Environ. Sci. Technol. 1992. 26. 725-733 problems. Ph.D. Thesis, Department of Chemical and Biochemical Engineering,University of Iowa, August 1990. (6) Silhnan, S.; Logan, J.; Wofsy, J. J. Geophys. Res. 1990,95, 1837-1852. (7) Venkatram, A.; Karamchandani, P.; Misra, P. Atmos. Enuiron. 1988, 22, 737-747. (8) Kleinman, L. J. Geophys. Res. 1987,91, 10889-10904. PERCENT
15.0
10.0
5.0 -5.0 -10.0
Flgure 14. Percent change in the event-averagesurface ozone for a 50% reduction In NO, emissions. Positive values represent an increase in ozone wnh a decrease in NO, emissions.
and photochemical oxidant production. Registry NO. NO,, 11104-93-1; SOx, 12624-32-7; SO2,74609-5;
HzOz,7722-84-1; O,,10028-15-6. Literature Cited (1) Cannichael,G.; Peters, L.; Kitada, T. Atmos. Enuiron. 1986, 20,173-188.
Carmichael, G.; Peters, L.; Saylor, R. Atmos. Enuiron. 1991, 25A, 2077-2090. (3) Shin, W.; Carmichael, G. Atmos. Enuiron., in press. (2)
(4) Atkinson, R.; Lloyd, A.; Winges, L. Atmos. Enuiron. 1983, 16,1341-1355. (5) Shin, W. Comprehensive air pollution modeling on mul-
tiprocessor environments: Applications to regional scale
Stockweu, W.; Milford,J.;McRae, G.; Middleton, P.; Chang, J. Atrnos. Enuiron. 1988, 22, 2481-2493. (10) Chang, J.; Brost, R.; Isaksen, I.; Madronich, S.; Middleton, P.; Stockwell, W.; Walcek, C. J. Geophys. Res. 1987,92, (9)
14681-14700. (11) Venkatram, A,; Karamchandoni, P.; Misra, P. Atmos. Enuiron. 1988,22, 737-748. (12) Misra, P.; Bloxam, R.; Fung, C.; Wong, S. Atmos. Enuiron. 1989,33,671-688. (13) NAPAP, National Acid Precipitation Assessment Program, State of the Science Reports, Findings of the NAPAP Project, 1990. (14) Roselle, S.; Pierce, T.; Schere, K. J. Geophys. Res. 1991, .W. .., 7271-7294 .- . . . - - .. (15) Fung, C.; Misra, P.; Bloxam, R; Wong, S. Atmos. Enuiron. 1991.25A. 411-423. (16) Cho,'S.; Chang, Y.; Carmichael,G. Atmos. Enuiron. 1989, 23, 1009-1031. (17) McKeen, S.;Hsie, E.; Liu, S. J. Geophys. Res. 1991, 96, 15377-15394.
Received for reuiew May 16,1991. Reuised manwcript receiued October 11,1991. Accepted Nouernber 15,1991. This research was supported in part by the Department of Energy PRECP program through contract with Battelle Pacific Northwest Laboratories.
Chemical Contamination and Associated Fish Diseases in San Diego Bay Bruce B. McCaln,' Sin-Lam Chan, Margaret M. Krahn, Donald W. Brown, Mark S. Myers, John T. Landahl, Susan Pierce, Robert C. Clark, Jr., and Usha Varanasl
Environmental Conservation Division, Northwest Fisheries Center. National Marine Fisheries Service, National Oceanic and Atmospheric Administration, 2725 Montlake Boulevard East, Seattle, Washington 98112
R Chemical pollution a t sites in or near San Diego Bay was investigated between 1984 and 1988. The mean concentrations of selected polychlorinated biphenyls (PCBs), metals (e.g., copper and lead), and aromatic hydrocarbons in sediments from sites in the southern and central portions of the bay were significantly higher (p 5 0.05) than those in sediment samples from nearby nonurban sites. Mean concentratiom of PCBs in liver tissue and of selected aromatic compounds (e.g., aromatic hydrocarbons) and their metabolites in bile were also significantly higher in white croaker (Genyonemus lineatus), barred sand bass (Paralabrar nebulifer), and black croaker (Cheilotrema saturnum) from one or more sites withii the bay compared to those from the nonurban sites. In addition, prevalences of fin erosion in white croaker, barred sand bass, and black croaker and of liver neoplasms in black croaker from sites in the bay were significantly higher than in individuals of the same species from nonurban sites. Introduction An assessment of pollution in San Diego Bay, CA, was conducted as part of the National Oceanic and Atmospheric Administration's (NOAA's) National Status and Trends Program (NSTP). The National Benthic Surveillance Project (NBSP), a component of the NSTP, is a multiyear monitoring program designed to measure concentrations of chemical contaminants in sediment and
tissues of bottom-dwelling fish species a t selected sites in coastal areas of North America and to determine the prevalences of suspected toxicopathic diseases (e.g., liver lesions and fin erosion) in these same fish species (I, 2). Bottom fish from a number of chemically contaminated coastal areas have been reported to have pathological conditions, including liver lesions such as neoplasms (M), and fin erosion (7,8), which have been shown to be associated with chemical pollution in certain locations and species. Therefore, certain pathological conditions in fish, in conjunction with supportive evidence demonstrating the presence of selected chemical contaminants, have become useful indicators of environmental degradation (9, IO). Cause-and-effect relationships between chemical contaminants and liver lesions have been inferred from field surveys (11)and further substantiated by long-term laboratory studies (12). Other than the present study, few multidisciplinary investigations of the pollution conditions in San Diego Bay have been conducted in the last 20 years. The Mussel Watch component of NOAA's NSTP has a site in the bay near Harbor Island. Indigenous mussels (Mytilus sp.) are collected annually and analyzed for the same chemicals quantitated in the present study. The results from the first 3 years (1984-1986) of this effort indicated that mean concentrations of aromatic hydrocarbons (AHs), polychlorinated biphenyls (PCBs), copper, and zinc in mussels
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from this site were among the 10 highest of the bivalve samples taken from the 150 sites sampled in the coastal areas of the United States (13). Young et al. (14) also collected indigenous mussels from the bay and reported high concentrations of PCBs, copper, lead, and tin in digestive glands of mussels from three sites in the northern part of the bay. Of these contaminants, lead and tin were not detected in mussels from a site just outside of the bay, and the concentrations of copper and PCBs in mussels from this site were a t least 3 times lower than those in mussels from inside the bay. Since 1977, the California State Mussel Watch program has monitored levels of PCBs in San Diego Bay by transplanting California mussels in cages to approximately 40 sites within the bay. The caged mussels were subsequently analyzed for PCBs. Although most of the results of the mussel transplantation program have not yet been published, Martin (15) summarized some of the work performed in 1982. He reported that mussels (Mytilus edulis) transplanted for 2 months at three sites along the eastern edge of the bay bioaccumulated substantially higher concentrations of PCBs compared to caged mussels from a site near the mouth of the bay and from a nonurban site. Even though these studies used different sampling and analytical methods, they tended to indicate that significant chemical pollution exists in certain parts of San Diego Bay. Due to the breadth of the geographical coverage of the NBSP, it was not initially possible to sample more than one site in San Diego Bay during 1984 and 1985. Because of the high levels of contaminants found initially in sediment and fish at this site ( I , 2), an additional site was sampled in 1986, and a total of seven sites were sampled between 1987 and 1988 in order to better evaluate the extent of pollution problems in this bay. The results of this 5-year investigation are reported here.
Figure 1. Locations of sites sampled in or near San Diego Bay. The sites were identified as National City (32'40.0' N, 117'07.6' W) (site l),28th Street Pier (32'41.0' N, 117'08.2' W) (site 2),East Harbor Island (32'43.2' N, 1 17' 1 1.3'W) (site 3),West Harbor Island (32'43.4'N, 117'12.4' W) (site 4),Shelter Island (32'42.5' N, 117'13.4' W) (site 5),Dana Point (33'26.7' N, 117'41.5' W) (site 6),and Outside Mission Bay (32'47.9' N, 117'15.8' W) (site 7).
Methods and Materials Sampling Strategy. Seven sites in or near San Diego Bay were sampled at least once between 1984 and 1988. These sites and the years that they were sampled were as follows: 28th Street Pier and Dana Point (a nonurban site) (1984-1988); East Harbor Island (1986-1988); National City, West Harbor Island, and Shelter Island (1987 and 1988);and Outside Mission Bay (1988) (a nonurban site) (Figure 1). All sites were sampled during June or July. In addition, two sites (28th Street Pier and East Harbor Island) were also sampled in February 1987. By use of procedures described in previous publications (1, 2), samples of sediment and samples of liver and bile from fish were collected for chemical analysis, and fish tissue samples were taken for histopathological examination. Surface sediments were collected with either a modified Van Veen grab sampler (0.1 m2) or a box corer (0.03 m2). Three sediment collections were made at each station (each site consisted of three stations), and three cores (15-19 cm X 3 cm) and a surface skim (1-2 cm deep) were taken from each collection. Cores and surface subsamples were frozen for future analyses of trace metals and organic compounds, respectively. Fish were collected by otter trawl, and adult fish were randomly selected and kept alive (to prevent autolysis of tissues) until necropsies were performed. Approximately 30 fish per target species were routinely necropsied at each site during each cycle. Sections from the central longitudinal axis of the liver were taken and preserved in Dietrich's fixative (16) for histopathological examination. The remaining liver tissue was frozen for later analyses of organic compounds and trace metals. Three fish species were sampled in the bay: barred sand bass (Paralabrax nebulifer) from three sites (28th Street
Pier, National City, and East Harbor Island) in the central and southern portions of San Diego Bay; white croaker (Genyonemus lineatus) from the two sites (West Harbor Island and East Harbor Island) in the northern and central parts of the bay; and black croaker (Cheilotrema saturnum) from the sites near Harbor Island and Shelter Island. Barred sand bass are nonmigratory bottom feeders found near rocky areas (17). Similarly, white croakers spend most of their time near the bottom and occasionally form schools (18). Black croakers are also bottom feeders and prefer rocky habitats (17); however, very few could be captured outside of San Diego Bay. Normally, only the target fish species for a specific site were examined for externally visible abnormalities; however, in 1987, a comprehensive survey of fin erosion prevalence was conducted in which all, or a subsample of specimens of both target and nontarget species were examined for external lesions at each site. Analytical Techniques. Sediments and fish stomach contents were analyzed for 18 aromatic hydrocarbons (AHs), 21 chlorinated hydrocarbons (CHs), and 15 trace metals (1,2,19). Three sediment samples were analyzed for each sampling site per year, one for each station. In turn, each sample from a station was a composite of sediment collected from three separate sediment grabs. Liver tissues were analyzed for the same suites of CHs and trace metals as were sediments, but not for AHs. For analyses of CHs, each liver sample was a composite of tissues from 10 fish, whereas for analyses of metals, each liver sample was from an individual fish. Generally, three samples of livers were analyzed for each site per year. Analyses of liver tissues for AHs are of limited value due to the extensive bioconversion of these compounds to more polar metabolic
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products (20). Therefore, exposure of fish to AHs was estimated by measuring fluorescent aromatic compounds (FACs) and their metabolites in fish bile using highpressure liquid chromatography with fluorescence detection (21,22). Each bile sample was from an individual fish, and 10 samples were analyzed per year for each site. Tissues from approximately 30 fish per site per year were preserved in the field for histopathological examination and then processed by routine histological procedures (23). Lesion classification followed Dreviously described diag. nostic criteria (6). S t a t i s t i c a l Methods. The relative concentrations of contaminants in sediment and fish at sites in or near San Diego Bay were compared statistically using GT2 comparison intervals (24,25). These intervals, unlike confidence intervals, have the property of graphidly displaying statistical differences between mean concentrations of sets of samples of unequal sizes; comparison intervals that do not overlap are significantly different (p C 0.05). The computation and plotting of comparison intervals is equivalent to performing a one-way analysis of variance (ANOVA) followed by a multiple-range test (26). Because environmental chemical concentrations are often lognormally distributed (27), the comparison intervals were calculated on the basis of In ( x 1)-transformed contaminant concentrations, resulting in comparison intervals that were asymmetric about the arithmetic mean. In cases where concentrations or other values are reported in the text, they are presented as mean standard deviation of untransformed data. Seasonal differences in concentrations of chemicals in fish were compared using the Mu-Whitney U test (25). To determine whether the prevalences of each major type of disease diagnosed in each of the fish species at sites within San Diego Bay were significantly higher than those at nonurhan sites (Dana Point or Outside Mission Bay), a multiple-comparisontest for proportions was performed (28). For both tests, where significant differences among chemical concentrations or lesion prevalences are mentioned, the p value is understood to be
