ABSTRACT DDT inhibits photosynthesis in natural populations of marine phytoplankton at levels as low as 10 ppb, and reduces it to 5% of the normal rate at 1 ppm. The rate of photosynthesis/unit chlorophyll A decreases with in- creasing concentration of DDT, with a corresponding in¬ crease in the rate of respiration. In exponentially growing cultures, the rate of chlorophyll A synthesis decreases with increasing concentration of DDT. DDE, the most common analog of DDT in the environment, in- hibits photosynthesis at much lower concentrations, and to a greater extent,,than DDT. -1- INTRODUCTION As the concentration of DDT and other polychlori¬ nated hydrocarbons increases in the world ecosystem, the fact that they are biologically harmful to many non- target organisms is becoming more and more evident. Harm- ful effects by these pesticides have been observed on every trophic level, from man, down through the very smallest phytoplankters. DDT is a residual organic compound, readily dis- solvable in lipid substances, and thus, becomes easily concentrated in the fatty tissues of organisms. As a result, it has reached lethal proportions at the highest trophic levels. The pathway of DDT through the food chain, and its accumulation at the top, is a major con- tributing factor to its lethality. How DDT enters the food chain is an important question, and examination of the lower trophic levels may provide a clue, since the marine phytoplankton form the base of many oceanic food chains, and are known to concentrate DDT from the water at levels equal to and greater than those of the envir- onment. Not only is DDT concentrated by these organisms, but it also exerts a harmful effect on their metabolic systems. And this fact is of great importance in view of the impact it might have on the entire oceanic food supply. Wurster (1968) found that DDT inhibits photosyn- -2- thesis in phytoplankton at concentrations as low as 8 ppb. However, it is still not known by what mechanism DDT in- fluences photosynthesis. There was some question as to whether or not the actual photosynthetic process was being harmed, or if general inhibition of the entire metabolic system of the organism was occurring. Therefore, the objectives of this investigation were: a) to evaluate to what degree various concentrations of DDT would alter the photosynthetic rate of a natural marine phytoplankton community, and, b) to attempt to determine the mechanism by which the photosynthetic process is altered by DDT. METHODS AND MATERIALS All phytoplankton samples were collected in Monterey Bay, from a depth of fifteen meters, approximately z mile off shore to the north of Hopkins Marine Station at buoy no. 4. Two sampling procedures were used during the study. The first involved taking whole water samples with a five liter Van Dorn sampler (Van Dorn, 1956), and im- mediately transferring the sea water to 300 ml. B.O.D. bottles with a siphon apparatus. The B.O.D. bottles were kept cool on ice and protected from direct sunlight by wrapping them in two layers of tin foil, Bottles were held under these conditions for an average of 1.5 hours be¬ fore subsequent utilization in various experiments conduc¬ ted ashore at the Hopkins Marine Station. The second sampling procedure involved 20 minute horizontal tows with a no. 25 phytoplankton net at depths of approximately 15 meters. These phytoplankton samples were also protected from direct sunlight and kept in glass jars on ice ap- proximately 1.5 hours before utilization in the laboratory. The effects of DDT on photosynthetic rates were measured using two different procedures. The first was the light-dark bottle method as described by Gran (1927) and modified by Strickland and Parsons (1968). This pro- cedure utilized 300 ml. B.O.D. bottles of whole water sam- ples. In the laboratory, they were inoculated with various concentrations of DDT. A light bottle and a dark bottle, wrapped four times with black electrical tape to exclude all light, were used for each concentration. An initial B.O.D. bottle was analyzed for O2 concentration to establish the oxygen content of the water. The bottles were incubated under flugrescent lighting for six hours. At the end of the incubation time, they were analyzed for 0 production or consumption by the Winkler method, as modified by Strickland and Parsons (1968). The second procedure for photosynthetic rate determination was the C-uptake method as described by Strickland and Parsons (1968). Again whole water samples were used, treated, and incubated in the same manner as those in the O production method, with the exception that each bottle received 50 of 5uc/ml radioactive NaC0. At the end of the incubation period, the samples were killed with 0.5 ml. 40% Formaldehyde per B.O.D. bottle, and fil- tered on.45u millipore filters. The filters were then folded, placed in scintillation viles, covered with Tol- uene scintillation fluid, and counted on the scintillation counter. All'controls were run with 95% ethanol, as the DDT was suspended in that. Cell density measurements were made with the Sedgwick- rafter cell and a hemocytometer concurrently. Cells making up long chains were counted individually. Six fields were counted and then averaged. Chlorophyll A concentrations were determined by a fluorescence technique (Holm-Hansen et al, 1968) on 25 ml. samples of phytoplankton filtered on.45u millipore filters. The chlorophyll was extracted with 90% acetone, and diluted 36,000x before readings were made on the Florometer. If readings could not be taken immediately, the filters were wrapped in tin foil and frozen until extraction with acetone could be done. RESULTS Experiment 1. Experiment 1 was designed to broadly establish a photo- synthetic inhibition curve of marine phytoplankton by DDT. Whole water samples were collected in the manner described above and incubated in DDT concentrations of 1, 3, 30, 300, and 1000 ppb. The results are shown in Table I, and the inhibi- tion curve, as well as the respiration rates are shown on Figure 1. Experiment 2. Based on the results of Experiment 1, three concentra¬ tions of DDT, 10, 50, and 100 ppb, were chosen to continue the study. These were selected because they were relatively low concentrations of DDT, yet produced clearly discernable effects on the rate of photosynthesis. Sunsequent testing confirmed the initial observation that these concentrations were not lethal to phytoplankton cells. Figures 2 and 3 show the % dead of cells exposed to these concentrations continu¬ ously over a 96 hour time period. Figure 2 shows the effects on a pure, uni-alga culture of the dinoflagellate species, Dunaliella; and Figure 3 shows the effects on a natural pop¬ ulation made up of primarily Nitzchia, Chaetocerous (2 species) and four or five other diatomsspecies in lesser numbers. The composition of the culture remained consistant through- out the study, with only small variations from day to day. Experiment 3. Experiment 3 was conducted to establish the long term effects of DDT on phytoplankton. Four five-liter erlenmeyer flasks, filled with three liters each of an enriched sea water broth, were inoculated with a concentrated natural popula- tion sample to bring the cell density in each flask to ap- proximately 2.2 x102 cells/ml. Each flask was then exposed to constant light intensity of 60 footcandles, intermittant mixing, and a constant temperature of 12°0. After a 24 hour adjustment period, the flasks were injected with stock solution DDT to bring their overall concentrations to 10, 50, -6- and 100 ppb DDT. The cultures were re-injected with DDT every six hours. At time 0, 24, 48, and 72 hours, sub¬ samples were taken from each flask, and tested for cell den- sity (Table II), rate of photosynthesis using the Cjl meth- od (Table III), and the amount of chlorophyll A/25 ml. (Table IV). The Cju method was the same as described above with the exception that 125 ml. samples were used in reagent bottles instead of 300 ml. samples in B.O.D. bottles. Experiment 4. Experiment 4 was designed to determine the effect of DDT on the rate of chlorophyll A synthesis in exponentially growing cultures of natural phytoplankton samples. Cultures were kept in 500 ml. round bottomed flasks, in 300 mls. of enriched filtered sea water broth. Florometer readings were made every 12 hours for a 40 hour period on 25ml. sub-sam¬ ples. The results are summarized in Figure 5. Experiment 5. A final experiment was conducted to test the inhibitory nature of DDE, the most common analog of DDT in the natural environment. Three hundred ml. B.O.D. bottles were filled with sea water, filtered through a.45u millipore filter, and inoculated with 50 ml. samples of a concentrated natural phytoplankton sample. The cultures were brought to 1, 10. and 100 ppb concentrations of DDE, and innoculated with Ca) (50 ), (5uc/ml. NaC03). Two controls were run, one with DDT and one with ethanol. The bottles were incubated for six hours, filtered and counted. The results are presented in Figure 6. DISCUSSION Inhibition of photosynthesis in marine phytoplankton communities becomes detectable at a concentration of 10 ppb, is reduced to 50% of the normal at 500 ppb., and at 1000 ppb. is reduced by 95%, as shown in Figure 1 and Table I. Correspondingly, a very marked increase in the rate of respiration occurs, the increase being greater at lower concentrations than higher ones, being observable even at a DDT concentration of 1 ppb. Figure 4 shows clearly that the rate of photosynthesis/unit chlorophyll A also de- creases over a period of lengthy exposure to DDT at various concentrations. In exponentially growing cultures, the synthesis of chlorophyll A is retarded, however, the degree of retardation as a function of DDT concentration is not clear as evident in Figure 5. DDE, the most common analog of DDT in the environment, inhibits photosynthesis at a much faster rate than DDT. Figure 6 shows that it has a measurable effect at a concentration of 1 ppb, whereas DDT does not, and its inhibitory capability seems almost three times as great as that of DDT. The results show that DDT does affect the actual photo¬ synthetic process rather than merely slowing the entire or¬ ganism down, as shown in Figures 1 & 4, and suggests that the synthesis of chlorophyll A is also inhibited in some man¬ ner, as shown in Figure 5, in the presence of DDT. One ex¬ planation compatable with the above results, and with re- sults obtained from other organisms, is that DDT could be damaging the cell membrane systems. The fact that the rate of respiration increases as the photosynthetic rate de- creases, as clearly shown in Figure I and Table I, and that the ability to photosynthesize of the chlorophyll A also decreases, (Figure 4), in the cell suggest that the cell membranes are being affected. If the external membrane system of the cell is being damaged in any way, respiration rates may increase to maintain osmotic balance with the environment. At high concentrations of DDT, cells were found to plasmolize, further indicating that the ability to regulate osmotic balance might be damaged. If energy was being utilized to maintain osmotic balance and/or repair membranes (as indicated by the increased respiration rate), the synthesis of chlorophyll A, along with any other energy requir¬ ing process, may be slowed down, as indicated in Figure 5. Furthermore, the chloroplasts of the cell are also sur- rounded by a relatively sensitive membrane, and if DDT were damaging it, the ability to photosynthesize would be les- soned, as my data indicates in Figure 4. It has been found also that DDT inhibits Hill reaction activity in barley chloroplasts (Lawler & Rogers, 1967), and this could happen in phytoplankton chloroplasts as well. Another interesting phenomena is that when cells were exposed to a given concentration of DDT once, and then their photosynthetic rate measured over a long period of time, they regained the ability to photosynthesize normally after ap- proximately 20 hours. Possibly DDT could be blocking or clogging the cell membranes, but not permanently damaging them, or possibly the cell is able to effectively repair the DDT damaged membranes at the expense of stored food reserves. The fact that DDE has a greater inhibitory ability than DDT is very significant. It has been demonstrated that DDT is reduced to DDE by ultra-violet rays. Therefore, due to sunlight alone, most of the DDT residues in the environ- ment may be in the form of DDE. The fact that DDE is a more potent substance could have dangerous biological reper¬ cussions in the environment. CONCLUSION DDT does affect the photosynthetic process of marine phytoplankton, but the actual mechanism by which damage is incurred remains unknown. It is known that respiration increases, the synthesis of chlorophyll A decreases, and at high concentrations of DDT, cells plasmolize. Further studies on this subject are needed. Possible approaches to the problem might involve using metabolic poisons with known inhibition abilities, and comparing results of these to those gained from DDT. Investigation of the phytoplankton ability to regain photosynthetic prowess could reveal pos- sible inhibition mechanisms. Long term respiration studies might also shed some light on the subject. The fact remains though, that much work is needed. The C -10. phytoplankton in the oceans are a major food source in our environment. If their ability to produce food is being seriously inhibited by chemical pesticided, such as DDT and DDE, which are being constantly dumped into the ocean from river run-off, rains and winds, the result could prove disasterous for many, if not all, biological communities. BIBLIOGRAPHY 1. Gran,H.H., Rept. Norwegian Fishery & Marine Invest., 3(8):1-74, (1927). 2. Lawler,P.D. and L.J. Rogers, Nature 215, 1515 (1967). 3. Riseborough, R.W., "Chlorinated Hydrocarbons in Marine Ecosystems", Rochester Conf. on Toxicity; June, 1968, Rochester University. 4. Strickland, J.D.H., and Parsons, A Practical Handbook of Sea Water Analysis; Fis. Res. Bd. of Canada; Ottawa 1968. 5. Fogg,G.E.; "Algal Cultures and Phytoplankton Ecology" Univ. of Wisconsin Press, 1965. 6. Pringsheim,E.G.; "Pure Cultures of Algae, Their Prepar- ation and Maintainance". Univ. of Cambridge Press, 1949 7. Strickland; "Measuring the Productivity of Marine Phytoplankton". Fis. Res. Bd. of Canada; Ottawa, 1960. 8. Wurster, Charles f, "DDT Reduces Photosynthesis by Marine Phytoplankton"; Science, 159(3822), 1474-1475, Illus. 1968. AMOUNT DDT: CONTROL 1 ppb 3 ppb 30 ppb 300 ppb 1000 ppb TRIAL: TABLE I. Accomparison of the amount of 0 produced or consumed by whole water samples incubated in 300 ml. B.O.D. bottles for six hours, at var- ious concentrations of DDT. The second num¬ ber in each box is the% of that amount of 02 to the control in each respective trial. LIGHT BOTTLE: PHOTOSYN. DARK BOTTLE: RESPIRAT'N mg-/Liter % of CONTROL mg-Og/Liter % of CONT. +2 7073 700 705 127, 065 02, 178, /1 1100. 1100. 1100 00 1100. / 00. 702 21 1112 181 129 013, 063 139/ 112 110 20 12. o 703 7 102 135 022 00 Ab 10 125 17 11 1113 17 103, /. /220 26 52 111 07 1 103 158) tb 1 910 1930 810 1152 1 111/ 010 3/ 08/ 128, S33) 6 2 113 /720 1122 015 158 35 / 0/ 08, 025/ 0287 Ob / 123 1165 130 1250 20 112 125 1 1 1 3 4 2 19 SAMPLE: CONTROL 10 ppb 50 ppb 100 ppb TABLE II. A comparison of the of cells alive in the natural population phytoplankton cultures, incubated at various DDT concentrations, for each given amount of time. Cells in long chains were counted individually. The en- tire population was counted with a Sedgwick- rafter cell and a hemocytometer. TIME IN HOURS 24 48 72 2.2 x10 1.9 x10 1.4 x10 1.3 x10 cells/ml cells/ml cells/ml cells/ml 0.8 x10 1.0 x105 2.1 x10 1.9 x10 cells/ml cells/ml cells/ml cells/ml — 1.5 x10 2.2 x10 2.3 x10 1.0 x10 cells/ml cells/ml cells/ml cells/ml 1.4 x10 2.2 x105 1.0 x10 0.6 x10° cells/ml cells/ml cells/ml cells/ml TABLE IV. A comparison of the amount of chlorophyll A found in 25 ml. aliquots of the natural population phy- toplankton cultures incubated in various concen- trations of DDT, at given points in time. Chloro- phyll measurements were made with the Florometer. TIME IN HOURS 48 72 24 CONCENTRATION: SAMPLE u-gram CHLOROPHYLL. A/25 m1. 2.02 x10 2.02 x10 1.43 x10 CONTROL 1.50 x10 1.50 x10 1.50 x10 10 ppb DDT 1.42 x10 2.34 x10 1.17 x10 50 ppb DDT 1.59 x10 1.70 x10 1.04 x105 100 ppb Dor C TABLE III. A comparison of the rate of photosynthesis of the natural population phytoplankton cultures incubated in various concentrations of DDT for giveh lengths of time, as measured by the up- take of radioactive Naco, (specific activ- ity: 5uc/ml.), The uptake was over a period of six hours. ATTMEIN HOURS 48 24 72 0. CONCENTRATION: RADIOACTIVITY ABSORBED AMIOUNT 3491 3013 1560 3840 CONTROL DPM DPM DPM DPM 5129 3698 1523 705 DPM DPM 10 ppb DDT DPM DPM 2859 1551 2520 1325 DPM 50 ppb DDT DPM DPM DPM 3583 3546 1043 1530 DPM 100 ppb DDT DPM DPM DPM TABLE V. CONCENTRATION CONTROL 10 ppb DDT 50 ppb DDT 100 ppb DDT A comparison of the rate of photosynthesis / unit chlorophyll A of the natural population phytoplan- kton cultures, incubated at various concentrations of DDT, for given lengths of time, as measured by the uptake of radioactive NaCO3 in six hours time. (Specific activity: 5uc/ml.). TIME IN HOURS 72 48 24 DPM'S per UNIT CHLOROPHYLL A% OF NORMAL 1.680 x 1.490 3 2.375 x -2 -2 -2 10 10 762.9 100 170.8 1 2.460x 1.015 X) 3.419 x -2 -2 10 7100 10 772.0 129.7 927 x 2.160 x 1.220 x 2 10 -2 10 56.5 100 43.0 655 X 2.095 X 3.455 % -2 -2 10 10 100 60.5 1.9 12 C Fig. 1. A comparison between the photosynthetic rate and the respiration rate of whole water samples in the presence of DDT. O +++ 8 ++ ++ ++ + ++++++ +++++ +++ ++++ +++++ + ++ L + + + + 35 100 150 20 958 5 380 10 70 g00 30 1o0 410 7o 750 0 886 700. RAI ONCE D S6 + + H +++ ++++ ++++ ++ + + E ++ ++ 000 ++ I +++ C C Fig. 2. A comparison of the % cells of Dunaliella alive in various concentrations of DDT, after given amounts of time. O H RE + + ++++++ 100 +++++++++ + ++ ++ 75 +++ +++ ++ ++ +++ ++ 10 + ++ 11 A +++++++ +++ + 2 + H + — tt ++++ ++++++ CONTROE JOPPE DDT -- m 5Opp» DDT DOE — 100 + ++++++++ + — ug +— U E + O Fig. 3. A comparison of the of cells of natural phytoplankton samples, alive after exposure to various concentrations of DDT, after a given amount of time. + ++ +++ 1 + ++ O + L + e + L + 1 5) t ++ crp + DOT — enn 51 — 2- 18 + + HOURS +++ ++ + 90 +++ + ++ + +++ 1 + ++ ++ ++++L +++ H +++ +++ +++++ + + C 0 Fig. 4. A comparison of photosynthetic rates / unit chlorophyll A, of natural population phytoplankton samples, exposed to various concentrations of DDT, after given a¬ mounts of time O 2 ++ 00 307 70 10 1504 40 30 ++++ 0 20 ++ O + öt + 1- ++++++ +++ ++ ++ +0 + + +++ ++ + ++ +++++ ++++ ++++ 24 X ++++ +++ —Co ++++++ ++1 DDI —-—- pob + un + +++++ —— DD + + — 18 EHE Houre + +++ +++ ++ + +++ +26 ++++ + + 8 O O Fig. 5. The relative amounts of chlorophyll A / unit cell of natural population phyto- plankton samples, incubated in various concentrations of DDT, for a 96 hour time period. O IL Q + I6UR 19. 1 + ++ ++ 112 S 10 + ++ ++++ + ++ C ++ +++ + + ++ 1 ++++ ++++++ H + +1 + +++ + + ++ ++ + +++ + + ++ + — +++ + +++ ++++++ ++++++ + COTRO PE DDT —— 50ppb DDT pp D + 72 2S t t + — ++++ ++ ++ 48 +++ ++ +++ ++ + + +++ + + +++ — + O ig. 6. A comparison of the effect of DDT and its analog, DDE, on the rate of photosynthesis on natural population phytoplankton sam- ples. ++ + +++ ++ + +++ ++++ +++ ++ + +++++ At + ++++++++ ++++++ ++++ ++ ++ ++ ++ 20 a S ++++ 90- ++++++ ++ a ++++++++ 1+ + ++ + D O 0 10+ —CONTEOL ++++ —-- 20 ++E — + DDE + p H ESTICIDELOC +++++++++ ++ +++ pot +++++++ LL ++++ ++++ +++++ +++ + ++4 + 8 +++++ + ++ +++ 0 + ++ +++ 100 NTON — ++ + + ++ ++ ++ H ++ ++ + +++