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POLYCHLORINATED BIPHENYLS OFF SOUTHERN CALIFORNIA Southern David R. Young California Coastal Water Research 1500 East Imperial HighwayEl Segundo, California 90245 Project Southern Deirdre J. McDermott California Coastal Water Research 1500 East Imperial Highway El Segundo, California 90245 Project Theadore C. Heesen Southern California Coastal Water Research Project 1500 East Imperial Highway El Segundo, California 90245 Paper presented at the International Conference on Environmental Sensing and Assessment, 14-19 September 1975, Las Vegas, Nevada. To be published in the proceedings volume. DSW 027969 STLCOPCB4011931 Summary Polychlorinated biphenyls are ubiquitous con taminants of the marine ecosystem off southern California. The greatest known source is the submarine discharge of municipal wastewaters; aerial fallout also appears to be an important input route. In contrast, surface runoff is only of secondary importance, and direct in dustrial discharge appears to be completely insignificant. Maximum concentrations of 1254 PCB found in bottom sediments off Palos Verdes Peninsu la were 10 ppm, with values falling 100 fold to baseline values over a depth of 20 cm. Muscle tissue from benthic crabs (Cancer anthonyi) and flatfish (Microstomus pacificus) collected from discharge regions also exhib ited 100 fold increases in 1254 PCB levels over control values. It appears that the numerous harbors in the Bight also have rela tively high levels of PCB contamination. Intertidal bay mussels (Mytilus edulis) con tained up to 20 times more 1254 PCB than cor responding specimens collected nearby along the open coast. Finally, an offshore biomonitoring sys tem has been developed, utilizing the inter tidal coastal mussel (M. californianus), which appears to offer good potential for indicating zones of greatest biological availability of synthetic pollutants released from submarine outfalls. Introduction Chlorinated hydrocarbons are among the most important pollutants yet identified in the Southern California Bight.1-6 The coastal plain adjacent to this marine ecosystem (Figure 1) is inhabited by approximately 11 million persons (approximately 5 percent of the U.S. population), and large quantities of waste materials are introduced both directly and indirectly into the waters of the Bight. Potentially significant sources and transport routes include submarines discharges of muni cipal wastewaters, direct industrial dis charges, antifouling paints and other vessel related materials, surface runoff, aerial 7 fallout, and ocean current advection. Here we summarize our findings from studies into the industrially important poly chlorinated biphenyls (PCB) conducted over the last several years while investigating the inputs and distributions of chlorinated hydro carbons off southern California. / PSW 027970 STLCOPCB4011932 -3^ - Figure 1. The Southern California Bight. Major outfall systems are (1) Oxnard City, (2) Hyperion, Los Angeles City, (3) JV7PCP, Los Angeles County, (4) OCSD, Orange County, and (5) Point Loma, San Diego City, Major harbors are (6) San Pedro, (7) Newport, and (8) San Diego. . Sampling Five major treatment plants* located along the southern California coast contribute more than 95 percent of the 4 x 10^ liters of municipal wastewater discharged daily into the Bight. In order to obtain an estimate of the impor tance of this input route, we analyzed oneweek composites (usually collected twice a year) of the final effluents obtained from each of these plants since 1972. In southern California, most industrial effluents discharged directly into marine waters (excluding power plant cooling waters) flow into San Pedro Harbor or San Diego Bay. * Joint Water Pollution Control Plant (JWPCP), Los Angeles County; Hyperion Treatment Plant, City of Los Angeles; Orange County Sanitation District Treatment Plant (OCSD), Orange County; Point Loma Treatment Plant, City of San Diego; Oxnard Treatment Plant, City of Oxnard. DSW 0^7971 Therefore, to estimate the level of pcb input from this source during 1973 and 1974, half day effluent composites obtained for each of the major types of industries discharging into both areas were analyzed. In addition, during 1973 we conducted an intensive survey to deter mine the composition and quantities of major brands of antifouling paints used on recreat ional, commercial, and naval vessles in the 14 Q harbors and marinas in southern California. We estimated the contribution of surface runoff by sampling major channels along the southern California coast during both storm and dry weather conditions between 1971 and 1973. To measure aerial inputs, replicate 1 week collections of dry aerial fallout were analyzed from 13 coastal and 5 island stations throughout the Bight during two 13 week peri ods in 1973 and 1974. Finally, to estimate the magnitude of ocean current advection in puts during 1973, we analyzed results of PCB measurements for replicate samples of surface seawater which we had collected in the Santa Barbara Channel at the edge of the Bight. During 1971, we collected ocean bottom sediments near the JWPCP outfalls off Palos Verdes Peninsula using a deliberate box corer. Utilizing traps and benthic trawls, samples of, the benthic crab (Cancer anthonyi) and a flat fish, the Dover sole (Microstomus pacificus) were collected from around the Hyperion, JWPCP and OCSD outfalls during 1971 and 1972; the Dover sole was subsequently resampled in these regions in 1974 and 1975. In addition, during 1974 we sampled the intertidal bay mussel (Mytilus edulis) from throughout San Pedro, Newport and San Diego Harbors. Later that year, to estimate uptake rates and steady state concentrations, we transferred 2,000 specimen of the intertidal mussel (M. californianus) from an uncontaminated control station to net bags suspended from a taut line buoy system situated above highly contaminated sediments near the JWPCP outfalls. Methodology Most of the various categories of samples were processed and analyzed utilizing well estab lished laboratory techniques in conjunction with electron capture gas chromatography. The aerial fallout samples were analyzed using a procedure developed by Dr. Vance McClure (National Marine Fisheries Service, La Jolla, California), and the seawater samples were 3 DSH 027972 STLCOPCB4011934 analyzed in collaboration with Brock de Lappe and Dr. Robert Risebrough, utilizing a tech nique they developed at the University of California at Berkeley. Results and Discussion Sources and Transport Routes Table 1 summarizes the estimated annual mass emission rates of 1242 PCB and 1254 PCB (42 and 54 percent chlorination, respectively) to the Bight via six modes of input, and Table 2 presents the breakdown of 1974 inputs from major municipal submarine discharges. Appro ximately equal concentrations of 1242 and 1254 PCB were measured in surface runoff; thus, although reliable measurements of 1242 PCB in dry aerial fallout have not yet been made, we estimated an upper limit for this input assum ing a 1 to 1 ratio of 1242 and 1254 PCB in fallout. Table 1. Estifj&ted annual' mass emission rates (kg/yr)"of polychlorinated biphenyls to the Southern California Bight. Route Municipal Wastewater Year 1974 1242 PCB 4300 1254 PCB 1100 Direct Industrial 1973-74 - 60 Antifouling Paints 1973 < 1 <1 Surface Runoff 1973 4 500 300 Aerial Fallout Total (Land) 1973-74 S1500* 4500-6000* 1500 3000 Ocean Currents 1973 - 4000 * Assuming a 1 to 1 ratio between 1242 and 1254 PCB in aerial fallout DSW 027973 Table 2. Estimated 1974 mass emission rates (kg/yr) of polychlorinated biphenyls to the Bight via major municipal waste waters. Treatment Plant JWPCP Flow (mgd) 350 1242 PCD 910 1254 PCD 360 Hyperion (5-mi) 330 50 110 Hyperion (7-mi) 5 . 470 320 OCSD 150 1890 210 Pt. Loma Oxnard 95 950 110 10 1 3 Total 940 4270 1110 These results indicate that municipal wastewater is the dominant mode of input for PCB to the coastal waters, followed by dry aerial fallout. Surface runoff contributions are an order of magnitude lower, while esti mated coastal inputs from direct industrial discharges and antifouling paint application are relatively insignificant. In view of the fact that the quantity of 1254 PCB (1,100 kg) introduced during 1974 was more than one-fourth the estimated quan tity (4,000 kg) carried annually by surface layer (0-50 m) currents flowing through the entire Bight, one would expect that local con tamination of nearshore sediments and orga nisms by this synthetic material would be clearly evident. Marine Sediments Figure 2 presents vertical profiles of 1254 PCB concentrations in bottom sediment layers from box cores collected at three sites within the monitoring zone and down current of the JWPCP outfall3 off Palos Verdes Peninsula.* * Distance downcurrent: Station BlS, 7 km; Station B21, 1.5 km; and Station B20, between the legs of the wye of the outfall. -r- DSW 027974 Figure 2. Vertical profiles of 1254 PCB con centrations in sediments collected northv/est of the JWPCP outfalls, box cores, July 1971. concentrations of 1254 PCD in nearsurface sediments (10 ppm, mg/dry kg) collected at Station B21, located 1.5 km from the nearest outfall diffuser, exceeded the lowest levels measured at the bottom of the three cores (0.1 ppm) by a factor of 100. Surface sediments freon the Santa Barbara Basin (180 km to the northwest) also contain about 0.1 ppm 1254 PCB.9 We previously calculated that, in 1972, the upper 30 cm of bottom sediments in a 50 sq km area of this discharge zone contained . approximately 200 metric tons of DDT and its residues^; we believe this estimate to be accurate within 25 percent of the actual value Although we have much fewer data on the dis tribution of PCB in these sediments, extra polation of our present information using observed PCB to DDT ratios suggests that the corresponding load of 1254 PCB in these sedi ments is on the order of 6 metric tons. k> DSW 027975 STLCOPCB4011937 Marine Animals Benthic Organisms. Samples of muscle tissue from crabs (C. anthonyi) and Dover sole (M. pacificus) collected in these discharge regions also exhibited significant levels of -PC3 contamination above baseline concentra tions (Figures 3 and 4, respectively). Levels Figure 3. 1254 PCB concentrations (mg/wet kg) in muscle tissue of the crab. Cancer anthonyi, collected off southern California, 1971-72. in both species from around major outfall sites were generally 100 times greater than those observed at island or coastal control stations. In addition, there has not been any significant change in PCB levels during the three years interval between 1971-72 and 1974 75; median 1254 PCB concentrations in Dover sole collected from off Palos Verdes Penin sula during the two periods were 1.9 and 1.3 ppm (mg/wet kg), respectively. Corresponding values for the Santa Monica Bay stations around the Hyperion outfalls were 1.5 and 2.0 ppm; off the Orange County outfalls, the median values were 0.8 and 0.6 ppm respectively. 4- DSU 027976 STLCOPCB4011938 Figure 4. 1254 PCB concentrations (mg/wet kg) in muscle tissue of the Dover sole, Microstomus pacificus, collected off southern California. 1971-72. " Bay Mussels. Our surveys of 5 cm bay mussels (M. edulis) from three of the largest southern California harbors revealed contamin ation levels up to 20 times those found in specimens of the same species collected from nearby coastal sites.^ Highest levels were found near regions of greatest vessel activity as illustrated by the results for San Diego Bay presented in Figure 5. Comparison of sea water levels (generally on the order of one DSW 027977 A' Figure 5. 1254 PCB concentrations (mg/wet kg) in whole soft tissues of the bay mussel, ' Mytilus edulis, collected in San Dieqo Bay,. January 1974. _ jjart per trillion, ng/1) and mussel concen trations of 1254 PCB found in San Diego and the other harbors suggests that the whole soft tissues of M. edulis accumulate PCB on the order of 100,000 times above seawater values. Although antifouling paints presently applied to vessel bottoms in southern Cali fornia generally contain PCB concentrations of /less than 1 ppm (mg/dry kg), a few samples of old paint chips averaged about 10 percent PCB (100,000 ppm).1 Thus it is possible that (thousands of kilograms of this synthetic ma terial could have been released annually to the harbor and coastal marine ecosystems, before the widespread use of non-recoverable PCB was discontinued in the United States during the early 1970's. f DSW 027978 STLCOPCB4011940 Offshore Biomonitoring System In June 1974, uncontaminated specimens of open coast, intertidal mussels (K. californianus), 5 cm in length, were transferred to net J3ags__f;astened. at__f ive . di f f erent_ levels .between, the sea surface and bottom (35 m) on a taut line buoy system installed over the highly contaminated sediments near the JWPCP outfalls, The rate and extent of PCB uptake was then monitored for 3 months in specimens collected at 1 to 2 week intervals. The mussels appeared to survive well under these conditions; less than 10 percent mortality at any level was observed over the study period. On the average, mussels living at Royal Palm Beach inshore of the buoy contained 20 times as much PCB as the control specimens at the time of their transfer to the buoy north west of the outfalls. Thus, exposure of these mussels to PCB was greatly increased upon their transfer to the discharge tegion. Resultant uptake of 1254 PCB with time in male specimens is presented in Figure 6; similar results were observed for female specimens, and application of the Wilcoxon signed-rank test revealed no significant effect of sex on PCB uptake. These data show that there is a direct relationship between uptake of PCB and proximity of the bioindi cator to the contaminated bottom sediments and .to the wastewater plume, which is trapped beneath the thermocline. The bottom specimens became approximately 10 times as contaminated as did the surface specimens. Projected "steady state" concentrations for the two levels of suspension appear to be on the order of 0.4 and 0.04 ppm (mg/wet kg). To date, the highest 1254 PCB concentrations measured in the water above the JWPCP outfalls is 4 parts per trillion. This suggests a concentration factor on the order of 100,000 for 1254 PCB in the whole soft tissues of M. californianus, in good agreement with the estimate for M. edulis in the harbors. Conclusions Municipal wastewaters and aerial fallout dom inate the known inputs of PCB to the Southern California Bight. More than 5 metric tons of 1242 and 1254 PCB were discharged during 1974 from the five major southern California treat ment plants. Such inputs have resulted in localized zones of relatively high bottom sediment contamination around submarine out fall systems. ' \0 . OSW 0 2 7 9 7 9 STLCOPCB4011941 Figure 6. 1254 PCB concentrations in whole soft tissue composites of male intertidal mussels, Mytilus californianus, translocated from Point Sal to the taut line buoy system off Palos Verdes, June through September 1974. Measured annual emissions of 1254 PCB from the three major outfall systems agreed within a factor of 2; similar agreements were observed in the 1254 PCB levels in crabs (C. anthonyi) and flatfish (M. pacificus) col lected from the three discharge regions. Thus it is apparent that PCB compounds are wide spread contaminants of.both coastal wastewater inputs and benthic organisms in southern California. Highest concentrations in the bay mussel (M. edulis) were measured near locations of greatest vessel activity, such as mooring and bottom repainting facilities. The contamina tion of harbor organisms may be the result of past usage of antifouling paints containing high levels of PCB, although inputs from other vessel-related materials (such as hydraulic fluids) could also be important. \\ STLCOPCB4011942 OSM 0 2 7 9 6 0 Although the bioindicator (M. California anus) used in the offshore biomonitoring " ' system is an intertidal organism, less than 10 percent mortality was observed, even at a depth of 35 m, over the 3 month study period. Thus, this mussel's hardiness, its ubiquitous distribution along many coast lines around the world, its very high ability for concentrating chlorinated hydrocarbons above seawater values (approximately 100,000 fold for 1254 PCB), and its apparent ability to rapidly respond to changes in environmental levels of such con taminants makes it a very useful bioindicator both in natural intertidal communities and on offshore monitoring substrates. Acknowledgements Dr. Robert Risebrough and Brock de Lappe (Bodega Marine Laboratory, University of Cal ifornia at Berkeley) provided seawater PCB con centrations discussed in this paper, and assis ted us in analyzing harbor water and municipal effluents. Dr. Vance McClure (National Marine Fisheries Service, La Jolla, California) devel oped the techniques used to collect and analyze dry aerial fallout. Bottom sediments and organisms were .collected with the assistance of Dr. Ronald Kolpack {University of Southern California) and Douglas Hotchkiss and the crew of the Sea-S-Dee (County Sanitation Districts of Los Angeles County). Municipal wastewaters were collected with the assistance of personnel from corresponding treatment plants. Members of this Project who contributed to this research include Willard Bascom (Director), Elliott Birkihiser, Rick Gammon, Joseph Johnson, Jack Mardesich, Dr. Alan Mearns, Michael Moore, Paul Smokier, Harold Stubbs, Ileana Szpila, and Michael Westbrook. This program was supported in part by the U.S. Environmental Protection Agency (Grant Number R801153), and in part by a contract with the University of California at San Deigo in connection with the Marine Research Commit tee, Department of Fish and Game (State of California Agreement M-ll). Equipment used to sample chlorinated hydrocarbons in seawater was developed with the support of the National Science Foundation International Decade of Ocean Exploration, (Grant Number ID072-06412 A02). Contribution number 50 of the Southern California Coastal Water Research Project. 0SW 027981 r References 1. Duke, T.w. and A.J. Wilson, 'jr. 1971. Chlorinated hydrocarbons in livers of fishes from the northeastern Pacific Ocean. Pest. Mon. Jnl. 5:228-32. 2. Risebrough, R.W., F.C. Sibley, and M.N. ' Kirven. 1971. Reproductive failure of the brown pelican on Anacapa Island in 1969. Axner. Birds 25:8-9. 3. Southern California Coastal Water Research Project. 1973. The ecology of the Southern California Bight: Implications for water quality management. Rept. TR104, So. Calif Coastal Water Res. Proj., El Segundo, Ca. 4. De Long, R.L., W.G. Gilmartin, and J.G. Simpson. 1973. Premature births in Cali fornia sea lion: Association with high organochlorine pollutant residue levels. Science 181:1168-70. 5. MacGregor, J.S. 1974. changes in the amount and proportions of DDT and its metabolites, DDE and DDD, in the marine environment off southern California, 1949 1972. Fish.Bull. 72:275-93. 6. McDermott, D.J., T.C. Ileesen, and D.R. Young. 1974. DDT in bottom sediments around five southern California outfall systems. . Rept. TM217, So. Calif. Coastal Water Res. Proj., El Segundo, California. 7. Young, D.R., C-S. Young, and G.E. Hlavka. 1973. Sources of trace metals from highly urbanized southern California to the adjacent marine ecosystem. in cycling and control of metals. Nat. Envir. Res. Ctr., Cincinnatti. 8. Young,.D.R., T.C. Heesen, D.J. McDermott * and P.E. Smokier. 1974. Marine inputs of polychlorinated biphenyls and copper from vessel antifouling paints. Rept. TM212, So. Calif. Coastal Water Res. Proj., El Segundo, California. 9. Ham, W., R.W. Risebrough, A. Soutar and 10. I D.R. Young. 1974. Deposition of DDE and polychlorinated biphenyls in dated sedi ments of the Santa Barbara Basin. Science 184:1197-99. Young, D.R. and T.C. Heesen. 1974. Inputs and distributions of chlorinated hydrocarbons in three southern California harbors. Rept. TM214, So. Calif. Coastal Water Res. Proj., El Segundo, California. DSM 027982 > STLCOPCB4011944