Concentration of C-DDT by a marine planktonic copepod: from sea water and from consumed phytoplankton Mona Baumgartel Hopkins Marine Station of Stanford California Pacific Grove, California 93950 Abstract The herbivorous marine planktonic copepod Calanus helgolandicus was incubated in sea water which contained C+4-DDT or phytoplankton labeled with C+4-DDT to study the entrance of DDT into the marine food web at a low trophic level. The copepods concentrated C++-DDT by a factor of about 10,000 in 24 hours and continued to take up C+4-DDT from low levels in the water in ten-day experiments. C+-DDT was also found in copepods which had been fed C+-DDT-containing phytoplankton. 32 Introduction The damage which DDT is causing to birds at the upper end of the marine food web is well documented (Wurster and Wingate, 1968). Although the levels of DDT which contaminate the world's oceans are low (of the order of parts per trillion), the pesticide is concen- trated in the food web and stored in lipid deposits so that it may be over a million times more concentrated in high level carnivores such as the Bermuda petrel and peregrine falcon. There has been no direct evidence of this concentration phenomenon at lower trophic levels. I examined the entrance of DDT into the marine food web by measuring the uptake of radioactively labeled DDT by the planktonic copepod Calanus helgolandicus. Groups of these animals were incubated in sea water containing 1-DDT or were fed C1-DDT-labeled phytoplankton. Methods and Materials Calanus helgolandicus individuals were selected from zooplankton tows taken in Monterey Bay, California. A one-meter diameter net (0.33 mm mesh aperture) was towed for 5-15 minutes at various depths. In April and early May, 1969, surface tows brought up large numbers of adult female C. helgolandicus, but later in May, only younger stages could be found and only at 20-60 meters. This species was much less abundant through the summer, and at times it was not possible to get enough individuals because of large numbers of salps. However, one tow in early August was nearly all Calanus helgolandicus. Stage V copepodites were used in some experiments. The copepods were kept in open jars at 9-14°C under reduced illumination. Once or twice a week stocks were transferred by pipette to fresh sea water which had been filtered through cotton or Whatman 1 filter paper and were fed small quantities of phytoplankton. The appear- ance of fecal pellets was evidence that the animals were feeding. Adult females survived very well under these conditions. After the first few days in the artificial environment, nearly all lived for many weeks. Stage V's survived less well, possible because of the high mortality during molting (Mullin and Brooks, 1967). -4- Incubations to determine the uptake of C-DDT from sea water were carried out in screw-capped gallon jars or sealed quart Mason jars to prevent loss of the pesticide by codistillation. The jars were kept in water baths at 9-14°0 under reduced illumination. The gallon jars, which were used for short term experiments, contained 40 copepods at a density of 50 ml/animal in previously- aerated, membrane-filtered sea water. The quart Mason jars, used for ten-day experiments, each contained 10 copepods in 500 ml of sea water. In both situations, C-DDT was added to the water in test jars before the animals. C-DDT was either used directly from a stock solution (100 ug of ring-labeled C-DDT from Amersham/ Searle Corporation per ml of absolute ethanol) or diluted first in ethanol or sea water so that very low concentra¬ tions would be made conveniently. In a control run with 0.258 ethanol (the highest ethanol concentration used in experiments), the behavior and survival of the copepods did not appear altered by the alcohol. At various inter- vals in the uptake experiments, copepods were removed from the gallon jars in groups of about ten along with enough water to maintain the original density of 50 ml/ animal. When quart jars were used, the contents of one whole jar were removed and the remaining animals were transferred to fresh C'"-DDT-containing sea water to 35 approximate conditions of constant flow. The copepods were filtered onto Whatman l filter paper, washed with distilled water, and place in liquid scintillation vials to which a solution of the dyes PPO (4 g/1) and POPOP (0.1 g/1) in toluene was then added. The vials were counted on a Nuclear-Chicago Unilux II Liquid Scintilla- tion Counter (95% confidence limits: 2n, where n is the number of counts). It was discovered that even if each copepod exoskeleton was punctured, the radio- activity did not dissolve completely in the toluene solution for 2-4 days. Hence, all the final data is based on counts made four days after the completion of each experiment. The specific activity of the C-DDT was 19 mC/mM, so that one disintegration per minute (dpm) represented 8.38 pug of C-DDT. Since drying C"-DDT-containing copepods may drive off radioactive DDT and contaminate equipment, average dry weight determinations were made on large numbers of stock animals instead of drying test organisms. Animals were dried at 50°C for 12 hours in 10 or more groups of 10 or 20 in aluminum cups. This was done for animals from each new tow. Computations using the student's t test showed there was little variability among groups from a single tow, but the range was great between the means for different tows, probably because of varying selector Je -6 biases: 120-200 ug for adult females and 90-120 ug for stage V copepodites. This means that experiments done with animals from a single tow are comparable because of a common factor, while data from experiments using animals from different tows can be related only qualitatively since the amount of radioactive DDT taken up by the copepods is expressed as uug C-DDT per ug average dry weight (or parts per million). Diatom cultures were grown in 250-500 ml Ehrlen¬ meyer flasks containing 50-200 ml of an enriched sea water medium (500 mole/1 KNO,, 50 mole/1 K,HPO), 500 mole/1 Na,SiO, plus trace amounts of Fecl,, MnSo, Znso,, Na,Moo, Cocl,, CuSO, EDTA, thiamine, B,», and biotin). The flasks were kept under constant illumination at 14°0 and were shaken occasionally. Fresh cultures were started by one-milliliter inoculations into fresh medium. The populations were mixed, but in April and May were rich with Skeletonema costatum, along with Thalassiosira sp., Chaetoceros spp., Nitzschia sp., and Asterionella sp. The cultures flourished much less consistently in the summer months with many not growing at all. The most successful diatom in June, July, and August was Asterionella. Skeletonema did not appear in summer phytoplankton tows, and the old Skeletonema cultures could not be recultured. Rhizosolenia was common in tows but did not grow in -7- cultures. The earlier Skeletonema cultures were followed closely by counting them in a Sedgwick-Rafter counting chamber. Doubling time was about 12 hours until the cell density reached 1 to 2 x 102 cells/ml. No successful means was found for counting the later cultures since the bouyant cells (mostly Asterionella and Chaetoceros) did not sink to the bottom of the counting chamber. An attempt to follow cell density by measuring optical density with the Klett spectrophotometer was also unsuccessful since the difference between no cells at all and maximum density was only about 10 Klett units. Those summer cultures which grew reached their peak in a week or longer. Only cultures which were still in logarithmic phase were used for feeding experiments. The cells were incu¬ bated in 10 ug/ml C-DDT for 15 minutes. Previous work (Södergren, 1968) indicates that the unicellular alga Chlorella removes 52-77 of a low concentration of C-DDT (0.6 ug/ml) from the medium in 15 seconds. The cultures were centrifuged briefly, washed twice in membrane-filtered sea water, and resuspended to the original volume. Non- radioactive cells which had undergone this treatment recovered and grew in fresh medium. Nearly all of the cells in predominantly Skeletonema cultures came down in the pellet so the final resuspension had the same density as the original culture. The washing procedure -8- diluted C-DDT not taken up by the cells to less than 0.01%. However, this procedure involving centrifugation was not successful with Chaetoceros cells and those in all the later cultures since these cells did not spin down. This unfortunate circumstance meant that only a few feeding experiments were successfully carried out. Radioactivity in the phytoplankton resuspensions was measured by counting 2.0 ml samples dissolved in 10 ml of Bray's solution (100 ml ethanol, 20 ml ethylene glycol, 4 g PPO, 0.2 g POPOP, and 60 g naphthalene to one liter in dioxane) in the liquid scintillation counter. Feeding experiments were carried out under the same conditions as uptake experiments with 30 animals per gallon jar in indirect light to maintain the phytoplankton. C'-DDT-labeled phytoplankton was added at a concentration of about 10" cells per ml of copepod culture. When the copepods were removed and filtered, they were gently washed off the first filter and refiltered to reduce contamination from labeled phytoplankton cells. Results Figures 1 and 2 show uptake of C-DDT by adult female Calanus helgolandicus over a 32-hour period from 0.1 and 1 part per billion (ug/1) in the water. In both cases, the DDT was about 10,000 times more concentrated in the animals, in terms of dry weight, in 24 hours. The copepods removed 3-4% of the C-DDT which had been added to the culture. A similar curve was obtained for stage V copepodites incubated in 25 part per trillion for four and a half days (Figure 3). Over the longer time period, the animals accumulated DDT from water of low concentration to intra-animal concentrations nearly as high as from water with four times more DDT. Figure 4 shows the data for uptake of C-DDT by adult female C. helgolandicus over a ten-day period from 50 ppt in the water in three separate experiments. The curves are not identical, probably because of varia¬ tions in the exact amounts of C-DDT present and in the animal dry weights (see discussion above in Methods and Materials), but each shows that the rate of uptake of C-DDT decreases after the initial rapid rate and suggests that concentrations in the animals may be stabilizing. Experiments with lower sea water DDT concentrations (Figure 5) also show this decrease in rate, and, in fact, 20 -10- these curves suggest after an initial period (two days), the copepods takeup -DDT at a constant rate which is proportional to the amount of C-DDT present. In all of these experiments, the amount of C-DDT was not limiting as less than 10% of that in the water over any period of time was removed by the animals. Figure 6 shows that the copepods did take up radioactive DDT from ingested phytoplankton in three tests with stage V copepodites. That the animals were accumulating C"-DDT as they ate the diatoms is clear, although it is not known why in one test, the second group of copepods removed had less C-DDT than the first. Of the stage V's in two of these test, more died in the test jars than in the control: 11 of 32 and 10 of 34 compared to 6 of 31 in the control. In a separate preliminary experiment with stage V's, molting individuals suffered a higher mortality rate in water with 1 ppb DDT than in 10 ppt DDT or in the control. But in the feeding experiment, two dead copepods from each of the test jars were filtered, washed, and counted and were found to contain less C-DDT than those which remained alive, so that whether DDT was associated with these deaths is unclear. In these two test situations, approxi- mately 243 of the starting radioactivity was accounted for in the live and dead copepods. The C-DDT concentrations C -11- in the animals were of the same order of magnitude as for uptake from 1 ppb in water although there was about one-tenth as much radioactive DDT present. This data. combined with a very rough determination of phytoplankton dry weight, suggests that the copepods ate 4 ug, dry weight, of phytoplankton tissue in 24 hours. -12- Discussion The solubilities of DDT in oil and water are about 10% (Södergren,1968) and 1.2 parts per billion (Bowman, Acree, and Corbett, 1960). In view of this high partition coefficient, it is not surprising that the copepod Calanus helgolandicus rapidly concentrates DDT from the surrounding sea water into its lipid-containing tissues, and the copepod may be compared to a small drop of lipid with a high surface-to-volume ratio. The experiments done in sea water C-DDT concentra¬ tions of 0.1 and 1 ppb are not ecologically significant because, although DDT is soluble in water up to 1.2 ppb, natural concentrations are much lower even in areas with high local contamination. But it is significant that uptake was detected at 5, 25, and 50 ppt, or nearer supposed natural ambient levels. The ten-day experiments suggest that a steady rate of uptake of DDT from low concentrations in the water into higher concentrations in the animals is established after a few days of rapid uptake and that this rate is higher when DDT in the water is more concentrated. Since the C-DDT taken up in these experiments was in addition to that cold DDT already taken up in the environment and since the natural levels of DDT in C. helgolandicus populations and in Monterey 43 -13- Bay water are not known, the environmental significance of the experimentally observed kinetics of uptake cannot be evaluated. ci DDT also concentrates in phytoplankton, and Calanus helgolandicus, by feeding, can take up this DDT more readily than that which is dissolved in sea water. This is direct evidence of transfer of DDT from a primary producer to a herbivore in the marine food web. Although the phytoplankton were exposed to non-ecological levels of C-DDT to load them for feeding to the copepods, transfer has nevertheless been demonstrated. These findings suggest that, in their natural environment, copepods may accumulated DDT from their food, as well as, to a lesser extent, straight from the water. It would appear that copepods would continue to get more and more DDT as they eat more DDT-containing diatoms. The DDT which is accumulated and stored in Calanus helgolandicus is further concentrated and stored in higher trophic levels because these copepods are part of the diet of some kinds of fish and other zooplankton predators. Uptake of DDT directly from water by planktonic organisms may help to maintain very low levels in the surrounding water while functioning as an entry point for DDT into the marine food web at its broad base. -14- Acknowledgements I wish to thank Professor Ellsworth H. Wheeler, Jr., for many kinds of help in this research. This work was supported in part by the Undergraduate Research Participation Program of the National Science Foundation, Grant 164-5878. -15- References Bowman, M. C., F. Acree, and M. K. Corbett. 1960. Solubility of carbon-14 DDT in water. Agricultural and Food Chemistry, 8:406-408. Mullin, M. M., and E. R. Brooks. 1967. Laboratory culture,agrowth rate, and feeding behavior of a planktonic marine copepod. Limnology and Oceanography, 12:657-666. Södergren, A. 1968. Uptake and accumulation of C-DDT by Chlorella sp. (Chlorophyceae). Oikos, 19:126-138. Wurster, C. F., and D. B. Wingate. 1968. DDT residues and declining reproduction in the Bermuda petrel. Science, 159:979-981. -16. PPO: diphenyloxazole; POPOP: phenyloxazolyl) benzene. 1,4 biss2-(5. 47 -17- Figure Legends Figure 1. Uptake of C1"-DDT by adult female Calanus helgolandicus from sea water containing 0.1 parts per billionC -DDT. Figure 2. Uptake of C14-DDT by adult female Calanus helgolandicus from sea water containing 1 ppb C -DDT. Figure 3. Uptake of C1"-DDT by stage V copepodid Calanus helgolandicus from sea water containing 0.025 ppb C -DDT. Figure 4. Uptake of C"-DDT by adult female Calanus helgolandicus from sea water containing 0.050 ppb C -DDT. Figure 5. Uptake of C'"-DDT by adult female Calanus helgolandicus from sea water containing 0.005 and 0.025 ppb C -DDT. Figure 6. Uptake of C-DDT from C-DDT-labeled phyto- plankton by stage V copepodid Calanus helgolandicus. 1.0 - — — 0.5 0.0 HOURS OF INCUBATION 24 32 0 — C — O 10 24 HOURS OF TRSCEATION 1.2 — — 0.6 O 0.0 DAYS OF INCUBATION Fge — 2 O E 0.5 0.0- 5 PP DAYS OF INCUBATION 5 PPT 1.0 25 PPT 8 S2 0 0 4.0 3.0 2.0- 1.0- 0.0- DAYS OF INCUBATION O . 1 STVWINV NI 1a0-15 Wad - — o — — LE O 0 0