C Abstract The effects of different concentrations of several heavy metals on the righting behavior of Littorina planaxis were studied. Part of the animals' shells were removed. They were then submerged in sea water that contained different concentrations of cadmium, copper, lead and silver. The effects of these treat¬ ments were assayed by timing the animals' righting response. The results obtained show that cadmium, copper and silver have significant effects only at high concentrations. Lead was shown to have no significant short-term effects. O )7 -1- Introduction: Much public attention has been drawn recently to pollution of the environment by heavy metals. Many symposia on the subject have been held to discuss problems such as cadmium poisoning and aerosol lead fallout. (Symposium on Metals and Ecology, 1969) Very little has been published in this field that deals with intertidal invertebrates and nothing has been done to assay the relative toxicities of heavy metals and their effects on animal behavior. The most common animal in the intertidal splash zone is Littorina planaxis, which ranges from Puget Sound to southern lower California (Ricketts and Calvin, 1952) It is found 1,5-3.1 meters above the height reached by the highest spring tides. (Light et al., 1954 and Hyman,1964) This is sigmificant because it means that littorines are never submerged by the tides and are exposed to the air at almost all times. While littorines are never completely covered with water, they are splashed with water from the air-water interface. The detrital matter and microscopic algae whicharewashed up by this spray suppl the animals' major source of food. The significance öf these facts is that littorines are exposed to pollution from both the air and the water. They are splashed by and eat the detrital matter washed up by the air-water interface, which is thought to concentrate heavy metals. -2- (Baxter and Lopez, 1971). Being exposed to the air, littorines are subject to aerosol metal fallout, notably that of lead. As littorines are scraper feeders, they ingest any metal fallout from the surrounding rocks when they eat. These facts make L. planaxis an interesting animal to study in connection with heavy metal pollution. L. planaxis is also useful because it has a marked an dependable behavior pattern. As it has a gill partially adapted for air breathing, it cannot live indefinitely in water and if forcibly submerged, it will ultimately drown (Ricketts and Calvin, 1952). It therefore reacts quickly to being submerged in sea water, and will immediately right itself and start to crawl up the nearest vertical surface. This behavior has been used in the past to assay the toxicity of sea aenemone nematocysts (Phillips and Abbott, 1957), and it provides an almost ideal system in which to study the effects of almost any toxicant on behavior. Heavy metals such as cadmium, copper, and silver would be expected to affect behavior in that they are toxic substances. These metals block the activity of many enzymes and would therefore be expected to alter bodily functions such as respiration and digestion. Lead affects the production of porphyrins, the respiratory pigments present in most animals and plants. In its organic form, lead causes severe nerve damage. Any one of these -3- things would interfere with the animals' normal functions and would therefore probably alter behavior. The purpose of this experiment was to assay the various toxicitiea of cadmium, copper, silver and lead and to see how much several different concentrations of each metal would differentially affect behavior of L. planaxis. I would like to acknowlege the patient and generous help of Dr. Malvern Gilmartin, Dr. D.P. Abbott, and Dr. John Martin in preparing this project. Materials and Methods: a. Sampling procedures: The snails were collected fresh for each day's experi- ments. The animals were used immediately after capturen and throughout the day up to 12 hours from the collecting time. They were selected from a single location at Hopkins Marine Station that was exposed to splash from heavy surf at high tide. (See figure 1) All animals selected were collected 1.8-3.1 meters above the high tide mark and were of as uniform size as possible. They varied in size from 0.8-1.6 grams with an average size of 1.2 grams. Since it has been shown that orientation to gravity effects the behavioral response (Klabunde, 1964) only animals from exposed, vertical surfaces were collected. As May falls within the breeding season for L. planaxis, only copulating pairs of snails were selected to insure a male-female )7 -4- ratio as close to l:l as possible, although it is recognized that such pairs are not necessarily male-female and may be male-male. (Gibson, 1964) b. Assay of the effects of heavy metals Solutions of cupric nitrate, lead nitrate, and silver nitrate were made separately in distilled water so that each principal metallic ionic species was in a concentration of 300,000 ug/1. Cadmium sulfate was dissolved in filtered sea water to the same concentration. The presence of Cd' ions already in the sea water was ignored as not being significant. These solutions were kept in plastic bottles and were used as the stock solutions for each day's work. The test solutions were made up daily in sea water that had been filtered through Whatman GF/C filter pape. The dilutions for silver, copper and lead were 3,000 ug/1, 600 ug/1, 300 ug/1 and 30 ug/1 in sea water. The presence of any metallic ions in the sea water was ignored as being insignificant at the concentrations used. The concentrations of 3,000 ug/1 for these metals actually represent saturated solutions in sea water. The cadmium solutions were made up in filtered sea water, and as cadmium is much more soluble than the other metals, it was therefore possible to meke up much more concentrated solutions. The solutions used were: 300,000 ug/1, 30,000 ug/1, 15,000 ug/1, 6,000 ug/1, 3,000 ug/1, 300 ug/1, -5- and 30 49/. Controls for copper, silver and lead were made by adding 1 ml of distilled water to 99 ml of filtered sea water, with successive 5,2, and 10 fold serial dilutions. The control for cadmium was filtered sea water. The test solutions were made in 50 mà Erlenmeyer flasks. All glasswear was rinsed in 4 N nitric acid before use. c. Testing procedures The animals were chosen randomly from the collected samples to make up test groups of 15 snails each. The first whorl of the animals' shells were filed off, thereby exposing the mantle cavity. The animal was further exposed by picking off the second whorl with a dissecting needle while being careful not to puncture the membranes surrounding the animals' internal organs. This procedure only uncovers the digestive gland (Fretter and Graham, 1962) and has no immediate effect on the amimal's behavior. However it can only be used for short-term experimants, as it leads to dessication. The animals were introduced to the testsolutions and kept forcibly submerged by wedging plastic screening down the neck of the flask. The test solution were refrig- erated at 12 C for 24 hours. -6- After the incubation period, the test animals were removed from the solutions and blotted on apaper towel. They were then dropped, spire-downward, at 2 second intervals into 15 150 mmx 16 mm round-bottom test tubes that had been filled with fresh, normal sea water. The time it took the animals to right themselves and the time it took them to climb 90 mm up the test tubes were noted to the nearest 10 seconds. For convenience, 30 minutes was chosen as the trial cut-off point. Three trials of 15 snails each were used for each concentration of each metal and the control. As 8% of the controls did not right themselves in 30 minutes, these animals were considered aberrant in behavior and were eliminated from statistical calculations. The highest 8% of the righting times were eliminated from all concentrations of the metals. For each concentration of each metal, the mean, variance and standard deviations were found. Each concentration of control was treated separately. Student's t-test were run for each control group against every other control group. (Simpson et al. 1960). It was shown that the controls were all the same within the.05 probability range. Then the mean, variance and standard deviation of all the controls, taken as a group were used in t-test with the concentrations of metals. 18 -7- Results: The relative toxicity of each metal at different concentrations is shown by figure 2 which plots the difference between the percentage of controls that righted themselves and the percentage of treated animals that righted themselves within a certain period of time. The relative toxicities of all the metals at a single concentration are graphed in figure 3. The vertical axis represents differences in percentages between the numbers of righted animals in the conrrol and the test solutions. The horixontal axis represents time in minutes. The means variances, and standard deviations with each concentration of all the metals arelisted in fiugre 4. To reach these figures 8% of the highest numbers were rejected. Student"s t-tests were run to determine uniqueness of groups. The starred groups were those found to be different from the control at the.05 level. The data on crawling times for the snails was rejected as being too erratic. Discussion: The results obtained by these experimants show that differentsconcentrations of cadmium, copper, and silver definitely affect the righting response of L. planaxis. With the exception of lead, the greater the concentration of the metallic ion in water, the longer the righting response /8 -8- was delayed. This trend is especially evident in the cadmium solutions where it was able to concentrate the solution enough to reach a lethal dose. Cadmium is also interesting in that there is a very marked threshold effect between 6,000 ug/1 and 3,000 ug/1; all the animals died at 6,000 u9/ and all lived at 3,000 ug/1 albeit they sho ed a delayed righting response. Silver and copper also trends that seemed to indicate that threshold effects would be observed at higher concentrations. Unfortunately 3,000 ug/1 represents a saturated solution in sea water for these metals. The only metal that had no clear cut effects on righting response was lead, As shown in figure 2, at high concentrations, all other things being equal, copper and silver showed a trend in being more toxic than either lead or cadmium. In lower concentrations, the relative toxicities of the different metals was not so obvious. Et lower concentrations copper semms to be the most toxic of the tested solutions, The data on crawling times was rejected because t-tests revealed them to be random functions. This can be explained by the fact that there are many more variables involved with crawling time than with righting time. Crawling time is influenced by the past history of the animal, notably the surface from wheih it was collected. It is also influenced by such physical factors such as 183 -9- light intensity and direction. All such factors make the experiment difficult to control. A problem with this experiment is that the concentrations of metals used in these experiments do not reflect the possible situations in nature. The actual concentrations of these metals in sea water are: Cd: 0.1 ug/1, Pb: 0.03 ug/1. Cu: 3 ug/1, and Ag: 0.3 ug/1. (Goldberg, 1963). Consequently, the results observed are due to acute conditions and could not possibly be duplicated in nature during the same length of time. A series of experiments that would better reflect the situation in the real world would be to dose the snails with heavy metals in low concentrations for a longer period of time. However, if these experiments were undertaken, the technique would have to be changed as th animals would show the effects of dessication after two days. A possible technique for long-term experimentation would be to fill the mantle cavity several times daily with treated water. Another method would be to culture microscopic algae so that heavy metals were concentrated in the culture which would then be fed to the littorines. The relative toxicities of any set substances depends greatly on how they actually act in the body. It is surprising t hat copper, which is contained in hemocyanin in moalusc blood, is so toxic to them. Copper in small amounts is an essential element for life, but in larger amounts, it is extremely toxic. The electronegative elements such as 1+ and Ag' have an affinity for amino, imino, and sulphydryl 185 -10- groups which are reactive sites for many enzymes and therefore undoubtedly block these enzyme functions. (Bowen, 1966). Cadmium is another trace metal that blocks enzyme action. It competes with zinc for binding sites on thiol groups; it is bound more firmly to these groups than zinc. (Schroeder et al., 1967). Cadmium is not an essential element for life. Lead, on the other hand, does not necessarily block enzyme functions, and, therefore, would not cause any immediate acute effects. It does have several long-term effects in that it can cause abnormalities in the synthesis of porphyrins. and, in the organic form, can cause nerve damage. (Air Resources Board, 1967). However, the long-term effects of these doses are quite toxic. Lead is particularly interesting with respect to L. planaxis in that this animal is one of the few intertidal animas that rarely, if ever, get sub merged by tides. Therefore they would also pick up more lead fallout when feeding because they scrape the tops of the rocks to gather up food and would, at the same tine. pick up lead aerosol fallout. It would prove to be an interesting experiment to measure lead content in L. planaxis from different areas to see how concentrations varied with location. 185 References Air Resources Board. 1967. Lead in the Environment and Its Effects on Humans. Sacramento. 81p. Baxter, Keith and Glenn Lopez. 1971. Trace Metal Concentrations at the Air-water Interface and Sub-surface waters of Monterey Bay. Unpublished manuscript on file Hopkins Marine Station. Bowen, H.J. 1966. Trace Elements in Biochemistry. Academic Bress. New York. 241p. Fretter, Vera and Alastair Graham. 1962. British Prosobranch Molluscs. Ray Society. London. 756p. Gibson, Daniel G. 1964. Mating Behavior in Littorin planaxis. Unpublished manuscript on file Hopkins Marine Station. Goldberg, E.D. 1963. The Oceans as a Chemical System. p. 3-25. In M.N. Hill (ed.) The Sea, v. 2. Interscience. New York. Hyman, Libbie Henrietta. 1967. The Invertebrates. v. 6. Mollusca I. McGraw-Hill. New York. 762p. Klabunde, Baul Jon. 1964. The Geotactic Responses of Littorina planaxis. Unpublished manuscript on file Hopkins Marine Station. Light et al. 1954. Intertidal Invertebrates of the Central California Coast. University of California Press. Berkeley. 446p. Phillips, John H. and Donald P. Abbott. 1957. Isolation and Assay of Nematocyst Toxin of Metridium Senile Fimbriatum. Biol. Bull. 113:296-301. 786 Stanford U Tic imps e2 ol0 luan w Yor rch Council. in. Betwe ivers nford, Ca. dR. 1960 t, Brace and W rld. lish Nationa logy. 1 3ulletin 5. S ockhol C Figure Legends Figure 1: Map of China Point showing collection site. Figure 2: Effects of different concentrations of heavy metals on righting time. Figure 3: Relative toxicities of heavy metals at different concentrations. Figure 4: Means, variances, and standard deviations righting times for Littorina planaxis tested at several concentrations of heavy metals in sea water. 188 0 Gnegun 17 n. 8 11 Sueeup 00 ulup % 88 1 8 O 1 t oudelup oO8 uep 01 11 10 0O 88 A 1t 110 04 o - 4 0 O +10 190 0 8 S2 11 8 ouaeup S.! 8 Sep % 100 +10 110 110 o aeup % 8 8 Suep % J 9 19 8 100 +10 0 8 o 0 8 C o,oo ug/1 30,o00 15,000 6,000 3,000 300 30 cu 3,oo ug/1 600 300 30 Pb 3,000 ug/1 600 300 30 Ag 3,o00 ug/1 600 300 30 Control, dist.water Control, sea water Figure 4 Stan. Variance Dey. Mean * 0* 8.95* 40.19 6.34 3.56 2.43 1.56 5.46 87.42 9.35 13.51* 96.70 9.83 6.91 79.74 8.93 86.89 8.17 9.32 4.76 13.00 3.61 5.39 24.27 4.93 3.65 9.61 3.09 3.42 3.06 1.75 4.29 16.11 4.01 13.964 103.80 10.19 4.60 5.72 2.39 3.18 3.37 1.84 2.76 1.92 1.39 3.71 10.76 3.28 4.01 31.16 5.52 72