmental-forensics/
  • 15. Parent PAH Fingerprint Watertech 2014 - © Chemistry Matters Inc. 2014
  • 16. Extended PAH Fingerprint Watertech 2014 - © Chemistry Matters Inc. 2014
  • 17. Diagnostic Ratios The relative concentration of specific PAHs can be indicative of a potential source. Often, dibenzothiophene (DBT) is a good indicator for crude products, and the ratio of alkylated DBTs with alkylated phenanthrenes (Phen) is a powerful diagnostic tool. Watertech 2014 - © Chemistry Matters Inc. 2014
  • 18. Double Ratio Plot Watertech 2014 - © Chemistry Matters Inc. 2014
  • 19. Double Ratio Plot Watertech 2014 - © Chemistry Matters Inc. 2014
  • 20. Double Ratio Plot Watertech 2014 - © Chemistry Matters Inc. 2014
  • 21. Better interpretation? Diagnostic ratios are indicators for 2 chemicals, and a double ratio plot is good for 4 chemicals. But, we can do better… we can develop analysis to consider variability within all chemicals – Principle Components Analysis (PCA) Watertech 2014 - © Chemistry Matters Inc. 2014
  • 22. Statistical tool that considers all variability within our PAH dataset. PCA takes the concentrations of all of our PAHs and presents an output that represent the major differences within all of that data. Principle Components Analysis Watertech 2014 - © Chemistry Matters Inc. 2014
  • 23. Principle Components Analysis Watertech 2014 - © Chemistry Matters Inc. 2014
  • 24. Principle Components Analysis Watertech 2014 - © Chemistry Matters Inc. 2014
  • 25. PAHs from release PAHs not from release Principle Components Analysis Watertech 2014 - © Chemistry Matters Inc. 2014
  • 26. Summary • PAHs are the focus of monitoring post-spill • Extended PAH analysis provides much more information • Fingerprinting • Diagnostic Ratios • Statistics Watertech 2014 - © Chemistry Matters Inc. 2014 For more information on PAHs and PAH fingerprinting visit our website on PAHs: http://chemistry-matters.com/chemicals/polycyclic-aromatic-hydrocarbons-pah/
  • 27. Questions? Contact Info: Chemistry Matters Inc. Court Sandau Twitter: @Chem_Matters Slideshare: www.slideshare.net/csandau Watertech 2014 - © Chemistry Matters Inc. 2014 Please visit our website for related information, case studies and blogs. www.chemistry-matters.com