FINAL REPORT Measurement and Modeling of Ecosystem Risk and Recovery for In Situ Treatment of Contaminated Sediments SERDP Project ER-1552 Phase I FEBRUARY 2011 Richard G. Luthy Stanford University Samuel N. Luoma Janet K. Thompson USGS This report was prepared under contract to the Department of Defense Strategic Environmental Research and Development Program (SERDP). The publication of this report does not indicate endorsement by the Department of Defense, nor should the contents be construed as reflecting the official policy or position of the Department of Defense. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the Department of Defense. 2 Title page ------------------------------------------------------------------------------------------- (i) List of acronyms ---------------------------------------------------------------------------------- (ii) List of tables -------------------------------------------------------------------------------------- (iii) List of figures ------------------------------------------------------------------------------------- (iv) Acknowledgements ------------------------------------------------------------------------------- (v) Content I. Abstract ................................................................................................................ 16 II. Objectives............................................................................................................. 17 III. Background ......................................................................................................... 21 IV. Material and Methods ........................................................................................ 31 V. Results and Accomplishments ........................................................................... 56 VI. Conclusion and Implications for Future Research .......................................... 99 VII. References .......................................................................................................... 105 VIII. Appendix ............................................................................................................ 113 (A) List of Technical Publications ............................................................................... 113 (B) Supporting data ...................................................................................................... 117 3 (ii) List of acronyms AC Activated carbon AE Assimilation efficiency AMW Artificial marine water DDT Dichloro-diphenyl-trichloroethanes ERL Effective Range Low ERM Effective Range Median FR Filtrations rate GC-µECD Gas chromatography - micro electron capture detector HPAH high molecular weight polyaromatic hydrocarbon HOC Hydrophobic organic compound IR Ingestion rate LPAH low molecular weight polyaromatic hydrocarbon LOQ Limit of quantification MDL Method detection limit PAH Polyaromatic hydrocarbon PCB Polychlorinated biphenyl PE Polyethylene PED Polyethylene devices PFC Perfluorinated chemical POM Polyoxymethylene PRC Performance reference compound RMSE Root Mean Squared Error SPME Solid Phase Micro Extraction SERDP Strategic Environmental Research and Development Program SOP Standard operational procedure SPMD Semi-permeable membrane device SQG Sediment Quality Guidelines US EPA United States Environmental Protection Agency 4 (iii) List of tables Table 1. PCB sediment concentrations. 46 Table 2. Values of physiological and model parameters for the benthic invertebrates. 47 Table 3. Measured total PCB sediment and pore water concentrations and computed Kd values for Hunters Point. 48 Table 4. Parameters for the heat transport model. 54 Table 5. Sediment PCB concentrations measured by immunoassay analysis and GC. 57 Table 6. Percent reduction in passive sampling and bioassays from untreated to AC amended Hunters Point sediment. 65 Table 7. Physiological parameters for benthic invertebrates and biodynamic modeling. 72 Table 8. Coefficients of determination among the four temperature profiles at various depths from the Aug 2007 sampling. 93 Table 9. Coefficients of determination among the four temperature profiles at various depths from the March 2008 sampling. 93 Table 10. Heat transport model simulation summary considering diffusion only and addition of an advection or dispersion term. Best-fit models are presented for Darcy velocity (v), the dispersion coefficient (Ddisp), and root mean squared error (RMSE). 97 5 (iv) List of figures Figure 1. Test organisms with different habitat and feeding strategies within the sediment and overlying water. ...........................................................................................25 Figure 2. Immunoassay Kit from Strategic Diagnostics Inc. (Newark, DE) with example test tubes. .............................................................................................................33 Figure 3. Schematic of test plots and mixing devices (left) and PE devises as deployed in the field (right). ..............................................................................................34 Figure 4. Pictures (top to bottom): deployment of passive sampler rods for vertical pore water profiles; sediment core; close-up of deployment rod with POM passive sampler. ..............................................................................................................................35 Figure 5. Benthic survey sample sites (squares) including intertidal benthic sites (triangles) and sediment chemistry sites (circled) in the Central San Francisco Bay and at Hunters Point, regional biomes are circled. ............................................................37 Figure 6. Picture of polychaete exposure setup to measure PCB uptake rates from sediment (left) and aqueous exposure studies with clams (middle) and polychaetes (right). ................................................................................................................................40 Figure 7. Schematic of field-deployed cages containing transplanted sediment and passive samplers in the surface layer (0.5 cm) and subsurface sediment (3 cm). The sediment surface in the cages lines up with the sediment surface of the field sediment. ..41 Figure 8. Pictures showing deployment of bioassay cages in the field. ............................42 6 Figure 9. Flow-chart representation of ecological recovery modeling to determine the re-colonization potential of possible recruits. ....................................................................45 Figure 10. Schematic of (A) San Francisco Bay; (B) Hunters Point Naval Shipyard and South Basin; and (C) four test plots used in the field-scale study of in-situ AC amendment [Cho et al., 2009]. The two plots indicated by shading (Plots D and F) were treated by mixing the sediment with AC to a nominal 30-cm depth. Plot C served as a control plot, and Plot E served as an unmixed reference plot. In this study, AC treated plot D and unmixed reference plot E were used for assessment of pore water movement. ................................................................................................................50 Figure 11. (A) Deploying temperature observation stations at the center of each plot; (B) The mico-weather station installed at the shore to measure solar radiation. ...............51 Figure 12. Left: schematic and pictures of a temperature logging station; Right: picture of a temperature probe. ..........................................................................................52 Figure 13. Illustrative activated carbon amendment and sediment mass transfer scenarios: Left, well mixed homogeneous conditions as in the laboratory; Center, homogeneous carbon distribution with diffusive mass transfer; Right, heterogeneous carbon distribution with advective pore water movement and diffusive mass transfer as may occur in the field. ...................................................................................................55 7 Figure 14. Uptake of PCBs over time in PEDs deployed in sediment in mixed-only Plot C (squares) and activated carbon amended Plot D (circles) at Hunters Point, San Francisco, CA (n = 3). .......................................................................................................56 Figure 15. Exchange rate coefficients (ke) as a function of log KPEW estimated from uptake of PCBs from contaminated sediment in the field (closed circles) and in the laboratory (open circles) or dissipation of PRCs in the laboratory (squares). ...................56 Figure 16. Comparison of the sediment PCB concentrations measured by immunoassay and GC. .......................................................................................................58 Figure 17. Correlation between individual measurements (non-averaged) of immunoassay (n=2-3) and GC analyses (n=3-5). ..............................................................59 Figure 18. Pore water concentrations measured by PEDs (in red) compared to measured immunoassay concentrations converted to GC-based values (a) and unconverted Aroclor 1254 based values (b). .....................................................................59 Figure 19. Correlations between converted immunoassay measurements and PED measurements. ....................................................................................................................60 Figure 20. Pore