INTRODUCTION There is mounting evidence that human activity re- sults in localized increases in the environmental levels of trace metals such as Pb, Hg, Cd, and that such increases are reflected in higher levels of these metals in organisms (Patterson, 1965). In order to be able to detect such in- creases, and to distinquish the effects of human activity from normal background levels, baseline values must first be determined in both environment and in representative species. Hermit crabs of the genus Pagurus are abundant and ubiquitous on Californian rocky shores and represent forms that can be studied both in undisturbed regions and in areas heavily influenced by man. Pagurus samuelis, a species which lives higher in the intertidal than any other hermit crab in Central California (Bollay, 1964), was selected for study. It is more easily obtained than the local edible crustaceans (eg. Cancer magister, the market crab or Pandalus jordani, the ocean shrimp; see Frey, 1971). Analyses were made of six metals (Ag, Cd. Cu, Mn, Pb. Zn). Specimens from various locations were tested to determine if the type of location correlates with changes in the heavy metal concentrations of a Pagurus population. Previous studies of trace metals in decapods are scanty. Bowen (1966) lists the following concentrations for Crustacea in general (in ppm dry animal tissue): Cd, O.15 ppm; Cu. 50 ppm; Mn, 2 ppm; Pb, 0.3 ppm; Zn, 200 ppm. Goldberg (1967) cites a study in which the zinc level in a Texas sample of the Blue crab Callinectes sapidus was determined to be 46 ppm. In another instance he quotes that Cancer pagurus has 35.0 ug/g (ppm) of Cu. It must be remembered, however, that differences in concentration factors for a given element in organisms exist among individuals and species as well as among families (Goldberg, 1957). MATERIALS AND METHODS Pagurus samuelis were collected from eight areas on the California coast between San Francisco and the Palos Verdes Peninsula. (Fig. 1) A) Pacificas latitude 37° 35'; near the San Pedro Sewage Treatment Plant and outfall. B) Monterey Harbor: latitude 36° 36', under Fisher- man's Wharf, Monterey Harbor, and for about 100 meters northwest. This area is within the Coast Guard breakwater. C) Mussel Point, Pacific Grove: latitude 36° 37 east of Hopkins Marine Station of Stanford Univer- sity. D) Point Pinos, Pacific Groves latitude 36° 38° 44 within 60 meters of the outfall from the Pacific Grove Sewage Treatment Plant. Carmel Mission Point, center of Carmel Bay: latitude 36° 32', south side of the point, about 500 meters north of the outfall from the Carmel Sewage Treatment Plant. Monastery Beach, south end of Carmel Bay: latitude F) 36° 31', about 700 meters south of the outfall from the Carmel Sewage Treatment Plant. The cur- rents run generally southward from the outfall. Malpaso Creek, Monterey County: latitude 36° 28' G) about 500 meters south of the creek on undeveloped private land which is locked to the general public. White's Point, Palos Verdes Peninsula: latitude H) 33° 43' from the beach closest to the Los Angeles County sewer outfall. This is one of the largest primary treatment outfalls on the West Coast. Samples were all taken at low tide near the upper intertidal limit of the brown alga Egregia. One hundred Pagurus samuelis were taken from each study area. In the laboratory, they were removed, without injury, from their shells by removing the tip of the shell and poking the crab out. When possible five pooled samples of males and five pooled samples of females were tested from each area. Among the females, only ovigerous individuals were used. and the eggs borne externally were removed before diges- tion to assure a more uniform population. For each sam- ple three individuals were pooled to insure adequate dry weight. The individual crabs used ranged in size from 0.2 to 0.6 grams dry weight. The method used for digesting the crabs is a modifi- cation of the Middleton and Stuckey technique (Christian and Feldman, 1970). Each sample was weighed wet and then dried at least overnight at 80° C. It was then weighed dry and pulverized with a ceramic mortar and pestle. These and all all other glassware used had been previously cleaned with 4-6 N HNO for 20 minutes. An aliquot (O.5- 0.6g.) of the powder was weighed out to 1.0000g. on a Sartorius balance and placed in a 30 ml. beaker. To the powder was added 6 to 8 ml. of 90% HNO3 (dropwise at first). The beaker was then covered with a watchglass and simmered, just under boiling, for one to three hours until the organic matter was well broken down. The watch- glass was removed and the solution allowed to evaporate to approximately 4 ml. Four or five ml. of 30% H02 was added (slowly to avoid bubbling over) and then heat was applied for another 15 to 30 minutes. Whenever the solu- tion was still cloudy the last two steps were repeated.. This resulted in a clear sample. Finally the solution was diluted to 25 ml. with distilled water. At this point the solution was tested for Ag, Cd, Cu, Mn, Pb, and Zn with a Perkin-Elmer 303 Atomic Absorption Spectro- photometer (Perkin-Elmer, 1968, 1971). Many problems were incurred in attempting to get reliable values for concentrations of lead. In all cases the samples were measured at a wavelength of 285) which is a very steady, easily readable line. Many of the samples were also run at 218.5/, a line which fluctuated a great deal on the a. a. spectrophotometer. In some instances the machine could not be zeroed adequately and measurements of the same sample taken two minutes apart differed radi- cally. In the cases where measurements at 218.5 were completed the concentration levels measured were about one- third to one-half those measured at 285). Probably the best assumption is that the true concentration value in each lies somewhere between the two. RESULTS AND DISCUSSION Concentrations of the six heavy metals considered are shown in Table 1 and Figs. 2-6. The results show that Pagurus samuelis ooncentrates the six metals to differing degrees and that levels of occurrence varied with the loca- tion. Significance of the differences between means of the sample populations were determined with the Student's t-test (Simpson, et. al., 1960). The graphs of Figs. 2-7 0 are based on the data of Table 1. The females were compared to the males at each loca- tion (Figs. 8 & 9).. In most cases the differences be- tween sexes were not statistically significant. Lead (Fig, 2) Lead acts as a cumulative poison in mammals where it is moderately toxic (Bowen, 1966). While absolute values are to be regarded as approximate the relative amounts at the various locations are probabCly reliable. The Mussel Point and Monterey Harbor samples are not significantly different; however, the Mussel Point results differ signi- ficantly from those at the remaining six locations, which are similar. Cadmium (Fig. 3) Cadmium is a cumulative poison in mammals and moderately toxic to all organisms (Bowen, 1966). Mean levels of Cd in P. samuelis were highest at Pacifica, and (contrary to expectations) lowest at White's Point. The latter was significantly lower than all the others at the,Ol level. Cadmium may precipitate readily and the Los Angeles out- fall is a mile offshore with another mile of diffuser pipe beyond that. It may be that the Cd is precipitating out before reaching the intertidal zone. Voe Manganese (Fig, 1 Manganese is only moderately toxic, and in small amounts is essential to all organisms. It is known to activate numerous enzymes (Bowen, 1966), and is necessary for normal growth, skeletal development, reproductive performance, and functioning of the central nervous sys- tem (Christian and Feldman, 1970). The levels of man- ganese found at Pacifica and at White's Point are signi- ficantly different from one another at the.Ol level and both are much higher than the levels found at the other six locations. The Monterey Harbor and Point Pinos values are similar but differ significantly from the level for Mussel Point which geographically lies in between them. Carmel Mission Point and Malpaso Creek have similar levels but differ significantly from Monastery Beach values. Silver (Fig, 5) Silver may be accumulated as an environmental contami- nant. It can inhibit or inactivate a number of enzymes by reacting with thiol groups on the enzyme at or near the ac- tive site. Silver is rarely found in plants (Christian and Feldman, 1970) so probably is not entering the Pagurus through the algal part of their omnivorous diet. Point Pinos shows the highest levels of silver while Carmel Mission Point shows the lowest. The Point Pinos, Pacifica. and Carmel Mission Point samples represent populations which differ at the.Ol level of significance. The samples from the Mussel Point and White's Point popula- tions are not significantly different; the same is true of the populations at Monterey Harbor, Malpaso Creek, and Monastery Beach with regard to silver concentrations. Zinc (Fig, 6) Zinc has a low toxicity to mammals and is an essential nutrient for all plants and animals (Bowen, 1966; Christian and Feldman, 1970). The levels of zinc at Monterey Harbor were significantly higher than those at all other loca- tions (.Ol level). These high readings at the Harbor are probably being influenced by the Monterey sewage plant effluent which on May, 1971 put into Monterey Bay about 7500 grams/day of Zn (Vieth, 1971). This effluent is dumped into the Bay approximately 2000 meters from the Harbor, and periodically the currents run from the out- fall toward the Harbor. Another major source of zinc in the Harbor is probably the zinc used externally on small ships to prevent electrolysis of the shaft and propellor. Point Pinos, White's Point, Carmel Mission Point, and Pacifica were statistically similar and ranked second highest in Zn concentrations. All four are fairly close to sewage outfalls. Gopper (Eig.2 While oopper is essential to all organisms, abnor- mally high levels may be highly toxic to invertebrates and moderately toxic to mammals (Bowen, 1966). Pagurus contains copper in its hemocyanin. Levels of Cu obtained at Carmel Mission Point, Monastery Beach, and Malpaso Creek were statistically similar and were the lowest. If this level is accepted as a general indication of the level necessary for Pagurus samuelis, then the other val- ues are much in excess of this. White's Point and the Monterey Harbor were not significantly different and showed the highest levels; with Mussel Point not far below. Pacifica and Point Pinos showed intermediate levels of Cu that were still very high. The high levels at Mussel Point and Monterey Harbor are probably affected by the effluent from the Monterey Sewage Treatment Plant, which on May, 1971 contained about 2500 grams/day of copper (Vieth, 1971).. Also copper is contained in the anti- fouling paiht used for many boat hulls. Some of the cop- per found may represent the local use of fungicides con- taining Cu and the use of copper sulfate to control fresh- water algae. SUMMARY Amounts of Ag, Cd, Cu, Mn, Pb, and Zn were measured in the hermit crab Pagurus samuelis from eight locations on the California coast between San Francisco and the Palos Verdes Peninsula. Highest and lowest average values obtained were: Ag (5.0-1.5), Cd (3.1-1.2). Cu (200.7-44.6), Mn (24.2-6.5), Pb (23.4-14.8), and Zn (108.8-76.4). Females did not differ significantly from males for most metals in most areas. High levels of zino and copper in Pagurus samuelis show some relation to possible local sources in the environment. ACKNOWLEDGMENTS 1 would like to thank my advisors Drs. D. P. Abbott and J. H. Martin, and Sue Swarbrick for their help during this research project. This work was made possible by Grant GY8950 of the Undergraduate Research Participation Program of the National Soience Foundation. 82 REFERENCES CITED Bollay, M. 1964. Distribution and utilization of gastropod shells by the hermit crabs Pagurus samuelis, Pagurus granosimanus, and Pagurus hirsutiusculus at Pacific Grove, California. Veliger 6 (Supplement). 71-76. Bowen, H. J. M. 1966. Trace elements in biochemistry, Academic Press. 241 p. Christian, G. D., and F. J. Feldman. 1970. Atomic absorp- tion spectroscopys: applications in agriculture. biology, and medioine. John Wiley & Sons, New York. 490 p. Frey, H. W. 1971. California's living marine resources and their utilization. State of California, Depart- ment of Fish and Game, California. 148 p. Goldberg, E. D. 1957. Biogeochemistry of trace metals. p. 345-358. In J. W. Hedgpeth (ed.), Treatise on marine ecology and paleoecology, V. 1. Ecology. Geol. Soc. Am. Mem. 67. 1967. Review of trace element concen- trations in marine organisms. Puerto Rico Nuclear Center. 535 p. Patterson, C. C. 1965. Contaminated and natural lead environments of man. Arch. Environ. Health 11. 344- 360. Perkin-Elmer. 1968. Analytical methods for atomic ab- sorption spectrophotometry. Perkin-Elmer Corp.. Norwalk, Conneoticut. 1971. Analytical methods for atomic ab- sorption spectrophotometry. Perkin-Elmer Corp.. Norwalk, Connecticut. 1760 Simpson, G. G., Roe, A., and R. C. Lewontin, Quantita- tive Zoology. Harcourt, Brace, & Co., New York. 440 p. Vieth, R. 1971. Trace metals in Monterey Peninsula sewerage. Unpublished MS. on file at Hopkins Marine Station Library. Vinogradov, A. P. 1953. The elementary chemical composi- tion of marine organisms. Sears Foundation Mar. Res. Mem. 2, New Haven. 647 p. PIGURE CAPTIONS Figure 1: A map of the eight collection sites. The location letters are referred to in figs. 2-7. Map of the relative amounts of lead present in Figure 21 the P. samuelis population at each location. Map of the relative amounts of manganese pre- Figure 3. sent in the P. samuelis population at each location. Figure 4. Map of the relative amounts of cadmium present in the P. samuelis population at each location. Figure 51: Map of the relative amounts of silver present in the P. samuelis population at each location. Figure 6: Map of the relative amounts of zinc present in the P. samuelis population at each location. Figure 7. Map of the relative amounts of manganese present in the P. samuelis population at each location. Figures 8 & 91: Means and standard deviations for females versus males by metal content level at each location. Note: Female value at White's Point (H) is based on one sample only and therefore has no standard deviation. 7 — 3 2 o He +2 O+ n HE oo sa 28 6 HE 830 POINT PINOS MUSSEL POINT+ CARMEL MISSION POINTE MONASTERY BEACH¬ MALPASO CREEKFG igiine San Francisco Bay. San Frangi sco PACIFICA Monterey Bay RMOMEREYHARBOR Carmel River— . . . „ e . 1 0" Long Beach G San.Pedro Bay. I WHITETSPOINT- i e . LEAD (ppm dry wt.) 15 15 15- 25 15 5 25 15- MONTEREY LeeniNSULn M 15 15 WHITE'S POINT 15 fiquv a 2 4 PACIFICA CADMIUM (pom dry wt.) 3- 3- 3- /MONTEREY PENINSULA r Pgure 3 PACIFICA WHITE'S POINT 663 MANGANESE (ppm dry wt.) 10 0 10 10- 10 5 10 1 MONTEREY PENINSULA 25 20- 15 10- 15 10 L Pure PPACIFICA WHITE'S POINT 2 SILVER (pom dry wt.) L LE MONTEREY PENINSULA 1 sgn 5 3 re WHITE'S POINT ZINC (ppm dry wt.) 95 85 75 85 75 85 75 105 95 85 L75- AMONTEREY PENINSULA 15- ige6 PACIFICA V 75 95 85 75 WHITE'S POINT 436 COPPER (ppm dry wt.) 00 50 50 50 L 50 150 100 50 200 150 oo 50 MONTEREY PENINSULA oo 150 00 50 150 100 ligave PACIFICA WHITE'S POINT o 4 250 200 0 500 50 I H + B B 4 4 — figige 8 Lnades Cemates signilicantly ditterent 40 35- 30 225 2 10 5 30 -25 -20 15 10 5- 15 0 75 50 A * H I + 43 Ggir Lnales Clemates * signiticantly ditferent H I