Naval Research Laboratory Washington, DC 20375-5320 NRL/MRI6110--05-8854 Ambient PAH and Metal Concentration in Intertidal Sediments of Coaster's Harbor and Narragansett Bay MI(cid:127)CHAEL T. MONTGOMERY THOMAS J. BOYD CHRISTOPHER L. OSBURN Chemical Dynamics and DiagnosticsB ranch Chemistry Division DAVID C. SMITH University of Rhode Island Narragansett,R I January 12, 2005 Approved for public release; distribution is unlimited. REPORT DOCUMENTATION PAGE Form Approved OMB No. 0704-0188 Public reporting burden for this collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data needed, and completing and reviewing this collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information, including suggestions for reducing this burden to Department of Defense, Washington Headquarters Services, Directorate for Information Operations and Reports (0704-0188), 1215 Jefferson Davis Highway, Suite 1204, Arlington, VA 22202-4302. Respondents should be aware that notwithstanding any other provision of law, no person shall be subject to any penalty for failing to comply with a collection of information it it does not display a currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS, 1. REPORT DATE (DD-MM-YYYY) 2. REPORT TYPE 3. DATES COVERED (From -To) 12-01-2005 Memorandum 1 January 2004- 10 November 2004 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER 61-5557-K4 Ambient PAH and Metal Concentration in Intertidal Sediments of Coaster's Harbor 5b. GRANT NUMBER and Narragansett Bay Sc. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER 5.. TASK NUMBER Michael T. Montgomery, Thomas J. Boyd, Christopher L. Osburn, and David C. Smith* 5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION REPORT NUMBER Naval Research Laboratory, Code 6110 University of Rhode Island 4555 Overlook Avenue, SW Narragansett, RI 02882-1197 Washington, DC 20375-5320 NRIJMR/6110--05-8854 9. SPONSORING / MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSOR I MONITOR'S ACRONYM(S) Engineering Field Activity Northeast NAVFAC NAVFACENGCOM 10 Industrial Highway, MSC82 11. SPONSOR I MONITOR'S REPORT NUMBER(S) Lester, PA 19113-2090 12. DISTRIBUTION I AVAILABILITY STATEMENT Approved for public release; distribution is unlimited. 13. SUPPLEMENTARY NOTES *University of Rhode Island, Narragansett, RI 14. ABSTRACT Previous studies of sediment adjacent to the Old Fire Fighting Training Area (OFFTA) in Coaster's Harbor, Rhode Island, compared values for polynuclear aromatic hydrocarbon (PAH) concentrations for intertidal stations with fully submerged reference stations. NRL and URI have previously reported that the ambient sediment PAH concentrations at that site are low and typical of urbanized estuarine sediments. Bacterial PAH degradation in these sediments results in pool turnover times that suggest the PAH concentrations result from current sources. A Navy fingerprint- ing study also indicated that the likely source of PAH to Coaster's Harbor sediment is urban runoff. If intertidal and submerged sediments are being impacted by current non-point inputs to surface water, then PAH concentrations may be higher in intertidal sediments. PAHs are relatively hydrophobic and tend to collect at marine interfaces, including the air-sea interface. Wave action in the intertidal zone could deposit hydrophobic contaminants on the surface sediment. An intertidal sediment sampling event was performed in the area adjacent to the OFFTA to evaluate PAH concentrations. In addition, metals analysis was also conducted. 15. SUBJECT TERMS PAH; Newport; Narragansett Bay; Contaminated sediment; Intertidal; Metals; OFFTA 16. SECURITY CLASSIFICATION OF: 17. LIMITATION 18. NUMBER 19a. NAME OF RESPONSIBLE PERSON OF ABSTRACT OF PAGES Michael T. Montgomery a. REPORT b. ABSTRACT c. THIS PAGE UL 24 19b. TELEPHONE NUMBER (include area Unclassified Unclassified Unclassified code) (202) 404-6419 Standard Form 298 (Rev. 8-98) Prescribed by ANSI Std. Z39.1 8 CONTENTS EXECUTIVE SUM MA RY ...................................................................................................................... 1 PAH CONCENTRATION ........................................................................................................................ 1 M ETAL CONCENTRATION .................................................................................................................. 2 CONCLUSIONS ...................................................................................................................................... 2 SUPPORTING REFERENCES ............................................................................................................... 10 APPENDIX I - Data from the Second NRL Sampling (October 2002) of OFFTA in Coaster's Harbor and Reference Stations in Narragansett Bay ................................................................ 11 APPENDIX II - Pictures of Intertidal Locations from May 2004 Sampling Event .................. 18 ini AMBIENT PAH AND METAL CONCENTRATION IN INTERTIDAL SEDIMENTS OF COASTER'S HARBOR AND NARRAGANSETT BAY EXECUTIVE SUMMARY Previous studies of sediment adjacent to the Old Fire Fighting Training Area in Coaster's Harbor, Rhode Island compared values for PAH concentration for intertidal stations with fully submerged reference stations (Battelle Ocean Sciences 1994, Brown and Root 1997, Montgomery et al. 2003). The Naval Research Laboratory and University of Rhode Island (Montgomery et al. 2003) have previously reported that the ambient sediment PAH concentrations at this site are low and typical of urbanized estuarine sediments. In addition, bacterial PAH degradation in these sediments results in contaminant pool turnover times rapid enough to suggest PAH concentrations result from current non-point sources and not historical input (Montgomery et al. 2003). A recent fingerprinting study conducted by the Navy (Emsbo-Mattingly 2002) also indicated that the likely source of PAH to Coaster's Harbor sediment is surface runoff typical of urbanized areas. If intertidal and submerged sediments are being impacted by current non-point inputs to surface water (e.g. street runoff, ship traffic), then PAH concentrations may be higher in intertidal sediments. PAl-s are relatively hydrophobic and tend to collect at marine interfaces including the air-sea interface. Wave action in the intertidal zone could deposit hydrophobic contaminants on the surface sediment. An intertidal sediment sampling event was performed from shore by the Naval Research Laboratory and University of Rhode Island on 12 May 2004 in the area adjacent to the Old Fire Fighting Training Area (OFFTA) and various reference areas to evaluate PAH concentrations and spatial distribution within intertidal sediments. In addition, metals analysis *as also conducted to assess concentrations and spatial distribution within the same areas. PAH Concentration Total PAH concentrations in nine intertidal sediment samples from Coaster's Harbor and six samples from Narragansett Bay (Figures 1, 2, Table 3) ranged from 0.8 to 24.1 ppm (Table 1). Two of the three highest PAH concentrations (24.1 and 13.5 ppm) were found in the intertidal sediment adjacent to the Middletown boat launch (Latitude: 41WN 34.47000; Longitude: 71'W 17.31040). We previously reported that submerged sediment PAIl concentrations near this boat launch reference site were 1.1 ppm (Montgomery et al. 2003). PAH concentrations in the intertidal areas of OFFTA ranged from 1.5 to 21.5 ppm and averaged 7.7 ppm for nine samples whereas the adjacent submerged sediment ranged from 0.11 to 1.3 ppm (Appendix I). PAH concentrations in the six samples from the boat launch and a Tetratech reference area (west side of Narragansett Bay) ranged from 0.8 to 24.1 ppm and averaged 7.1 ppm but the adjacent submerged sediments ranged from 0.03 to 0.22 ppm (Appendix I). For each of these three intertidal sites, the average PAH concentrations from the intertidal sediments are higher than those for the nearby submerged sediment (Montgomery et al. 2003, Appendix I). In addition, the individual PAH compounds that have the highest concentration in the intertidal boat launch sediments (phenanthrene, fluoranthene, and pyrene) are the same compounds that are highest in the most impacted samples from the Coaster's Harbor survey site (Stations 2, 7, 9). These findings support the hypothesis that current surface water inputs are impacting the ambient PAIl concentrations in the sediment. Though a major PAH transport study was not performed during the course of this site investigation, the elevated PAH concentrations at the boat launch suggest that local ship traffic may be a significant non-point source. These findings also indicate that submerged reference stations should not be used as reference sites for intertidal sediments because of their differential susceptibility to current day inputs of hydrophobic contaminants to surface waters. Manuscript approved November 29, 2004. Metal Concentration Metal concentrations (measured by Battelle Marine Sciences Laboratories, Table 2) in Coaster's Harbor sediment were generally unremarkable relative to that reported for natural soil (http://pubs.usgs.gov/prof/p 1634j/html/fm range.htm) and compared with the reference sites. Conclusions This sampling compared intertidal sediment reference sites in Narragansett Bay with intertidal sediments from Coaster's Harbor. Previous samplings of intertidal sediment at Coaster's Harbor were compared with submerged sediment at reference sites. Analyses of data collected in previous samplings of the Coaster's Harbor site by Tetratech (Emsbo-Mattingly 2002), University of Rhode Island (Quinn et al. 1998), Brown and Root Environmental (1997), Battelle Ocean Sciences (1994) and the Naval Research Laboratory (Montgomery et al. 2003) have provided evidence that ambient PAH concentrations are the net result of current day inputs and biodegradation and not the result of historical input. In this study, we found elevated PAH concentrations in the intertidal sediments at both Coaster's Harbor and the boat launch relative to the submerged sediment concentration at both sites. These data support the site conceptual model that non-point source petroleum inputs (e.g. surface runoff, ship traffic) to surface water are the primary influence on ambient PAH concentrations in Coaster's Harbor sediments. Petroleum input via this pathway to these intertidal sediments would be exposed to rapid photodegradation, volatilization, and biodegradation in this relatively high energy environment. The alternate site conceptual model that the PAHl concentrations in the submerged and intertidal sediments are the result of historical input is not supported by the data. In the absence of substantial, conflicting information on PAH flux and transport in Coaster's Harbor, it is not scientifically defensible to expect that removal or manipulation of either the submerged or intertidal sediments will result in a net long term reduction in ambient PAH concentrations. In addition, it is recommended that in the future any intertidal sediment samples collected in Coaster's Harbor, adjacent to the OFFTA site, be compared to reference samples that are also collected from intertidal areas with similar environmental influences. 2 / U It I // 1 1/ < I (cid:127)I,, I o i 1 -I Ii(cid:127) !,,,,I;.,i ! SI1.2 .5llll SU Nk..I'iibhkhI Figure 2. May 2004 sampling stations for Middleton boat launch (Stations 1OM (high), 1I M (mid), 12M (low water line)) and for the Tetratech background site on the west side of Narragansett Bay (Stations 13B (high), 14B (mid), 15B (low water line)). 0 MWpPoint, Boat launch 1 Baya I1 Aq'Isk Island TrTef Coaster'$ 0 0 R T , ]i~lIMapfint*(cid:127) SNarragnett Sft ., (cid:127) Bay S"(cid:127) 0 4 Table 1. Individual and total PAH concentrations (ppm) for intertidal sediment in Coaster's Harbor (Stations 1-9), the Middleton boat launch (Stations 1OM-12M), and the west Bay reference site (Stations 13V- 15 B) for May 2004. 0 0r 2 .7 09r.8 03 .107 .24.104n.807 .0 08 .104 0.925 1 0.01 0.03 0.00 0.01 0.17 0.04 0.33 0.27 0.12 0.12 0.08 0.09 0.09 0.00 0.06 0.06 1.5 5 .0 0.23 0.100 .802 .8 10 .302 0.1 0.1 0.1 0.0 0.0 00 . 2 0.17 0.95 0.08 0.30 4.61 0.77 5.52 4.51 0.45 0.78 0.72 0.80 0.89 0.11 0.42 0.39 21.5 3 0.02 0.09 0.01 0.04 0.56 0.12 0.75 0.64 0.22 0.19 0.10 0.12 0.12 0.02 0.07 0.07 3.1 4 0.04 0.08 0.01 0.02 0.42 0.10 0.57 0.49 0.13 0.13 0.06 0.07 0.07 0.01 0.04 0.05 2.3 5 0.04 0.23 0.01 0.06 0.98 0.23 1.38 1.05 0.33 1027 0.13 0.16 10.17 0.01 0.10 0.09 5.2 6 0.12 0.37 0.03 0.11 1.76 0.20 2.43 2.13 0.61 10.48 0.33 0.39 0.43 0.06 0.25 0.25 9.9 7 0.09 0.42 0.02 0.10 2.14 0.44 2.64 1.97 0.59 0.47 0.22 0.26 0.29 0.04 0.16 0.14 10.0 8 0.07 0.30 0.03 0.14 2.84 0.62 2.46 1.91 0.61 0.49 0.24 0.29 0.30 0.04 0.16 0.14 10.6 9 0.06 0.26 0.02 0.14 2.08 0.36 0.12 1.01 0.28 0.23 0.11 0.13 0.14 0.02 0.08 0.06 5.1 10M 0.08 0.00 0.34 0.27 2.64 0.56 2.42 2.39 0.99 0.97 0.56 0.56 0.81 0.11 0.35 0.42 13.5 11M 0.11 0.00 0.71 0.62 5.49 1.20 5.22 4.24 0.47 j1.22 1.09 1.18 1.42 0.15 0.27 0.74 124.1 12M 0.01 0.00 0.03 0.03 0.30 0.05 0.34 0.37 0.18 0.21 0.10 0.10 0.16 0.02 0.08 0.09 2.1 13B 0.00 0.07 0.00 0.00 0.07 0.03 0.20 0.20 0.08 0.09 0.05 0.05 0.06 0.01 0.03 0.03 1.0 14B 0.00 0.05 0.01 0.00 0.05 0.03 0.18 0.18 0.07 0.07 0.04 0.04 0.05 0.001 0.03 0.03 0.8 j0.03 15B 0.00 0.09 0.02 0.01 0.06 0.00 0.17 0.19 0.07 0.07 0.04 0.04 0.05 0.01 10.03 10.9 5 Table 2. Metals concentrations (ppm) for intertidal sediment in Coaster's Harbor (Stations 1-9), the Middleton boat launch (Stations 1OM-12M), and the west Bay reference site (Stations 13V- 15 B) for May 2004. BATTELLE MARINE SCIENCES LABORATORIES Jill Brandenberger, Project Manager 1529 West Sequim Bay Road Sequinm, Washington 98382 (360) 6814564 SPONSOR Percent CODE Moisture Ag Al As Ba Be Ca Cd ICP- IcP- ICP- ICP- Method: GFAA OES ICP-MS OES OES OES ICP-MS Digestion: BA BA SE BA BA BA SE Achieved MDLs 0.0280 7.17 0.0277 0.104 0.0262 1.24 0.0105 Achieved RLs2 0.0890 22.8 0.088 0.331 0.0833 3.94 0.0334 NRL-1 10.2 0.0334 J 40030 5.01 278 1.35 29655 0.203 NRL-2 6.01 0.0327 J 50467 5.21 488 1.99 6872 0.331 NRL-3 7.39 0.0280 U 44128 5.87 325 1.54 57156 0.196 NRL-4 26.2 0.140 41634 4.24 399 1.44 11124 0.283 NRL-5 17.7 0.0404 J 41262 6.60 1 344 1 1.29 1 22158 0.296 1 NRL-6 25.3 0.0531 J 36540 5.93 335 1.17 26051 0.314 NRL-6 25.3 0.0524 J 40242 4.15 675 1.28 18775 0.285 NRL-7 8.03 0.0677 J 45834 7.91 386 1.51 31217 0.265 NRL-8 10.7 0.0488 J 42254 6.06 337 1.49 24187 0.214 NRL-9 4.18 0.0280 U 46505 15.0 295 1.67 1 20207 0.204 NRL-10M 3.26 0.0280 U 32911 5.75 275 1.06 5492 0.174 NRL-11M 11.3 0.0280 U 33440 2.84 306 1.05 4997 0.115 NRL-12M 3.55 0.0280 U 33611 4.49 270 1.12 13401 0.131 NRL-13B 18.4 0.0280 U 38723 1.44 1 335 1 1.33 4722 0.174 NRL-14B 16.0 0.0280 U 42271 1.63 330 1.53 1 5765 0.189 NRL-15B 16.9 0.0280 U 36212 1.68 312 1.34 5112 0.242 - 6 Table 2. Metals concentrations (ppm; continued). BATITELLE MARINE SCIENCES LABORATORIES Jill Brandenberger, Project Manager 1529 West Sequim Bay Road Sequim, Washington 98382 (360) 681-4564 SPONSOR Percent CODE Moisture Co Cr Cu Fe Hg K Mg ICP- IcP- ICP- ICP- Method. ICP-MS ICP-MS MS OES CVAA OES OES Digestion: SE SE SE BA SE BA BA Achieved MDLs' 0.0103 0.0631 0.153 1.0 0.0043 1.05 1.29 Achieved RLs2 0.0328 0.201 0.487 3.2 0.014 3.34 4.10 NRL-1 10.2 7.47 29.1 16.8 20129 0.0315 12643 17189 NRL-2 6.01 7.28 25.7 19.1 29820 0.0377 18035 7242 NRL-3 7.39 7.85 22.8 12.5 23434 0.0145 14698 12781 NRL-4 26.2 6.12 23.5 20.1 21520 0.0190 16820 6150 NRL-5 17.7 8.11 35.5 1 19.3 1 26629 1 0.0223 1 15044 1 5200 NRL-6 25.3 7.18 31.1 28.9 25071 0.0362 14764 5921 NRL-6 25.3 5.42 27.6 20.6 51364 0.0327 14289 6029 NRL-7 8.03 10.2 36.5 22.0 28664 0.0178 17895 9353 NRL-8 10.7 7.03 34.6 18.4 31443 0.0138 J 16100 6354 NRL-9 4.18 14.3 33.7 31.9 27233 0.0088 J 16466 11811 NRL-10M 3.26 8.00 19.1 13.2 25203 0.0118 J 10156 2322 NRL-11M 11.3 3.65 19.2 8.60 13050 0.0222 12773 2210 NRL-12M 3.55 4.60 21.2 13.9 15238 0.0107 J 11447 2195 NRL-13B 18.4 4.88 24.8 10.8 15362 0.0133 J 15055 4174 NRL-14B 16.0 6.57 24.2 9.90 22802 0.0128 J 16259 4133 NRL-15B 16.9 5.22 23.1 10.7 17618 0.0127 J 13926 3174 7