1. A Comparison of SPME Approaches for the Analysis of Alkylated PAHs in Pore Water Porewater: The Interaction between Sediment, Biota, and Water 2015 Fall Workshop Jim Occhialini Nathan Sorelle Alpha Analytical

2. Overview ASTM D7363 Wrap up Topics for Discussion “A COMPARISON of SPME Approaches for the Analysis of Alkylated PAHs in Pore Water”

3. 2 EVALUATING ECOLOGICAL RISK TO INVERTEBRATE RECEPTORS FROM PAHS IN SEDIMENTS AT HAZARDOUS WASTE SITES EPA/600/R-06/162F ERASC-011F October 2009

4. Sediment (& Tissue Analysis…) Difficult samples Great expectations –Sensitivity & quality

5. Sampling Pore Water for Subsequent Analysis in the Laboratory Acquire pore water in the field –Direct sampling Piezometers, syringes Centrifuge in the lab –Assume ~1:4 pore water / sediment This ratio can vary, i.e. “sandy” sediments Both are generally volume-limited options Considering typical 1L extraction volumes… Relationship between extraction volume and sensitivity

6. 5 Championed by Dr. Steven Hawthorne, EERC, University of North Dakota EPA SW-846 Method 8272

7. 6 EVALUATING ECOLOGICAL RISK TO INVERTEBRATE RECEPTORS FROM PAHS IN SEDIMENTS AT HAZARDOUS WASTE SITES EPA/600/R-06/162F ERASC-011F October 2009 EMAP 34 List (EPA Monitoring & Assessment Program) 34 parent & alkylated PAHs (18 parent & 16 groups of alkyl PAHs listed for EPA’s equilibrium partitioning sediment benchmark (ESB) model [2003])

8. Target Analyte List 10 parent and 14 alkylated groups – contribute 95% of the toxic units EMAP 34 list 7

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10. Colloids removed utilizing a flocculation procedure Direct measurement of truly dissolved fraction D7362 Procedure Minimal pore water volume required ~ 5 mLs –Generated by centrifugation in the lab –Temp control – 4 o C –7,400 RPM Direct measurement of truly dissolved fraction - Colloids removed utilizing a flocculation procedure

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14. D7362 Procedure Sample introduction technique –SPME (solid phase micro extraction) concentration equilibrium is established between the sample matrix and the extraction phase. PDMS (polydimethylsiloxane) coated fiber

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19. 18 USEPA SAMS #3, Guidelines for using Passive Samplers to Monitor Organic Contaminants at Superfund Sediment Sites

20. 19 28 day hold time

21. Different approach… Time consuming process –Every analytical run performed in duplicate Long equilibration, GC run times Typical analytical sequence –[CCV, CCV], [IB, IB], [MB, MB] Samp 1, Samp 1 IB, IB Samp 2, Samp 2 IB, IB Etc. ~ 3 field samples / day 20

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23. 22 C1 – phenanthrenes / anthracenes

24. D7363-13a Sensitivity 23 1

25. 24 Questions? Jim Occhialini jocchialini@alphalab.com (508) 380-8618