Abstract The ambient levels of DLE (approximately 80% of total DDT residues) were determined in the Northern Anchovy from gas chromatographic analysis of 25 samples of 6 different tissues: female gonad, male gonad, liver, muscle, gill, and brain. Levels were found to range between O.11 and 0.35 ppm by wet weight. Direct uptake from sea water by live fish was measured with the use of C+-labeled DDT for h hour incubations in 1 ppb concentrations. Results showed very high concentrations of the DDT in liver, gill, and brain. In h hours liver tissue concentrated DDT an average of 240 times over the initial level, with gill and brain tissue averaging 65 and 45 fold concentrations, respectively, in the same time period. Results show large variations between individual fish in amount and site of deposition. Comparison of normal levels and uptake show that DDT is highly mobile within the fish and seems to move from liver to muscle tissue after original uptake. Introduction The work of Risebrough (Risebrough et al, 1967) and others with chlorinated hydrocarbons in the marine ecosystem has generated growing concern for the concentration and effect of these pesticides in the world's oceans. The harmful effects of DDT and its residues on marine birds has been a topic of much discussion (Wurster and Wingate, 1968). Since the bird is at the top of the marine food web and because DDT is passed on and accumulated as it moves up the food chain, it would be expected that this animal would be among the first organisms affected by increasing concentrations of this hydrocarbon in the environment. In order to study the relationship between DDT and the next lower trophic level, the fishes, an extremely important pelagic bait fish was chosen for this work. The Northern Anchovy is abundant in California coastal waters and is the primary source of food for most of California's game fish and a large number of its coastal birds. In turn, this species is a voracious omnivore, feeding extensively on phytoplankton and zooplankton. Thousands of tons of anchovy are taken commercially each year and used in various forms for human consumption and for raising hatchery fish, poultry, and livestock. This fish is easily obtainable, can be kept alive in captivity, and is of small size. The study analysed ambient levels of p,p'-DDT (1,1,1-2- 2bis (p-chlorophenyl) ethane) and its residues in 5 tissues of the anchovy (gonad, liver, muscle, gill, and brain). The uptake 188 and deposition of C+DDT from sea water was investigated to relate the normal levels and uptake results. Materials and Methods Specimens of E. mordax were taken from Monterey Bay and kept in a large circular cement pool with a circulating current. The sample was relatively homogeneous, consisting of about 300 fish ranging from 150mm to 170mm standard length. They were mature adults, estimated at 1-5 years. Frozen brine shrimp were given as food each evening. Water temperatures in the pool ranged from 11C to 15°0. The fish survived with only low mortality after adjustment to these conditions. The gas chromatographic analysis was done with a Beckman GC h gas-liquid chromatograph using a 3% OF 1 column on 80-100 mesh chromosorb W and as elctron capture detector. The acid extraction method of Stanley and LeFavoure (1965) was used to isolate the pesticide. All chemicals were checked for possible pesticide contamination. The glassware was carefully washed and then rinsed with petroleum ether and nannograde hexane, and the last hexane rinse was condensed and injected into the column to check for contamination. The analysis itself was done on each of 6 tissues from a group of 25 fish, except for the male and female gonads. where only 15 fish were included in the samples. The results are thus an average of the 25 and 15 fish samples, respectively. In addition, samples of two anchovy products, oil and meal, were obtained from a commercial plant processing Monterey Bay anchovy 3. 15 catches. Only DDE was measured because the chromatograph was unable to resolve DDT or DDD significantly and because DDE makes up approximately 80% of the total DDT residues in the Northern Anchovy (Risebrough, Menzel, Martin, and Olcott, unpublished results). The uptake experiments were conducted with fish chosen to be approximately the same size (160mm). One fish was placed in each one gallon screw-capped jar containing 2 liters of sea water at 8 - 10 C. The sea water was aerated for thirty minutes before each experiment. The radioactive DDT (100 ppm in ethanol) was then added. For the bulk of these uptake experiments, 20ul of clppT solution was added to each two liters of sea water to give a 1 ppb concentration. The jars were kept tightly closed to prevent codistil- lation of the radioactive DDT and were kept at 8°-10'C. It was previously determined that the anchovies could only live from A to 6 hours in this type of incubation, thus l hour limits were placed on the incubations to insure that the fish would live through the experiments. At the end of h hours, the fish were killed and dissected. Six types of tissue were removed for counting: the gonads, the liver, a portion of the muscle or flesh, a portion of the skin, the gills, and the brain. Each tissue was weighed and then homogenized in 2 ml of N,N-dimethylformamide. One ml of this homogenate was pipetted into a scintillation vial and 10 ml of toluene scintillation fluid (l gm PPO and O.1 gm POPOP per liter) were added to each vial before counting on a 184 Nuclear-Chicago Unilux II two-channel scintillation counter. All equipment which touched any tissues was rinsed twice with 952 ethanol between each tissue homogenization. Each vial was counted for one minute and disintegrations per minute were converted into parts per billion uptake for the h hour period. Variations in the number of tissue samples are due to the use of other tissues at the beginning of the study which were later standardized to the 6 listed above. Three fish were also run at 15 ppt C+DDT under the same conditions to simulate more closely the 15 ppt concentration found in normal sea water as determined by the California Department of Fish and Game (Odemar et al, 1968). One feeding experiment, with fish, was run under the same conditions using frozen brine shrimp which had been incubated in 10 ppb C+DDT for 1 hour and then washed twice with sea water. This last experiment was not pursued because results showed only very limited actual feeding due to the excited state of the fish. Limitations on the size of containers for the experiments were imposed by the problems of handling volütile, radioactive materials. Results The results of the gas chromatography are listed in Table 1. The results of the uptake experiments at 1 ppb for H hours are listed in Table 2, with one standard deviation. The results of the incubations in 15 ppt were in the same percentage proportions as those of Table 2, with the highest values being 6.80 ppb in the 5. liver and 8.20 ppb in the brain for the h hour study. The feeding experiment also showed approximately the same proportions among the tissues except that the stomach tissues averaged 21.6612.86 per cent as compared to the l.671 1.20 per cent found in A stomachs of fish run in the normal 1 ppb uptake experiments. Ten samples of muscle from the same fish were run to determine accuracy of the uptake technique. Results showed an average of 30.99 with a standard deviation of+5.30. Discussion The results of the gas chromatography are slightly lower than those found by Risebrough for Monterey Bay anchovies in November. 1965 (Risebrough, Menzel, Martin, and Olcott, unpublished results). These analyses were of whole fish and averaged O.65 ppm with a standard deviation of 0.19. However, the lipid content of the Northern Anchovy fluctuates greatly during the year and is much higher in November than in May, when the results of Table 1 were determined. This is due to reproductive cycles and is significant because the gas chromatographic method is based on lipid extraction. The lipid content in the spring averages 7% as compared to an average of 15% by weight in the fall (Parish, personal communication). The uptake experiments showed high variation between individual fish under constant conditions, as shown by the high standard deviations for all tissues in Table 2. Much of the data on pesticide residues is cited for a limited number of samples, often one or two, and the variability found in this study tends to show that little confidence can be placed in small sample sizes where DDT is concerned. Figure 1 shows the differences in 6 uptake experiments. Figure 2 shows the variations between sites of DDT concentration in ambient levels and in uptake. This suggests that the DDT is highly mobile within the anchovy after initial uptake. Liver tissue was a site of heavy concentration in the uptake experiments, while its value in ambient level is very low. The opposite is true in muscle tissue, indicating that DDT residues seem to move from the liver to muscle after uptake. There is also a positive indication that the anchovy is capable of either metabolizing DDT or excreting it directly. This conclusion comes from the extrapolation of the 15 ppt uptake results to the ambient levels in approximately 6 days. The ambient level values for the processed oil and meal are significant in that DDT residue concentration in the oil is above the Food and Drug Administration's interstate trade limit of 5 ppm in products for human consumption, and because the meal is fed directly to animals intended for human consumption. The results of the one feeding experiment are significant in that the high stomach concentration shows feeding was taking place and concentrations are again seen in liver, brain, and gill tissue (in that order). Further work is needed to determine the far-reaching effects of these results. The ambient levels must be determined throughout the year in order to understand the relationship of DDT content to lipid cycles. Further work is also needed on the movement of pesticide residues within the anchovy, possible metabolism and detoxification, and excretion back into the environment. This study has shown the Northern Anchovy to be a link in the movement of DDT and its residues in the marine food web. Acknowledgements The author would like to thank those of Hopkins Marine Station in Pacific Grove who were so helpful throughout this study. Special thanks are given to Dr. Ellsworth Wheeler, John Miller Phillip Murphy, and Joe Balesteri of the Hopkins staff, and to Richard Parish of the California Department of Fish and Game. This work was supported in part by the Undergraduate Research Participation Program of the National Science Foundation, Grant fGY-5878. 8. 1 References Odemar, M.W., P.W. Wild, and K.C. Wilson. 1968 A Survey of the Marine Environment From Fort Ross, Sonoma County, to Foint Lobos, Monterey County. Final Report of the California Department of Fish and Game to the San Francisco Bay-Delta Water Quality Control Program: 140. Risebrough, R.W., D.B. Menzel, D.J. Martin, Jr., and H.S. Olcott. 1967. DDT Residues in Pacific Sea Birds: A Persistant Insecticide in Marine Food Chains. Nature, 216: 589-591. Stanley, R.L., and H.T. LeFavoure. 1965. Rapid Digestion and Cleanup of Animal Tissues for Pesticide Residue Analysis. Journal of the Association of Official Agricultural Chemists, 48: 666-667. Wurster, C.F., and D.B. Wingate. 1968. DDT Residues and Declining Reproduction in the Bermuda Petrel. Science, 159: 979-981. 15 O Toßle 1. Tissue Gonad Female Gonad Male Liver Muscle Gill Brain Processed Meal Processed Oil PPM Wet Weight 0.1613 0.1065 0.1844 0.3502 0.3328 0.2750 ——— 6.8117 PPM PPM Dry Weight Lipid Lipid 0.50u1 2.20 7.3186 0.3328 2.76 3.8553 0.2526 3.33 5.5347 0.5837 1.96 17.8462 0.7396 3.35 9.9265 0.3274 11.13 2.4702 0.6248 3.43 18.2225 6.8117 1100.00 6.8117 C 16 O 1olt 2 Tissue Gonad (13) Male (6) Female (7) Liver (11) Muscle (13) Skin (12) Gill (12) Brain (12) Total Average PPB 17.1518.31 18.91 15.62 240.70 +120.27 17.7517.64 19.29 112.95 64.11 +25.96 16.15 123.33 Total Average 8 in Fish 1.2672.29 18.98 +12.02 1.62 11.75 13.51*1.29 16.10 15.69 16.72 15.35 C 161 5001 400- 300- PB E 4DDT 200 00 90 1 Pg SAMPLE baute 2. 500 400 300+ P B ODDT 200 00 MUSCLE GLL BRAIN LIVER GONAD GONAD M. SAMPLE C Captions Table 1. Ambient concentrations of DDE in Engraulis mordax Girard as determined by gas chromatography. All tissues except male and female gonads are averages of 25 fish samples. Gonad samples included 15 fish. Table 2. Results of CDDT uptake experiments with Engraulis mordax Girard. Number of samples of each tissue in parenthesis. Incubations were in 1 ppb concentrations for 4 hours in sea water at 8 -10 C. Figure 1. Example of variations in uptake results at 1 ppb for I hour incubations with Engraulis mordax Girard. Brain tissues are open circles and liver tissues are closed circles. Both tissues are from the same fish in each sample. Figure 2. Comparison of ambient levels and uptake results as to site of depostion in Engraulis mordax Girard. Uptake results (open circles) are added to ambient levels (closed circles) to show variations. 16 O Footn 1. Author's Permanent Address: Paul F. Kaplan 3710 W. 230th Street Apt. 5 Torrance, California 90505 166