C Abst Trace metal analysis of 23 species of common Pacific Coast marine foods revealed high cadmium values for Bent-nosed clams (Macoma nasuta), Bay mussels (Mytilus edulis), Bay oysters (Ostrea lurida), Pacific oysters (Crassostrea gigas), and Littleneck clams (Protothaca staminea). Metals were found to concentrate in the gills, heart, and visceral mass of all 10 species of bivalve mollusks examined. Swordfish (Xiphias gladius) and Salmon (Oncorhynchus tshawytscha) demonstrated the highest cadmium values for fish flesh. Introduction In light of the recent concern over contamination and toxicity of cadmium (Nilsson, 1969), (Schroeder, et al, 1966, 1967, 1968), (Pringle, 1968), an examination of cadmium, zinc, copper, and manganese concentrations in the edible portions of bivalve mollusks, 10 species of fish, and 3 species of crustaceans was undertaken. Particular attention was given to the soft bodies and organs of the mollusks since other workers have reported that they concentrate trace metals (Schroeder, 1967), (Brooks and Rumsby, 1965), (Pringle, 1968). Six species of mollusks and 2 species of fish were collected from Elkhorn Slough, which flows into Monterey Bay near Moss Landing, California. This area is particularly abundant in estuarine animals although it has been condemned by the county health department as a health hazard due to high E.coli counts. It is also the receptor of both the Pacific Gas & Electric generator plant and the Kaiser Aluminum plant waste water effluents. No attempt was made to determine the metal contents of the effluents. Accord- ing to Veith (1971), Monterey Bay sewage effluents pour as much as 175 grams of cadmium into the Bay per day. Methods Mollusks were collected and removed from shells, rinsed with dis- tilled water and disected (where applicable). Fish and crustacean samples were purchased at local fish markets. All samples were weighed, dried for about 12 hours at 1000C and reweighed. Digestion of dried material was accomplished 55. 563 by adding 90% nitric acid and heating in acid-cleaned 30ml Pyrex beakers. Drops of capryl alcohol were added to minimize foaming where necessary, (as in Middleton and Stuckey, 1953). Blanks were treated exactly as the marine samples. Once the tissues were in solution, they were heated until charred, on hot plates, in order to burn off lipid particles. Samples were cooled, redisolved with 90% nitric acid, and cleared by adding hydrogen peroxide dropwise with heat. Once clear, samples were diluted with distilled water, covered, and analyzed within 3 days. Samples were analyzed for metal concentrations by atomic absorption spectrophotometry (Perkin-Elmer 303), using a triple slot burner head. The detection limits for cadmium, copper, and manganese were 0.05 ug/g dry weight, and for zinc was 0.5 ug/g dry weight. Results & Discussion Tables of the results indicate the common and scientific names of samples, which samples were disected, and which samples were analyzed whole (since they are eaten whole). The right hand column of the tables lists the dry to wet weight ratio. Multiplication of this value by the dry parts per million (ppm or ug/g) figures gives the values for ppm wet weight. Metals were clearly concentrated in bivalve mollusks of all species. The highest concentrations were found in the heart, gills and visceral mass of individual animals. The clams tended to concentrated the metals to a lesser degree than did the non-siphoned bivalves, i.e. the scallop, oysters, and mussels, in every case except for the Bent-nosed clams. Three Bent-nosed clams (Nacoma nasuta) from Elkhorn Slough averaged 30 ppm dry weight of cadmium and 1,076 ppm dry weight of zinc (See Table 1). This particularly hardy species of clam has a separated siphon which acts as a "vacuum cleaner" combing the surface of the slough bottom. Whole oysters, and especially Ostrea lurida from San Francisco Bay, were noted to have high concentrations of zinc (900 ppm dry) and copper (173 ppm dry) (See Table 2). The nephridium of one scallop (Hinnites multi- rugosus) taken from San Pedro Harbor in Los Angeles, contained the highest cadmium level of the study (181 ppm dry) (See Table 4). Interestingly enough, the nephridium corresponds in function to the mammalian kidneys, which are also the site of cadmium concentration (Schroeder, 1967). Although the Gaper clams (Tresus nuttalli) from Elkhorn Slough, had low metal concentrations, the outer skin, covering the neck was found to have the highest manganese content (1,200 ppm dry) (See Table 5). Since manganese is a common metal component of sediments, it is possible that the sample of neck skin included some clay particles, although it was thor- oughly washed. Unfortunately a substrate analysis of the Slough sediment was not taken. Although cadmium values in fish flesh were relatively low,(less than 1.5 ppm dry) Swordfish and Salmon contained more cadmium than the crustaceans and edible portions of the Gaper clam (Table 6). The figures presented here should not be considered as representitive for species from the entire Pacific Coast. Note, for example, that the cadmium concentration was 5 times higher in Littleneck clams (Protothaca staminea) from Elkhorn Slough than those from Canada (See Table 1). 54 According to Schroeder, a normal human intake of cadmium is 215 ug/ day (Nilsson, 1969). Of this, 984 is excreted. Of the 24 retained, most is stored in the kidneys and liver. Bowen (1966) indicated that 3mg of cadmium ingested per day is "toxic" to humans. In order to achieve such an intake of cadmium per day, one would have to eat 1½ pounds of Bent-nosed clams or 17 whole oysters from Elkhorn Slough. Likewise, 84 pounds of scallop muscles from San Pedro Harbor, or 174 pounds of Swordfish steak would account for such a quantity of cadmium. (These amounts were calculated from the cadmium concentrations in ppm wet weight.) 55 C Acknowledgements I would like to thank John Martin, Phd., and D.P. Abbott, Phd., both of Hopkins Marine Station, for their aid and advice. I would also like to thank Dr. and Mrs. Wm. Burget for making this research financially possible. Special thanks goes to Prof. Hadley Kirkman and his bride. 566 10. 11. 12. Bibliography Bowen, H.J.M.: Trace Elements in Biochemistry, Academic Press, New York, 1966, p.116. Brooks, R.R. & Rumsby, M.G.: "The Biogeochemistry of Trace Element Uptake by Some New Zealand Bivalves", Jr. Limnol. Oceanog., 10: 521-527, 1965. Christian, G.D. & Feldman,F.J.: Atomic Absorption Spectoscopy, Wiley- Interscience, New York, 1970. Middleton,G. & Stuckey, R.E.: "The Preparation of Biological Material for the Determination of Trace Metals", Analyst, vol.79: 138-142, March 1954. Pringle, B. et al: "Trace Metal Accumulation by Estuarine Mollusks", Proc. Am. Soc. of Civil Eng., p.455-475, June 1968. Ricketts, Ed & Calvin,J.: Between Pacific Tides, Stanford University Press, Stanford, California, 1939. Nilsson, Robert: Aspects on the Toxicity of Cadmium and its Compounds, Nat. Science Research Council, Stokholm, Sweden, May 1969. Schroeder,.H.A., et al.: "Trace Metals in Rat Tissues as Influenced by Calcium in Water", Jr. of Nutrition 93: 331-335, 1967. Schroeder, H.A., et al.: "Influence of Cadmium on Renal Ischemic Hypertension in Rats", Jr. of Physiology, 214: 469-473, March 1968. Schroeder, H.A., et al.: "Essential Trace Metals in Man: Zinc Relation to Environmental Cadmium",J. chron. Dis., 20: 179-210, 1967. Tipton,I.H.; "The.Distribution of Trace Metals in the Human Body" in Seven,M.S, & Johnson,L.A. eds.: Metal Bindings in Medicine, Lippincott pp. 27-42, 1960. Veith, Rob: "Trace Metals in Monterey Peninsula Sewerage", unpublished, Hopkins Marine Station of Stanford Univ., Pacific Grove Calif., 1971. Legend for Graph 1 The following bar graph represents cadmium concentrations in weight of edible samples. In the cases where the whole animal (shell-less) is eaten, such as the smaller clams and oysters, whole body concentrations are depicted. Samples listed as "ND" are the cleaned edible portions in which the metal concentration was below the detection limit. Tables i through 7 list the genus species names of the animals examined along with the ppm dry weight values and the dry/wet weight ratios. 555 22 Bent-nosed Clamt (Elkhorn Slough) Pacific Oyster (Elkhorn Slough) 181.18 Bay Musse. (Elkhorn Slough Pacific Oyster (Shelton. Mash. ittle Neck Clam (Elkhorn Slough) Scallop muscle (L.A. Harbor) Razor Clam Sword Little Neck Clam (Canada) Rosetta Clam (East Coast Dungenest (canned) Dungeness (fresh) Salmont Prauns Pacific Shrimp Gaper Clam Rock Codt ,Solet Sableffish", Red Snapper CADMU TCONDON MARTNE FOOD rgrwet weight ofsample (ppm wetwe Cleaned edible portion Deconcentrat tdetect 565 pon 560 Table 1 Bivalve Mollusks Concentrations of trace elements in whole individuals (Average PPM dry weight) Zinc Copper Manganese dry/wet" Cadmium Mercenaria mercenaria Eastern Rosetta clams .242 62.0 15.0 10.8 average of 3 whole bodies 1.2 (18.5) (2.5) (.1) (1.1) (standard deviation) Protothaca staminea Little Neck clams; Elkhorn Slough .208 65.0 8.5 average of 5 whole bodies 5.1 6.2 (0.8) (3.2) (9.2) (1.5) .260 8.2 2.8 1.0 59.3 average of 3 whole bodies from British Columbia (44.4) (8.3) (0.3) Macoma nasuta Bent-nosed clams; Elkhorn Slough .177 30.0 1076.0 42.0 29.0 average of 3 whole bodies (100.0) (15.0) (10.6) (6.7) Tresus nuttall Gaper clam; Elkhorn Slough .564 5.0 31.0 17.0 0.7 one whole body Saxidomus nuttalli Butter clam; Elkhorn Slough .220 37.8 2.4 4.5 one whole body 1.3 Siliqua patula Razor clams; Sunset Beach, Oregon average of 3 by parts 63.0 1.5 3.0 Neck and mantle .213 (10.0) (1.4) (1.8) (0.3) nd* .234 65.0 6.3 18.0 Visceral mass + contents (16.5) (2.0) (8.3) 2.0 144.7 25.0 3.1 .29 Gills (36.0) (1.4) (0.9) (1.2) (* ratio of grams dry weight/grams wet weight) * concentration not detectable) Table 2 Bivalve Mollusks Concentrations of trace elements in whole individuals (Average PPM dry weight) Cadmium Zinc Copper Manganese dry/wet" Ostrea lurida Olympia Oysters; San Francisco Bay average of 3 whole bodies 6.2 906.0 173.0 21.7 .272 (.9) (3.7) (50.0) (40.0) (Standard deviation) Crassostrea gigas Pacific Oysters; Shelton Wash. Commercially harvested 124 average of 3 whole bodies 2.5 290.0 28.5 6.1 (50.0) (3.4) (1.0) (0.4) Mytilus edulis Mussels; Elkhorn Slough 37.7 5.6 .248 average of 3 whole bodies (1.2) (16.7) (0.8) (0.7 cont Table 3 Bivalve Mollusks Concentrations of trace elements in individual organs (PPM dry weight) drylwet Cadmium Zinc Copper Manganese Crassostrea gigas Pacific Oyster; Elkhorn Slough Oyster fl nd* 3.0 256.0 8.0 .172 Adductor muscle ant 574.0 10.0 2.0 .167 65.0 Mantle + gonad .240 3.0 320.0 31.0 25.0 Gonad 11.0 .190 Gills 660.0 96.0 52.0 uth 5.0 461.0 47.0 .272 Mouth palps 632.0 .250 50.0 nd 24.0 Heart .228 23.0 477.0 87.0 10.0 Digestive gland minus gonad Oyster #2 .176 1.5 174.0 Adductor muscle 8.0 6.0 458.0 24.0 57.0 .213 Mantle + gonad 17.0 3.4 154.0 27.0 5.0 .250 Gonad 25.0 658.0 92.0 .195 Gills 96.0 .286 Mouth palps 12.0 10.5 377.0 74.0 64.0 415.0 84.0 13.0 Heart .233 214 5.0 Digestive gland 16.7 271.0 41.0 plus gonad 263.0 40.0 10.6 11.0 .270 Whole oyster 63 grams wet--17 grams dry: Analyzed and dryed by parts. (* ratio of grams dry weight/grams wet weight) (** nd - concentration of element was not detectable) Si Table 3 cont. Bivalve Mollusks Concentrations of trace elements in individual organs (PPM dry weight) Cadmium Copper Manganese dry/wet" Zinc Crassostrea gigas Pacific Oyster; Shelton Wash. Commercially harvested 419.0 29.0 Adductor muscle 5.0 9.0 .200 230.0 46.0 2.0 Mantle + gonad .222 nd* 230 Gonad 387.0 74.0 7.5 167 197.0 6.0 15.0 Gills 628.0 5.6 287.0 34.0 nd .250 Mouth palps 442.0 .200 7.0 130.0 nd Heart 567.0 94.0 7.5 218 Digestive gland 10.0 minus gonad 56 Table 4 Bivalve Mollusks Concentrations of trace elements in individual organs (PPM dry weight) Copper Manganese dry/wet" Cadmium Zinc Hinnites multirugosus Scallop; San Pedro Harbor, L.A. Adductor muscle 3.5 1.4 83.0 1.0 .22 12.0 90.0 3.0 .195 Mantle 3.0 nd* 191.0 nd .085 Foot nd Gills 467.0 105.0 .084 8.6 21.0 .065 Labial palps 304.0 75.0 13.0 54.0 41.0 7.3 .093 212.0 31.0 Heart .104 53.0 25.0 181.0 311.0 Nephridium .720 Visceral mass 77.0 87.0 37.6 5.5 plus gonad 564 Table ! Bivalve Mollusks Concentrations of trace elements in individual organs Values represent ugrams of metal/gram dry weight of tissue Copper Manganese dry/wet Cadmium Zinc Saxidomus nuttalli Butter clam; Elkhorn Slough .264 8.7 Anterior adductor muscle 0.1 21.0 0.8 37.0 1.0 1.8 0.5 Foot muscle nat .234 2.9 50.0 Neck muscle 0.5 40.0 .250 1.8 19.0 Mantle 0.7 .164 83.0 6.0 1.8 Gills + contents 1.7 2.4 .198 81.0 6.2 8.2 Heart, palps, alimentary canal and contents 123.0 12.0 3.7 Visceral mass + contents 3.2 (* ratio of grams dry weight/grams wet weight of sample) (* not detecable) Tresus nuttalli Gaper clam; Elkhorn S. clam l .23 58.0 Anterior adductor muscle nd .139 nd 101.0 Foot muscle .170 53.0 Neck muscle (skinless) nd .119 109.0 17.0 1.0 Gills .144 59.0 81.0 16.0 15.0 Heart and alimentary canal 38.0 33.0 5.8 0.75 .530 Visceral mass + contents 1200.0 .16 122.0 4.0 Neck skin nd Aié 566 Table 5 cont. Bivalve Mollusks Concentrations of trace elements in individual organs (PPM dry weight) Cadmium Zinc Copper Manganese dry/wet resus nuttalli Gaper clam; Elkhorn Slough Clam +2 nd* .149 87.0 nd Anterior a ductor muscle .135 4.0 73.0 Foot muscle nd nd .149 47.0 4.0 0.9 Neck muscle (skinless) 18.0 .135 103.0 nd nd Mantle .119 108.0 nd nd 21.6 Gills 1. Heart and alimentary 42.0 .108 190.0 8.5 18.0 canal 48.0 58.0 16.0 .192 Visceral mass + contents 0.9 * ratio of grams dry weight/grams wet weight of tissue sampled) (* concentration of element was not detectable = nd) 566 Table 6 Fishes Concentrations of trace elements in fish flesh (Average PPM dry weight) Zinc Copper Manganese dry/wet Cadmium Oncorhynchus tshawytscha King Salmon nd* .308 19.0 2.9 Average from 2 fillets 0.6 (0.0) (7.0) (1.0) (standard deviation) Xiphias gladius 39.0 nd 25 1.5 1.25 Swordfish, one sample Gadus macrocephalus Rock Cod; Monterey Bay 1.0 .229 16.4 Average from 3 fillets nd 0.2 (2.0)) (0.0) (0.0) Sebastodes miniatus Vermillion Rockfish or Red Snapper 23.6 1.9 .221 nd Average of 3 fillets (0.6) (7.0) Anoploma fimbria Black Cod; Sable fish nd 2.5 Average from 2 fillets .321 (225) (0.0) 62 Sole-species unknown .155 2.0 23.0 1.2 Average of 3 fillets (3.0) (0.4) (0.9) Atherinos affinis Top Smelt; Pajaro River, Cal. 66.0 average of 3 fillets (0.1) (6.0) (0.1) Cymatogaster aggregata Shiner Perch; Elkhorn Slough 43.0 3.6 2.0 0.2 Average of 10 fillets (13.0) (1.7) (0.7) (0.3) Platichthys stellatus Starry Flounder; Elkhorn Slough 1. Average of 5 fillets nd (0.2) (0.2) (0.2) Roccus saxatilis Striped Bass; Pajaro River 20.0 1.2 Average of 3 fillets 10.6) (2.0) (0.4) (* ratio of dry weight/wet weight of sample) (*concentration not detectable) (4 data from Jim Prickett, Hopkins Marine Station, Pacific Grove, California) 56 68 Table 7 Crustaceans Concentrations of trace elements in flesh (Average PPM dry weight) Manganese dry/wet" Copper Cadmium Zinc Pandalus jordani Ocean Shrimp; fresh 18.5 (3:5) (8.0) 0.5 (standard deviation) Average of 7 shelled (0.0) tail portions Prawns; species unknown 47.0 12.0 nd** .221 Average of 3 shelled tails 0.2 (15.1) (2.2) (0.0) Cancer magister Dungeness Crab meat 16.0 fresh 73.0 (6.0) (1.6) (0.8) (0.1 93.0 7.2 0.8 .3 canned (0.1) (7.6) (1.5) (0.1) (* ratio of dry weight to wet weight of sample) (** concentration of element, not detectable)