Metals in Dipterans and Amphipods, 1. ABSTRACT Beach dipterans and amphipods were analyzed for heavy metal levels using atomic absorption spectroscopy. Flies showed higher concentrations of all major metals. Very high levels of cadmium were noted in both beach animals. An increase in metal level with age was evident in the dipterans. Concentrations of iron, zinc, copper, and lead were found to fluctuate sig- nificantly with time. Metals in Dipterans and Amphipods, 2. INTRODUCTION The study of major elements in plant and animal tissue dates back to antiquity (Pliny, Celsus), and by the middle of the eighteenth century a true trace element, lead, had been de tected in animals (Henkel, 1755). Recent advances in organic chemistry and analytical techniques have enabled precise es- timates of trace metals in diverse organisms (Vinogradov, 1953; Goldberg, 1966). As late as 1953, however, none of the 750,000 known species of insects had been tested for trace element composition, and only 100 out of 15,500 species of crustaceans had been analysed (Vinogradov, 1953). Although more recent studies have begun to fill the vacuum in this area (Spector, 1956; Stamm, 1958; Warnick and Bell, 1969), no work to date has focused on metal levels in arthropods of the sandy beach. Over a seven week period, I attempted to determine trace ele- ment levels in a marine and a terrestrial arthropod inhabiting the beach. I was especially interested in the general question of how a primarily marine and a land animal would compare in metal levels, as well as in how concentrations would vary geographically, temporally, and with age. Beach hoppers amphipods of the genus Orchestoidea - and marine flies were selected for comparison because they are known to exploit the same food source, the beach wrack. I hoped to set a base line with which future analyses could be compared in a temporal study of pollution, as well as to establish reasonable ranges of daily fluctuation for each metal. Metals in Dipterans and A lipods, MATERIALS AND METHODS Beach hoppers were collected at four points on the Monterey Peninsula (figure 1): Orchestoidea corniculata from two pocket beaches adjoining Hopkins Marine Station; O. calif- orniana from Del Monte beach at the Monterey sewage outfall and from the southern end of Carmel beach. Hoppers were found by digging in the sand with a shovel or by lifting segments of wrack. In the former case, the sand was combed by hand and no hoppers which had been contacted by the metal shovel were collected. Flies of the species Coelopa van- duzeei and Fucellia rufitibia were caught at the same sites A butterfly net was used to trap the flies as they swarmed above the wrack. In addition, larvae of the coelopid fly were collected from Carmel and lady bugs from Del Monte beach. These were taken by hand directly from the wrack and underlying sand. Sterile flasks were used in all cases to transport the animals from the collection sites to the laboratory. Beach hoppers were retained in collection flasks for 24 hours, after which they were frozen, washed in distilled water to remove sand and paracitic mites, and dried at 60° for one day. The same procedure was followed for the fly larvae and lady bugs. Fly specimens were Killed immediately, however, with ethyl acetate in a clean killing jar. They were then sorted by species, washed, and dried. Triplicate samples were col- lected when possible. Dried samples were ground to a fine powder and approximately gram or half-gram aliquots were digested. Ten ml of 90% nitric acid were added to each sample, which was allowed to reflux for at least one hour or until clear. The solutions were then simmered down to 5 ml, cooled, and treated with hydrogen Metals in Dipterans and Amphipods, 4. peroxide until visible oxidation ceased. One ml of hydro- chloric acid was added, and the samples were diluted to 25 ml with distilled water. A blank containing the reagents and water was prepared as a control in each digestion. Analysis for silver, cadmium, copper, iron, manganese, nickel, lead, and zinc was carried out on a Perkin-Elmer atomic absorp- tion spectrophotometer model 303. Laboratory standards were run along with each series of tests to calibrate the absorp tion scale. As there was no correction for background noise, values up to 2% absorption were discarded due to possible inaccuracy. A sample of ethyl acetate was analyzed as a control for fly specimens. It proved to have no trace metals of detectable amounts. RESULTS AND DISCUSSION Zinc, Iron, Copper and Cadmium: Beach flies showed consis- tently higher levels of Zn, Fe, Cu and Cd than did amphipods (figure 2). For the first tiwoe metals this relationship is anticipated by former research on insects and crustacea (Bowen, 1966). Unusually high concentrations (up to 240.0 ppm) of iron on the Hopkins Marine Station back beach may be related to scrap metal from the Monterey Boat Works. Large pieces of rusting iron are buried in the sand from surface level to two feet in depth. These are covered by water at high tide. Runoff from Cannery Row's remaining industries and restaurants may also circulate metals to this beach. In addition, erosion of the adjacent loosely-packed soil and air-borne dust could contribute iron to this beach. Elevated iron levels (as high as 298.1 ppm) near the Monterey outfall seem not to be due to especially high metal levels on the Metals in Dipterans and Amphipods, 5. beach itself (Koski, 1972), and may reflect iron-rich wrack, Copper is important as a respiratory pigment in arthropod blood, and Bowen (1966) suggests that flies and amphipods contain an equal amount of this metal, 50 ppm. My results fall short of this figure except at Hopkins back beach where copper may enter the ecosystem from boat paint intended to leak the element to discourage fouling by marine animals. Zinc, iron and copper are all essential to living organisms as constituents of metalloenzymes and proteins. Cadmium levels reported by Bowen (1966) indicate too little of the metal for detection in insects and only 0.15 ppm in crustacea. Warnick and Bell (1969) found that cadmium was acutely toxic to fresh water insects in concentrations of 0.016 to 0.064 ppm. In light of these figures, the beach arthropods showed very high (up to 149.7) levels of this metal, suggesting a local source of contamination. Lady bugs, which are predaceous terrestrial insects and swarm the beaches following hibernation (Borror, 1964), contained no detectable cadmium. This indicates that the metal's input may be largely marine despite its low (0.05 microgram/liter) level in "normal" sea water (Riley and Chester, 1971). Pro teins containing cadmium have been found in several animals (Vinogradov, 1953; Kagi and Vallee, 1961), but the metal is considered toxic due to its ability to replace zinc in en- zymes. Nilsson (1970) has compiled a list of the 20 known toxic effects of cadmium, demonstrating that the metal is a very wide-spectrum toxin. Manganese: Manganese was low in all beach arthropods tested (less than 10 ppm). Flies were slightly higher than hoppers at each site, but not to the extent reported by Bowen (1966) - a five-to-one ratio. The lady bugs had higher Mn content (24.8 ppm) than the beach dwellers. This may be due to very high concentrations in land plants - up to 630 ppm (Bertrand and Silberstein, 1954) - or to accumulation in the gut walls Metals in Dipterans and Amphipods, 6. (Bowen, 1950). High levels of this metal are moderately toxic, but the element is essential in trace amounts for activating enzymes and as a protein constituent. Lead, Nickel and Silver: Lead, nickel and silver occur in truly trace amounts in hoppers and flies. The recorded levels are subject to inaccuracy because of background noise and difficulty in chart reading. Despite these limit- ations, it is clear that amphipods concentrate more lead than do the beach insects. This may reflect the 'mineral armor" of calcium salts that cover the crustaceans since lead accumulates in calcareous tissue. The hoppers' lead level is up to thirty times the amount found in crustacea from Bowen's (1966) summary, indicating possible local pol- lution. As yet, no biological function is known for lead. It is a cumulative poison in animals as it may inhibit protein and gene synthesis, cellular oxidations, and other essential functions (Underwood, 1971). Both silver and nickel, which may be highly toxic in large amounts, are barely detectable in beach hoppers and flies with the techniques of analysis I employed. Because they are so scarce, it is impossible to define any major trends or comparisons in insects and amphipods. Higher trace element levels in flies than in beach amphipods may have several causes. From my own observations in the field and lab and those of Remmert (1964), it is clear that both hoppers and flies prefer the same food - brown algae (in Monterey, Macrocystis pyrifera). Secondary foods of the two animals differ, however. Flies are attracted to car- rion and may eat bacteria off the wrack rather than the sea- weed itself. Borror (1964) states that coelopid flies feed on flowers near the beach, although I did not find any evi- dence of this practice at my test sites. The Orchestoidea species will eat the dead of their own populations but pre- Metals in Dipterans and Amphipods, 7. fer cardboard and chewable trash to the bodies of fish and birds (Bowers, 1964). In addition, the animals' habitats vary. Hoppers constitute a stable and non-migratory pop- ulation on the beach. They burrow in the sand during the day, occasionallyhbeing covered by a high tide, and search for food in a local area at night. The ecology of marine flies is not as clearly understood, but it is obvious that these insects have a wider range of movement than the amphipods. Flies invade a beach following the deposition of wrack and may live inside the rotting seaweed or in dry holdfasts. Their stay is temporary, and Cole (1965) believes that Coelopa may have migratory flights. Whether the flies exploit ter restrial food sources during some period of their lives is not known. A final reason why metal levels may be higher in flies than in beach hoppers is a biochemical one. Under- wood (1971) reminds us that knowing the concentration of a metal is not meaningful unless its interaction with other elements is also understood. The insect's absorption of metals through the intestine and tracheole wall (Goodwin, 1965) may exceed that of the amphipod. Metabolic pathways could also be sufficiently different in the two animals to cause consistent variations in metal levels. A comparison of larval and adult coelopid flies and of old and young beach hoppers is shown in figure 3. Lower metal levels in the larvae for all elements but Mn may be due to their shorter lives, less varied diets (they are physically limited to the decaying kelp in which they are scavengers, while the adults range over the entire beach), or juvenile set of enzymes and hormones. Bowen (1950) found that Mn accumulated in juvenile wasps until pupation, at which time levels dropped.. His finding may apply as well to the dipterans I tested. In contrast, the adult and juvenile hoppers were very similar in trace metal levels. This is probably because the two age groups share a habitat, food source, and metabolic complement. Metals in Dipterans and Amphipods, 8. Variation in trace element levels onoone beach would be expected over time due to chance importation of actual metal or metal-rich food, terrestrial rumoff, rainfall, etc. The results of a day-to-day study of the Hopkins back beach hopper, 0. corniculata, are summarized in figure 4. Iron was found to fluctuate dramatically over the time period tested (variations up to 200 ppm). This may represent var- iations in leaching caused by high tides covering the beach's scrap iron, changes in food source, orrdust contamination. Copper, lead and zinc fluctuated moderately over time, while cadmium, manganese, nickel, and silver showed stable levels. Each metal varied independently. The range of fluctuation in Fe, Zn, Cu, and Pb is significant enough to justify studies over time rather than single day sampling for these metals on a particular beach. The results throw doubt on data from single collections, especially in pollution studies. Variation in metal levels due to species differences was studied for the beach flies, Coelopa vanduzeei and Fucellia rufitibia, re collected from the same wrack beds. Over the Monterey Peninsula, no significant difference in elementary composition was noted. A comparison between the two beach hopper species was not possible because the animals did not occur sympatrically in any of my collection sites. It is of interest that the beach "visitors" - the flies- showed higher levels of all major metals than the stationary amphipods. Elevated cadmium levels are particularly un- expected and suggest that contamination of a possibly mar- ine origin has more impact of the terrestrial ecosystem than was previously suspected. Metal analyses of other terrestrial animals that find food on the beach would be an important follow-up to this study. No fewer than seven species of birds, only two of which are considered shore dwellers, have been observed to eat fly larvae from the beach wrack (Baldridge, 1972). Glynn's stomach analyses of Metals in Dipterans and Amphipods, 9. black turnstones and gulls in 1965 showed that both of these scavengers consume intertidal insects. In addition, an at- tempt to track down the source of cadmium pollution in Mon- terey Bay and to determine the metal's physiological effect on local dipterans and amphipods would be of interest. ACKNOWLEDGMENT My thanks to Dr. John Martin for his theoretical and technical advice. Metals in Dipterans and Amphipods, 10. FIGURE CAPTIONS Collection sites on the Monterey Peninsula. Figure 1: A. Del Monte beach B. Hopkins Marine Station back beach C. Hopkins Marine Station front beach D. Carmel beach Metal levels in ppm dry weight for dipterans Figure 2: and amphipods at four locations; "nd" indic- ates that metal was not detectable. Comparison of metal levels in juveniles and Figure 3: adults.by ppm dry weight. Flies and larvae from Carmel; hoppers from Hopkins back beach. Variation in metal concentration (ppm dry Figure 4: weight) with time. Continuous slope between sampling points does not imply constant levels. Metals in Dipterans and Amphipods, 11 ewoge ete otworks ourist A R po e Row GONTE AEN TrmeRive FIGURE 1 Metals in Dipterans and Amphipods, 12. Os0 O Site FIGURE 2 Amphipod pte p Metals in Dipterans and Amphipods, 13. FIGURE 3 Metals in Dipterans and Amphipods, 14. FIGURE 4 Metals in Dipterans and Amphipods, 15. LITERATURE CITED Baldridge, Alan, personal communication, 1972. Bertrand, G., Silberstein, L., "Sur la teneur en manganese des phanerogames," Ann. Inst. Pasteur, 86 (3): 370-371, 1954. Borror, Donald J, DeLong, Dwight M., An Introduction to the Study of Insects, Holt, Rinehart and Winston, New York, 1964. Bowen, H.J.M., Trace Elements in Biochemistry, Academic Press, New York, 1966. Bowen, V.T., "Manganese metabolism of social vespidae! J. Exp. Zool., 115: 175-205, 1950. Bowers, Darl E., The natural history of two beach hoppers of the genus Orchestoidea (crustacea: amphipoda) with reference to their complemental distribution," Ecology, 45 (4): 677 - 696, 1964. Celsus, cited by Vinogradov, 1953. Cole, Frank R., The Flies of Western North America, Uni- versity of California Press, Berkeley, 1969. Glynn, Peter W., "Community composition, structure, and interrelationships in the marine intertidal Endocladia muricata - Balanus glandula association in Monterey Bay, California," Beaufortia, 12 (148): 1 - 198, 1965. Netals in Dipterans and Amphipods, 16. 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Stamm, Maria, "Estudio sobre bioquimica de insectos," Rev. Espan. Fisiol., 11 (1): 63-81, 1958. Metals in Dipterans and Amphipods, 17. Underwood, E.J., Trace Elements in Human and Animal Nut- rition, Academic Press, New York, 1971. Vinogradov, A.P., The Elementary Chemical Composition of Marine Organisms, Yale University Press, New Haven, 1953. Warnick, Stephen L., Bell, Henry L., "The acute toxicity of some heavy metals to different species of aquatic insects,' J. Water Pollution Control Federation, 41 (2 Pt. 1): 280- 284, 1969.