DDT UPTAKE IN EMERITA ANALOGA AND LEVELS OF DDT RESIDUES OF POPULATIONS FROM ASILOMAR BEACH AND NEAR THE MOUTH OF THE SALINAS RIVER Richard E. King Hopkins Marine Station Stanford University Pacific Grove, California "Permanent address: 16 INTRODUCTION While most of the DDT residues found in the oceans were probably transported there by wind and subsequent chemical fallout, DDT residue levels in marine organisms in Monterey Bay, California (Risebrough et al., 1968) are high enough to suggest that pesticides are also being carried directly into the bay by drainage from adjacent farmlands. This suggestion is supported by studies of Emerita analoga described in this paper. The 100 mile long Salinas Valley is a rich agricultural region producing annually large amounts of lettuce, broccoli, celery, dried beans, carrots. sugar beets, and artichokes. Accompanying this large production is the widespread use of DDT. For the past ten years over 125,000 pounds of DDT each year has been sprayed on crops in the valley (Scott, 1969). The valley is drained by the Salinas River which originates in the northern part of the Los Padres National Forest and winds for 150 miles in a northwesterly direction through the Salinas Valley and reaches Monterey Bay about 5 miles south of Moss Landing. A sandbar across the mouth of the river prevents the shallow river from directly emptying into Monterey Bay for a large part of the vear. However, the river drains approximately 1000 square miles and during the rainy season (December to April), the Salinas River rises and empties directly into the bay. It is highly likely that DDT present in the top surface layer of soil in the fields is carried into the river with some of the soil in agricultural run-off. In addition, even larger amounts of DDT may be added directly to the river during heavy rains in January and February when the farmlands bordering the river are flooded. At one critical flood period in February 1969, the river became a mile wide in some spots, while flooding thousands of acres of farmland and emptying 110,000 cubic feet of water per second into Monterey Bay (Monterey Peninsula Herald, February 25, 1969). After the rainy season, the water level of the river gradually decreases and 167 a sandbar usually forms and closes the river mouth. A population of Emerita analoga, the sand crab, which inhabits the stretch of beach approximately 100 to 600 yards from the mouth of the river was chosen for a study of the influence of the Salinas River in the marine environment. Emerita burrow in the wash zones of sandy beaches and migrate with the tides (Cubit, 1968). When the tide rises, Emerita ride incoming waves to higher positions on the beach. At a falling tide, they are carried by the back wash waves to lower beach positions. Emerita are exposed directly to DDT in the water not only during their tidal migrations up and down the beach. but also when they are burrowed in the sand and circulating water through the gill chambers. Emerita are filter feeders and feed on plankton and detritus between bu and 2mm long (Efford, 1966). Because DDT is readily adsorbed to particles (Odum et al., 1969) and the Salinas River contains a large amount of organic material and silt, DDT may be entering the Emerita in the food chain, as well as possibly by direct uptake. Mature female Emerita are from 12 to 18 months old (Barnes and Wenner 1968) and would be indirectly exposed to outflow from the Salinas River for 4 to 6 months of the year when the river mouth is open to the sea. Sand crabs are very abundant in the sandy beaches along the California coast and constitute a large portion of the diet of several marine organisms. Over 90% of the food by volume of the Barred Surfperch consists of sand crabs (Carlisle et al., 1960). Emerita also forms as much as 75% of the diets of the Western Sandpiper, Semipalmated Plover, Snowy Plover, and Sanderling (Reeder, 1951). Emerita is thus in a position to concentrate DDT residues from water, plankton, and detritus, and pass them on to fishes and birds through the food chain. 160 WATER SALINITY AND SAND CRAB DISTRIBUTION All sand crabs used were non-egg carrying females ranging in wet weight from 2.5 to 7 grams. They were collected in two areas separated by about 11 airline miles. One area was Spanish Bay, just south of Asilomar State Park, on the open coast. The other area was 100 to 600 yards north of the mouth of the Salinas River on the shore of Monterey Bay. Collecting stations are shown in Fig. 1. Salinity was measured in the field with a refractometer. In the river channel and mouth water samples were taken from the top 3 inches of water where total water depth was about 2 feet at the time of sampling. Samples were gathered at different times at the Salinas beach and river to study the effects of incoming and outgoing tides on the river flow into the ocean. At Asilomar Beach (Figs. 1, 2) sand crabs were collected only between stations L and 5, although sand crabs were found at all stations. Fresh water seepage is slight and most of it disappears into the sand before reaching the water. The water washing the beach shows normal sea water salinity. and sand crabs here are probably well beyond the influence of the Salinas River. At the mouth of the Salinas River (Figs. 1, 2) sand crabs were only found at stations 13 through 18. Emerita used in experiments were collected between stations 14 and 17. Results obtained (Fig. 2) show that the salinity of the water washing the beach is affected by the tides. During a rising tide, the water outside the river channel maintains salinities of 93% to 1002. At a falling tide, beach salinities are lowered, though the salinity of the shore water decreases gradually with increasing distance from the mouth of the river. The population of Emerita living 100 to 600 yards away from the river mouth is exposed to 25% to 10% river water for six hours every other six hours or during each falling tide. DDT in the river, either dissolved in 16 the water or adsorbed to particulate matter is diluted before reaching the sand crab population. UPTAKE OF C14-DDT In order to determine the ability of Emerita to take up DDT directly from solution in the surrounding water, experiments were carried out using DDT labled with C+. A 100 ppm (parts per million) solution of CHDDT dissolved in ethanol, with a specific activity of 19 curies/mole was used to make up the C+DDT-sea water solutions. All sea water used was filtered once through an 8u millipore filter and a 3u millipore filter to remove particles. The filtered sea water was aerated for 5 to 10 minutes before addition of C+DDT in ethanol. Where different concentrations of C+DDT were used, additional ethanol was added to insure that each jar contained equal amounts. Two types of C-DDT uptake experiments were conducted, both on sand crabs obtained from Asilomar Beach. (1) Three Emerita were placed in a sealed one gallon glass jar containing only 2.5 liters of a C-DDT sea water solution. Sand crabs in these experiments lacked a substratum in which to burrow. They were not observed continuously for 12 hours, but on every occasion when they were seen they were either swimming or actively scrambling along the bottom of the jar. (2) Three Emerita were placed in a sealed one gallon glass jar with 2.5 liters of a C+DDT sea water solution and in addition a lcm layer of sand on the bottom which allowed the animals to bury themselves completely, On all occasions when these sand crabs were observed they were completely buried with only the antennules protruding above the sand. Sand crabs were circulating water down the antennular funnel and ejecting it from the branchial chamber below the sand. The sand crabs were incubated overnight for 12 hours. Both types of experiments were conducted at concentrations of DDT of O.1, 0.2, O.4, 0.6, 0.8, and 1.0 ppb (parts per billion). After the 12 hour incubation, the Emerita were taken out of the jars, rinsed in a beaker of sea water for 30 seconds, and placed on paper towels to dry off for 5 minutes. The wet weight of each sand crab was determined to an accuracy of one milligram on a Mettler scale. Each Emerita was then cut into small pieces with scissors and ground up with a hand homogenizer in 10 mls of dioxan for 20 to 30 minutes to extract the CLDDT. The liquid homogenate was poured into a test tube leaving the large granular material at the bottom of the homogenizing tube. A 1.0 ml aliquot of the liquid homogenate was placed into each of two scintillation vials containing 10 mls of Bray's solution and counted for 1 minute in a Unilux II Scintillation Counter. The quenching of radioactivity was corrected for and the actual disentegrations per minute were calculated using an average of the counts per minute from the two vials. The wet weight of each crab was used to determine the CDDT content in ppb. The results of the uptake experiments (Fig. 3a and b) show that Emerita can concentrate large amounts of DDT (55x increase over initial concentration) over a short period of time while freely swimming in water at ambient DDT levels of 0.2 to 1.0 ppb. A similar increase in the rate of DDT uptake with increasing initial DDT concentration was not observed in the Emerita buried in the sand. This may be explained by one or more of the following reasons. (1) Much of the C+DDT may have been adsorbed to the sand and unavailable to the sand crabs. Samples of the water after incubation were counted in the scintillation counter and although too close to background level to calculate actual C-DDT concentrations, the counts in the jars with sand were always less than the counts in the jars without sand. (2) The increased activity of the Emerita swimming in the jar without sand may have placed them in more continuous contact with C+4DDT in the water, increasing the opportunity for uptake. (3) The higher rate of activity in the swimming sand crabs was doubtless accompanied by increased metabolic activity, which may in turn have been related to increased CDDT uptake. IEVELS OF DDT RESIDUES IN NATURAL POPULATIONS If DDT is entering Monterey Bay by way of the Salinas River, it can be expected that the population of sand crabs located near the mouth of the Salinas River would contain more DDT residues than a population of sand crabs located at an ocean exposed beach several miles away. In order to test this hypothesis, the DDT and DDE levels of sand crabs from the Asilomar Beach and the mouth of the Salinas River were measured and compared. Samples consisting of 5 sand crabs were allowed to dry on paper towels for 5 minutes and then weighed to the nearest milligram. The sand crabs were digested in a glacial acetic acid- perchloric acid mixture for 24 hours, followed by lipid extraction with nanograde hexane, and lipid removal by passage through a column of celite and sulfuric acid. The cleaned-up sample was concentrated if necessary. For details of this procedure see Stanley and LeFavoure (1965). The Beckmann GC h chromatograph with a electron capture detector was used for all experiments. The DDE values were determined using a 3% OF-1 column, and the DDT values were determined using a 10% DC 200 column, both of which were on DMCS treated Chromosorb 1, 80 to 100 mesh. Conditions during runs were as follows. Temperatures: inlet 220°0, column 200°C, detector 280°c. Helium pressure: input 40 psig. Flow rate of helium: 10 ml/min for OF-l and 200 ml/min for DC 200. Column injections were made with Hamilton 10-ul syringes. The DDE and DDT content of female Emerita from Asilomar Beach and near the mouth of the Salinas River are summarized in Fig. 4. There is no statistically significant difference between the DDE content of the two Emerita populations. The probability of exceeding the t value of 1.008 is between.3 and.l. However, there is a very clear difference in the DDT content in the two populations. The DDT content of sand crabs from near the mouth of the Salinas River was approximately 110 ppb, while the DDT content of the sand crabs at Asilomar Beach was too low to be measured with the gas chromatograph. The DDT content of the two populations of sand crabs suggests that the Emerita from the mouth of the Salinas River are exposed to DDT which is not present in the sea water at Asilomar Beach. The DDE content of the two populations are identical and suggests that the DDE concentration in the water washing the beach is the same. A possible hypothesis to explain the similarity in DDE level and the difference in DDT levels of the two populations is as follows. DDT is broken down by ultraviolet light, and consequently most of the DDT residue present in the ocean is DDE. However, during the rainy season, DDT reaches the fast flowing Salinas River and is transported rapidly to the mouth of the river and into Monterey Bay. The small amount of DDE that has been formed during the short trip down the river does not effectively alter the concentration of DIE present in the ocean. However, because the DDT concentration of the ocean is extremely low, the amount of DDT emptied into Monterey Bay from agricultural run-off and the flooding of farmland significantly raises the DDT concentration of the water surrounding the mouth of the river. During low tide, the population of Emerita near the mouth of the Salinas River are exposed to both DDT from the river and DDE already present in the ocean. Eventually all of the DDT reaching the bay is broken down into DDE but this amount is too small to change the DDE concentration of the ocean. Consequently, the DDE concentration is the same in the sea water washing the Emerita population at Asilomar Beach and near the mouth of the Salinas River. The levels of DDT and DDE found in either of the populations of sand crabs 12 do not appear to be high enough to produce any harmful effects to the sand crabs themselves. However, as already noted the Barred Surfperch, Sanderling. Snowy Plover, Semipalmated Plover, and Sandpiper regularly feed on large numbers of sand crabs. DDT residues taken in with the sand crabs may be stored and accumulated in the tissues of these birds and fishes, and studies should be made to determine whether thse animals are approaching harmful levels of DDT residues or even already suffering from the effects of high concentrations of the pesticide. SUMMARY The filter feeding sand crab, Emerita analoga, is abundant in sandy beaches on California shores. It is an important food source for the Barred Surfperch and several shore birds including the Snowy Plover, Sanderling. and Sandpiper. Several California birds and fished contain high levels of DDT and its derivitives. Emerita is in a position to concentrate DDT residues from water, plankton, and detritus, and pass them on to fishes and birds through the food chain. To measure the rate of uptake of DDT from sea water, sand crabs were exposed to solutions of C+DDT at concentrations of 0.1, 0.2, 0.4. 0.6. 0.8. and 1.0 ppb for 12 hours. Sand crabs burrowed in sand took up a constant amount of DDT in concentrations of 0.l to 1.0 ppb (increases from lOx to 25x). Sand crabs free in sea water took up amounts of DDT proportional to the DDT concentration in the sea water (an increase of 55x). Natural levels of DDT residues were determined by gas liquid chromatography in populations of sand crabs from the mouth of the Salinas River, which drains an agricultural valley where DDT use is widespread, and from Asilomar Beach, an exposed ocean beach several miles away. Approximately 80 ppb of DDE were found in both populations. Only trace amounts of DDT were present in sand crabs from Asilomar Beach, while approximately 110 ppb were found in sand crabs from the mouth of the Salinas River. 174 C ACKNOVLEDGEMENTS This work was supported in part by the Undergraduate Research Participation Program of the National Science Foundation Grant GY-5878. I would like to thank the faculty and staff at the Hopkins Marine Station for their help and encouragement throughout this course with special thanks to Dr. Donald P. Abbott, John Miller, Philip Murphy, Larry Eickstaedt, and Sam Johnson. LITERATURE CIEED Barnes, N. B. and Wenner, A. M. (1968). Seasonal variation in the sand crab, Emerita analoga (Decapoda, Hippidae) in the Santa Barbara area of California. Limnology and Oceanography. 13 (3), 164-475. Carlisle, J. G., Schott, J. W., Agramson, N. J. (1960). The Barred Surfperch (Amphistichus argenteus Agassiz) in Southern California. State of California Department of Fish and Game Marine Resources Operation. Fish Bulletin No. 109, 18-52. Cubit, J. (1968). Behavior and physical factors causing migration and aggregation of the sand crab Emerita analoga (Stimpson). Ecology. 50 (1), 118-123. Efford, I. E. (1965). Feeding in the sand crab, Emerita analoga (Stimpson) (Decapoda, Anomura). Crustaceana. 10 (2), 167-182. Monterey Peninsula Herald, February 25, 1969. Monterey County again disaster area. IXXXX (18). Odum, W. E., Woodwell, G. M., Wurster, C. F. (1969). DDT residues absorbed from organic detritus by fiddler crabs. Science. 164, 575-577. Reeder, W. G. (1951). Stomach analysis of a group of shorebirds. The Condor. 53, 43-45. Risebrough, R. W., Reiche, P., Peakall, D. B., Herman, S. G., Kirven, M. N. (1968). Polychlorinated biphenyls in the global ecosystem. Nature. 220 (5172), 1098-1102. Scott, D. (1969). Speech to students and faculty of Hopkins Marine Station in May 1969. Stanley, R.,and LeFavoure, H. (1965). Rapid digestion and cleanup of animal tissues for pesticide residue analysis. Journal of the Association of Official Agricultural Chemists. 18, 666-667. 176 FIGURE CAPTIONS Fig. 1: Map of Asilomar Beach and the mouth of the Salinas River. Numbered collecting stations are 50 yards apart. Sand crabs were found only at dotted stations. The large dot on the graphs of tide movement represent the period of salinity testing. The vertical axis is height and the horizontal axis is time. Underlined times indicate A.M. Fig. 2: Percentages of normal sea water found at collecting stations at Asilomar Beach and the mouth of the Salinas River. Salinity was measured at both the surface (T) and belows the surface (B) in the river channel. Sample number refers to the graphs in Fig. 1 showing the period of sampling in relation to tidal position. Fig. 3a,b: DDT uptake by Emerita analoga at various DDT concentrations, Fig. 3a shows uptake of CDDT by sand crabs burrowed in sand while Fig. 3b shows CDDT uptake by sand crabs swimming freely in sea water. Each dot represents one sand crab. The circles in Fig. 3a indicate that CH4ppT uptake was to close to background levels to calculate. Uptake is expressed in wet weight of whole Emerita per 12 hours. Fig. I: DDE and DDT levels expressed in ppb of wet weight of whole Emerita found in samples consisting of 5 sand crabs from Asilomar Beach and near the mouth of the Salinas River. The DDT levels of the Asilomer Beach sand crabs were too low to be measured and the standard deviation could not be calculated. a 9 00-0 92e eo +o 9o ee 2. abo o o o — a o P 4 0. 8 J P++ no H8 H PPP. oo .. .. L L 178 e 8 ... 88 88 E 88 ** .. de8. OC 88 .. .. de 8 5 ded *. *. 8 8 .. .. 88 86 de pe oo ei BeN de 8e — — 5 10 No. 799 d ge s ANIMALS BELOW SAND 15 2 02 0 05 03 DOLIN SEAWATER (PPB) F16. 32 AMIMALSTER : IMWATER 45 30 5 o. 0.2 04 015 FIG. 35 LDOT IN SEA WATER (PP 1 BEACH ASILOMAR Sample DDE Wet (ppb) Weight (9) Number 95 29.705 28.032 85 2 32.514 3 4 30.157 80 84 5 24.533 Standard 6.0 Deviation SALINAS RIVER Sample Wet DDE Number Weight (g) (ppb) 33.024 65 35.65 71 27.630 3 87 4 28.375 97 Standard 14.2 Deviation FIG. 4 (ppb) TRACE TRACE TRACE TRACE TRACE DDT (pph) 140 122 154 155 15.4 g