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HomeMy WebLinkAbout1989 Contaminant Loading to Puget Sound from 2 Marinasit EPA 91019 -89 -014 Puget Sound Estuary Program CONTAMINANT LOADING TO PUGET SOUND FROM TWO MARINAS JULY 1989 s SURVEY OF CONTAMINANTS IN TWO PUGET SOUND MARINAS Contract No. 68 -03 -3319 Work Assignment No. 2 -113 July 1989 Submitted to U.S. ENVIRONMENTAL PROTECTION AGENCY REGION 10 Seattle, Washington Prepared by E. A. Crecelius T. J. Fortman S. L. Kiesser C. W. Apts 0. A. Cotter Battelle, Marine Sciences Laboratory Sequim, Washington for Battelle Ocean Sciences 397 Washington Street Duxbury, Massachusetts 02332 EXECUTIVE SUMMARY In the summer of 1988, Battelle conducted a survey of sediment and water quality for two marinas in Puget Sound located in Port Townsend and Anacortes, Washington. The objectives of this survey, conducted for the U.S. Environmental Protection Agency (EPA), were to determine the level of selected contaminants (copper [Cu], lead [Pb], zinc [Zn], polynu- -fear aromatic hydrocarbons [PAH], tributyltin [TBT], and fecal coliform bacteria [FC]) in sediments inside and outside two marinas and estimate the mass transport of these contaminants through the entrance channel of these marinas. This survey was comprised of four major tasks: • Sediment sampling and chemical analysis at ten stations both inside and outside the ,marinas. • Water column sampling in the entrance channel during ebb and flood tides and analysis of these samples. • Collection and analyses of sediment trap samples from within and outside the marinas. • Estimate of mass transport of contaminants through the entrance channel. The sediment and water samples from within the marinas were contaminated with Cu, Pb, Zn, PAH, TBT, and FC compared to samples taken outside the marina. Outside the marinas, sediment contamination was limited to stations within about 150 m of the marina entrances. The contaminant with the greatest elevation in marina sediments compared to reference sediments was TBT. Few of the sediments exceeded Puget Sound Apparent Effect Threshold (AET) sediment quality values, but most of them exceeded Puget Sound Dredged Disposal Analysis (PSDDA 1988) screening levels for in -water disposal of dredged sediment indicating more testing would be required in order to evaluate for in -water disposal. There are no AET or other sediment values for TBT. Sediment traps were an efficient method of sampling to characterize the contamination of suspended sediments in the marinas. The concentrations of iii It contaminants were generally higher and more uniform in the trap samples than in the surface sediments, which varied greatly in grain size and contaminant level. The concentrations of contaminants in the water column of the entrance channel were significantly higher during ebbing tides than during flooding tides. The estimated net flux of contaminants out of each marina was on the order of hundreds of grams of metals /day, tens of grams of PAH /day and a few grams of TBT /day. Both marinas accumulated suspended sediment at a rate of 460 kg /day. Marinas are estimated to contribute less than one percent of the total mass loading of Cu, Pb, and Zn to the main basin of Puget bouna. ine contribution of TBT from marinas to Puget Sound may be much more significant than for other contaminants if antifouling paints are the major source of this highly toxic compound to Puget Sound. The contribution of PAN to Puget Sound was not estimated because the concentrations of PAH were frequently below detection. Fecal coliform concentrations in water were higher inside the marina than outside. The fecal coliform concentrations in the two marinas were occasionally above the State Department of Ecology criteria for AA water, and the federal standard for shellfish protection. iv 1 It ACKNOWLEDGMENTS This document was prepared by Battelle for the U.S. Environmental Protection Agency (EPA), Region 10, Office of Puget Sound and the Office of Marine and Estuarine Protection, under EPA /Battelle Contract No. 68 -03 -3319 and as part of Work Assignment 1 -113. The Technical Monitor for Battelle was Mark Curran. John Armstrong and Michelle Hiller served as Work Assignment Managers for EPA. Clare Ryan and Lawrence McCrone served as Work Assignment Managers for the Washington State Department of Ecology. Terry Walker of the Washington State Department of Social and Health Services coordinated the scheduling of the fecal coliform analyses that were conducted by the Public Health Laboratory in Seattle, Washington. v I CONTENTS EXECUTIVE SUMMARY . . . . . . . . . . . . . . . . . . . . . . . . . i i i INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 METHODS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 FIELD STUDY DESIGN. . . . . . . . . . . . . . . . . . . . . . . 1 SAMPLING METHODS. . . . . . . . . . • • • • • • • • • • • 2 Sediment Sampling. . . . . . . . . . . . . . . . . . . . 2 Sediment Trap Sampling . . . . . . . . . . . . . . . . . . . 2 Water Column Sampling . . . . . . . . . . . . . . . . . . . . 5 Bacteria Sampling . . . . . . . . . . . . . . . . . . . . . . 5 ANALYSIS OF CHEMICALS AND CONVENTIONAL PARAMETERS . . . . . . . . 6 QUALITY CONTROL RESULTS . . . . . . . . . . . . . . . . . . • • • • • • 6 CONVENTIONAL PARAMETERS IN SEDIMENTS. . . . . . . . . . . . . 9 METALS IN SEDIMENT. . . . . . . . . . . . . . . . . . . . . . . 9 METALS IN ,SEAWATER. . . . . . . . . . . . . . . . . . . . . . . 9 TRIBUTYLTIN IN SEDIMENTS AND SEAWATER . . . . . . . . . . . . . . 9 PAH IN SEDIMENTS AND SEAWATER . . . . . . . . . . . . . . . . . .10 RESULTS AND DISCUSSION . . . . . . . . . . . . . . . . . . . . .12 SEDIMENT CHARACTERISTICS AND CHEMISTRY. . . . . . . . . . . . .12 SEDIMENT CHEMISTRY COMPARED TO PUGET SOUND SEDIMENT QUALITY VALUES . . . . . . . . . . . . . . . . . . . . .15 FECAL COLIFORM BACTERIA IN SEDIMENT . . . . . . . . . . . . .16 CHEMICALS IN SEDIMENT TRAPS ... . . . . . • • • • • • . . . . .17 CHEMICALS IN MARINA WATER . . . . . . . . . . . . . . . . . . .20 vi It FECAL COLIFORM BACTERIA IN SEAWATER . . . . . . . . . . . .25 SEDIMENTATION FLUX OF CHEMICALS . . . . . . . . . . . . . . . . .27 CONCLUSIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 REFERENCES . . . . . . . . . . . . . . . . . . . . . . . .29 APPENDIX A - QUALITY CONTROL DATA . . . . . . . . . . . . . . . . .A.1 APPENDIX B - SEDIMENT GRAIN SIZE DATA AND CONCENTRATIONS OF INDIVIDUAL PAH COMPOUNDS . . . . . . . . . . . . . .B.1 vii TABLES Page 1 Method Detection Limits Obtained for This Project . . . . . . . . 7. 2 Summary of Analytical Methods for Chemicals and Conventional Parameters . . . . . . . . . . . . . . . . . . 8 3 Concentrations of Contaminants and Conventional Parameters in Sediments from the Port Townsend Marina .. . . . . . . . . . . 13 4 Concentrations of Contaminants and Conventional Parameters in Sediments from the Cap Sante Marina. . . . . . . . . . . . . 14 5 Sediment Accumulation Rates in Sediment Traps From Port Townsend and Cap Sante Marinas . . . . . . . . . . . . . . . 18 6 Concentrations of Contaminants in Sediment Trap Samples Collected in Marinas (June - October 1988) . . . . • . . . 19 7 Concentrations of Contaminants in Water Samples Collected in Marinas (June - October 1988) . . . . . . . . . . . . . . . . . 22 8 Mean Concentrations of Contaminants in Entrance Water Composite Samples and Net Discharge of Contaminants FromMarinas . . . . . . . . . . . . . . . . . . . . . . . . . . 23 9 Concentrations of Fecal Coliform Bacteria in Grab Samples of Marina Waters (Units Most Probable Number per 100 mL) . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 FIGURES 1 Locations of Sediment and Sediment Trap Sampling Stations in the Port Townsend Marina, Port Townsend, Washington . . . . . . . . . . . . . . . . . . . . 3 2 Locations of Sediment and Sediment Trap Sampling Stations in the Cap Sante Marina, Anacortes, Washington 4 viii I TABLE B6. CONCENTRATIONS OF PAH IN CAP SANTE SEDIMENT TRAP SAMPLES IA /k9 dry et Sts. CS -1 Sta. CS -1 Sts. CS -2 Sts. CS -2 Sts. CS -3 Compound 7/19/88 9/13/88 7/19/88 9/13/88 9/13/88 Naphthalene 226 859 876 493 859 2- eathyinaphalene 163 640 624 283 640 Acensphthylene 66 166 117 123 156 Acenapthene 101 132 6e B1 132 Flucrene 227 291 68 182 291 Phenanthrene 1,314 1,226 818 821 1,225 Anthracene 264 404 843 317 404 Fluoranthene 2,367 3,241 2,438 2,872 3,241 Pyrene 1,711 2,671 1,932 1,976 2,671 Benzo (a) anthracene 608 671 370 377 671 Chrysene 930 1,616 806 962 1,815 Benzo (b) fluoranthene 663 722 371 451 722 Benzo (k) fluoranthene 268 332 406 186 332 Benzo (a) pyrene 208 119 248 151- 119 Indeno (1,2,3 -c d) pyrene 216 835 556 632 835 Dibenz (s,h) anthracene 227 360 232 221 350 Benzo (g,h,i) perylene 268 521 349 346 621 INTRODUCTION Marinas have been shown to be a source of contamination to aquatic environments, especially from copper (Cu), lead (Pb), zinc (Zn), tributyltin (TBT), polynuclear hydrocarbons (PAH), and fecal coliform (FC) bacteria (U.S. EPA 1989; Marcus and Stokes 1985). In Puget Sound, located in northwestern Washington State, there are approximately 140 marinas that provide year -round moorage for about 26,000 recreational and commercial fishing boats (personal communication, Glen St. Amant, Institute of Marine Sciences, University of Washington). Approximately half of the boats are moored in the main basin of Puget Sound, which extends from the Tacoma Narrows to the southern end of Whidbey Island. Governmental agencies that are responsible for pollution abatement in Puget Sound include the U.S. Environmental Protection Agency's (EPA) Office of Puget Sound, the Washington State Department of Ecology, and the Washington State Department of Social and Health Services (DSHS). These agencies funded the following study, which had the following objectives: • Determine the extent to which sediments within and outside two selected marinas in Puget Sound exhibit increased concentrations of Cu, Pb, Zn, TBT, and PAH relative to reference areas in Puget Sound. • Estimate gradients in the concentrations of these chemicals in sediments outside the marina entrances. • Estimate the mass transport by tidal currents of chemicals and fecal coliform bacteria through the entrance channel of two marinas. METHODS Field Study Design Two marinas were selected from a list of 12 candidate marinas in Puget Sound. The selection was discussed with two staff members of the Seattle District of the U.S. Army Corps of Engineers, Kay McGraw and Bob Parry. The requirements for marina selection included 1) a single entrance channel to an enclosed marina, 2) greater than 300 boats in the marina without major s� 1 I construction activities during the last several years, 3) fine -grain sediments outside the marina, and 4) no major point sources of pollution from industrial, sewage treatment, or storm water outfalls inside or near the marina. Based on these requirements, the harbor masters of marinas and staff at the U.S. Army Corps of Engineers were contacted and the two following marinas were selected: Port of Port Townsend Marina (450 boats), and Cap Sante Marina in Anacortes (950 boats). Sampling Methods SEDIMENT SAMPLING Surface sediment samples (0 -2 cm) were collected in July 1988 using a modified van Veen grab at 10 or 11 stations within and 10 stations outside both marinas. The sediment stations were established based on tidal current patterns and water depth. Locations of the sediment stations are shown in Figures 1 and 2. Sediments were mixed in a stainless steel bowl with a stainless steel spoon before packaging sediments in appropriate containers for organic chemicals, metals; grain size, and organic carbon. _Al sampling tools and sediment containers were cleaned with either acid or *lvent according to the Puget Sound Protocols (Tetra Tech 1986). SEDIMENT TRAP SAMPLING During June to September 1988, suspended particulate matter was collected at two sediment trap stations located inside and one located outside of each of the marina entrances. The traps located outsid . he marina functioned as reference stations with little` influence from ,.`e: marina. The sediment traps were constructed of 16- cm- diameter PVC Pe with a length of 70 cm. During deployment the traps were filled with a liter of high- salinity water (4% NaCl) which also contained 2% sodium azide as a preservative and red dye as a visual indicator of disturbance of the trap. When traps were recovered, the red color was present in the bottom of the traps, indicating no disturbance. At each trap station, two traps were 2 • • a i i 1 f i f ::•:• IN 0 t0 T• O C1 T• co T• O C O Z Q W Ch Z Oa C d w E C L/ d U. o Z _ to V1 �a E � H • N ' v:a• C T• W r f r coo . r4 0 vo the m� ::•:• IN 0 t0 T• O C1 T• co T• O C O Z Q W Ch Z Oa C d w E C L/ d U. o Z _ to V1 �a E � H n� Z•t� C 3 0 L O w� W L C .r C O N b N C C •r• O E C rp •.- N .0 N � 3 L 41 C E 3 F� N � L � d � C o � N 4- C 0.4U N c 3 co to ++ O o J d ry W C.7 lt- C O Q 4) N C d w E C L/ d U. to V1 3 0 L O w� W L C .r C O N b N C C •r• O E C rp •.- N .0 N � 3 L 41 C E 3 F� N � L � d � C o � N 4- C 0.4U N c 3 co to ++ O o J d ry W C.7 lt- FIGURE 2. Locations of Sediment and Sediment Trap Sampling Stations in the Cap Sante Marina, Anacortes, Washington 4 I N GAP SANTE MARINA ...CAP. SANTE -MARINA. _' Olympic Peninsula Seattle Tacoma LUUJ ~ •1 •2 O U + Q •5 •4 •3 Z •6 •7 021 •8 09 010 012 015 017 i 20 - *13 r'a Y•16 .Sediment Station ♦ Sediment Trap. •19 0 250 S00 Scale Feet FIGURE 2. Locations of Sediment and Sediment Trap Sampling Stations in the Cap Sante Marina, Anacortes, Washington 4 I c mounted in the vertical position on a frame resting on the sediment. The water depth in the marinas was approximately 3- to 4 -m MLLW, and the top of the trap was about a meter above the bottom. The traps were sampled twice. The first sampling period was mid -June to mid -July, the second period was mid -July to mid - September. The contents of the traps were transferred to a precleaned glass container and stored on ice during transport to the laboratory. The trap-samples were centrifuged to remove the overlying water, then stored frozen and processed as a sediment sample. The overlying water was not analyzed. WATER COLUMN SAMPLING The water column near Station 10 at the entrance of each marina was sampled on three days spaced about a month apart during the period of June through September 1988. Water column samples were collected during the ebb tide and again during the flood tide on each sampling day. The samples were collected using a Teflon pump and Teflon tubing. The sampling system was flushed between samplings. The depth of the water sampling intake tube was varied systematically so that an integrated sample of the water column was taken. Care was taken to not sample within 10 cm of the surface microlayer or 0.5 meters of the bottom. Three water column samples (4 L each) were taken and composited into one ebb tide or one flood tide sample for chemical analysis of Cu, Pb, Zn, PAH, and TBT on each sampling day. Chemical analyses were conducted on unfiltered water. The suspended load was determined by filtering an aliquot of the water sample through a preweighed polycarbonate filter. BACTERIA SAMPLING Surface water grab samples (about 30 -cm depth) were collected using techniques from the Puget Sound Protocols (Tetra Tech 1986) at the same locations as the sediment stations (Figures 1 and 2) in the marinas on 3 days for enumeration of fecal coliform bacteria. Surface sediment (0 -2 cm) 5 samples were taken for bacteria analysis along with the sediment chemistry samples. No replicate field samples were collected. Bacteria samples were sent on ice to the State of Washington Department of Social and Health Services (DSHS). Suitable containers were provided by DSHS. Battelle collected and delivered the samples to DSHS for analysis. The results of these analyses were used to estimate the transport Iof bacteria out of the marinas. Analysis of Chemicals and Conventional Parameters Chemical analyses of sediment and water samples were performed for the chemicals listed in Table 1. This list includes copper (Cu), lead (Pb), zinc (Zn), 16 polynuclear aromatic hydrocarbons (PAHs), and butyltins (tributyl [TBT], dibutyl [DBT], and monobutyl [MBT]). A summary of the analytical methods for chemicals and conventional parameters is provided in Table 2. The QC requirements for chemical analyses of metals and organic compounds described in the Puget Sound Protocols were followed (Tetra Tech 1988). The conventional sediment parameters of grain size, total organic carbon (TOC), and total solids were determined according to methods described by Tetra Tech (1986). Analyses of fecal coliform bacteria in sediment and seawater were conducted at the Washington State DSHS Public Health Laboratory in Seattle, Washington, using the most probable number (MPN) technique (APHA 1985). QUALITY CONTROL RESULTS All chemical and conventional data were reviewed according to guidelines of the Puget Sound Protocols (PS Protocols, Tetra Tech 1986) for quality' control (QC) (Tetra Tech 1986 and 1988). A summary of the QC results is included in this section. More complete details of the QC review and discussion are given in the QA /QC section of this report in Appendix A. A TABLE 1. METHOD DETECTION LIMITS OBTAINED FOR THIS PROJECT Sediments (dry wt) MDL* /gZ Metals 0.1% —'— 0.1% 2,8 Copper 0.1% 5.1 Lead 1.5 Zinc Seawater MDL /L 0.02 0.02 0.5 Metal Copper Lead Zinc Polynuclear Aromatic Hydrocarbons Conventional Parameters Grain size Total organic carbon Total solids 200 µg /kg in sediments (dry wt) for individual PAH compounds listed below 2 µg /L in seawater naphthalene 2- methylnapthalene acenaphthylene fluorene phenanthrene anthracene fluoranthene pyrene benzo(a)anthracene chrysene benzofluoranthenes benzo(a)pyrene indeno(1,2,3- c,d)pyrene dibenzo(a,h)anthracene benzo(g,h,i)perylene But ltins LOD 11 µin sediments (dry wt) 0.002 µg /L in seawater *MDL = Method detection limits based on three times the standard deviation of procedural blanks or replicate analyses of a sample. 7 • N d' W W i Q a J a z 0 H Z W Z O w p Z 4 N J Q w r.r W S w 0 La. pN LAJ S J w H J Z Q Li O CC N CV W J m d M•� H O v c O L O w G1 Cr ' N •C O t w L d r.+ O E L d c+ w c L CO CO CO .� N ch CT CT �D tp tO ..� .� ..r r CT CO CO CO Esue'. >, co ++ ++ 41 w V •� • t+'f Q ; .CN•n rCNi C7 C7 +.+ a ++ CL O Q rd R) R) c Ch L r J >\ J cm J J 41 u u Li .0 L6. .0 -r C J ••- C.) O O ++ O O O O C N � •r CA 1••• H F� .: c `.L C 4. ::L :L e�P eke able C t0 L L of O E 4) O to A R = C O O —,o O U t L L L �C Q CJf CA O c O O r.+ 41 .w +•j L d C C •r f!f r- L O O O 0) Y W > > Z V) m w a) F•• !� H w 41 L 41 N 41 N V- U 41 RS O L U •r U -r U L U 1 41 C •r LL •Q O •r m N gO N O O L Q7 dc L L c L •= L= ep U 0. > O C 4.0 O 41 0 w\ 41 \ L f0 c c+ w c L ae ; O .� Esue'. >, C ++ ++ 41 w V •� •-gyp Q ; ; ; C7 C7 +.+ a ++ CL O Q Y >1 L r J >\ J cm J J 41 L L Li .0 L6. .0 -r C J ••- C.) O O ++ CT CT CA cm cm cm CA � .: c `.L C 4. ::L :L e�P eke able �7 c c L O O C G) w V �p •-gyp Q C7 C7 +.+ a ++ CL O Q go >1 r T >\ •r C 41 10 Li .0 L6. .0 -r C J ••- C.) O O ++ � � L C7 L C7 U •r � O CL 40 .r �.d C7 O cz O L C L (D •� O � C O 0 �� O r c +1 C 41 C c O EO O i O c s E C E L E c � �•, c a) �� (� +� L 41 L 41 N 41 N V- U 41 RS O L U •r U -r U L U 1 41 C •r LL •Q O •r m N gO N O O L Q7 dc L c L c L •= L= ep U 0. > O C 4.0 O 41 0 w\ 41 \ L f0 c X U X U X C.) X U 1 L L •r d. 3 W v W v W C7 W C'3 x G. G9 N J CO �7 L C G) O r •r L 10 U CL .r �.d +► H L U � C c �� O r •r N s E � E L c � �•, c a) �� (� •r 4) •r O N 3 L O N Ct +--- 41 •N -.► O •r •r L O dc ++ +► N O N •r t/9 3 Ln 3 N .G f0 c C v �..i v v ,--• d d. 3 O C r �••� �C W > •r f0 �O L Q Q co to O O O C O L O O CO d CL !- S U Cj N V C7 F- h- �7 Conventional.Parameters in Sediment • The holding times, detection limits, procedural blanks, and replicate analyses were acceptable for grain size, TS, and TOC based on PS Protocols (Tables Al to A3). • The coefficients of variation (CV) for triplicate field samples were about 15% for grain size, 2% for TS, and 1% for TOC. Metals in Sediment • The holding times, detection limits, and procedural blanks were acceptable based on PS Protocols (Table A4). • The concentrations of metals in the certified reference sediment material (NBS -1646) were within the certified range. • The CV for triplicate field samples ranged from 3% to 8 %. Metals in Seawater • The detection limits for Cu, Pb, and Zn in seawater were calculated using 5 times the standard deviation for procedural blanks as recommended in the PS Protocols. The detection limits were lower than required (Table A4). • Results for the analysis of a certified reference seawater material were within the certified range. w Tributyltin in Sediments and Seawater Only TBT analyses were required, thus QA results for TBT were emphasized. However, DBT and MBT were also frequently detected and the results reported. All butyltin results are reported for sediments as Ag /kg dry weight as Sn and for seawater as ng /L as Sn. Results were not corrected for procedural blanks or surrogate recoveries. • The detection limits for TBT in sediment and seawater were acceptable. • Holding times for frozen sediments and extracts were acceptable. Holding times for water samples before extraction exceeded the 7- day requirement by 3 weeks for several samples. This may result in lower than actual concentrations if TBT was lost during holding. 9 • Matrix spikes for TBT and DBT in sediment had recoveries in the range of 94% to 191 %. Recoveries of MBT in sediment were usually below 25 %. Spike recoveries for TBT in seawater ranged from 64% to 130% (Table A5). • The CV for TBT in field replicates were about 10% (Table A4). • The results for TBT in the intercomparison sediment, Sequim -L, are similar to those reported by NOAA -NMFS (Table A4). • A surrogate compound tripropyltin (TPT) was spiked into each sediment and seawater sample. The surrogate recoveries for sediments and water were usually in the range of 70% to 130% recommended by PS Protocols (Tables A7 -A10). PAN in Sediments and Seawater Sediments and seawater samples were spiked with three deuterium - labeled PAN surrogates before extraction. The sediments were tumbler - extracted and prepared for GC -FID analysis by a HPEC cleanup step (Krahn et al. 1988). The waters were extracted by separatory flask using the U.S. EPA.610 method. Results were not blank corrected. Usually 16 compounds were quantified individually and then summed to provide total PAN concentrations. The results for the individual analytes are reported in Appendix B, Tables B3 -B6. • The holding times for frozen sediments before extraction were acceptable based on Puget Sound Protocols (Tetra Tech 1988); however, some sediment extracts slightly exceeded the holding times for injection. Six sediment extracts were held for 60 days; that is, 20 days past the 40 -day recommended holding time for extracts. The surrogate recoveries were acceptable (Tetra Tech 1988) so the data are not qualified. The holding times for water samples collected in July exceeded the 7 -day holding time. 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V O A! .••1 b A@ O P1 A p- 1V m@ O O p f b 01 N V V p f 1A @ A O@ -a 17 A b- !V N N N N R7 N {7 ca m 03 �+@ @ A@ f A M O O f {7 f m /7 b 6" to m f �• V @ w Ip a Go W J A < um v Q.� ti N M-w b m A@ a ~ 44 -w A co N J 42 no .Or N .N.1 .@n .p.•1 N 14 w V V c V M r c w � 0 E � _ A � C C w m c v w n c c s I c Yoc t c o d 1 pt 0 w•- w- wwcc.. w w w2i w c 0.- Y �Fn•- w O.O V v i H V 1- w c 0 A w 0 w• •'b � O V w Y 0 E O d i I. .a o •- o YJx H. u 11 w °z ° as v s J x • Matrix spike recoveries for 86% of the sediments ranged between 50% and 150% (Table Al2). The Puget Sound Protocol guidelines (Tetra Tech 1988) for matrix spike recoveries is 50% to 150 %. Spike recoveries from seawater were below 50% for the two lowest molecular weight analytes but usually ranged between 60% to 150% for the other analytes (Table A5). The seawater data was qualified because of low recoveries. • The intercomparison sediment, Sequim -1, was analyzed five times to determine precision and comparability with NOAA -NMFS. The CV is usually 20% to 30% and there is good agreement with NOAA's results (Table A13). • Surrogate recoveries were usually within the Protocol range of 50% to 150 %; however, for d8- naphthalene in seawater the recoveries were below 50% and the seawater data were qualified for PAN. 11 RESULTS AND DISCUSSION Sediment Characteristics and Chemistry Surface sediments (0 -2 cm) were collected from about ten stations within each marina and at ten stations outside each marina with the objectives of determining sediment quality and the aerial extent of contaminationloutside the marinas. The station locations are presented in Figures 1 and 2. These sediments were analyzed for total solids, total organic carbon (TOC), grain size, Cu, Pb, Zn, LPAH, HPAH, TBT, DBT, MBT, and fecal coliform bacteria (FC). The results are presented in Tables 3 and 4, along with the Puget Sound Dredged Disposal Analysis (PSDDA 1988) screening levels for chemicals in sediments and the lowest apparent effects threshold (AET) values for Puget Sound sediments (Barrick et al. 1988). The sediment grain size in the Port Townsend Marina was sandy within the marina and muddy outside. The concentrations of solids, TOC, and grain size (as percent mud, <63 Am) appeared to be correlated. Coarser sediments had higher solids (less water), lower TOC, and lower mud content than did fine- grain sediments. The sediments within the Port Townsend Marina (Stations 1- 10) were sandy except at Station 9, which was 72% mud. Stations 11 and 12 located just outside the entrance of the marina were sandy. However, Stations 13 to 20, which were in deeper water, contained relatively greater than 70% mud. The TOC pattern generally followed the mud content with low TOC at sandy stations. In the Cap Sante Marina, the sediments within the marina (Stations 1 -10 and 21) were muddy (greater than 81% mud) and contained relatively high levels of TOC (greater than 3.3 %). Sediments at the three stations outside the marina (11, 12, and 15) in the entrance channel were muddy. Sediments at other stations outside the marina were coarser and lower in TOC than sediments within the marina. The concentrations of Cu, Pb, Zn, LPAH, HPAH, TBT, DBT, and MBT in surface sediment within the marinas were elevated compared to sediments of similar grain size located outside the marina (Tables 3 and 4). The finer 12 grain size sediment samples contained higher concentrations of TOC, mud, and contaminants than the sandy sediment samples. This relationship was most pronounced at Station 9 in the Port Townsend Marina where the concentrations of TOC, mud, and contaminants were 2 to 3 times higher than in the other sandier sediment in that marina. The sediments in the Cap Sante Marina were more contaminated, muddier, and more uniform in composition than those in the Port Townsend Marina. Tributyltin and its degradation products DBT and MBT were the contaminants with the greatest elevation in marina sediments compared to sediments outside the marinas. TBT concentrations ranged from 23 to 872. (mean 170) µg /kg as tin in the marinas compared to a range of 0.7 to 43 (mean 8) µg /kg outside the marinas. Because the baseline concentration of TBT is very low (about 1 to 3 µg /kg) in fine -grain sediment of Puget Sound (PTI 1988), this chemical should be a good tracer for sediment transported out of marinas or ship maintenance yards where TBT paints are applied and removed. Station 21 in the Cap Sante Marina was located within 30 m of a tidal grid which was used when painting boat hulls. The concentrations of contaminants at Station 21 of Cap Sante Marina were similar to those of other sediments in the marina. There was less elevation of the other contaminants in the marina sediments compared to TBT. Cu, Pb, and Zn are elevated in marina sediments by about a factor of 2 to 5 and LPAH or HPAH by a factor of 2 to 20 compared to sediments outside the marinas. The sediments outside the marinas exhibited little influence from contaminants in the marinas except within about 150 m of the entrance. The concentrations of contaminants in the sediments beyond 150 m outside the marinas were similar to those reported for sediments in non -urban bays of Puget Sound (U.S. EPA 1989; PNL 1986). Sediment Chemistry Compared to Puget Sound Sediment Quality Values Sediment quality values based on apparent effect threshold (AET) concentrations are available for Puget Sound. The AET value indicates the concentration of a chemical above which toxic effects have always occurred. 15 The AETs have been determined using results from several hundred sediment samples for a number of.contaminants in Puget Sound sediments (Garrick et al. 1988). The four types of AET values include 1) amphipod sediment bioassay, 2) benthos abundance, 3) oyster larvae bioassay, and 4) Microtox bioassay. For each contaminant there may be four different AET values derived from these four types of sediment quality tests. The AET values differ greatly for each contaminant and no test is consistently more sensitive. In Tables 3 and 4, the sediment chemistry results from 41 sediments collected within and outside the two marinas have been compared to the lowest AET (most sensitive for a specific chemical). Six sediment samples exceeded the lowest AET for the sum of HPAH, five from Cap Sante and one from Port Townsend (Tables 3 and 4). Only one sediment sample from Cap Sante exceeded the lowest AET for LPAH. There are no sediment quality criteria or AET values for butyltins or fecal coliform bacteria. The metals were well below the lowest AETs of 390 µg /g for Cu, 450 µg /g for Pb, and 410 µg /g for Zn. In order to maintain navigation in these marinas, dredging is occasionally required. The current regulations for in -water disposal of dredged sediments in Puget Sound allow disposal of sediments containing less than the following concentrations of chemicals without additional testing: 80µg /g Cu, 70 µg /g Pb, 160 µg /g Zn, 610 µg /kg, and 1,800 µg /kg HPAH (PSDDA 1988). Much of the sediment in these two marinas exceeds these PSDDA "screening levels" shown in Tables 3 and 4 and, therefore, will require additional testing before a decision can be made regarding in -water disposal of dredged sediments from the marinas. Fecal Coliform Bacteria in Sediment The concentrations of fecal coliform (FC) bacteria in ten surface sediment samples collected from within each marina were in the range of 150 to 11,000 MPN /100 mL of wet sediment (Tables 3 and 4). The concentrations of FC were highly variable and did not appear to be related to location or other parameters. There are no sediment quality criteria for bacteria in Puget Sound sediments. A recent study conducted in Burley Lagoon in Southern Puget 16 Sound reports concentrations of FC in the range of 230 to 11,000 /100 mL in an area that has been closed to commercial shellfish harvesting for 10 years due to FC contamination from streams (Struck 1988). Considering that recent studies, such as Struck (1988), have shown a closer relationship between FC in sediments and shellfish than between FC in seawater, these marinas would probably also be closed to shellfish growing as was Burley Lagoon-. Chemicals in Sediment Traps Sediment trap samples were collected both inside and outside the two marinas with the objective of determining the concentrations of chemicals in suspended sediment. The sediment trap samples represent an integrated sample of particles that settle out of the water column. Two traps were located inside each marina and one trap was located as a reference site about 300 m outside the marinas (Figures 1 and 2). The traps were installed in mid -June 1988 and sampled in mid -July and again in September or early October. At Station 3 of Cap Sante Marina, one trap was lost in July apparently because of strong currents, so another trap was installed, attached to a group of creosoted pilings. This trap, which was analyzed later, contained barnacle shells that sloughed off the pilings and probably was contaminated by PAH. The accumulation rate of sediment ranged from 11 to 24 g dry wt /m2 /day dry wt in the Port Townsend traps and 21 to 91 g /m2 /day in Cap Sante traps (Table 5). Dredging action may have had some effect on the accumulation rate in the Cap Sante traps and may account for the highest flux in Trap No. 1 collected on July 19, 1988. The concentrations of TOC, Fe, Al, and Si in the 11 trap samples were very uniform and similar to the concentration of these elements in Puget Sound muddy sediments (Table 6). The concentrations of Cu, Pb, Zn, PAH, and TBT were much higher in trap samples from inside the marinas than from outside. The eight traps from within the two different marinas had similar concentrations of contaminants, and these concentrations were similar to those in the fine -grain sediments inside the marinas. The two sediment trap 17 samples taken at Station 3 outside the Port Townsend Marina contained slightly higher levels of contaminants than the fine - grain sediments offshore of trap Station 3. TABLE 5. SEDIMENT ACCUMULATION RATES IN SEDIMENT TRAPS FROM PORT TOWNSEND AND CAP SANTE MARINAS Sample Sediment(a) Gras art f Dry Cslc. art # of Daya Deposition rate Marina Date Trap # wet Sod. it Dry Sod. Sampled g dry .t day giaZIday Port Townsend 7/15/88 1 in 89.47 is 13.42 28 0.479 12.0 2 in 79.93 16 12.79 28 D.457 11.4 3 out 82.00 21 17.22 28 0.815 16.4 9/12/88 1 in 245.10 23 66.37 69 0.955 23.9 3 out 138.20 21 29.02 59 0.492 12.3 10/2/88 2 in 199.19 22 43.82 79 0.555 13.9 Cap Santo 7/19/88 1 in 186.02 41 76.27 21 3.632 91.0 2 in 80.67 32 25.78 21 1.228 30.8 9/13/68 1 in 263.01 31 81.63 66 1.235 30.9 2 in 171.96 32 65.03 66 0.834 20.9 3 out 496.88 29 143.81 66 2.179 51.5 (a) Sediment traps 1 and 2 were located inside the marinas and trap 3 was located outside the marinas. The major difference between trap samples from the two marinas is that Cu and PAN are higher in Port Townsend trap samples. These higher concentrations in Port Townsend trap samples may be due to either more contamination in the marina or, conversely, more dilution of the Cap Sante trap samples with resuspended bottom sediments inside the marina. The accumulation of sediment in traps was about a factor of 2 greater in Cap Sante than in Port Townsend; the increased flux would dilute the Cap Sante contaminants. 18 p m Y i 01 S S O e+ 29 m S ON 29 WD d D W sn c Z= ~ 4 N � v p dc r.w ar �� 3q °v= _ Cc V/ w O LI J d° i� W Lai 4c CD 4c V 1� 44 w LLI e Ljj Z . a°. O V GIY .a C O • V Y H d Lid J m Q � V D O y N w 3 i ♦ wr Rf w Rf w A ti N w 10 .�i w N p rl O N Rl Rf f A 10 N w+ b f R) R! w A R) O H V #a N 10 1 R! O w 4n O m N co ..r ti 10 ow C-4 1' w IS v f O ♦ N f0 f ti O O O e O O O O O O O O 1 0 0 O O O O O O O O O '. N b O A w f (O O� N - LO O f p H w N so N m. o♦r .Oi IMN w w lac. w O O .4 wr w Rf p w O- to f A O N N i 91 f♦ N N Q i 1 R) R R 1 i w ° e c c ca •A L w A 0 A A O A 6. A R! w w Rf w /n to 7 A cm p 1-- p b w wAi w 7 O O c N ♦ w f0 10 w C 10 m N 6" w & w 1 Ir N N N N "o N N N N N N O N I 1 N w p to O ON ^+ IA w La O 'f Ri w f f f to L: b 10 ♦ w p O m p O w at w A O c R) Re w w N N Rf R) Rf R! R7 f O m 0 w.1 IA w e f p O♦ p 10 m v A w O O N'a w ♦♦ p ♦ 10 10 f to 60 f f 01 f f R! w N N AS w 10 N �0 N b N p m p^ RJ 0 A p A A p A p A p p O i t 1 1 A 10 A 10 1 1 b 1 / 1 1 w p w p 1 p > 0 rl .� w�l w•1 .A+ N ti N r1 r+ S V w A w A w A w A w IO O � � C C . N N Rl Rf .r N N N w d J d z w .=s as aa3a b� a, : :: ; : C o . N H H N H < << w 7 V h� YO- cr CL Ck. CL CL pS O O O O O d G. < -C -C t w W V V V V V b cis 19 `p � �4 09 A comparison of the level of chemicals in sediment traps with bottom sediments indicates that although the Port Townsend Marina bottom sediments are less contaminated than Cap Sante bottom sediments, the levels of contaminants in the suspended sediments are similar. The mystery is where do the suspended sediments in the Port Townsend Marina accumulate. Perhaps the suspended sediments are deposited and diluted with sand that is transported into the marina. The trap samples at Station 3 outside the Port Townsend Marina contained detectable TBT that may be originating from the marina. The sediment traps may be a more sensitive method for determining the fate of suspended particulate contaminants transported out of marinas than bottom sediment samples, which are highly variable in composition due to changes in grain size. Sediment trap samples have been used to monitor water quality in the John Wayne Marina in Sequim Bay, Washington, for three years (Apts and Crecelius 1988). The concentrations of chemicals in sediment trap samples from this relatively new (built in 1984) small marina (300 boats) are much lower than in the Port Townsend or Cap Sante Marinas. Sediment trap samples from the John Wayne Marina contain approximately_ 40 Ag /g Cu, 15 Ag /g Pb; 100 µg /g Zn, and 300 µg /kg PAH. Chemicals in Marina Water The concentrations of Cu, Pb, Zn, PAH, TBT, DBT, and MST were determined in water samples collected inside and outside the two marinas. The PAH results are qualified because some samples exceeded the 7 -day holding time and recoveries of several surrogates and matrix spike compounds were outside the acceptable range (Tetra Tech 1988). Composite water samples were collected in the entrance channel during periods of ebbing and flooding tides so the net transport of chemicals out of the marinas could be estimated. Each seawater composite was obtained by combining at least three water samples taken about one hour apart. The water samples were collected by pump with an all- Teflon pump and tube. The depth of the tubing inlet was varied during the sampling so an integrated sample of the water column was obtained. 20 In addition to the water column samples taken on three different days in the entrance channel, a "reference" water sample was taken about one -half mile outside the marinas and several "backwater" samples were taken in the marina at the end opposite the entrance. The purpose of the reference samples was for comparison to seawater not influenced by the marina. The backwater samples may be representative of the most contaminated water in the marinas. The concentrations of total suspended solids (TSS) and contaminants in water samples are presented in Table 7. The TSS concentrations were fairly uniform and ranged from 1 to 4 mg /L, except during a period of dredging activity in the Cap Sante Marina on June 28 when TSS were higher. The water samples that were analyzed for chemicals were not filtered and contained both dissolved and particulate chemicals. The concentrations of metals were generally higher in the ebb water and backwater than in the flood water or reference water. The reference water metal concentrations are typical for Puget Sound (Feely et al. 1988). The concentrations of the three metals increased with time during an ebbing tide in the Port Townsend marina on June 17. This trend is consistent with the assumption that during an ebbing tide the last water to leave the marina will be more contaminated since it has been in the marina for more hours or days than the water near the entrance. However, the contaminant concentrations in the marina water will also depend on water circulation and location of the sources of contaminants. The concentrations of metals are usually below the concentrations of the U.S. EPA chronic water quality criteria shown in Table 7. The concentration of Cu exceeded the water quality criteria in three of the 20 marina water samples. Lead and Zn did not exceed their criteria. The concentrations of PAH and butyltins were lower than anticipated and below the limit of detection limits for many of the water samples. However, later in the project, large water samples (4 L) were extracted and the organic compounds were detected. As with the metals, the backwater and ebb samples were more contaminated than the flood water. The flux of contaminants from the marinas to the surrounding waters can be estimated by multiplying the concentration of contaminants in the entrance water column on an ebbing tide times-the volume of water that is flushed out 21 N _ Z - j 0 b b o 40 A O m 0 O u O.O-� O�COO DO ^��.mn mm0 .•�.r tVON .+.r ..+ c o O w\ S 2 2 2 Z 2 .••� .•• Z .� Z O Z v ar J » »> » »> » > » »> O "- Im bbbbb bb .,.,.. bbOOCb ..o .,.•. c 2 W F� m p b b b b b b b N N A b b 0 0 0 b M- m ! N O O N W » »>. » » >. » >O QOQ oT 00 S\ O p 00000 00 bbb NNN O00 ZOi.:. OyZ w..r .. blwb bN� 000 mMM1 C 2 N C �pp11 p A -► O to N m as O N m lV .•+A O6 N 00 P f m N O O O ♦ M N N O N .+ O N O Q 3 mp NON !� �+0b♦ A ♦ATM O MO Ems OOm d pf O O w .. 0 r! .. O .r m m m 0 .• f O - .r CM N o00o0 00 000 caCDca 0 ooe . ca cm wi Z z �►10 M pN0 ♦M O. a.� V 4� MlD O b l4 O O f N WN p N10 A M N m1wA - O N N C Q U !�� V7 \p r t CM ID ► N.+NwM to NM 10 �M- 4c! mmo+AiO 0 NOO mmft .AAA+ . ftm 2 m wr Af M �+ L4. (G��7 O 01 v v T- n w g q 0 �• O O Z N 0 0 L O O L. � L L L •- v O .- O •- O O •- •- +a • •- O •- .a }� O q b W N O Is - O •O O O O •O •O 0 O •O t q - O •O •R. a V Q~ O p O ++ w O t O■ • O 4 O E b n0 0 % V a0 O N �Q o cm O y v e n0. ■v a0 O ■vw na0 V a evv c.A 0wAa ru.a w .A- - Z 1 a & .s s o w w w- 0 w ap o w v.0 t o o ar w vw-0 -0 . s v �D w o 40, n W W A OwO. L O 00 v LL 8 O.O- v o� V L v 7 .0L,O .0 .0 .2 O tip �W �LLc; L.. COD 11..a 'a (� v M O. m m m m m m N A N m P C I� CK W v m rte`. to p Z J d ow u - Q c f- c 0 h V c i 0 +o+ a w {f1 3 n N a w V � 22 v v v 0 v ac 0 4 ■ v O C 0 L O 'O c w q •O 0 u n a 0 7 q A w r � O M O I y : a o q q i w � c A 0 ■ ` = 116 C C > A O Go a.a w v v v a o � w c 0 E • o O O v O to n c q O O O 70 '00 C • O 3% c• -t •.O w SA v O .0 q 0.0 c u p- N � • � a wiv `o -'cc w vo w c O w G E q O�Z w 0 N.a� D �. 2 ■ C 11 • Z O of the marina on a given tidal cycle. The assumptions are that 1) concentrations of contaminants in the ebb and flood composite samples are representative of seawater leaving and entering the marina, and 2) there is only one tidal exchange per day that has a range of 9.1 feet. The tidal prism volume was estimated for each marina using the area of the water surface at mid -tide height (about +4.5 feet) and an average tidal- excursion of 9.1 feet. The tidal prism volumes are 3.0 x 105 m3 for Port Townsend and 5.3 x 105 m3 for Cap Sante. The net flux of contaminants was estimated from the differences in the mean concentrations of contaminants in the ebb and flood composite water samples (Table 8). TABLE 8. MEAN CONCENTRATIONS OF CONTAMINANTS IN ENTRANCE WATER COMPOSITE SAMPLES AND NET FLUX OF CONTAMINANTS FROM MARINAS No. of TSS Cu Pb Zn PAM TBT Composites (mg /L) (µg /L) (µg /L) (µg /L) (ng /L) (ng /L) Port Townsend Marina Ebb 8 2.2 1.41 0.12 1.36 <25 7 Flood. 3 3.65 1.10 0.10 0.94 <25 5 Ebb -Flood - -1.53 0.31 0.02 0.42 <25 2 Net Flux g /day -4.6 x 105 93 6 126 <8 0.6 Cap Sante Marina(a) Ebb 2 2.46 1.47 0.15 1.22 58(b) 20 Flood 2 3.32 0.72 0.06 0.71 28(b) 6 Ebb -Flood - -0.86 0.75 0.09 0.51 30(b) 14 Net Flux g /day -4.6 x 105 400 48 270 16 b 7 (a) Data for June 28 were not included because of dredging activity. (b) PAM based on only four water samples from Cap Sante Marina. PAH data for seawater were qualified because of holding times, low matrix spike or low surrogate recoveries. 23 v The net discharge results presented in Table 8 are in units of grams per day. The flux of TSS is negative which indicates the marinas are accumulating sediment, each at a rate of 4.6 x 105 g /day or 0.46 metric tons /day. The marinas are discharging metals, PAH, and TBT. The discharge rates range from as low as 0.6 g /day of TBT to as high as 400 g /day of Cu. Cap Sante Marina discharges more than Port Townsend because the marina is larger and more contaminated. The obvious sources of Cu and TBT in marinas are antifouling paints (Champ and Bleil 1988). Although most pleasure boats are now prohibited from using TBT paint, there are still boats coated with TBT paint that will release TBT for several years. Copper may also be released from the corrosion of copper, brass, and bronze hardware on boats. A conservative estimate for the amount of antifouling paint used per year in a marina is one quart of paint (containing 100 g of Cu and 50 g of TBT) per boat (Champ and Bleil 1988). Assuming half the chemical content of bottom paint is released to the water column, and does not settle out but is flushed out of the marina, Port Townsend would be discharging 62 g Cu /d, 31 g TBT /d, and Cap Sante would be discharging 130 g Cu /d and 130 g TBT /d. These approximations for bottom paint underestimate Cu discharge rates and overestimate TBT. The breakdown of TBT into DBT and MBT has not been accounted for, which may account for the poor agreement between assumed release rate and field measurements. Also, some of the chemicals have accumulated in the sediment. If the measured discharge rate of contaminants from Cap Sante Marina were extrapolated to all the 13,000 boats that are moored in slips in the main basin of Puget Sound, the annual release of contaminants to the main basin of Puget Sound water column would be 2,000 kg Cu; 243 kg Pb; 1,350 kg Zn; 80 kg PAH; and 35 kg TBT. In comparison, other known sources of contaminants to the main basin of Puget Sound contribute much more of the Cu, Pb, Zn, and PAH than marinas. The total annual inputs of Cu, Pb, and Zn to the main basin of Puget Sound are 222,000 kg, 109,000 kg, and 369,000 kg, respectively, of which about 20% to 40% are contributed by municipal and industrial outfalls (Paulson et al. 1988). Marinas are estimated to contribute less than 1% of these 24 metals to Puget Sound. Because of the limited number of water samples that contained detectable PAH, the estimated contribution of PAH from marinas was not determined. We are not aware of estimates of annual loading of TBT to Puget Sound. Limited analyses of Puget Sound sediment for TBT indicate that sediments near marinas and ship maintenance areas have increased levels of TBT (Crecelius et al. 1989; PTI 1988). Fecal Coliform Bacteria in Seawater The concentrations of fecal coliform (FC) bacteria in the entrance channel composite samples were very low, usually near the detection limit of 1.8 MPN /100 mL (Table 7). Additional water samples were collected for bacterial analysis at several locations throughout the marina. These grab samples were collected at a depth of about 30 cm below the water surface, near the locations of the sediment stations. The geometric means for FC concentration ranged from a high of 49 MPN /100 mL in Port Townsend on September 12 to a low of 2 MPN /100 mL in Cap Sante on July 19 and September 9 (Table 9). TABLE 9. CONCENTRATIONS OF FECAL COLIFORM BACTERIA IN GRAB SAMPLES OF MARINA WATERS (UNITS MOST PROBABLE NUMBER PER 100 mL) Number of Surface Water Grab Geometric Mean Samples Collected Throughout Fecal Coliform Bacteria Date the Marina MPN /100 mL Port Townsend Marina 9/12/88 9 49 10/2/88 12 10 10/9/88 12 4 Cap Sante Marina 7/19/88 7 2 9/13/88 9 2 25 The State of Washington Department of Ecology (WDOE 1980) has set standards for the concentrations of FC for classification of water quality. Marine waters of the highest quality (Class AA- extraordinary) shall not exceed a geometric mean of 14 FC /100 mL and not more than 10% of the samples are to exceed 43 FC /100 mL. A Federal marine water quality limit of 14 MPN /100 mL was set by the Public Health Service under the National Shellfish Sanitation Program (Department of Health, Education and Welfare 1965). The geometric mean concentration for 33 samples from the Port Townsend Marina was 11 FC /100 mL with 36% of the samples exceeding 14 FC /100 mL. The geometric mean for the Cap Sante Marina was 2 FC /100 mL with no samples exceeding 14 FC /100 mL. For comparison, levels of FC ranged from <1.8 to 33 with a geometric mean of 4 MPN /100 mL for grab samples taken quarterly in the John Wayne Marina located on Sequim Bay, Washington (Apts and Crecelius 1989). These limited surveys indicate FC levels in these marinas occasionally exceed the WDOE AA standard. However, outside of marinas dilution should rapidly reduce the concentration of FC below the WDOE standard of 14 FC /100 mL. The number of FC discharged from a marina can be compared with the quantity discharged by a point source such as a sewage outfall or stream. Because near - surface water samples may contain higher concentrations of FC than samples at depth,-these estimates for FC discharged from marinas may be greater than actual. The Port Townsend Marina exchanges 3.0 x 105 m3 /d, or 76 million gal /d (MGD). of seawater due to the tidal prism of the marina. For comparison, Bell Creek, a small creek that drains farm land and flows into the entrance of Sequim Bay, discharges 12.8 x 103 m3 /d. Samples from Bell Creek contained 2,200 FC /100 mL and discharged 2.8 x 1011 FC /day during a survey conducted by Brastad et al. (1987). If the Port Townsend Marina water contains a geometric mean of 11 FC /100 mL, this would result in the discharge of 3.2 x 1020 FC /day, or contribute a tenth as much bacterial contamination to seawater as a small contaminated creek. 26 Sedimentation Flux of Chemicals The accumulation of chemicals in the sediments within the marinas cannot be accurately estimated from the sediment traps because of resuspension. Another method to estimate contaminant sediment accumulation rate in the marinas is to assume the TSS that is accumulating in the marinas at a rate of 460 kg sediment per day has the composition of the sediment collected in the traps. In the Port Townsend Marina this will result in the daily removal from the water column of 114 g Cu, 16 g Pb, 98 g Zn, 19 g PAH and 0.23 g TBT. By comparison, if the sediment trap flux of 15.3 g /m2 /d was extrapolated over the area of the Port Townsend Marina, the daily removal rate of particulate contaminants would be 417 g Cu, 59 g Pb, 360 g Zn, 71 g PAH, and 0.82 g TBT. 27 CONCLUSIONS The methods used in this study to determine the loading of contaminants from marinas to the surrounding environment were successful. However, because this limited survey only covered the summer season in two marinas, the results may not be applicable to other seasons or marinas. Two marinas were examined for sediment quality, water quality, and the geographical extent of contamination near the marinas. Although sediments within the marinas contained elevated levels of Cu, Pb, Zn, PAH, and TBT, the levels usually did not exceed the Puget Sound lowest sediment AET values but did exceed the PSDDA screening levels. The distribution of these contaminants in sediments outside the marina entrances indicates only minor local contamination resulting from contaminants transported out of the marinas. The concentrations of Cu, Pb, Zn, PAN, TBT, and fecal coliform bacteria are significantly higher in water flowing out of the marinas during ebbing tides than in water entering the marinas on flooding tides. The water in these marinas usually does not fail the U.S.- EPA marine water quality criteria. The estimated annual flux of contaminants from marinas to the main basin of Puget Sound is estimated to contribute less than 1% of Cu, Pb, and Zn compared to the total input of these contaminants to the main basin of Puget Sound. Because of limited data on the sources and fate of PAH and TBT in coastal waters, the significance of marinas as a source of PAH and TBT to Puget Sound cannot be assessed at this time. The concentrations of FC in marina waters were occasionally higher than the WDOE criteria for AA water quality and the Federal standard for shellfish protection. Marinas should have little impact on water quality and shellfish quality located outside the marinas because dilution will reduce the concentrations to acceptable levels below water quality criteria. REFERENCES APHA. 1985. Laboratory Procedures for the Examination of Seawater and Shellfish. 5th ed. American Pub Tc Health Association. 144 pp. Apts, C. A., and E. A. Crecelius. 1989. A S Traffic on the Levels of Coliforms in Li Ange es, Port Ange I es, Washington. Effects of Boat ms. Protothaca Port Barrick, R., S. Becker, L. Brown, H. Bellar, and R. Pastorok. 1988. Sediment Qualitv Values Refinement: 1988 Update and Evaluation of Puaet Sound AET, Volume I. Puget Sound Estuary Program, Office of Puget Sound, Region 10, U.S. Environmental Protection Agency. Bloom, N. S., and E. A. Crecelius. 1984. '"Distribution of Silver, Mercury, Lead, Copper and Cadmium in Central Puget Sound Sediments." Mar. Chem. 21:377 -390. Brastad, A., S. Waldrip, and B. White. 1987. Sequim Bay Water Quality Pro *Jec..t.. Final Report. Clallam County Department o Community Development, Division of Environmental Health. Champ, M. A., and D. F. Bleil. 1988. Research Needs Concerning Or anotin Compounds Used in Antifouling Paints in Coast a Environments. Prepared by Science App ications International Corporation for NOAA. Department of Health, Education, and Welfare. 1965. "Sanitation of Shellfish Growing Areas." In National Shellfish Sanitation Pro ram Manual of Operations, Part I, e . L. S. Houser. U.S. Department of Health, Education, and Welfare, Public Health Service, Washington, D.C. Feely, R. A., A. J. Paulson, H. C. Curl, Jr., and D. Tennant. "The Effect of the Duwamish River Plume on Horizontal Versus Vertical Transport of Dissolved and Particulate Trace Metals in Elliott Bay," pp. 172 -184. In Proceedinas of the First Annual Meeting on Puaet Sound, Volume 1. Krahn, M. M., C. A. Wigren, R. W. Pearce, L. K. Moore, R. G. Bogar, - W. D. MacLeod, Jr. 1988. Standard Analytical Procedures of the NOAA National Analytical Facilitv. 1988--New HPLC Cleanup and Revise Extraction Procedures for Organic Contaminants. Prepared for NOAA National Status and Trends Program and the Outer Continental Shelf Environmental Assessment Program by Environmental Conservation Division, Northwest and Alaska Fisheries Center, National Marine Fisheries Service. Marcus, J. M. and T. P. Stokes. 1985. "Polynuclear Aromatic Hydrocarbons in Oyster Tissue Around Three Coastal Marinas." Bull. Environ. Contam. Toxicol. 35 :835 -844. 29 Nielson, K. K., and R. W. Sanders. 1983. "Multielement Analysis of Unweighed Biological and Geological Samples Using Backscatter and Fundamental Parameters. Adv. X -Ray Anal. 26:385 -390. Pacific Northwest Laboratory. 1986. Reconnaissance of Eioht Bays in Pu et Sound Volumes I and II. Prepared for the U.S. Environmental Protection Agency, Region X by Pacific Northwest Laboratory, Battelle Marine Research Laboratory, Sequim, Washington. Paulson, A. J., R. A. Feely, H. C. Curl, Jr., E. A. Crecelius, and C. P. Romberg. 1988. Sources and Sinks of Pb Cu Zn and Mn in the Main Basin of Puget Sound. NOAA Technical Memorandum, ERL PMEL- Puget Sound Dredged Disposal Analysis. 1988. Management Plan Re ort MPR Unconfined Open-Water Disposal of Dredged Material, Phase I Centra Pug et Sound). PTI Environmental Services. 1988. Puget Sound Dred ed Disposal Analysis Baseline Survey of Phase I Disposal Sites. Draft Report. Prepared for Washington Department of Ecology, Olympia, Washington. Struck, P. H. 1988. "The Relationship Between Sediment and Fecal Coliform Levels in a Puget Sound Estuary." Journal of Environmental Health July /August 403 -407. Tetra Tech, Inc. 1988. Recommended Protocols for Measurina 0 anic Compounds in Puget Sound Sediment and Tissue Samples. Draft Report TC- 33 8 -14. Prepared for U.S. Environmental Protection Agency, Region 10. Tetra Tech, Inc. 1986. Recommended Protocols for Measurfno Selected Environmental Variables in Pu et Sound. Final Report No. C- 9 1 -04, Prepared for Puget Sound Estuary Program by Tetra Tech, Inc., Bellevue, Washington. U.S. Environmental Environmental Protection Agency. 1989. 1988 of Unger, M. A., W. G. MacIntyre, J. Greaves, and R. J. Huggett. 1986. "GC Determination of Butyltins in Natural Waters by Flame Photometric Detection of Hex 1 Derivatives with Mass Spectrometric Confirmation." Chemosphere 15c4 :461 -470. Washington State Department of Ecology. 1980. Laws and Regulations; Water Pollution. Washington State Department of Ecology, Olympia, Washington 30 APPENDIX A QUALITY CONTROL DATA �i t TABLE Al. QUALITY CONTROL REVIEW - CONVENTIONALS Grainsize Gravel 1. Sample collection, preparation and storage - Acceptable Samples were collected in July using methods recommended in QA Project Plan and PSEP protocols. 5.89 % 60.30 % Recommended Procedure Actual Procedure Used surface collection 0 -2 cm) same clean plastic jars 40.39 same on ice (4 °C) 0.00 same max., holding time - 6 months 4 months 2. Detection limits - Acceptable 7.02 Recommended 37.90 Actual 0.11% 0.03 0.01% 3. Procedural blanks - Not Required 4. Replicate Analysis - Acceptable Field Reolicates A.1 Gravel Sand Silt Clay CS -1 Rep -1 0.00 % 5.89 % 60.30 % 33.81 CS -1 Rep -2 0.07 4.64 54.90 40.39 CS -1 Rep -3 0.00 10.53 49.97 39.50 mean 0.02 7.02 55.06 37.90 S.D. 0.03 2.53 4.22 2.91 A.1 TABLE A2. QUALITY CONTROL REVIEW - CONVENTIONALS Total Solids 1. Sample collection, preparation and storage - Acceptable Samples were collected in July 1988 using methods recommended in QA Project Plan and PSEP protocols. Recommended rocedure Actual procedure used surface collection k0 -2 cm) same clean plastic jars same on ice (4 °C), max. holding time - 6 months same 4 months 2. Detection limits - Acceptable Recommended Actual 0.10 ---- 0.01% 3. Procedural blanks - Not Required 4. Replicate Analysis - Acceptable Field Replicates % Total Solids mean S.D. RPD CS -1 Rep 1 28.69 29.09 0.46 1.6% CS -1 Rep 2 28.86 C5-1 Rep 3 29.73 A.2 TABLE A3. QUALITY CONTROL REVIEW - CONYENTIONALS Total Organic Carbon 1. Sample collection, preparation and storage - Acceptable Samples were collected in July 1988 using methods recommended in QA Project Plan and PSEP protocols. Recommended rocedure Actual procedure used surface face collection (0 -2 cm) same clean plastic jars same frozen same max. holding time - 6 months 4 months 2. Detection limits - Acceptable Recommended Actual 0.1% 0.01% 3. Procedural blanks - Not Required 4. Analysis of Standard Reference Material (SRM) - Acceptable % Total Sample Organic Carbon mean S.D. RPD MESS -1 REP 1 2.28 2.32 0.04 1.7% MESS -1 REP 2 2.35 5. Replicate Analysis - Acceptable Field Replicates TOC (dry wt) mean S.D. RPD CS -1 Rep 1 3.49 3.51 0.04 1.1% CS -1 Rep 2 3.57 CS -1 Rep 3 3.48 A.3 TABLE A4. QUALITY CONTROL REVIEW - METALS ANALYSIS 1. Sample collection, preparation and storage - Acceptable Samples were collected between July and September 1988 using methods recommended in QA Project Plan and PSEP protocols. Recommended rocedure surface co ection 0 -2 cm) acid clean plastic or glass containers frozen sediments acidified seawater max. holding time - 6 months 2. Detection limits - Acceptable Actual procedure used, same same same same 4 months All analyses achieved level of detection required. Detection limit required Sediments (µq /-q) Cu 1 Pb I Zn 1 Butyltin 0.02 Seawater (ag/L) Cu 0.05 Pb 0.05 Zn 0.5 Butyltin 0.02 Detection limit obtained 1 1 1 0.001 /L 0.04 0.02 0.22 0.015 3. Procedural (preparation) blanks Procedural blanks were analyzed where appropriate. Metals in sediment were analyzed by XRF which does not provide blanks. Graphite AA for Cu, Pb, and Zn in seawater A.4 (tt4 /L) Cu Pb Zn Rep. 1 0.036 0.023 0.22 u Rep. 2 0.024 0.023 0.22 u Rep. 3 0.042 0.023 0.22 u A.4 TABLE A4. CONTINUED Rep. 4 0.036 0.035 0.023 0.023 0.22 u 0022 u Mean S.D 0.001 5 times S.D. 0.04 0 0.02 u 0.22 u Blanks for But ltins in Sediment (Aqlkq ssumin 10 q dry sediment Tri -butyl Di -butyl Mono -butyl t__ — tin tin Rep. 1 0.5 u 0.8 0.6 u 1.4 u 0.9 u 1.1 u Rep. 2 Blanks for Butvltins in Seawater (nq /L Assumino 1 L sample size TBT DBT MBT Rep. 1 2.2 u 0.6 u 3.2 u 0.8 u 1.4 u 0.3 u Rep. 2 4. Analysis of Standard Reference Materials (SRM's) Graphite AA for Metals in Seawater /L Standard Cu Pb n CASS -1 0.273 0.227 0.899 CASS -1 (cert. values) 0.291 *0.021 0.251 :0.021 0.980 *0.099 The percent difference between actual recovery and certified values is given below. Recovery is required to be within 20 %. Percent Difference Cu Pb Zn -6.2• -9.6% -8.3% 0 X-ray Fluorescence Method for Cu Pb and Zn in Sediment Conc.-in ua /o dry wt (except Al, Fe given in %) Standard Cu Pb Zn NBS 1646 STD Rep 1 21 29 135 Rep 2 21 26 136 Rep 3 19 25 135 A.5 TABLE A4. CONTINUED NBS 1646 Cert. 18 18 28 .2 28.8 138 :6 Values Percent difference 6 2 Rep 1 16 1 Rep 2 6 11 2 Rep 3 n,+�tt;ns in Intercomparison sediment (µg /kg as Sn dry wt) Tri -butyl Di -butyl Mono -butyl Standard Tin T— Tin- -- Tin Sequim -1 66 4 u 4 u Rep 1 Rep 2 37 1 u 2 u Sequim-1 (value 30 N.S. N.S. anal zed by NOAA� 5. Matrix spikes Butyltins in Sediment (µg /kg as dry wt) TST DST MST Sediment Trap CS -2 9 -13 -88 461 Spiked 231 jcg /kg 748 104 406 32 87 % recovery 124% 131% 24% Sediment PT -3 Spiked 54 µg /kg 26 73 11 61 3 7 % recovery 94% 100% 9% Sediment CS -21 Spiked 98 gg /kg 226 412 60 166 6 58 % recovery 191% 110% 545o, A.6 TABLE A4. CONTINUED 6. Replicate Analysis Field Replicates (Ag /g dry wt) ,X-rav Fluorescence Method for Metals in Sediments Cu Pb Zn CS -1 Rep 1 7-2 87 7 30 19 156 CS -1 CS4 Rep 2 Rep 3 80 30 152 mean 79 6.1 29 0.94 147 9.6 S.D. Butyltins in Sediment (µg /kg as Sn dry wt) Tri -butyl Di- butyl Mono -butyl Tin Tin _ Tin CS -1 Rep. 1 2 264 316 57 70 6 13 CS -2 CS -3 Rep. Rep. 3 298 65 14 mean 293 64 5 11 4 S.D. 22 A.7 W H 6 Q W N Z p.l H m H D a Q Q a O N W r.n a N X sH i Li O W O V W H W V Q: W a Q W J m Q F� J 7A C L o 0 v o o .r K v 1- m y i � e 0 0 V i tY w CL O v I d O O a O O O b f M b ti♦ b f o b -I 13 i b 90 1 0..� ti N O N 1 w.l ♦ 1 N ♦ M p O 1 rl 1 M b O P O a•1 M b 1 a in .w b ♦♦ M O /► O O a a O cm N 1 f b m m ti �. 1 ti N N N M O cm 1 .Oq wel .♦•1 w♦i ti N 1 O O m♦ M N N O O A O N N O 1>D O O M 1 b b A m m O O f ♦ M M M O b 1 f 0 O .+ 1. rl .r rl r•1 wa .••1 .r N .•r r+ N 'Co. M N N 1 Rf f O O O 0 0 M M N N O O♦ 1 M b ti 1 b .. 0 o u o 0 O O 0 - .. C C O p 1 1 1 1 1 I t 1 1 O O O c O C o t o 0 0 l w u— .> c •- '40 I I 1 1 03 0 me c.0 "I !� G- w al C O O i v d 0 O O 0 O C t O L C L o o w O ,L w v v pl w w ■ w p. L v c v v v v w a c w w .c S p p 0 C a o O O N L O Y .O. .Ni L ♦ w w L w L L c O w O O O C C O b b O� C c S H _ ,p. 16 oC pc .00_ OC m V m 0 0 30C m m K Z N< t 1L E< lL P.L. p to M 1 1 1 1 t 1 1 1 1 1 1 1 1 1 1 1 1 a M - O O Op m N ♦ N IL I 1 / 1 1 1 1 1 1 1 1 1 1 1 1 I i m 1 1 1 1 O � O p' rl ♦ b p O 1 1 1 1 i 1 1 1 1 1 1 1 1 1 1 1 1 tD 1 1 1 1 N ~ p' b t� O oc wl vp OC CL 0 p p c 0 p ■o v A O a O O O b f M b ti♦ b f o b -I 13 i b 90 1 0..� ti N O N 1 w.l ♦ 1 ♦ O M O A b b r+ O O N b M N N ♦ M p O 1 rl 1 M M to m A a O1 M N -I N N P. b M 1 M b O P O a•1 M b 1 a in .w b ♦♦ M O /► O O a a O cm N 1 f b m m ti �. 1 ti N N N M O cm 1 .Oq wel .♦•1 w♦i ti N 1 O O m♦ M N N O O A O N N O 1>D O O M 1 b b A m m O O f ♦ M M M O b 1 f 0 O .+ 1. rl .r rl r•1 wa .••1 .r N .•r r+ N 'Co. M N N 1 Rf f O O O 0 0 M M N N O O♦ 1 M b ti 1 .. 0 o u o 0 O o 2% c S a p w- 0 - .. C C O ai .i L fl L v w C 0^ w a w o IV .0 Lo rl os c e 0 w vI L L L c u C p O O O c O C o t o 0 0 l w u— .> c •- IS v O O O C >> `y� M O w .G O �. L w .G O w �• �' p N i c.0 "I !� G- w al C O O i v d 0 O O 0 O C t O L C L o o w O ,L w v v pl w w ■ w p. L v c v v v v w a c w w .c S p p 0 C a o O O N L O Y .O. .Ni L v .► G w w L w L L c O w O O O C C O b b O� C c S H _ ,p. 16 oC pc .00_ OC m V m 0 0 30C m m K Z N< t 1L E< lL P.L. p m c a Y L O L O w O L 0 0 0 e L 0 p w x L w y ■ i 0LO 0 n L 0 .Oi w f c Y V r � .o w C 7 Q 0 L w 0 c C OC L O M v n w o c w •� r CL. w c L wLTa " A of a N - N TABLE A6. QUALITY CONTROL REVIEW - PAH 1. Sample collection, preparation and storage - Acceptable Samples were collected during the summer of 1988 using methods recommended in QA Project Plan and PSEP protocols. Recommended procedure sur ace collection -2 cm) glass with teflon lined lid frozen ( -20 °C), max. holding time - 12 months 2. Detection limits - Acceptable Actual procedure used same same same 4 -6 months All analyses achieved level of detection required. Level of detection (Based on 5 times the standard deviation of replicate method blanks, see Tables All and A13) Aromatic Hydrocarbons Sediment (Ag /kg dry wt) Required Achieved 0 Water (8g /L) Required Achieved i' naphthalene 200 25 2 0.1 2- methylnaphthalene 200 25 2* - -* acenaphthylene 200 25 2 0.03 fluorene 200 25 2 0.03 phenanthrene 200 25 2 0.03 anthracene 200 30 2 0.5 fluoranthene 200 25 2 0.03 pyrene 200 20 2 0.05 benzo(a)anthracene 200 20 2 0.03 chrysene 200 20 2 0.03 benzofluoranthenes 200 20 2 0.5 benzo(a)pyrene 200 20 2 0.03 indeno(1,2,3- c,d)pyrene 200 20 2 0.2 dibenzo(a,h)anthracene 200 20 2 0.5 benzo(g,h,i)perylene 200 20 2 0.3 *2- methylnaphthalene was not quantified in water samples. 3. Procedural (preparation) blanks - Acceptable For all compounds listed above the results were ND (not detectable). See Table A -11. A. 9 1 TABLE A6. CONTINUED 4. Matrix spikes in water and sediment are presented in Tables A5 and Al2. Four compounds had poor recoveries so PAH data for seawater are qualified. 5. Surrogate recoveries of three compounds are given with results in Tables A7 -Al2. Compound d8 was usually below the acceptable recovery of 50% in seawater and the seawater data were qualified. 6. Replicate analysis of five samples of the Sequim -1 intercomparison. Sediment are reported in Table A13. A.10 W 1- <_ O C �z p W Z N G Z 2 W O p C Z O = W M- Z cc w.� p za o_ � d W F- O G- X L" E W N N W � C � G O � C W W N C N P4. G W J C G M- r L f A A .+ N W N A n. O♦ O f N O, N m f f O 0 0 0 W O O A O n O �w A ,w m n 0 m A O r V Y s O Y° w w w w w N �+ �+ •'+ cr .a c O A00 wf OWfA00 A OA N wl fn .m Y O n A A O O 40 O A b ° w d N Y! f N A O N O O m O e 0 w w n n f f n o f b W A o f o A f io A f m m o m m o 0 0 0 o m o m m o m o m o 0 .� o O O O O O O O O O O O O O O O O O O O O Y V y Y 1 1 1 1 1 1 I I 1 n1 r m r m o o mo 0 0 o e o m m m o 0 0 0 0 0 0 o m o m o 0 o m o 0 0 0 ID wm f . wf w o f f O o` wi o wf wf us wl N N N o 0 o N N N o N o o cv o 0 o N o 0 0 o m m m o m m m e o o e o m o m m m m o m I I 1 G i N N I N N N N C" -r N N N N m O N N O N w N y Y w I I 1 , I 1 , 1 , I 1 , 1 w w N N '. I .Ni O .N., ..- — .N., — .N-, ..- O .Nn O — — — — = L m m m m m m m m m m o o m m m m m m m m v y Y V I I I N N n Cv m m m w !9 A A Rf .0.. A A A A n w N N w N N w w I , I I I I I , ,o O Y w D. w N 1 c A.11 W 1-- G C7 a G C Z N C D� C W 1� u¢ G N � C O U 1�1 Z W ►� 7 m r � O C N C C J X OW i W.1 Lei W C.7 W J � C W W N C N G W m G f .w A tl P m o-- f tl A A m ^ ^ P ^^ o f o O o Z. P P C O v O .w uO .r ., ... ., .., .. .. m J _ O f tl N O tl A• o o A tl ^� m P o o A N N A Y .0.. W tl tl O tl A O m A 40 @ w 10 m tl f f P tl 10 a Y) fa o 0 L f O O 1�1 wy P A N7 �► 10 P! f N M! P f M m M tl f of tl A f m tl f f f W to tl R! CD m m rf f wf v m m m m m m m m m m m e m m m m m m m m o m ae .� o m m o o m m m m m m m m m m m m m m m m m m m ._ 1 1 1 1 1 1 1 1 1 1 1 f 1 1 / 1 1 1 I 1 1' y N N N N N N N N N O N N N N N N N N N N N N O o u o 0 0 0 0 0 0 o of o o 0 0 0 0 0 0 0 0 0 J o m m m m o o m o o m m m O m O m m o o v m m O e m m r C4 j. e m m m O. O H. O N . ^ ^ N m O ^ e V A N N N N N Cr N . ' ' ' ' ' ' ' CI C& ^ O N O m 0 O 0 0 0 O O O W y m m o m m 1 m m 1 o 1 w m m ' ' m ' m p y O O O O O N O O O O O O O O O O O N O O N O J D A •o O wr .+ .r ..r ..I .^ 4 N N N N ^ N y Co C r - - - w ^ t L @ @ @ @ m P @ @ m m m m @ m m m m P@ m m @ m u m m ao m m m m m m m® m m m m m m m m m@ m m J tl O m6 O P t0 .tll O O @ e7 o a .O..I N1 Nf I� �O . a:, l7 w t'9 J 1t r I o u c e N �+ N N I Ew C^ N y... .:. .+ N O f 10 m A m P .•r •• I I •• •• "^ .r N N I w v �.o v v v u u v v u v u u v u A.12 A.13 ►� N Pf O � .►�. O r+ O O� .Na r W 2 .y. Y � O U yj we o w w .► w o a o o• Q ° w m b O A m e W Y d Q m O m Y/ m e N ca o 40 w m o O N C W CC J N m m m o o e o e o 0 0 •2 m o o m o 0 0 o m o m C W t� r- m C v m m m o 0 0 0 o e m o 'Z y m m o 0 0 o e o 0 0 0 Z �.. v A ^ LZ — — U N W ZZ e 101, o m m o 0 o m o m m o 0 N N N H " "- M N N .•s ww wr N O y Y ,,.r C M d •o h- � - Y y m m O O m P P 4602 e e m m m m m m m m m m X W Q Y V N m A A A ti P P RJ 6" 40 A O O O O O N .0. Z C ° yx y T.. J C. m m o m o 0 o e 2 0 0 0 m m o 0 0 o m o 0 0 - P. a.. - .e. y .N. - w. P A^ r► w a w P O O O O O O O O O C W d � e C y .. .r N N N N s� � � � d i w v u v N a C- a a A.13 Z Q =_ W1•� h- m Q � D O oa v c W G. ZC' � O W Z Vf N �rWnJ C W.J O H r- v X W C W C W Z C 3 P.1 C CC J O Z G G ... O G liJ J C� C H A.14 A on A O O N a c M O O + a a P P H. ° N + AI a + A Z P a N A O m A m G �.•� Af 0 0 �+ N �+ P m .On N M+ b m Y rs a O 10 a N 0 0 O �► m y Q m e P O v O + O A e 0 '�► a P+ O P a N O b O 00 3 C b O O m m m a m e o m o m o m m o m o 0 0 0 o m o N N r h r o 0 0 0 0 0 cr N N N 0 0 0 O 0 0 0 0 0 Pl O O Af 0 N � � A � A A P a a P P a a P co P P O O O O O O O O O O O O O co O O O O O O m 0 0 0 o e o o e o o e m e o e o e o e m o o m o o m o m o o• o 0 0 o m m m m o w u i N N N N N h o e o o m o 0 0 o m o o e P o. ea a s ow 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 e e o 0 o e e o o e o o e o 0 0 o m O e c_ m m o 0 0 o e O m m o m o o m m o m o m y p N N V N N N N A A A A N P P N 111, P N PN O O O O O O p r 0 0 0 0 0 0 0 0 0 0 0 0 0 0- •O'� "" "" "' x a o v y w A A A A A m m m m N N -+ ..� N N N N N N N N N 1 V�t� ' W t 1 1 1 m O e e m e e m m m m m O m a a a a P P 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 M m o m o 0 0 0 0 0 o m e e o m o 0 o m m m m m m m o 0 m o o m m m m m o m m m o v ° m A b b P N- w - - - wO+ .Ar .P. 1 p N m C 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 W C W W W y o p O O C Y O O Y O < w .O•+ O O W W< b J ©� J C C J O O t J p m < LL O O Z .3 O 2= LL c Z N S C {.� W 1� W m l . W O ti I an to u = a u u u u1c: v a L a v v 1. a- a. A.14 • TABLE All. PROCEDURAL BLANKS FOR PAN AND TBT IN DEIONIZED WATER (ng /L) Compound Rep. 3 Rep. 1 Rep. 2 Naphthalene 6.8 11 44 2- Methylnaphthalene 9.3 18 Acenaphthylene 7.6 1.7 2.4 17 Acenapthene <1.6 X5.2 <21 Fluorene Phenanthrene 7.6 7.6 <14 Anthracene <1.5 <0.96 150 <2.5 -- <9.9 Fluoranthene <0.84 24 <18 Pyrene Benzo (a) anthracene <3.9 <2.7 3.2 <2.3 <13 <9.1 Chrysene Benzo (b) fluoranthene <3.0 Q .8 <11 Benzo (k) fluoranthene 7.7 <3.9 17 <5.2 92 <21 Benzo (a) pyrene Indeno (1,2,3 -cd) pyrene <4.5 <17 <67 Dibenz (a,h) anthracene <8.9 <43 <173 <54 er lene Benzo (g,h,i) P y <3.3 <0.1 <13 <0.55 <2.2 TBT DBT <2.2 <0.81 <3.2 MBT 1.0 <0.34 <1.4 ?-.Surrogate Recovery d8 naphthalene 32 53 73 d10 acenaphthene 38 67 88 d12 perylene 44 91 143 tripropyl tin 20 84 54 *2- Methylnaphthalene was not quantified in water samples. A.15 °c �E u D O O 2 o J A C Vf K ~ O �Q! � �q P ►� m �w m A N W f O A y/ m O N Z �R N O �O �• O O a- �O rw f f b N m O m P V P A N f N i O O f b P O A C C P C A^ '► N A . r n W w ¢ o J m szc a o a O. .i p N f f f N f Ai Rl w'1 :i Rl N ti O W W J p. o s. O` a o c c o i i/ nc • d. z C - z � N at O P C` 6~ O a (O ..r O wf m m f f O �► A en O O W m O N A ^ N m /► N M M N N N n N ^ ^ C LL O .� N N W uj G/Y o s. W. C C6 N O' W o .r /► N w 10 N O �O r 2 A f 0 p+ O p W o O V A P N f m .n .+ N N O . VC rnz x W" L&J i:. `�„� cm Y. N a' O a N �► e m m N A m m e N M f •••� O m 0 10 N 0.4 O. p N .r q A ^ N w) A b f in m A A O ¢ C. ^ N 'w' w N C K L 2 N A m ma 0 C V V N • ^ �.� .. N A N G o 6L: ~ d A "um b N A O O O P J G� ` �a f m M O 10 RJ f A m m w! m C> w ¢ o w0+ C v`'i F� o o e o e o c c c * c o c s .oc o a. C C d V t V C Y O. L O O C N r. � d N L •_. V V C L O w O v A v v v ...i C y r V C O M Z C O w O O O C C O L O C C O C L O O M t c ' c w O O w C O +A 9 � C C C O. E O O pCp Z H i t 1i 6. i IL d m V -0 0 m m wC+ C G1 A.16 °c �E u D O O 2 A.17 c 0 o: a s -e c w w V w o w .s 'O �o O G C � �, z � .4 0 0 m m b O >> 7 >> 7 7 >> co N b In N b b b W A O a m w A A A m f < < b f ,+ \ p h e w °m W W 00 N b A N W J c 6. ♦ f M '! r N Q b t t r m A N \ \. m Z d r- w � 0 `mom. co A .. to o a b m b a w A m�� f� e0 O � � .. � m u .• .•r ... N _ O C J � C�Zt1f W` t w A o o o m wi m o w� e o e N m m m O Cf O A C �O o 0 0 0 0 0 J� <= < b b Q A b .P. r r 2 .� r N r r r .. S S r r 2 ? 2 2 2 2 mm p N Q m W O .••� 10 Pf w r m N A m b m H w O O a _ b\ �• s+ A ci Z Z I\ a d Y O wi O r 0 m 0 M o A A o ti A r N r r A r r. r r r r .� �+ ^ 00 h O C' N W 3: Lhi dc r W. N N A N O O O O O -+ O `Or. 1 a A m A N 1 m b m W ^ A w P ad O tl N m A A r ••� NC M r r m •+ ^ r r C N ...� r r C N N �O O G' cm '. go 4D Z W N cm °' 0 w m o a o o w 0-4 F-- 1.— :L a 10 r O w P O A A a N S b`` T J %.w C C r N A r N C Q u.I 0 m o C C f- Of p 0 A N O m r O A m m A O m �+ O \\ I.L. O G7 O Z Z d N v b N O b m O� A b w) �O O a• b .••� C2, O O N r el .•� .- N .• N C" r .- r 0 r r r r 7 b 10 -W- Z p.r r r L.6 Z C O O Ile) W r ob o. �� Mr N J= .+ N N A N m .•• �' N � m -► w) m m A � A A w en A O N N C W J a Cr v O A m b r N m 4 C4 r en c 4D WJ cc h'- ICU 0 Z OW>-W oe r o o w = JCCaN Y w a� C `o °s ec w w • c u c u c a o_ o 0 w o r i o o o w u c u w M C6 t O O O G �► r'. C s w Y .-w ■ o a o e e w .. der i .+ a a, w •� x C { O L.7 C w ?s Y Y •- 0 C i o ../� .•• w w p. Y w -I-- a v v v v v ..Oi O t. V e W C G i a Y G A e • O N O O N w w i w w w w �. w ► G O w O O O c c ti m R 'am J i O C C O G M a. + w w O M 'O G a ■ 0 0 Y :a e e c v w e v Z 0 LY : m m -Y - O m K Lo L LO L. A.17 c 0 o: a s -e c w w V w o w .s 'O �o O G C � �, z � .4 APPENDIX B Sediment Grain Size Data and Concentrations of Individual PAH Compounds TABLE B1. SEDIMENT GRAIN SIZE RESULTS FOR PORT TOWNSEND SEDIMENTS Sito Clay % Tots Estimated Grove I Soad Silt I. D. Solids Recovery )2.00 w 0.063 -2.00 an 63.00 -4.00 N (4.00 Im PT -1 61.161 94.31 0.08 72.56 16.95 11.32 PT -2 69.77% 96.1% 2.64 81.79 8.63 6.84 PT -3 66.42% 94.4% 1.06 88.17 6.01 5.76 PT-4 70.04% 98.4% 0.00 92.60 4.24 3.16 PT -6 52.02% 102.31 2.72 86.64 1.92 5.81 PT -8 62.041 93.7% 0.00 65.48 21.74 12.76 PT -7 63.111 96.6% 0.30 82.20 10.37 7.13 PT -8 57.07% 96.0% 0.11 85.12 9.73 6.04 PT -9 34.641 96.4% 0.25 27.73 37.53 34.40 PT -10 60.34% 94.9% 0.93 62.66 9.41 7.00 PT -11 63.99% 96.9% 0.95 63.27 9.83 5.96 PT -12 63.25% 108.7% 7.46 86.73 2.76 3.07 PT -13 60.35% 96.9% 0.18 46.43 34.03 19.36 PT -14 42.38% _97.1% 0.23 29.27 43.89 26.51 PT -16 39.121 94.1% 0.26 23.28 46.76 29.71 PT -16 37.29% 96.6% 0.08 26.98 44.32 26.61 PT -17 33.810 92.2% 0.11 17.24 49.27 33.38 PT -18 35.801 100.8% 0.00 8.99 69.12 31.89 PT -19 34.06% 92.4% 0.20 11.57 65.84 32.39 PT -20 29.725 103.8% 0.21 17.65 53.06 29.08 B.I TABLE B2. GRAIN SIZE RESULTS FOR CAP SANTE SEDIMENTS site % Total Estimated Grave Sand Silt 63.00 -4.00 M Clay 4.00 < As I.D. Solids Recovery )2.00 n 0.063 -2.00 n CS-1-REP-1 28.69% 100.1% 0.00 3.89 60.30 64 64.97 33.81 40.39 CS- 1-REP-2 26.86% 91.8% 0.07 1 4.84 0.63 .90 39.30 CS-1-REP-3 29.73% 91.81 0.00 4.49 40.94 44.67 CS -2 24.79% 96.3% 0.00 4.69 64.22 40.98 CS -3 27.43% 90.7% 0.11 3.73 66.44 40.63 CS -4 28.14% 99.3% 0.00 4.69 68.32 36.98 CS -6 27.36% 93.1% 0.02 4.28 61.66 30.98 CS -6 30.73% 90.8% 0.00 4.02 67. 14 38.84 C5-7 28.83% 100.3% 0.00 6.37 52.84 31.69 CS -8 31.09 % 96.1% 0.41 7.38 61.66 30.98 CS-9 33.33% 90.1% 0.00 11.46 68.77 29.49 CS -10 37.71% 92.E 0.29. 12.33 67.80 28.41 CS -11 41.24% 97.1% 1.46 14.10 68. 94 26.92 CS -12 36.88% 98.2% 0.03 44.40 45.44 9.16 CS -13 48.89% 98.6% 1.00 42.10 28. 96 6.70 CS -14 67.03% 96.3% 22.23 13.63 60.39 26.01 CS -13 38.14% 94.1% 0.00 44.34 42.21 12.92 CS -16 64.00% 94.4% O 38.22 20.89 CS -17 37.96% 107.2% 6.94 49.77 36.76 13.34 CS-18 59.48% 92.3% 0.14 42.67 44.51 12.92 CS -19 60.59% 99.0% 0.00 36.E 39.61 23.86 CS-20 40.91% 103.0% 0.00 18.21 6D .80 30.80 CS -21 36.96% 98.3% 0.19 w Q Z Q Ti. W C/9 Z Q ^rte ii 1i. N W J d N Z I�l 0 W N Z F�1 4 d O N Z Q N Z W ci Z I M m W J m Q L �o s. 7 A R O p M1♦ b p 0 b b N .•� b CD f .r p O N or ♦ C7 40 cc A f♦ n m N N r+ co w y H tq b M1 CD M1 f b ♦ A b N f O O O b p p A CD .r CD b m Cp M1 CD t0 f O b A b A N l' O b .r b N N p N b /D CM1y O f O ... N a 'f A y N f f b f NJ b f C7 as b. b .� b- p ♦ ..� b .� p ♦ ♦ .. b N .r .r ..i Cn y N O M !q pJ W ♦ b .� .r N m .•. CD O O N .r IN O p w wr = b b CD N N N y N p O O N A O O f p ^ A p A AJ p Cq lq CD A f f f b O b .+ A w.1 N r1 N M1 A M1 p A RJ O p M1 to M1 m ..I f Pl A 0) y h b r1 f f N A na O f b r1 A p p O A A f b M1 b CD .� f " N N N A to CD w b N p Rf m b CD N Oi S f N .+ .r .N 17 to w H at p ♦ b R7 .� m b m N CD A N f w p N r1 A .+ N 19 d; M1 N N ..� O N m La ED 03 p so .p. p .� p O � fpC U) N! b 0 M1 N p w N M1 H N v v m O pA h A K O b y b ^' N N O p CD „y A m f to N N CD p .+ f b fA d p p N N CM CD f N O N N f M1 m N M1 A p o .y N O m CD N CD b CO N wr N � N N !P7 .•y p O f0 .� m O f b m p M1 f A p b CD N O. N W p CD O N A N p m b CC m m N CD b O CD f b M1 N O m CD M1 b N CD p CD O� O CD p 03 b f M1 m cm -W f m so O! N w�a ~ Ob qr a♦r wR11 b CD rr O ..r f OCD h O C O C C V O C °c = t I o w o y y 34 oc u c o p !7 C CL f 3-1 ^ O V O c c O L C — y L O L O t Ec .D a O i .Y a v v w a. t y c y u J c — c— •• v — _ L L O. O. 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O O r r to In r In In A O p r b N N +� .•� h r .ri .pn O v tl r O N N A Lo O O p p O N to � in O O r tl O r O O to o h O �+ h p 0 f0 N wn h .r N ♦ p r N N N .� O O 90 fA p 0 p 0 0 .^� A r b tl p 0 N O to O to O p O O ..� N ... .r C2 0 O r b b O r b b r eq w b C. b N1 C% CV .. N h N -W O .. O c c � o c n a —o C s� O L O O. O I A d w c O d— O C c C 0 M 4. d N L C w h C O O C c O L Y S d O - L n O -M w v v p S d -0 C w L L d d 0 c w J c v c v v v v w O O O N S V — O. t C O z v 4 y c L c c c i.2 c w w 1 0 w— L C N c t a< O F- h f1 L O t� m Q m LL d m V m m 2 LL 'O 8.5 W w .r C O V m W J m a N cN tl! A O O tl b m A tl tl tl .�. A tl O A tl tl O In A w tm.f N to N V3 O f P ...� /9 d• In N O tl A ! to f N .'+ A N N O N b O O! tl Ob N! N N! m m N .+ N CD b r tl .� go N .+ N .+ -W tl 03 40 O v ! N O► P Pf r q 01 .r tl ^ O ^ O O ww . 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