Abstract Preliminary investigations of several aspects of DDT residue flow through the food chain were carried out using DDT tracer. These consisted of measurement GLC analysis and( of field concentration levels, uptake from water, uptake through feeding, and determination of accumulation sites. Results indicate that more DDT is available to the organism over time than is accumulated, suggesting an equilibrium of DDT residue concentration between animal and environment. A thorough description of DDT flow in the food chain will require more detailed information on the kinetics at each level. The study will continue with investigation of DDT kinetics in Hermissenda. 340 DDT residues are concentrated when transferred into higher trophic levels. Although several studies deal with the kinetics of DDT assimilation in a single organism, there is little research that elucidates the details of DDT transfer through several steps in a marine invertebrate food chain. 2 This study represents some preliminary investigations of the transfer of DDT residues in a 3-level epibenthic food chain comprised of Campanularian hydroids, the eolid nudibranch Hermissenda crassicornis, and the tectibranch Navanax interminis. There are three aspects to this study: 1) measurements of field concentrations of DDT residues in the organisms; 2) a determination of the kinetics of DDT uptake from solution; 3) a determination of the efficiency of removal of DDT from food and its storage sites in the organism. Navanax were collected intertidally from White's Point on the Palos Verdes Peninsula near Los Angeles, and from a depth of 10 feet in Los Angeles Harbor. Hermissenda were collected from Los Angeles Harbor, from floating piers in the marina of Monterey, California, and primarily the pilings of Pier #2 at Monterey from depths of 2 to 25 feet. Sufficient quantities of the hydroid on which Hermissenda were observed to feed could not be collected for feeding and uptake studies. DDT residue concentrations were determined in Obelia from the floating piers. Uptake studies were with Bowerbankia gracilis, a bryozoan very abundant on pilings, and on which the nudibranchs were generally found grazing on the small hydroids interspersed among the stolons. Although Bowerbankia probably constitutes a minimal portion of Hermissenda's diet, its 393 surface to volume ratio, general structure, and feeding habits are similar to those of hydroids, and DDT uptake is comparable in the two. FIELD CONCENTRATIONS Samples, digested in 1:1 perchloric and glacial acetic acid, were extracted with hexane. Extracts were cleaned-up using a silica gel microcolumn to which 1% Nuchar Attaclay was added to insure removal of pigments. Samples were injected into a Beckmann GC-4 gas-liquid chromatograph equipped with an electron capture detector. The results are summarized in Table 1. The high value for Hermissenda from Los Angeles Harbor is probably due to large inputs of DDT into the nearby White's Point sewage outfall by the Montrose Chemical Corp. of California, sole producers of DDT in the U.S.% The value for Hermissenda from floating piers at Monterey is a factor of 2.3 above the mean value for those obtained from submerged pilings nearby. This suggests that these nudibranchs, always near the surface, are exposed to more DDT, perhaps from input into the surface layer from aerial fallout. The concentration factors are expressed as the ratio between the concentration of DDT residues in an organism and that of its food supply in its particular location. The decreasing factor with high trophic level may be a reflection of differing feeding habits, and additional autecological information is needed to interpret this trend. In order to determine a relationship between weight and DDT concentration, weight classes of .2gram intervals from o to 1.8 gram 349 of Hermissenda were analyzed separately; each class containing enough animals to provide an optimal analytical sample weight of 3 grams. Concentrations vs. weight are shown in Figure 1. There is a clear increase in the concentration of DDT residues with greater weight. Though weight is presumably a rough indication of age, it would not appear that this merely represents à oonstantly increasing accumulation over the animal's life span. Since Hermissenda have higher concentrations in areas with higher environmental levels of DDT, the population sampled in this experiment cannot have reached a saturation point. It seems likely that a Hermissenda of any size will have consumed more than five times its weight in hydroids, roughly the amount needed to account for its level of DDT residues. It would then be retain¬ ing less than 100% of its intake and presumably be in an equilib- rium condition. The increase must then be due to some other factor. Experiments discussed later showed the cerata as the principal site of at least short-term accumulation of DDT, and casual obser- vations indicate that larger Hermissenda have relatively more cerata. This may account for a greater lipid fraction in larger animals, and thus a greater concentration, since values are based on the weight of the entire animal. Even among Hermissenda of the same approximate weight the number of cerata varies, and could account for some of the scatter in the data. Further experiments will be done to test these possibilities. 296 DDT UPTAKE FROM SOLUTION Colonies of Bowerbankia, divided into 50 approximately 1 gram clumps, were placed in a glass container with 16 liters of sea water. Ring-labelled C DDT dissolved in ethanol was added to bring the initial concentration in the water to 100 parts per trillion (PPT). Samples of Bowerbankia were removed at various times and prepared as in the GLC analysis procedure, except for the clean-up. Pigments were removed instead by shaking with Nuchar Attaclay which was then removed by centrifugation. 10 ml aliquots of the water were also taken at various times and extracted by shaking with redistilled petroleum ether. Extracts, evaporated to .5 ml and combined with 10 ml of scintilation fluid, were counted in a Nuclear Chicago Unilux II scintilation counter. In a similar experiment, 40 Hermissenda were placed in 40 liters of sea water with an initial concentration of 50 PPT of C DDT, and samples were removed and analyzed in the same manner over a 38 hour period. The results of the two experiments are presented in Figure 2 and Figure 3. In both cases the rate of uptake decreases with decreasing concentration in the water. Although the curves tend to level off, it is difficult to tell at what point the systems would have reached an equilibrium condition since the ratio between concentration in the animals and concentration in the water increased linearly with time in both cases over the periods measured. Since various factors including an inconstant volume of water per animal and competition for the available label were not taken into account in this experiment, the data is not 34 sufficient for further interpretation. Additional experiments will be carried out in order to determine the mechanisms of DDT uptake in Hermissenda. DDT UPTAKE FROM FEEDING A group of 14 Hermissenda were fed portions of C'' DDT labelled Hermissenda and were the placed in 2 liters of clean sea water. An additional 3 labelled Hermissenda were fed to a single Navanax which was also placed in clean sea water. Feces were removed from the container and analyzed, and water samples were removed and analyzed periodically. At the end of 48 hours, the Hermissenda were dissected into samples of total cerata, viscera, and muscle tissue (foot and head). The Navanax was likewise dissected and the tissues divided into separate samples. The results of liquid scintilation counting of the samples is presented in Table 2. Percentages are based on the total 'DDT recovered. Two results are evident: 1) the major fraction of DDT in both cases was accumulated in the digestive glands; 2) the efficiency of DDT assimilation from food is high: 96% in Hermissenda and 97% in Navanax. It is assumed that the label recovered from the feces represents all that was lost from the animals, since the water samples did not vary from background over the entire period. DISCUSSION The results of this study suggest that more DDT residues are available to these organisms over time than are actually accumulated, and that an equilibrium condition is reached 39 between the concentration level in the organism and the level of DDT residues in its environment. The concentration in the animal is dependent upon a number of variables determining rates of uptake, retention and loss. A complete description of the flow of DDT residues through this food chain will require eluci- dation of the nature of the equilibrium in each trophic level. This study will continue with the investigation of this problem in Hermissenda. 39 REFERENCES AND NOTES 1. Only p.p' DDT (1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane), p.p' DDD (1,1-dichloro-2,2-bis (p-chlorophenyl) ethane) and p.p' DDE (1,1-dichloro-2,2-bis (chlorophenyl) ethylene) were measured. DDT residues refers to all three compounds. 2. J.L. Cox, Ph.D. thesis, Stanford University (1970). 3. D.J. Reish, K.E. Maxwell, J.R. Austin, Western Society of Naturalists, Abstracts of Contributed Papers to the 49th Annual Meeting, (1968). 4. A.M. Kadoum, Bull. Environ. Contam. Toxicol. 3, 65 (1968); ibid., p. 354. 5. All GLC parameters were those suggested in Pesticide Analysis Manual (U.S. Dept. of Health, Education and Welfare, Food and Drug Administration, revised 1968), vol. 2. 6. County Sanitation District of Los Angeles County, Pesticides and Heavy Metals, Progress Report, prepared by C.W. Carry. J.A. Redner, (1970). O Acknowledgements I wish to thank Mr. Robin Burnett for his patient assistance. 35 FIGURE LEGENDS Figure 1. Concentrations of DDT residues vs. weight of Hermissenda. Each point is the value measured for a sample composed of from 4 to 30 animals with weights ranging over the.2 gram interval. Points are plotted at the mean weight/animal in each sample. Figure 2. Removal of C DDT from sea water by Bowerbankia. The curves indicate increase of concentration of label in the Bowerbankia (solid line) vs. decrease of the concen- tration in the water. Figure 3. Removal of C DDT from sea water by Hermissenda. The curves indicate increase of concentration in Hermissenda vs. decrease of concentration in water from an initial calculated value of 50 PPT. The fluctuation was probably due to varying temperature. TABLE LEGENDS Table 1. Field concentrations of DDT residues in the food chain. The number of animals measured (colonies in the case of the bryozoan and hydroid) is noted along with the location. All walues are based on wet weight. No measurement was made of the water from Monterey Harbor. Value here is very rough estimate based on values for open ocean water. ** Condition of the GLC column did not allow quantification of the DDT peak. O Table 2. CDDT measu. and various tissues of iinf Hermissenda and Navanax 48 hours after feeding on labelled Hermissenda. TABLE I PARTS PER BILLION DDE DDD DDT WATER, INCLUDING SMALL approx..Ol" PARTICULATE MATTER BOWERBANKIA (4) 3.04 (WHARF PILINGS) 5.55 2.58 OBELIA (10) . . (FLOATING PIERS) 15.5 9.4 HER PTSSENDA (PILINGS) (62) 29.6 18.2 9.1 * . (FLOATING PIERS) 65.5 (7) 45.7 . . (L.A. HARBOR) (14) 416 194 NAVANAX (1) . . (L.A. HARBOR) 756 162 CONCENTRATION FACTOR approx. 102 approx. 2.5x10 1.5 3 8 L O O 8 )( ) )( * X a * ) OE 9 * X O 2 0 Sod 3814 Q L E D L 8 8 PPT IN WATER 8 8 9 8 .* . .. )( ** IR 0 X X r R-X 8 VINNVGNSMOS NI gad (O 358 2 8 7 XI X Ar )e o o./o . X/X LE * * (0 * X XX X SSIVM NITad VGNZSSINAZH :NI 8ad 8 8 10 O HER ISSENDA CERATA VISCERA FOOT and HEAD FECES NAVANAX DIGESTIVE GLAND FOOT and HEAD TENIDIUM BUCCAL MASS STOMACH FLUIDSS CES TABLE 2 nu gm C DDT RECOVERED 9580 995 650 450 70240 10025 3210 775 690 365 2295 PPB 3.68 .79 93 26.22 1.10 8.88 .60 .82 — % OF TOTAL 82.1 8.5 5.5 3.9 80.0 11.7 3.6 .9 8 4 2.6 351