UPTAKE AND DEPOSITION OF DDT-C1+ BY THE INTERTIDAL TELEOST CEBEDICHTHYS VIOLACEUS AYRES by James Edward Sutton" Hopkins Marine Station of Stanford University Pacific Grove, California 93950 * Send proofs and correspondence to: James Edward Sutton Hopkins Marine Station Pacific Grove, California 93950 INTRODUCTION That DDT and other chlorinated hydrocarbons are con- centrated by freshwater fishes is well documented by nu- merous studies (Johnson, 1968). The uptake has been shown to occur by concentration through the food chain (Hickey and Anderson, 1968; Woodwell, 1967), as well as by direct uptake from environmental waters (Holden, 1962; Anderson and Peterson, 1969). Recent studies have indicated sig. nificant amounts of DDT in marine organisms, particularly marine fish and birds (Risebrough et al., 1967). Although in birds DDT is taken up through the food chain, the mech- anism of DDT uptake by marine fishes has not been exten- sively studied. In order to assess the ability of marinefishes to concentrate DDT from the environment, a study was made of the intertidal teleost Cebedichthys violaceus Ayres, the monkey-faced blenny eel. Rates of uptake and sites 14 of deposition were studied through the use of DDT-C Studies were also made of the ability of the fish to take up DDT from extremely dilute concentrations to determine if significant amounts could be absorbed at the levels of DDT naturally present in sea water. MATERIALS AND METHODS Specimens of Cebedichthys violaceus Ayres were obtained during periods of low tide in April and May, 1969. They were taken from the lower intertidal region, primarily in the harbor of Monterey, California, and also off the Point Pinos and Hopkins Marine Station beaches. The fish were not fed during captivity, and for the most part only fish of 7-9 cm in length were used in the experiments. During experiments each fish was incubated in 500 ml of sea water in a one quart capacity screw cap jar, to which was added 0.005-0.05 ml of DDT-C.dissolved in ethanol (specific activity: 19 mC/mM). The jars were placed in running sea water at a temperature of 1441°C. Controls were run under similar conditions except that no DDT was added. No ill effects were observed in any of the test animals, or in controls placed in twice the volume of ethanol in sea water as the test animals. To prevent loss of DDT from the water by evaporation or co¬ distillation (Acree et al., 1963; Wurster,1968), the jars were kept closed. After incubation each fish was weighed, swabbed with 95% ethanol to remove surface DDT, and sacrificed. The brain, gills, liver (excluding gall bladder), and a sample of skeletal muscle from the body wall were removed, placed in tared pieces of aluminum foil, and wet weights obtained on a Mettler H15 or HéT balance. The tissues were then homogenized in 2.0 ml of N,N-dimethylformamide (DMF) (Mathe- son, Coleman and Bell) and a 1.0 ml aliquot placed in a scintillation vial. To this was added 10.0 ml of a tol- uene-PPO-POPOP scintillation fluid: Counts were taken for ten minutes in a Nuclear Chicago Unilux II Liquid Scin- tillation Counter. Background vials contained 1.0 ml DMF and 10.0 ml scintillation fluid. Quench correction was made by the channels-ratio method. RESULTS Preliminary analyses on the extent of DDT-C uptake were made on skin, skeletal muscle, liver, intestine, stomach, heart, gills, brain, eye, and bladder of Cebe¬ dichthys. A twelve hour incubation in one part per billion (ppb) DDT showed that liver and brain concentrated DDT to the greatest extent, and on that basis these tissues were chosen for further study. Although muscle did not concentrate DDT to very high levels, it was also selected for study as it constitutes the bulk of the animal's weight. Entrance of DDT into the body is through the gills, intestine, and skin. Gills were selected for further study because levels in this organ were nearly as high as those of brain tissue, and because there is evidence from studies with non-feeding freshwater fish that the gills are the primary means of entry (Holden, 1962). Low levels were found in the stomach, but the intestine was much higher, with concentrations approximating those found in the gills. This may have been due to swallowed water carrying DDT into the intestine, or to the blood supply of this organ. Only very small amounts of DDT were found in the skin, suggesting that absorption through the skin contributes little to the total amount entering the body. As the fish secretes a rather heavy mucus coat, the constant shedding of this mucus might have limited the penetration of DDT. From the above considerations liver, brain, gills, and skeletal muscle were chosen for further analyses of uptake phenomena. Table 1 and Figure 1 show the uptake of DDT-Ct" into the above organs from a 1 ppb solution in sea water as a function of time. Each point in Figure 1 is the mean of three fish incubated for 2/3, one, two, four, and eight hours. It is seen that in each tissue there is a very rapid absorption during the first two hours of incubation, followed by a decreased rate of uptake. The high amount of DDT indicated in the brain after one hour is the result of an extremely high reading in one fish (114.6 ppb as compared to 47.5 and 44.7 ppb in the other two fish); this disproportionately affected the mean uptake. Table 2 and Figure 2 indicate the extent of uptake by the four tissues at three different concentrations after eight hours of incubation. Each point in Figure 2 is an average of three fish, except for the brain and gill readings in the 0.1 ppb series, which is the average of only two fish. In all cases the liver accumulated the greatest amount of DDT. It is also interesting to note that the amount of DDT in the brain and liver is much greater than in the gills at the higher concentrations than at the lower concentrations. Table 3 and Figure 3 show the number of times the DDT has been concentrated by the tissues over the concen¬ tration originally present in the sea water (i.e., the concentration factor). Although an apparent decrease in the concentration factor is seen for liver tissue in the 0.015 ppb series, this is actually due to an unusually high concentration (393.9 ppb), as compared to 87.3 and 41.6 ppb in the other two fish, in one fish of the 0.1 ppb series. The concentration factor would increase from the 0.1 ppb series to the 0.015 ppb series if this one value were disregarded. DISCUSSION The results of these experiments are in general agree- ment with those performed on other teleosts (Holden, 1962; Bridges et al,, 1963; Anderson and Everhart, 1966). Other workers at the Hopkins Marine Station, using similar tech- niques, have found closely related results in studies of the speckled sanddab, Citharichthys stigmaeus, and the Northern anchovy, Engraulis mordax (Phillips, 1969; Kap- lan, 1969). Liver tissue appears to concentrate DDT to the greatest extent, but it is possible that much of the DDT in this organ is actually present in the blood, as is suggested by Johnson (1962). This may also be the case in the brain. However, as Bridges et al. (1963) found 10.1 ppm of DDT in bullhead brain tissue as opposed to only 2.8 ppm in muscle and 2.7 ppm in the blood, ample amounts of blood may not be sufficient to account for the high levels in these organs. Similarly the large amounts of lipid in brain tissue would certainly seem to be con- ducive to absorption of significant amounts of DDT in that organ. Holden (1962) in his study of uptake of DDT-C by brown trout found that 80-90% of the DDT in the incubation tank was removed from the water by the fish within the first ten hours of the experiment. Attempts were made to measure the amount of DDT remaining in the water after the completion of the present experiments, but the results were highly inconsistent, probably due to sampling problems. Since DDT adheres to surfaces and codistills with water, it might be expected to have a markedly heterogeneous distribution (Acree et al., 1963). This would not only affect sampling, but also change the effective concen- tration in the immediate volume of water surrounding the fish. Thus the fish could be concentrating DDT from water containing much less than the amount in the original solution. This great reduction in the amount of DDT actually available in the water might account for the decrease in the rate of uptake observed in all tissues after the first two hours of incubation. Ittis also possible that the tissues have become partially saturated and so cannot absorb DDT as fast as before, or that a redistribution of DDT to other tissues begins to occur, so that the amount in the measured tissues decreases as the level in the other tissues increases. As regards redistribution, however, since uptake in all tissues decreased about the same time (two hours after the start of incubation), it would not appear that redistribution is the factor. As regards saturation, since much higher concentrations of DDT have 39. been found in natural populations of many other fish, it is probable that the saturation point of the tissues of this fish has also not been reached. For these reasons, it would seem that the decreased rate of uptake resulted from the decreased availability of DDT in the sea water. The ability of Cebedichthys to greatly concentrate DDT directly from sea water indicates several important points. First, it shows that DDT can enter organisms, and so the food web, directly at many levels and can con¬ tribute significantly to the overall buildup of DDT in tissues. Thus, the amount of DDT in the animal cannot of itself be considered a reliable indicator of trophic level. Second, the fact that Cebedichthys can take up sig- nificant amounts of DDT from as low as 15 parts per trillion (ppt) from sea water (also containing an unknown amount of DDT dissolved in it) is ecologically significant. Bailey and Hannum (1967) have reported concentrations of DDT at the Golden Gate of San Francisco Bay of 20-60 ppt, with an average of 41 ppt. The experiments I performed show that Cebedichthys is able to concentrate DDT from similar or more dilute solutions in a short period of time. Thus, even the dilute concentrations found in sea water are sufficient to permit DDT to be taken up into organisms, and so enter the food web, where further concentration through the food chain can occur. Since species closely related both taxonomically and ecologically to Cebedichthys are the prey of predatory fish and fish-eating birds, partic- ularly the guillemot (Carl, 1964), it might be expected that Cebedichthys may contribute to the further concen- tration of DDT in the higher trophic levels. Thirdly, it is apparent that continued direct uptake of DDT from environmental waters may result in the accumul- ation of very high levels of DDT in tissues within rela- tively short periods of time. For example, if sea water contained 15 ppt DDT, the liver would concentrate to a level of 25.5 ppb per eight hour period, or 76.5pppb per day. At the end of one year the fish would have 27.9 ppm of DDT in its liver. This does not include the unknown but presumably substantial amounts of DDT which would be accumulated as a result of feeding on contaminated food sources. There are several hypotheses to explain why such levels are not often found in natural populations: attainment of lethal concentrations and thus death; sat- uration of tissues; partial metabolism to DDE or DDD (Bridges et al., 1963); complete metabolism and/or excre- tion; or simply that the concentration of DDT insea water is much less than 15 ppt, although measurements of similar or higher levels have been made (Bailey and Hannum, 1967; Odemar et al., 1968). Although lesser amounts of DDT are taken up from more dilute solutions, the concentration factor was found to increase. This significant finding indicates that the animals are able to concentrate DDT more efficiently from more dilute solutions, such as would be found in sea water, than from the more concentrated and probably unnatural solutions used in most experiments. The reasons for this phenomenon are unknown. It may be that the dilute solu- tionsis more homogeneous and hence that a greater percen- tage of the DDT in the solution is available for uptake. It may also be that the uptake from more dilute concen- trations occurs at a greater rate. It is apparent that numerous aspects of this problem remain to be studied, including ambient concentrations in natural populations, effects of DDT on metabolism and reproductive activities, rates of uptake lethal doses, and the accumulation of DDT through the food chain. These must be accompanied or preceded by studies of the ecology, behavior, reproductive, and feeding habits of Cebedichthys, which have not been studied to date. It is difficult to draw conclusions concerning the uptake and effects of DDT when such parameters remain unknown. SUMMARY A study was performed on direct uptake and deposition of DDT-C from sea water by the intertidal teleost Cebe- dichthys violaceus Ayres. It was found that the liver concentrated DDT to the greatest extent, followed by brain, gills, and muscle. After a rapid uptake during the first two hours of incubation, the rate was seen to decrease to a certain extent, possibly due to removal of most of the DDT from the water. The ability of the fish to absorb and concentrate DDT from concentrations comparable to those found in natural waters was also studied, and it was found that the total amount of DDT absorbed decreased in more dilute solutions, but that the factor of concentration greatly increased. The significance of direct uptake from very dilute con- centrations is discussed. 10 ACKNOWLEDGEMENTS I wish to thank the entire faculty and staff of the Hopkins Marine Station for their kind assistance and advice, and in particular Dr. David Epel for many valuable sug- gestions and for his patient guidance throughout all phases of this research. I also wish to thank Mr. John Miller for his long hours of technical assistance in the lab and with the scin- tillation counter, and Mr. Sam Johnson for his assistance in the lab. This project was supported in part by the Dietz Fel- lowship of Stanford University. 11 FOOTNOTE 1. The scintillation fluid is a mixture of 1.0 liter of toluene, 4.0 grams of 2,5-diphenyloxazole (PPO) (Amer- sham/Searle; Scintillation Grade) and 0.1 gram of 1,4- bis (2-(5-phenyloxazolyl)) benzene (POPOP) (Amersham/ Searle; Scintillation Grade). 12 408 Table 1. Table 2. Table 3. TABLE LEGENDS Uptake of DDT-C by Cebedichthys violaceus, as a function of time, from a 1.0 ppb solution of DDT in sea water. Uptake of DDT-C by Cebedichthys violaceus, as a function of concentration, after an eight hour period of incubation in 1.0, 0.1, and 0.015 ppb solutions of DDT in sea water. Factor of concentration (the number of times the DDT was concentrated in the tissues above that of the original solution) by Cebedichthys violaceus, after an eight hour period of incuba- tion in 1.0, 0.1, and 0.015 ppb solutions of DDT in sea water. 13 405 Figure 1. Figure 2. Figure 3. FIGURE LEGENDS Uptake of DDT-C from a 1.0 ppb solution of DDT in sea water by tissues of Cebedichthys violaceus, as a function of time. Each point is an average of three fish incubated for the indicated length of time. Key: O, brain; E, gills; A, liver; Q, muscle. Uptake of DDT-C from 1.0, 0.1, and 0.015 ppb solutions of DDT in sea water by tissues of Cebedichthys violaceus, Each point is an average of three fisn incubated for eight hours, ex- cept for the brain and gill tissues in the O.1 ppb series, which are the averages of two fish. Key: B, brain; G, gills; L,liver; M, muscle. Factor of concentration of DDT-C by tissues of Cebedichthys violaceus as a function of incubation concentration. The horizontal scale decreases from 1.0 ppb on the left to 0.O ppb on the right. Key: O, brain; m, gills: A, liver; o, muscle. 14 4 LITERATURE CITED Acree, Fred, Jr., Morton Beroza, and Malcolm C. Bowman. 1963. Codistillation of DDT with water. J. Agri. Food Chem. 11: 278-280. Anderson R. B., and W, H. Everhart. 1966. Concentrations of DDT in landlocked salmon (Salmo salar) at Sebago Lake, Maine. Trans. Amer. Fish. Soc. 95: 297-309. Anderson, John M., and Margaret R. Peterson. 1969. DDT: sublethal effects on brook trout nervous system. Science 64: Lho-Lli. Bailey, Thomas E., and John R. Hannum. 1967. Distribution of pesticides in California. Jour. Sanit. Engineer. Div., ASCE, 93(SA5) Proc. Paper 5510: 27-13. Bridges, W. R., B. J. Kallman, and A. K. Andrews. 1963. Persistance of DDT and its metabolites in a farm pond. Trans. Amer. Fish. Soc. 92: 421-127. Carl, G. Clifford. 1964. Some common marine fishes of British Columbia. British Columbia Provincial Museum. Dept. of Recreation and Conservation Handbook 23: 75-76. Hickey, Joseph J., and Daniel W. Anderson. 1968. Chlorin- ated hydrocarbons and eggshell changes in raptorial and fish-eating birds. Science 162: 271-273. Holden, A. V. 1962. A study of the absorption of C labeled DDT from water by fish. Ann. Appl. Biol. 50: 167-477. 15 19. Johnson, Donald W. 1968. Pesticides and fishes-a review of selected literature. Trans. Amer. Fish. Soc. 97 398-424. Kaplan. 1969. Personal communication. Odemar, Melvyn W., Paul W. Wild, and Kenneth C. Wilson. 1968. A survey of the marine environment from Fort Ross, Sonoma County, to Point Lobas, Monterey County. Calif. Dept. of Fish and Game MRO Reference No. 68-12. Phillips, Gregory. 1969. Personal communication. Risebrough, Robert W., Daniel B. Menzel, D. James Martin, Jun., and Harold S.OOloott. 1967. DDT residues in Pacific sea birds: a persistent insecticide in marine food chains. Nature 216: 589-591. Woodwell, G. M. 1967. 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Science 159: 1474-1475. 16 40 INCUBATION (HOURS) 2/3 2/3 2/3 2/3 2 2 4 TISSUE Brain Gills Liver Muscle Brain Gills Liver Muscle Brain Gills Liver Muscle Brain Gills Liver Muscle Brain Gills Liver Muscle TABLE 1 SAMPLES MEAN (PPB 28.0 49.6 18.6 32.1 21.0 34.6 27.7 27.8 76.3 133.6 110.8 106.9 14.9 27.0 17.6 19.8 114.6 47.5 44.7 69.0 41.0 5.7 35.7 27.5 150.4 72.7 178.3 133.8 39.9 0.0 14.0 16.0 56.0 63.9 58.2 59.4 32.4 32.7 27.0 37.6 147.9 165.0 171.0 161.3 10.9 19.7 11.6 14.1 62.6 141.5 66655 90.2 50.h 78.7 45.4 58.2 244.0 172.0 280.2 279.7 29.3 62.9 18.6 36.9 118.0 92.7 156.4 122.1 111.3 54.1 147.5 104.3 257.4 318.7 321.4 299.2 44.3 4h.1 43.0 45.7 STANDARD DEVIATION 15.9 6.8 28.9 6.4 17.1 19.0 54.7 13.9 4.1 5.3 6.9 4.9 44.5 18.0 62.3 23.1 31.6 47.1 35.9 1.4 CONCENTRATION TISSUE (PPB) 1.0 Brain 1.0 Gills 1.0 Liver Muscle 1.0 Brain O.1 O.1 Gills 0.1 Liver Muscle O.1 0.015 Brain 0.015 Gills 0.015 Liver Muscle 0.015 TABLE 2 SAMPLES MEAN STANDARD DEVIATION 24.7 138.1 139.8 181.7 153.2 85.2 24.4 57.3 102.7 995.5 181.5 213.0 309.8 234.7 66.9 13.4 30.3 44.6 55. 12.5 93.7 71.4 --- 82.6 15.7 90.1 38.0 --- 64.0 36.8 393.9 87.3 95.5 192.2 174.7 5.4 18.2 8.3 9.7 12.7 24.7 22.2 16.7 21.2 3.9 21.1 16.2 38.9 17.4 7.1 11.2 13.7 21.5 25.5 14.1 4.4 4.6 4.2 4.3 0.2 o CONCENTRATION (PPB) 1.0 1.0 1.0 1.0 O.1 O.1 0.1 0.1 0.015 0.015 0.015 0.015 TABLE TISSUE CONCENTRATION FACTOR MEAN STANDARD DEVIATION Brain 138.1 139.8 181.7 24.7 153.2 24.4 Gills 57.3 102.7 85.2 95.5 Liver 181.5 213.0 309.8 234.7 66.9 13.4 44.6 55.3 Muscle 12.5 30.3 714.5 --- 825.6 Brain 936.7 157.2 ——— 640.2 Gills 900.7 379.6 368.5 873.0 955.2 1922.5 1747.1 Liver 3939.3 Muscle 182.2 83.1 97.0 126.8 55.3 Brain 1646.3 1476.9 1111.9 1411.7 273.1 1081.6 Gills 2593.8 1159.8 474.3 1409.3 241.8 Liver 2744.0 916.3 1435.7 1698.6 13.6 Muscle 308.2 282.6 287.6 292.8 kog o O O 300- 275 250 225 150 — 125 2 100 75. 50- 25- Figure ime in OUTS 250 225 200 175 9. 2 150 a 125 100 75 50 25 O ( DDI Figure 2 BGL M M 0.015 Incubation Concentration, in Parts per Billion M - 20 10 Figure 3 05 O.10.015 DDT Incubation Concentration, in Parts Billion per