1. Use of Solid Phase Microextraction (SPME) to Assess the Contribution of PAHs to Toxicity of Sediments at a Former Manufacturing Plant Battelle Sediment Conference Jacksonville, Florida February 5, 2009 Susan Kane Driscoll, Margaret McArdle, and Pieter Booth

2. Introduction Former manufacturing and assembly plant Former manufacturing and assembly plant Several site investigations have been conducted, subject to audit by state Several site investigations have been conducted, subject to audit by state Area of concern: Area of concern: –Brook Contaminants of concern: Contaminants of concern: –PAHs, metals, phthalates, PCBs, and pesticides

3. Site Habitat and Surroundings Urban setting with mixed industrial, commercial, and residential uses Urban setting with mixed industrial, commercial, and residential uses Stream quality is impacted by typical urban stressors Stream quality is impacted by typical urban stressors –Impervious surfaces influence stream flow –Riparian habitat loss from development –Degradation from storm water discharges –Ephemeral water flow limits fish community

4. Conceptual Model: Brook Assessment Endpoint 2: Reduced survival, growth, or reproduction of benthic invertebrates in the brook Assessment Endpoint 2: Reduced survival, growth, or reproduction of benthic invertebrates in the brook Measurement Endpoints: Comparison to sediment benchmarks, chronic toxicity tests, and PAH toxicity models Measurement Endpoints: Comparison to sediment benchmarks, chronic toxicity tests, and PAH toxicity models

5. Exposure Assessment: Freshwater Brook 25 sediment samples screened for metals and SVOCs 25 sediment samples screened for metals and SVOCs 14 sediment samples selected for further analysis 14 sediment samples selected for further analysis –Chronic sediment toxicity with Hyallela azteca –Pesticides –34 PAHs –Total organic carbon –Grain size –Black carbon –Solid-phase microextraction (SPME) and analysis of 34 PAHs in pore water

6. Freshwater Brook: Sample Locations

7. Freshwater Brook Sediment Sediment – Lead was detected up to 6,400 mg/kg – Zinc was detected up to 900 mg/kg – Antimony was detected up to 200 mg/kg – Total PAHs were detected up to 900 mg/kg – Pthalates were detected up to 1,000 mg/kg – Total PCBs were detected up to 1 mg/kg – Total DDT was detected up to 0.09 mg/kg Porewater Porewater – SPME used to measure PAHs in a subset of samples

8. Effects Assessment for PAHs based on U.S. EPA Guidance Documents U.S. EPA. 2003Procedures for the Derivation of Equilibrium Partitioning Sediment Benchmarks (ESBs) for the Protection of Benthic Organisms: PAH Mixtures U.S. EPA. 2003Procedures for the Derivation of Equilibrium Partitioning Sediment Benchmarks (ESBs) for the Protection of Benthic Organisms: PAH Mixtures U.S. EPA. 2000Draft Methods for the Derivation of Site-Specific Equilibrium Partitioning Sediment Guidelines (ESGs) for the Protection of Benthic Invertebrates: Nonionic Organics U.S. EPA. 2000Draft Methods for the Derivation of Site-Specific Equilibrium Partitioning Sediment Guidelines (ESGs) for the Protection of Benthic Invertebrates: Nonionic Organics

9. U.S. EPA ESB Approach Calculates toxic units for 34 PAHs as: Calculates toxic units for 34 PAHs as: –Note: EPA FCV provided as mg/kg OC or mg/L If Sum-TU for 34 PAHs < 1.0, concentration of total PAHs in sediment is protective of benthic invertebrates If Sum-TU for 34 PAHs < 1.0, concentration of total PAHs in sediment is protective of benthic invertebrates C SED, PAH i Final Chronic Value PAH i

10. U.S. EPA ESB Approach Three methods used to calculate Σ-TUs: Three methods used to calculate Σ-TUs: –One-phase model estimates PAHs in pore water from PAHs in bulk sediment and TOC –Two-phase model estimates PAHs in pore water from PAHs in bulk sediment, TOC, and black carbon –Solid phase microextraction (SPME) method directly measures PAHs in pore water

11. One-Phase Model for Calculating the Sum of Toxic Units where: C SED = concentration of each PAH in sediment (µg/kg dry wt) C W = concentration of truly dissolved PAH in pore water (µg/L) f TOC = weight fraction of TOC (kg organic carbon/kg dry wt) K OC = organic carbon-water partition coefficient (L/kg) The equation is rearranged and used to solve for C W. C W for each PAH is divided by its corresponding F CV to calculate a toxic unit. C SED /C W = f TOC K oc

12. Two-Phase Model for Calculating the Sum of Toxic Units C SED /C W = f NPOC K OC + f BC K BC C W n-1 where: C SED = concentration of each PAH in sediment (µg/kg dry wt) C W = concentration of truly dissolved PAH in pore water (µg/L) f NPOC = weight fraction of non-pyrogenic organic carbon in sediment (kg non- pyrogenic organic carbon/kg dry wt, calculated from the difference between TOC and black carbon) K OC = organic carbon to water distribution coefficient (L/kg) f BC = weight fraction of black carbon in sediment (kg black carbon/kg dry wt) K BC = black carbon to pore water partition coefficient (L/kg) n = Freundlich exponent, which accounts for nonlinear sorption behavior (n=0.6) (Accardi-Dey and Gscwend 2002) An iterative approach was used to solve for C W. C W for each PAH is divided by its corresponding FCV to calculate a toxic unit.

13. Relationship of log K OW to log K BC Data from Accardi-Dey and Gschwend 2003

14. Station TOC (%) BC as % of TOC Lead (mg/kg) Total (34) PAHs (mg/kg) Avg Survival (%) Avg Repro (# offspring) 10.61.67.92.0968.2 21.40.72610947.3 32.62.55211917.4 42.212.36400 662782.4 52.32.4110068937.7 621.51900 114842.8 72.74.52500 895633.2 81.78.52600 150834.5 93.22.42700 22520 101.90.571084945.3 111.90.542072937.3 122.02.11200 57101.0 131.417.834048906.3 142.02.324010192 4.7 Results of Physical Analyses for the Brook Study Site Significantly reduced survival = green Significantly reduced growth = yellow

15. Sum ESB Toxic Units for Modeled and Measured PAH Concentration in Porewater

16. Concentrations of PAHs in pore water measured by SPME were much lower than predicted from the one-phase or two-phase model, which could be influenced by the values of K BC used in the 1-phase and 2-phase models.

17. Conclusions of SPME Analyses PAHs were ruled out as contributing to observed toxicity PAHs were ruled out as contributing to observed toxicity –ΣTU SPME indicates that PAHs would not result in toxicity –ΣTU for any method (one-phase, two-phase, or SPME) did not correlate strongly with survival and reproduction

18. Correlation Analysis Several metals, PAHs, PCBs, and phthalates were strongly correlated with each other and with survival and reproduction Several metals, PAHs, PCBs, and phthalates were strongly correlated with each other and with survival and reproduction –Lead exceeded probable effect concentration (PEC) to much greater extent; lead PEC-hazard quotient ranged from 2 to 50 Target cleanup level for lead set to 1,150 mg/kg Target cleanup level for lead set to 1,150 mg/kg Numbers = Stations

19. Proposed Remediation Area

20. Summary and Conclusions Previous ERAs indicated that brook sediments adjacent to the plant posed an unacceptable ecological risk and would need to be remediated Previous ERAs indicated that brook sediments adjacent to the plant posed an unacceptable ecological risk and would need to be remediated Collecting site-specific data and using innovative approaches in sediment bioavailability provided more realistic estimates of ecological risk and the extent of remediation required in these areas Collecting site-specific data and using innovative approaches in sediment bioavailability provided more realistic estimates of ecological risk and the extent of remediation required in these areas