f)S L_!HE HEAVY METAL COMPOSITION OF THE RED ABALONE, HALIOTIS RUFESCENS <1 J A thesis submitted to the faculty of California State University, San Francisco in partial fulfillment of the requirements for the degree Master of Arts by VICTOR J. COSTANTINO ANDERLINI ~,--' San Francisco, California June, 1973 i· I i '' ACKNOWLEDGMENTS Once By The Pacific The shattered water made a misty din. Great waves looked over others coming in, And thought of doing something to the shore That water never did to land before. The clouds were low and haiJ;"y in the skies, Like locks blown forward in the gleam of eyes. You could not tell, and yet it looked as if The shore was lucky in being backed by cliff, The cliff in being backed by continent; It looked as if a night of dark intent Was coming, and not only a night, an age. Someone had better be prepared for rage. There would be more than ocean water broken Before God's last Put out the Light was spoken. Frost I would like to express my sincere gratitude to Drs. Robert Beeman, John Martin, and Albert Towle for their inspiration, guidance, encouragement, and friendship throughout the period of this research. I thank them for their constructive criticism and understanding in the preparation of this thesis. I also want to thank the divers of the California Department of Fish and Game in Long Beach and Morro Bay for their help in the collection of specimens. I especially would like to thank Mr. David Binney and Dr. R. Risebrough whose help and friendship I greatly appreciated. iii ~-------------------------------- I also thank those friends and relatives who have helped me during my collections or who have offered advice and encouragement for so many years. iv TABLE OF CONTENTS Page ACKNOWLEDGMENTS. iii LIST OF TABLES. vi LIST OF FIGURES vii INTRODUCTION . 1 MATERIALS AND METHODS. 10 RESULTS . 21 RESULTS OF ANALYSES. 21 MATHEMATICAL DISTRIBUTION OF ELEMENTS 21 GEOGRAPHIC DISTRIBUTION OF ELEMENTS. 22 TRENDS . • . • . 45 DISTRIBUTION OF ELEMENTS WITHIN OTHER SPECIES . • . 47 COMPARISON OF NBS INTERCALIBRATION SAMPLES 48 DISCUSSION . 61 SUMMARY AND CONCLUSIONS. 67 LITERATURE CITED .•.... 70 v LIST OF TABLES Table Page 1. Sample Collection. .. , ........... 11 2. Concentrations of eight heavy metals in tissues of H. rufescens from five locations. 24 3. Mean and median concentrations of heavy metals in Pedro Point and Morro Bay samples .... 26 4. Comparison of Cu and Ag at all locations 27 5. Comparison of Zn and Cd at all locations 28 6. Comparison of Ni and Hg at all locations 29 7. Cd/Zn molar ratios in all tissues from all locations . 49 8. Comparison of the concentrations of eight heavy metals in the species H. rufescenes, !:!· cracherodii, and a hybrid species (H. rufescens x H. fulgens) ....... 50 9. Comparison of results of National Bureau of Standards Intercalibration Samples . 51 vi LIST OF FIGURES Figure Page l. Collection sites ...... 9 2. H. rufescens without shell, analyzed tissues indicated. ........... 16 3. Concentration of silver (ppm/dry weight) in all tissues at all locations . 52 4. Concentration of cadmium (ppm/ dry weight) in all tissues at all locations . 53 5. Concentration of copper (ppm/dry weight) in all tis sues at all locations . 54 6. Concentration of mercury (ppm/ dry weight) in all tissues at all locations . 55 7. Concentration of nickel (ppm/dry weight) in all tissues at all locations ..... 56 8. Concentration of zinc {ppm/dry weight) in all tissues at all locations ...... 57 9. Comparison of concentrations of copper and silver versus body weight in Mendocino sample collection . 58 10. Comparison of concentrations of nickel and mercury versus body weight in Mendocino sample collection . 59 11. Comparison of concentrations of cadmium and zinc versus body weight in Mendocino sample collection . .. 60 vii INTRODUCTION Man's increasing awareness of his to r the :marine environment the ss introduction of l, and industrial wastes has prompted numerous, recent investigations of the effects of a variety of s and natural compounds, including the heavy trace elements" Many of synthetic compounds sed to the environment r degrade to their elementary components are subs recycled through various biogeochemical processes. Other ic compounds, however, such as some chlorinated hydrocarbon pesti~· c sand po rinated bi (PCB' s) are not degraded in the environment and their presence in the :marine bio- s re at all tro ls can only be attributed to :man1 s activities, trace elenl.ents, unlike rinated carbons and PCB' s, are natural world ecos Many of the trace elements, s as Cu, and are s of important metalloenzy:mes essential to life and are found in all living systems ( er, 1950; Vvillia:ms, 1 9; r, etal., 1967; and Underwo 1971). r trace elernents, such as and Hg no known bio lo al funct l 2 are found in various concentrations in most organisms (Vinogradov, 1953; Bowen, 1966; and Goldberg, 1967). Since the trace elements occur naturally in the world eco­ system, detection of deleteriously elevated levels of these metals as a result of man's activities is often difficult. Natural "background11 levels of the heavy metals in the marine biosphere are poorly known and are often obscured by the local, coastal input of technological wastes. The majority of the increasing industrial uses of heavy metals are for non-recyclable commodities (Wallace et al. , 1971; Browning, 1969; Fulkerson and Goeller, 1972). Increased economic use of heavy metals have led to the increased mobilization and introduction of these elements to the marine environment. Lead is being introduced into the world's oceans at a rate 7-27 times greater than the rate of introduction by natural weathering during the Pleistocene era (Chow and Patterson, 1962; Tatsumoto and Patterson, 1963). This increase is due primarily to a greater use of tetra-ethyl lead gasoline additives which account for 19% of the yearly consumption of lead (Chow and Earl, 1970), and for 98% of the lead aerosols annually entering the atmosphere in the U.S. (Chow and Earl, 1972). The effects of this increased introduction of lead into the marine biosphere are, at present, unknown. The annual, global production of cadmium is between 12, 000 and 14,000 metric tons of which approximately 11,000 metric tons -------------------------------------------- 3 are dissipated to the environment as wastes (Man's Impact on the Global Environment, 1970). An estimated 2,100 metric tons of cadmium per year are released to the atmosphere in the U.S. A,, primarily from the processing, refining, and resmelting of cadmium bearing ores and scrap (Fulkerson and Goeller, 1972). Cadmium is used in a great number of products and the quantity of cadmium entering the environment suggests it may become a significant pollutant of wildlife artd livestock as well as humans. The potential toxicity of mercury compounds and their detection in a number of wildlife species has led to investigations of the biogeochemistry of this element. Klein and Goldberg (1970), have estimated the amount of mercury entering the environment to be 5000 metric tons per year. This figure is greater than the estimated yearly amount transferred to the oceans by natural weathering and represents one half of the annual, global production of mercury. An estimated 25, 000 to 150, 000 metric tons of mercury per year are released to the atmosphere by the natural degassing of mercury bearing formations and approximately 2/3 of this mercury reaches the world's oceans (Weiss, et al. , 1971 ). Inc rea sed input of these toxic metals into the environment J suggest that present environmental levels, especially in local eco­ systems, are higher than pre-technological levels. Heavy metals reach the coastal waters via natural weathering, aerial transport, ------------------------------------ 4 river runoff or local discharges of industrial and domestic wastes,. Sewage effluents been to contain high levels of some trace sand very large marine sewage outfalls in southern California and proposed marine outfalls in northern California could refore, contribute significant arnounts of toxic trace s to costal C rnia waters (Bradford, 1971; Vieth, 19 71; Braman, 1971; Anonymous, 1972). background levels of most of heavy trace eleme:nts in rnarine organisms are poorly known. The majority of ea studies concerning trace elements in marine organisms are re- viewed by Vinogradov (1953), Bowen ( 1966), and Goldberg (1967). Early investigations by Hiltner and Wichmann (1919), Clarke and Whe (1922), and Webb (1937) detected high concentrations trace elements, espec Zn, and Cd 5 1n marine rr1olluscs., .l!'-:1.- number of recent studies have determined of trace ele- ments in a variety of marine organisms including cs. studies of Chipman et (1958), Yager and Harry (1964), of rnolluscs to selectively accmnulate trace ele:rnents to times ir environnJ.ental levels. Fox and Ramage (1930), were first to detect Cd in during ir inve of trace in the s Pecten r.naximus and in 1956, Mullins and Riley inve occurrence 5 of Cd in molluscs and r rnarine o ms. Cr and Pb were cted in :molluscs c and (1958) and Schroeder (1961 :McFarren et al. (1961) investigated occurrence of Cu and Zn in and found to wide geographic variation. studies by Parker (1962), Matsumoto et (1964), Fukai (1965), Fukai and B (19 ), Sastry and (1965), and u.s. and Wildlife Service, Bureau o£ ial Fi ries (1966) determined concentrations o£ Zn, Cd, Cu, C r and Pb in several species of stropods, bivalves and, cephalopods. In 1965, Brooks and Rums by attempted to relate of Ag, C Cr, Cu, Fe, Mn, wio, Ni, Pb, Sb, V, and Zn by e New Zealand bivalves to the environmental of these s, and r and Pringle ( 968) inve effects of various trace s on estuarine :molluscs.