ABSTRAC In an effort to determine the effectiveness of the sand crab, Emerita analoga, as an indicator species of DDT levels in the California coastal marine environment, specimens were collected from different beaches on Monterey Bay and analyzed using gas-liquid chromatography (GLC). After all initial samples were analyed, it was found that ovigerous animals contained much lower levels of DDT than non-ovigerous animals. Since the bulk of the samples from the different beaches had differing proportions of ovigerous to non-ovigerous animals. and this difference was not recorded, the effectiveness of this species as an indicator of DDT was not fully demonstrated. However, the specimens collected do represent natural populations from the various beaches, and a rough comparison is possible. Since DDE is reported to increase with time in a biological system, the relative amount of DDE to the total residues of DDT was determined for each beach and the data was analyzed for possible trends. Sand samples were also collected at each beach when the Emerita were collected, and comparison of DDT levels in the sand with those in the animals was made. 25 INTRODUCTION The presence of p.p'-DDT and its principal metabolites, p.p'-DDD, and p,p'-DDE (hereafter referred to as sDDT) in the global ecosystem (Risebrough, et. al., 1967; Woodwell, etl. al., 1967; Tatton and Ruzicka, 1967), its affinity for and con- centration in biological systems (Woodwell, et. al., 1967; Robinson, 1967; West, 1967), and its relative stability within these systems (Cox, 1971: Risebrough, et. al., 1967; Nash and Woolson, 1967) has been widely documented. Since DDT tends to be concentrated by organisms at the upper trophic levels of a given food web (Rudd, 1964; Woodwell, et. al., 1967; West, 1966), special concern is warranted when considering levels of sDDT at the bottom of such food webs. Emerita analoga, the common sand crab of exposed sandy beaches on the West Coast, is a filter-feeding primary consumer (predominantly) which has been found to contain a mean sDDT level of 7200 ppb (wet weight) near a point source of heavy sDDT input into the marine environment (Burnett, 1971) and up to 252 ppb in an area of apparently more subtle input, Monterey Bay, California, the geographical focus of this study (King, 1969). Burnett (1971) found the sand crab to be a good biological indicator of sDDT concentrations since: 1.) It is readily available on nearly all exposed sandy beaches from San Francisco to Ensenada, Mexico. 2.) In a survey of that stretch of coastline he found it to exhibit marked gradients of sDDT concentrations relative toand indicating point sources of sDDT input. 3.) It is the main food source for a variety of marine and maritime organisms. For example, it represents 90% of food, by volume, of the Barred 260 -2- Surfperch (Carlisle, et. al., 1960), and 75 of the diets of the Western Sandpiper, Semipalmated Plover, Snowy Plover and sanderling (Reeder, 1951). Monterey Bay is the focus of drainage for three rivers draining an area in excess of 6000 square miles. The Salinas River with a drainage of 43000square miles, covering essentially the entire basin of the agriculturally rich Salinas Valley and having an annual average flow of 320,000 acre feet, is by far the largest surface water input into the bay. The Pajaro River (1400 square miles, 120,000 acre feet) also drains a large agricultural area. The San Lorenzo River, with a drainage area of only 140 square miles drains a predominantly non- agricultural, mountainous area, but nevertheless yields 106,000 acre feet per year. (Yancey, 1968). Although air transport of sDDT-ladened dust particles has been reported to be the greatest input source of these particular chlorinated hydrocarbons into the pelagic marine environment (Risebrough, et. al., 1968), input into littoral and estuarine waters is influenced most by surface runoff as evidenced by substantially higher residue concentrations found along inhabited coastlines as compared to those found in the open ocean. Since DDT usage in Monterey County (encompassing the Salinas Valley) alone averaged about 125,000 pounds per year during the period 1959-1969 (Scott, 1969) and as per acre agricultural usage of DDT does not differ markedly over the watershed being considered, the Salinas River is clearly the main source of sDDT input into the bay. 26 l -3- The study reported herein represents an effort to substantiate the effectiveness of Emerita as an indicator of subtle changes of sDDT in the littoral marine environment. In order to try to pinpoint areas of high sDDT levels and possible sources of sDDT in Monterey Bay, sand crabs were collected from 22 beaches around the Bay, and analyzed for sDDT. MATERIALS AND METHODS All specimens were collected within a five day period (April 18-22, 1971) from 23 beaches encompassing the entire. configuration of Monterey Bay (Fig. 1). Onlyfemale animals were taken and these were easily determined by size alone (Eickstaedt, 1969). Ovigerous females had their eggs removed at the collection site and these were placed in a glass test tube until analyzed (All glassware used was heated overnight at 400 C to remove impurities). These eggs were found to be at about the same stage of development, as determined by color (Lee and Gilchrist, 1971), which coincided nicely with Eickstaedt's (1969) findings that the mean developmental stage of eggs for any given month of the year should be approx- imately the same for different animals from the same general area. Whole animals were wrapped in aluminum foil. Burnett (1971) noticed that smaller specimens of E.analoga tend to accumulate higher sDDT concentrations than larger animals and Cox (1971) noticed the same thing in Euphausia pacifica, a large zooplankter. An attempt was thus made to use only specimens weighing more than two grams, above which sDDT levels are not significantly affected by body weight (Burnett.1971). 263 -4- Only one of the 145 animals analyzed weighed less than two grams. Sand samples were obtained by skimming the surface sand with a test tube at the point of collection. Eggs, animals and sand were immediately frozen, until needed for analysis. The wet weight of frozen animals was determined by allowing each animal to thaw for five minutes, removing excess water and ice and weighing to the nearest.Ol gram. Individual animals were digested overnight in a 50% mixture of glacial acetic acid in perchloric acid. Three extractions with nanograde hexane removed lipids, pigments and chlorinated hydrocarbons. An additional cleanup was carried out be running an aliquot of the hexane (about one ml) through a microcolumn (5 3/4" L. X 7.0-7.5 mm.) of silica gel (60-200 mesh, grade 950) and eluting with 8 ml of 20-80% mixture of benzene and hexane (both nanograde). The cleaned sample was either used directly or concentrated under reduced pressure, if necessary. A Beckman GC 4 gas-liquid chromatograph with an electron capture detector was used for all analysis. DDT and all its detectable congeners were determined using a mixed 62 OFi. 5% DC200 cloumn on 80-100 mesh chromosorb W (acid washed and DMCS treated). Wet wet weight of eggs was determined by allowing the frozen seawater around the eggs to melt, removing eggs and weighing them immediately. Cleanup was with silica gel mixed with nuchar-attaclay mixture (K-3213, Kensco, Oakland, California). Otherwise, the procedure was as described above. Sand samples were automatically shaken with hexane (nanograde) for 20 hours and cleanup was the same as with the whole animals. -5- RESULTS The actual mean levels of sDDT found at each beach tested is given be Fig. 2. The highest value was found at Monterey Wharf + 2,(site 5), which had a significantly higher value than the next four highest peaks, Asilomar (3), Cannery Row (4). Zumdoski State Beach (14) and Natural Bridges State Beach (23). It is interesting to note that Carmel (city) Beach had a level commensurate with some of those found in Monterey Bay. Big Sur (BS) also exhibited a level similar to those in the Bay. Seacliff State Beach (20) had the lowest level, and it should be noted that that beach had had most of its sand scoured away--a situation not found at any other beach. Fig. 3, which illustrates the relative levels of DDT and its metabolites, DDE and DDD, shows parallel distributions for DDD and DDT, but an erratic distribution of DDE. For this and other reasons ratios of DDE to sDDT were calculated (Fig. 4) and their possible significance considered. It can be seen that the highest values are found in the region of the Salinas River (10), Elkhorn Slough (13) and Pajaro River (15). sDDT levels in the sand samples collected are given in Fig. 5. Definite peaks exist at the Elkhorn Slough (13), Pajaro River (15), Manresa State Beach (17) and the San Lorenzo River (22) areas. A low level at the Salinas River may be due to the fact that a sand bar blocks the mouth of the river during most of the year (including the period when the sample was taken there). These values are particularily vulnerable to exper- imental error, since only one sample from each beach was analyzed. 264 68 -6- Perhaps the most significant data obtained is presented in Table 1. Cox (1971) suggested that a possibly significant amount of sDDT might be lost through the gonads of the particular organsim he was studying (Euphausia pacifica). Unfortunately, all collections and analysis were already completed before this hypothesis was tested in Emerita analoga. It is obvious from the table, that ovigerous females that had their eggs removed contained significantly lower levels of sDDT than the non-ovigerous animals. The eggs that were removed were analyzed and it was determined that although they had higher levels of SDDT than did the whole animals from which they were removed, this did not make up for the large discrepancy. Values for DDE were found to vary by only 118 in the two groups. It SDDT can be seen that DDE seems to be disproportionately accumulated in the eggs, relative to both ovigerous and non-ovigerous female Emerita. DISCUSSION After all collections and analysis had been made it was discovered that ovigerous specimens contained significantly lower levels of sDDT than non-ovigerous females (Table 1). While this, in itself is very interesting, it also means that most of the sDDT data that was collected must be qualified. The fact that eggs were removed at the collection sites and ovigerous females with eggs removed were not marked or seperated from non-ovigerous females introduces a possibly significant error in the results. Essentially, different beaches may contain different levels of sDDT, but the results of any analysis 266 -7- might depend totally on the proportion of ovigeroussto non- ovigerous animals collected from each beach. Hence, if the sand crab is to be used as an indicator of actual relative levels of sDDT, only animals at the same reproductive stage should be used. Since the female Emerita, once she begins to reproduce continues to lay eggs until the end of the season (usually about eight months of reproductive activity) it is reasonable to hypothesize that there might be a continual loss of sDDT throughout the reproductive season. If this were the case, only non-reproductive animals should be used as indicators of SDDT levels, since the length of the reproductive season is functionally related to environmental parameters (Eickstaedt, 1969) which are likely to be different at different beaches. In short, it is highly unlikely that female Emerita at the same reproductive stage would be collected at two different beaches at the same time. While Fig.2 can be considered as representative of naturall levels of sDDT in populations of Emerita the data from these samples cannot be used for a systematic comparison between populations. For example, animals from site 5 have significantly higher levels than those from any other site. Yet, this may be due to the fact that all animals from that site were non- ovigerous. However, Swarbrick (1971) also found high sDDT levels in that area (Monterey Wharf + 2) when analyzing hermit crabs (Pagurus samuelis) during the same period. Therefore, it seems that this graph may,in fact, offer a rough estimation only of the relative sDDT levels. Clarification of the anomalous -8- results results obtained between ovigerous and non-ovigerous females would allow for an acceptable interpretation. There seems to be relatively low levels between the Pajaro and San Lorenzo River (sites 15-22) and at the Salinas River mouth (site 10, Fig. 2). Since sDDT levels in the sand samples (Fig. 5) showed peaks at the major drainage outlets (except the Salinas River which was blocked by a sand bar at the time of collection), and the aforementioned low sDDT levels exist at all the drainage outlets, it seems reasonable to hypothesize that sDDT input must first get into the marine ecosystem--adherred to particulate matter and/or ingested by marine plankton-before its presence is revealed in the Emerita, If, during low runoff periods, most of the sDDT is deposited on the beach adjacent to the drainage outlet, rather than dispersed in the ocean (as would occur during a flood), it is unlikely that the Emerita would accumulate much of it since they do not actively ingest sand while feeding (Efford, 1965). Analysis of organic detritus and phytoplankton in the surf zone would probably offer a better correllation, since the sand crab's food is comprised of this material, and since body¬ weight concentrations of sDDT have been found to be a function of daily intake of sDDT in many animals (Robinson, 1967). Examination of Fig.3 shows a fairly good relationship between the distribution of DDT and DDD, but an erratic trend for DDE distribution. Since DDE is thought to increase with time in a biological systim (Cox, 1971) and values for DDE may SDDT be an indicator of that time, (lower values corresponing to a 6 26d -9- shorter presence in a biological system) it could be valuable to consider the ratio of DDE to sDDT. Such a comparison between DDE and sDDT is presented in Fig. 4. The results show a definite trend towards lower DDE values away from the Salinas SDDT River, a trend seemingly contradictory to the argument developed above. One would expect a shorter "system time" near a point source of input. However, since recent usage of DDT in the area has decreased sharply and the Salinas River has not flooded in over two years, it is likely that the last significant input of sDDT (mostly DDT) into the bay (at least from this river) occurred in Feb., 1969, when the river flooded thousands of acres of farmland. Since it is now established that the majority of the sDDT being translocated in such a river is adsorbed to fine sediment particles rather than sand-sized particles (Routh, 1971; Lee, 1971) and since the heavier sand particles have faster sedimentation rates than the finer material, the majority of sDDT would be washed out into the ocean instead of settling on the beach (as it would if adsorbed to sand particles). Current patterns off the mouth of the Salinas River are seasonally variable, but in general, offshore bottom currents off the mouth of the river tend to move in a northerly and southerly direction parallel to the shore (Wolf, 1968). The majority of sDDT input, having moved out into the bay, would be distrib- uted throughout the bay by surface and bottom currents, where longshore currents which run in a northerly and southerly direction parallel to the southern and northern parts of the bay respectively before turning seaward just south of the 269 -10 Salinas River (Wolf, 1968), may recirculate the sDDT, increasing the relative amounts of DDE all the while. After the 1969 flood, King (1969) found levels of sDDT in Emerita at the mouth of the river with higher values for DDT than DDE, which is reasonable, SDDT SDDT since extreme local effects would necessarily contaminate the immediate area with sDDT (adsorbed in part to the fraction of fine sediments that were not washed out to sea immediately) and a short "system time" for sDDT to reach the Emerita resulted. Animals tested from the same site in this study (two years later) showed considerably higher values for DDE than for DD SDDT SDDT It is doubtful that sDDT that has remained in the sediments of the riverbed over a period of time (and are thus mostly DDE) contribute a relative significant amount of DDE to the runoff during a flood, since according to usage figures the vast majority of sDDT being translocated would be in the form of technical grade DDT that had been recently applied to agricultural lands of the watershed. The trend seen in Fig. 4, therefore, is not unreasonable. Of course, it is possible that Fig. 4 merely represents the effect of differential ecological parameters in different parts of the bay such as standing crop density, trophic level interchange (and concommitant differential accumulation of sDDT). Any pattern that exists may either be coincidental or directly related to the river runoff. Since DDE values of ovigerous to non-ovigerous animals SUDT differs by only 11% (Table 1), the data presented in Fig.4 needs little qualification. 27 -11 Unfortunately,time considerations and lipid cleanup problems prevented a thorough analysis of all of the egg samples. How- ever, those that were tested showed a considerable concentration of sbpT compared to animals they were taken from. However. egg removal alone does not account for the discrepancy between non-productive animals and ovigerous ones with eggs removed (Table 1). This suggests that ovigerous females have at some point lost a considerable amount of sDDT. Without further study, one can only speculate as to the mechanism involved. Since it is quite unlikely that all of the six non-ovigerous animals tested (Table i) were non-reproductive (they all had noticeable ovaries)and some may have just lost their eggs) and there was no overlap of sDDT values for ovigerous versus non-ovigerous animals. a rapid but short-lived elimination of the sDDT is suggested. A plausible time for this to occur would be when the rate of lipid translocation from the female to the eggs is greatest. If, in fact, all the non-ovigerous animals were also non-reproductive. then a more uniform elimination of the sDDT is suggested. It has been reported that Emerita may build up lipid reserves prior to the energy-consuming egg laying season, and used them up during the season (Lee and Gilchrist, 1971; Eickstaedt, 1969). Because the largest animals, which would tend to store more lipid, are the first to become reproductive (Eickstaedt, 1969). this hypothesis seems reasonable. It is doubtful that the hydrophobic, lipid-soluble sDDT would be lost from the eggs, which -12 are exposed to the seawater, via some diffusion mechanism across the egg membrane. All these hypothesis could be tested without too much difficulty. Whether or not Emerita analoga is, in fact, a good systematic indicator of comparative sDOT levels has not been fully demonstrated in this study, principally because it was found that sDDT levels differ markedly between ovigerous and non-ovigerous animals. This difference could not be attributed entirely to the amount of sDDT lost in the egas when they were experimentally removed from the animals. It is therefore suggested that the pertinent difference occurs between reproductive and non-reproductive animals rather than between ovigerous and nen-ovigerous specimens. In order to determine the effectiveness of Emerita as an indicator species, then, perhaps only non-reproductive animals should be used. Until further information is gained concerning the stage of reproduction in relation to loss of uptake of sDDT the problem must necessarily remain unresolved. 27 elt Good J KNOWEDGE TS ppe t a or ank you, everybody, f 1 Mrs. sof ugave wa 27. LITERATURE CITED Burnett, R. (1971). DDT residues: Distribution along coastal California of concentrations in Emerita. Submitted to Science, June, 1971. Carlisle. J.G., Schott, J.W., Agramson, N.J. (1960). The Barred Surperch (Amphistichus argenteus Agassiz)in Southern California. State of California Department of Fish and Game Marine Resources Operation. Fish Bulletin No. 109, 48-52. Cox, J.L. (1971). DDT residues in coastal marine phytoplankton and their transfer in pelagic food chains. (PhD Thesis, Stanford University). Efford, I.E. (1965). Feeding in the sand crab, Emerita analoga (Stimpson) (Decapoda, Anomura). Crustaceana. 10(2), 167-82. Eickstaedt, L.L. (1969). The reproductive biology of the sand crab Emerita analoga (Stimpson). (PhD thesis, Stanford University). King, R.E. (1969). DDT uptake in Emerita analoga and levels of DOT residues in populations from Asilomar Beach and near the mouth of the Salinas River. Spring Quarter report, Hopkins Marine Station, Pacific Grove. California. Lee, W.L. (1971). Hopkins Marine Station, Pacific Grove, California. Personal communication. Lee, W.L. and Gilchrist, B.M. (1971). Carotenoid metabolism and reproduction in the sand crab Emerita analoga Decapoda, Anomura). In preperation. Nash, R.G.. and Woolson, E.A. (1967). Persistance of chlorinated hydrocarbon pesticides in soils. Science. 157 924-7. Reeder, W.G. (1951). Stomach analysis of a group of shorebirds. The Condor. 53, 43-5. Risebrough, R.W., Menzel, D.J., Martin, D.J. and Olcott, H.S. (1967). DDT residues in Pacific sea birds: A persistant insecticide in marine food chains. Nature 216, 589-90. Risebrough, R.W., Reiche, T., Peakall, D.B., Herman, S.G., Kirven, M.N. (1968). Polychlorinated biphenyls in the global ecosystem. Nature. 220 (5172), 1098-1102. I. (1967). Dynamics of organochlorine insecticides Robinson, in vertebrates. Nature. 215, 33-5 (1971). DDT residues in Salinas River sediments. Routh, J. Spring Quarter report. Hopkins Marine Station, Pacific Grove, California. Rudd, R.L. (1964). Pesticides and the Living Landscape, Chapter 20. University of Wisconsin Press, Madison. Swarbrick, S. (1971). DDT residues in the marine intertidal hermit crab (Pagurus samuelis) (Crustecea, Decapoda) in California waters. Spring Quarter report. Hopkins Marine Station, Pacific Grove, California. Tatton, J.O'G., and Ruzicka, J.H.A. (1967). Organochlorine pesticides in Antarctica. Nature. 215, 346-8. West, I. (1966). Biological effects of pesticides in the environment. In Organic Pesticides in the Environment (American Chemical Society). 309 pages. 274 Wolf, oodwel Yancey, T or re SO 2near- In go Co residue: DDT — ide. persi iene. ents fornia. versity of California raulic Engineering Labor ratory. Site Number 2. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. BS COLLECTION SITI Location Carmel (city) Beach Not listed: Too few and too small animals collected. Asilomar State Beach Cannery Row, Monterey Wharf + 2, Monterey Del Monte Beach Beach near Seaside sewage outfall Beach near Ft. Ord sewage outfall Beach near county animal shelter Mouth of Salinas River Moss Landing State Beach Beach behind Moss Landing marine research station Mouth of Elkhorn Slough Zumdoski State Beach Mouth of Pajaro River Northern Boundry of Sunset State Beach Manresa State Beach Beach half way between sites 17 and 19 Mouth of Aptos Creek Seacliff State Beach Twin Lakes State Beach Mouth of San Lorenzo River Natural Bridges State Beach Point Sur ig.1 analog Collection sites fre whi were collected April 22 I 2 O 3 22 N 27. rsid ea (SDD Tota 110 the loatic omwhich Emerita a . wel collected and anal Site 2 1: abse rom the graph becau few and o0 small animals were ollee type point marks represent st different popultons fo stands f 3ig S (Point — O N D N 0 N ppb Wet Wt. R O Ooooo ) ( O OO g. viation Act rica DT, mea els DDD bars represent standar O A 0 O 0 — O 8 + N P 3 0 8 N P H —4 — — pph Wet Wt. O p Fig. dues. deviatio DDE (total resi¬ lines represent standard 4 — 0 R OI O 00 — — — A O — N 0 N C U — O — P L O + — — 8 DDD,DDE ound in sand samples le on sit (tota aken from eh L sid I e O R 1 O O — 00 O N 3 3 O D 8 — ppD Dry Wt. a Comparis D 1d vigerou: SDI erita analoga llected Asiloma h, May 2. tate B 971.Simila infe mation is giv the eggs that were removed f athe ovigerous animal Si ana type were analyzed. 5 A X( o O â 02 O s. 2