Trace Element and Biotic Changes Following a ... - Science Direct

Volume21/Number 3/March 1990 Marine Polhttion Bulletin, Volume 21, No. 3, pp. 131-137, 1990. Printed m Great Britain.

0025-326X/90 $3.00+0.00 © 1990 PergamonPressplc

Trace Element and Biotic Changes Following a Simulated Oil Spill on a Mudflat in Port Valdez, Alaska H. M. FEDER, A. S. NAIDU and A. J. PAUL

Institute of Marine Science, University of Alaska Fairbanks, Fairbanks, Alaska 99775-1080, USA

A mudflat in Port Valdez, Alaska, was examined to determine effects of experimental additions of Prudhoe Bay crude oil on metal chemistry and harpacticoid copepod abundance. Hydrocarbon concentrations were at background levels 30 days after final addition of oil. The short residence time of oil added to sediments is attributable to physical removal of oil by tides, low sediment permeability, and low affinity of hydrocarbons for periglacial clay surfaces. Elemental concentrations, except Si, were lower in oiled than in unoiled sediments. Elemental depletion in oil-impacted sediments is attributable to mobilization of metals from oxide/hydroxide sediment phases or to desorption from clay due to lowering of Eh-pH of sediments subsequent to oil addition. In oiled sediments, abundance of the harpacticoid copepods Harpacticus uniremis, Halectinosoma gothiceps, and Heterolaophonte sp. was similar to or higher than values within unoiled plots. The reasons for lack of deleterious effects of oil on copepods in Port Valdez are not yet understood.

reviews (Wolfe, 1977; Malins, 1977; Jordon & Payne, 1980; National Academy of Science, 1985; Quinn, 1988). This paper examines the effects on element chemistry and meiofaunal copepods following simulated spills of Prudhoe Bay crude oil on a mudflat in the summer of 1974 in Port Valdez, three years prior to operation of the marine terminal. Methods

Study site The site selected (Fig. 1) is influenced by a tidal range of 6 m and consists of poorly sorted silty clay with 0.1% or less organic carbon (Hood et al., 1973; Naidu et al., 1978). The surficial 3 cm sediments are oxygenated. Summer bacterial counts are low with a density peak in August (Norrell & Johnston, 1976). Macroalgae never occur at the study site. Meiofauna is restricted primarily to the upper 3 cm of sediment (Jewett & Feder, 1977; Feder & Paul, 1980). The Port Valdez environment is discussed in Shaw & Hameedi (1988).

Sampling scheme Port Valdez, a fjord in Prince William Sound (Fig. 1), is the terminus for a pipeline transporting crude oil from Prudhoe Bay, Alaska, to the sea. Tankers loading there contain either oil-contaminated ballast water or crude oil (Colonell, 1980; Shaw & Hameedi, 1988). A few limited spills of crude oil (up to 500 barrels) and untreated ballast water (up to 5680 1.) have occurred, and oil was deposited intertidally (Alaska Dept. of Envir. Conservat., In litt.; Rucker, 1983; Feder & BrysonSchwafel, 1988). It is assumed that spills will continue to pose a potential danger to intertidal organisms there. For example, reproductive biology and recruitment of mussels, Mytihts edulis, and acorn barnacles, Balanus balanoides, were affected after spills (Feder et al., 1983; Rucker, 1983; Feder & Shaw, 1986; Feder & Bryson-Schwafel, 1988). Further, a recent (March, 1989) major oil spill in Prince William Sound near Port Valdez emphasizes that the potential for spills is always present wherever oil tankers operate. Environmental concerns about oil spills are discussed in a number of

A mid-tide site (0.0 m) was occupied at Island Flats (Fig. 1). On two occasions, prior to adding oil, fifteen sediment cores were collected. An ANOVA determined that concentrations of the copepods Harpacticus

uniremis, Halectinosoma gothiceps and Heterolaophonte sp. were not significantly different between cores. Thus, it was assumed that a relatively homogeneous copepod distribution existed. In addition, it was assumed throughout our experiment that there were no largescale excursions of copepods from the sediment into the overlying water column at high tide. Such excursions are known to occur elsewhere (e.g., in Japan: Ito, 1971). However, harpacticoid copepods in Port Valdez are intolerant of low salinities and would rarely be expected to move into the water column in summer (when our experiments were carried out) where salinities may be as low as 1%o. Salinity of interstitial water during summer in Port Valdez is always higher than the overlying tidal waters, often by a factor of at least two (Feder et al., 1976). Additional cores were collected for analysis of 131

Marine Pollution Bulletin

clay mineralogy and chemistry of sediments prior to oil addition. Glass rings, 3.5 cm high with a radius of 7.3 cm, were placed on the shore at low tide. On 19 and 20 June, the rings were filled with seawater and 0.25 ml of Prudhoe Bay crude oil (equivalent to 500 ppm) added to 30 rings, 0.50 ml (1000 ppm) to an additional 30 rings, and 1.0 ml (2000 ppm) to another 30 rings. Twenty rings served as unoiled controls. At the next low-tide series, 20 cores (3.0 cm 2) were taken from each of four rings at each oil concentration for copepod abundance estimations. Core contents were preserved in formalin. Sampled rings were removed after each collection. The remaining rings were subjected to oil as above on 3-7 July, 20-24 July, 1-5 August, and 16-20 August. The same sampling procedures were repeated throughout the experiment, with a final collection made 15 September. Additional rings were subjected to oil at 250 ppm (0.1 ml) on each of the above dates. However, copepods were only collected at ;46"~0'

146040 ,

the end of the experiment. The latter oil additions examined the long-range effect of low oil concentrations. Sediments were collected from rings exposed to oil at various concentrations and periods of time to assess the effect of oil on concentrations of certain chemical elements and petroleum hydrocarbons.

Laboratou Analysis Table 1 lists parameters analysed in sediments, and analytical methods and instrumentation used. Precision of elemental analyses was within 5 and 10%, respectively, for total elements and leachates. Accuracy of total elemental analysis was checked against USGS Standards G-2 and AGV-1, and results were within 5% of reported average values (Flanagan, 1969). Hydrocarbon levels in sediments were either taken or extrapolated from Shaw et al. (1977), who conducted oil studies simultaneously on an adjacent study site. Meiofaunal samples were washed through a 64 ~tm - - -1 4-6-0-3 0-

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Method/instrument used

Reference

Clay mineralogy

X-ray diffraction; Rigaku Geigerflex XRD unit

Naidu & Mowatt, 1983

Si, AI, Fe, Mn, Ti, Na, K, Mg, and Ca in total sediment

LiBO 2 fusion, followed by HCI dissolution; Beckman Model V DC plasma unit

Medlin et aL, 1969

Zn, Cu, Ni, Co, and Pb in total sediment

HF-HNO 3 digestion; atomic absorption spectrometer, Perkin-Elmer Model 603 Sediment treated with 1 M hydroxylamine hydrochloride in 25% acetic acid; AAS with HGA graphite furnace

Rader & Grimaldi, 1961; Sweeney & Naidu, 1989 Chester & Hughes, 1967

Fe, Mn, Cu, Co, Ni, and Zn in sediment leachate

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screen. Three harpacticoid species (Harpacticus uniremis, Halectinosoma gothiceps, Heterolaophonte sp.) were counted. The within group variance for each species, in the first collection, was tested with an ANOVA. No significant difference was observed for population estimates from individual rings. Therefore, samples from each collection date were treated as a single group of 80 oiled cores rather than four subgroups of 20 cores each. Similarly, unoiled control samples were also considered as a single collection of 80 cores. Abundance of copepods and elements in oiled and unoiled cores were compared with a Student t test. Results

Hydrocarbon Levels in Sediment As water drained from oiled rings, a slick settled on the sediment and remained visible for up to three days. Total hydrocarbons in surface sediments prior to oil application ranged between 6-7 gg" g-i dry sediment. Oil in the upper 1 cm of sediment (after five successive additions at a single tide series) measured over a 44 day period varied from 5-76 and 420-3900 gg. g-~ of sediment for additions of 250 and 1000 ppm, respectively. Estimated maximum values for oil in sediment were 380, 760, 19 500, and 39 000 ~g- g-i for additions of 250, 500, 1000, and 2000 ppm added, respectively. Thirty days after final oil addition, hydrocarbon concentrations measured in the upper 3 cm of sediment were at background levels. Sediment Composition Clay minerals of control and oil-impacted sediments were similar and consisted almost entirely of chlorite (42-60%; mean of 49%) and illite (40-58%; mean of 46%). Concentrations of trace elements showed differences (P=0.95) between control and oiled sediments

(Table 2). Concentrations of all elements were lower, with the exception of Si, in oiled sediments, Concentrations of Si were higher in oiled sediments.

Harpacticoid Copepods Abundance values of three species of copepods examined within the sediment, after addition of oil at all concentrations (250, 500, 1000, and 2000 ppm), were generally similar to or higher than that of the unoiled controls (Figs 2-4). The greatest increases in abundance, relative to the controls, occurred within Halectinosoma gothiceps, the only reproductively-active species during the experiment (Feder et al., 1976; Jewett & Feder, 1977). Discussion

Residence time of crude oil added to sediments at Island Flats was relatively short based on hydrocarbon analysis (Shaw et al., 1977). This observation was substantiated by lack of increase in organic carbon in sediments prior and subsequent to exposure of these sediments to various dosages of oil (Feder et al., 1976; Naidu et al., 1978). Some possible reasons for the short residence time or retention capability for stranded oil on sediments in Port Valdez are: 1. physical removal of oil by tides; 2. low sediment permeability of glacial flour (Naidu et al., 1978; Malinky & Shaw, 1979); 3. low affinity of hydrocarbons to clay constituents of this glacial flour. The bulk of the crude oil hydrocarbons, which are non-polar and hydrophobic, generally do not bond with natural clay surfaces unless suitable intermediary material with surfactant properties is initially 3C • . . . . . ...... .......

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133

Marine Pollution Bulletin

adsorbed onto the clays to render the clay surfaces oleophilic (van Olphen, 1977). It seems probable that in Port Valdez sediments suitable natural surfactants do not occur, especially organic molecules, on clays in the required critical concentrations. Thus it is suggested, based on investigations of Karickhoff et al. (1979) and Schwarzenbach & Westall (1981), that a predominant factor that could impede sorption of petroleum hydrocarbons onto sediments in Port Valdez is a low concentration of natural organic surfactants on sediment particles, as evidenced by the very low natural concentrations of organic carbon (0.1%) in sediments there (Naidu et al., 1978). Additionally, the periglacial clays of Port Valdez would be expected to have little propensity to fix hydrocarbons as interlayer materials since such clay minerals typically have very low cation exchange capacities (Naidu & Mowatt, 1983). 4. Ingestion of oil by biota. Oil uptake by calanoids is reported (Conover, 1971; Parker et al., 1971), but no data are available for harpacticoids. However, meiofaunal abundance is sufficiently high in Port Valdez sediments (Feder & Paul, 1980) to make the latter process important if oil ingestion occurred. Concentrations of all elements decreased in oiled sediments, except for Si. Variation in the clay mineral •

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assemblage is probably not a factor for this elemental decrease because all sediments had similar relative abundances of clay mineral types. Likewise, influence of texture on the overall chemistry of Valdez sediments does not seem plausible, as suggested by a lack of difference in concentrations of Cu, Zn and Ni in control samples of silty-clay and sandy-silty-clay composition (Naidu et al., 1978). Presumably, this lack of chemical difference in sediments of different grain sizes is explained by the peculiar mode of origin of the deposits, which are essentially sediment flours derived from mechanical weathering of rocks under glacial conditions (Naidu & Mowatt, 1983). Perhaps depletion of metals in the oiled sediments results from partial mobilization in solution as a result of change in natural oxidation-reduction potential (Eh), and, to some extent, acid-base (pH) relationships at the oiled sediment surface. It is conceivable that with successive additions of oil to sediment, there would be a lowering of Eh and pH (Stumm & Morgan, 1971; Berner, 1971) resulting from oxidative decomposition of hydrocarbons within the oxic sediment and consequent generation of weak acids. After lowering of Eh at the oiled sediment surface, the proportions of Fe and Mn present as oxides and hydroxides, as well as metals coprecipitated with these phases, will be reduced and solubilized. Some release of metals will also be expected from the adsorbed/exchange sites of clay minerals upon a lowering of sediment pH by substitution of H + for 0 r~

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Fig. 4 Trends in abundance (mean of 80 cores/sampling period) of Heterolaophonte sp. during an oil-addition experiment on Island Flats, Port Valdez. Numbers above the vertical arrows represent the days after oiling at which time core samples were taken (see Methods). Samples at the 250 ppm addition site were only collected 90 days after the original oiling. All values marked * are significantly different from the controls at P = 0.99.

Volume 21/Number 3/March 1990

cations in the minerals (Robinson, 1962). Apparently the bulk of the metals in Port Valdez sediments are partitioned into aluminosilicates and oxyhydroxides and not in carbonates, as suggested by the extremely low (about 1%) carbonate content in the sediments (Feder et al., 1976). Once solubilized, metals could be readily removed from surficial sediments by tides. Although decrease in E h - p H after oil addition could not be verified in the field for the surficial (1-2 cm) sediments, a subsequent laboratory experiment designed for leaching metals from sediments with an acid-reducing agent substantiates the foregoing contentions. Data in Table 3 show the mean concentrations (p.g. g-a) of Fe, Mn, Co, Cu, Ni, and Zn mobilized into leachates from 1 gm of control sediments. Differences in average content of Mn, Co, Cu, Ni, and Zn between control and oil-impacted sediments were similar to those in leachates (Tables 2, 3). However, much less Fe was mobilized into the leachate. This suggests that most of the Fe is more tightly held in some discrete mineral phase and is not readily mobilized by the relatively mild acid-reducing leaching agent used in our experiments. The 4 - I 6 p.m grain sizes of Port Valdez sediments provide ample surface area for bacterial microcolonies (Dale, 1974). However, close packing of sediment particles (Naidu et al., 1978) reduces interstitial spaces through which nutrients or oil might be delivered to sediment-bound bacteria. Further, organic material (e.g. plant matter or oil) deposited on sediment is readily removed by tidal action (Feder & Bryson-Schwafel, 1988). Low bacterial metabolic activity (Q10=2.5: Norrell & Johnston, 1976), resulting from low air and water temperatures prevalent in the Port, as well as low retention of organics, preclude rapid bacterial utilization and digestion of organic material. Further, low bacterial counts and numbers of anaerobic sulfate reducers (Norrell & Johnston, 1976) support the conclusion that sediments in Port Valdez do not normally maintain even a modest microbial biomass and would not rapidly respond to an organic carbon source added to the surface following an oil spill. Nevertheless, it is possible, as observed by Pierce et al. (1975) for an estuarine beach elsewhere, that decomposition of oil by bacterial action may have occurred for a relatively short time soon after oil application to the sediment. They found an enrichment of hydrocarbon degrading bacteria within 4-16 days after an oil spill. However, in the experiments in Port Valdez by Norrell & Johnston (1976) the immediate response by hydrocarbon degrading bacteria could not be confirmed as their samples were always taken two weeks or more after oil addition to sediment. TABLE 3 Concentrations of metals in experimental hydroxylamine hydrochloride acetic acid leachates in Port Valdez control sediments. The values of Fe and Mn are in dry wt %; the rest are in ~tg • g-~ dry wc Sample No. VLDZ374-2 VLDZ374-3 VLDZ374-5 VLDZ374-10 VLDZ374-14 Mean

Fe

Mn

Co

Ni

Cu

Zn

0.348 0.338 0.377 0.344 0.402 0.362

0.0110 0.0115 0.0140 0.0110 0.0145 0.0124

10.0 9.5 11.5 9.5 10.0 10.0

15 16 17 16 16 16

25 30 28 26 25 27

28 26 27 25 29 27

Increased oxygen-consumption by sediments mixed with oil in vitro (Norrell & Johnston, 1976) suggests that Port Valdez bacteria can respond rapidly to organic enrichment under special circumstances. For example, in 1974 on a shore in Port Valdez (relatively remote from the experimental site), oil was leaking at depth from damaged fuel tanks buried by tsunamis generated by the 1964 earthquake (Feder et al., 1976; Feder & Bryson-Schwafel, 1988). This oil was diffusing through sediments to the surface. Bacterial numbers in these sediments in 1974 were higher than those measured on other beaches within the Port (Norrell & Johnston, 1976). Maintenance of copepod populations or increases in their abundance in Port Valdez sediments subjected to oil applications up to 39 × 103 ~g" g-1 dry sediment, is similar to findings of Fleeger & Chandler (1983). In the latter study, conducted on a Louisiana salt marsh with methods similar to those of the present study, meiofaunal abundance increased and no oil-induced decrease in nelnatode and harpacticoid numbers occurred after applications of south Louisiana crude oil up to 20.3 × 103 ~tg. g-1 dry sediment. Stacey & Marcotte (1987) examined the chronic effect of No. 2 fuel oil on harpacticoid copepods in an experimental mesocosm and found that the copepod E n h y d r o s o m a baruchi increased during the recovery period. Two other copepod species in that study did not show statistically discernible effects while two species were adversely affected by oil additions. Van Bernem (1982), after repeated addition of crude oil (Arabian light, Kuwait crude, and Iranian light) on a mud flat, found an increase in abundance of oligochaetes. Fricke et al. (1981) observed that one heavily oiled (crude and fuel oil) South African station had increased harpacticoid numbers compared with control sites. None of the above studies, however, determined why oil additions to sediment resulted in enhanced meiofaunal abundance. The increase in meiofaunal abundance described by Fricke et aL (1981), van Bernem (1982), Fleeger & Chandler (1983), Stacey & Marcotte (1987), and this paper is contrary to findings of Wormald (1976), Giere (1979), Boucher (1980), and Bonsdorf (1981), where copepod abundance declined after oil additions to sediment shores. However, a few studies show that nematodes are relatively insensitive to all but heavily oiled shores (Boucher, 1980; Bonsdorf, 1981; Fricke et al., 1981) and recover rapidly following population decline (Wormald, 1976; Giere, 1979). Laboratory experiments show a contradictory picture of effects of oil on copepods with toxic effects in some cases (Mironov, 1968; Nelson-Smith, 1972; Barnett & Kontogiannis, 1975; Ustach, 1977; Berman & Heinle, 1980; Frithsen et al., 1985) and high tolerance in others (Dalla Venezia & Fossato, 1977). Long-term monitoring of meiofaunal densities after the A m o c o Cadiz oil spill by Boucher (1985) suggests that the generalization that copepods are generally more sensitive to environmental stress than nematodes (e.g. Heip, 1980; Elmgren et al., 1983) can no longer be accepted as a general rule. Further, the relatively low spatial heterogeneity of harpacticoids (compared with nematodes) makes them 135

Marine Pollution Bulletin

particularly suitable for pollution monitoring (Heip, 1980). Lack of toxic effects of oil on copepods in Port Valdez is probably attributable to low permeability of sediments and rapid removal of relatively more toxic aromatic fractions by tidal waters. Reasons for increases in copepod abundance are not clear. Possible explanations include improved survivorship due to short-term availability of a new food resource (e.g. oil and associated bacteria), attraction to oil, or reduction in predation (Bell & Coull, 1978; Alongi et aL, 1983; Fleeger & Chandler, 1983). Boucher (1985) suggests that enhanced densities of meiofauna in oiled sediments within estuaries may reflect preadaptations to cope with new stresses typical of these environments. Additional studies on the ability of harpacticoid copepods to survive oil pollution are required to understand the results of existing investigations. The importance of such studies is obviously critical in the context of the importance of harpacticoid copepods as a food source for juvenile pink salmon (Oncorhynchus gorbuscha) in Prince William Sound (Urquart, 1979), the site of a recent major oil spill. This research was supported by Grant No. R800944-02-0 from the Environmental Protection Agency. The authors thank Judy McDonald, University of Alaska Fairbanks, for field assistance; Dr. R. Hamond, Melbourne University, for copepod identifications; the Marine Sorting Center, University of Alaska Fairbanks, for technical assistance; and Mike Sweeney for assistance in the metal leaching experiment. Prudhoe Bay crude oil was furnished by Ben Hilliker of the Alyeska Pipeline Service Company. Thanks are due to the two anonymous reviewers for their valuable comments. This is Institute of Marine Science Contribution No. 778.

Alongi, D. M., Boesch, D. F. & Diaz, R. J. (1983). Colonization of meiobenthos in oil-contaminated subtidal sands in the lower Chesapeake Bay. Mar. Biol. 72,325-335. Barnett, C. J. & Kontogiannis, J. E. (1975). The effect of crude oil fractionation on the survival of a tidepool copepod, Tigriopus californicus. Envir. Poll. 8, 45-54. Bell, S. S. & Coull, B. C. (1978). Field evidence that shrimp predation regulates meiofauna. Oecologia 35, 141-148. Berman, M. S. & Heinle, D. R. (1980). Modification of the feeding behavior of marine copepods by sublethal concentrations of wateraccommodated fuel oil. Mar. Biol. 56, 59-64. Berner, R. A. (1971). Principles of Chemical Sedimentology. McGrawHill, New York. Bonsdorf, E. (1981). The Antonio Gramsci oil spill. Impact on the littoral and benthic ecosystems. Mar. Pollut. Bull. 12,301-305. Boucher, G. (1980). Impact of Amoco Cadiz oil spill on intertidal and sublittoral meiofauna. Mar. Pollut. Bull, 11, 95-101. Boucher, G. (1985). Long term monitoring of meiofauna densities after the Amoco Cadiz oil spill. Mar. Pollut. Bull, 16,328-333. Chester, R. & Hughes, M. J. (1967). A chemical technique for the separation of ferromanganese minerals, carbonate minerals and adsorbed trace elements from pelagic sediments. Chem. Geol. 2, 249-262. Colonell, J. M. (Ed.) (1980). Port Valdez, Alaska: Environmental Studies 1976-1979. Occasional Publication No. 5, Inst. Mar. Sci., Univ. of Alaska Fairbanks. Conover, R. J. (1971). Some relations between zooplankton and bunker C oil in Chedabucto Bay following the wreck of the tanker Arrow. J. Fish. Res. Bd Can. 28, 1327-1330. Dale, N. G. (1974). Bacteria in intertidal sediments: factors related to their distribution. Limnol. Oceanogr. 19, 509-518. Dalla Venezia, L. & Fossato, V. U. (1977). Characteristics of suspensions of Kuwait oil and corexit 7684 and their short and long term effects on Tisbe bulbitosa (Copepoda, Harpacticoida). Mar. Biol. 4 2 , 2 3 3 237. Elmgren, R., Hansson, S., Larsson, U., Sundelin, B. & Boehm, P. D. (1983). The "Tsesis" oil spill--Acute and long-term impact on the benthos. Mar. Biol. 73, 51-65.

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Feder, H. M. & Bryson-Schwafel, B. (1988). The Intertidal Zone. In Environmental Management of Port Valdez, Alaska: Scientific Basis and Practical Results (D. G. Shaw & M. J. Hameedi, eds), pp. 117164. Springer-Verlag, New York. Feder, H. M. & Paul, A. J. (1980). Seasonal trends in meiofaunal abundance on two beaches in Port Valdez, Alaska. Syesis 13, 27-36. Feder, H. M. & Shaw, D. G. (1986). Environmental studies in Port Valdez, Alaska in 1985. Final Report to Alyeska Pipeline Service Co., Institute of Marine Science, University of Alaska. Feder, H. M., Cheek, L. M., Flanagan, P., Jewett, S., Johnson, M., Naidu, A. S., Norrell, S., Paul, A. J., Scarborough, A. & Shaw, D. (1976). The sediment ecosystem of Port Valdez and the effects of crude oil on this environment. Final report to the Environmental Protection Agency (U.S.), Rep. EPA600/3-76-086. Feder, H. M., Gosink, T. A., Naidu, A. S. & Shaw, D. G. (1983). Environmental studies in Port Valdez, Alaska, 1980-82. Final report to Alyeska Pipeline Service Co., Institute of Marine Science, University of Alaska, Fairbanks, 585 pp. Flanagan, F. J. (1969). U.S. Geological Survey Standards. II. First compilation of data for the new U.S.G.S. rocks. Geochem. Cosmochim. Acta 33, 81-120. Fleeger, J. W. & Chandler, G. T. (1983). Meiofauna responses to an experimental oil spill in a Louisiana salt marsh. Man Ecol. Prog. Ser. 11,257-264. Fricke, A. H., Henning, H. F.-O. & Orren. M. J. (1981). Relationship between oil pollution and psammolittoral meiofauna density of two South African beaches. Mar. Environ. Res. 5, 59-77. Frithsen, J. B.. Ehngren, R. & Rudnick, D. T. (1985). Responses of benthic meiofauna to long-term low-level additions of No. 2 fuel oil. Mar. Ecol. Prog. Ser. 23, 1-14. Giere, O. (1979). The impact of oil pollution on intertidal meiofauna. Field studies after the La Coruna-spill, May 1976. Cah. Biol. Mar. 20, 231-251. Heip, C. (1980). Meiobenthos as a tool in the assessment of marine environmental quality. Rapp. R. VB. Reun. Cons. [nt. Explor. Men 179, 182-187. Hood, D. W., Shiels, W. E. & Kelley, E. J. (Eds.) (1973). Environmental Studies of Port VaMez. Inst. Mar. Sci. Occas. Publ. No. 3, Univ. of Alaska, Fairbanks. ito, T. (1971). The biology of a harpactieoid copepod, Harpacticus uniremis Krryer. J. Fac. Sci. (Hokkaido Univ., Ser. VI, Zool.) 18, 235-255. Jewett, S. C. & Feder, H. M. (1977). Biology of the harpacticoid copepod, Harpacticus uniremis Kr6yer on Dayville Flats, Port Valdez, Alaska, Ophelia 16, 111-129. Jordan, R. E. & Payne, J. R. (1980). Fate and Weathering of Petroleum Spills in the Marine Environment: A Literature Review and Synopsis. Ann Arbor Science Pub. Inc., Ann Arbor, Michigan. Karickhoff, S. W., Brown, D. S. & Scott, T. A. (1979). Sorption of hydrophobic pollutants of natural sediments. Water Res. 13,241-246. Malinky, G. & Shaw, D. G. (1979). Modeling the associations of petroleum hydrocarbons and subarctic sediments. Proceedings of the 1979 Oil Conference (Prevention, Behavior, Control, Cleanup), March 1979, Los Angeles, Califorrfia, pp. 621-623. Malins, D. C. (1977). Effects of Petroleum on Arctic and Subarctic Marine Environments and Organisms. Academic Press, New York. Medlin, J. H., Suhr, N. H, & Bodkin, J. B. (1969). Atomic absorption analysis of silicates employing LiBO 2 fusiom Atom. Absorp. Newsletter 8, 25-29. Mironov, D. G. (1968). Hydrocarbon pollution of the sea and its influence on marine organisms. Helgolander Wiss. Meeresunters. 17, 335-339. Naidu, A. S. & Mowatt, T. C. (1983). Sources and dispersal patterns of clay minerals in surface sediments from the continental-shelf areas off Alaska. Geol. Soc. Amer. Bull. 94,841-854. Naidu, A. S., Feder, H. M. & Norrell, S. A. (1978). The effect of Prudhoe Bay crude oil on a tidal-flat ecosystem in Port Valdez, Alaska. Tenth Offshore Technology Conference, Houston, Texas, pp. 97-104. National Academy of Science (1985). Oil in the Sea: Inputs, Fates, and Effects. National Academy Press, Washington, D.C. Nelson-Smith, A. (1972). Oil Pollution and Marine Ecology. Paul Elek (Scientific Books) Ltd., London. Norrell, S. A. & Johnston, M. H. (1976). Effects of oil on microbial components of an intertidal silt-sediment ecosystem. In Assessment of the Arctic Marine Environment: Selected Topics (D. W. Hood & D. C. Burrell, eds), pp. 305-327. Occasional Publication No. 4, Institute of Marine Science, University of Alaska, Fairbanks. Parker, C. A., Freegarde, M. & Hatchard, C. G. (1971). The effect of some chemical and biological factors on the degradation of crude oil at sea. Water Pollution, Oil Instit. of Petroleum. Pierce, R. H., Cundell, A. M. & Traxler, R. W. (1975). Persistence and biodegradation of spilled residual fuel oil on an estuarine beach. Applied Microbiol. 20, 646-652.

Volume 21/Number 3/March 1990 Quinn, J. G. (1988). Sedimentation of Petroleum in the Marine Environment. Background Paper Prepared for the National Academy of Science, Petroleum in the Marine Environment. National Academy of Sciences, Washington, D.C. Rader, L. F. & Grimaldi, F. S. (196l). Chemical analysis for selected minor elements in Pierre Shale. U.S. Geological Survey Prof. Paper 391 -A. Robinson, B. P. (1962). Ion-exchange minerals and disposal of radioactive wastes--a survey of literature. Geol. Survey Water-Supply Paper 1616. US Govt. Printing Office, Washington, D.C. Rucker, T. L. (1983). The life history of the intertidal barnacle, Balanus balunoides (L.) in Port Valdez, Alaska. Thesis, University of Alaska, Fairbanks. Schwarzenbach, R. P. & Westall, J. (1981). Transport of nonpolar organic compounds from surface water to groundwater. Laboratory Sorption Studies. Environ. Sci. Technol. 15, 1360-1367. Shaw, D. G. & Hamcedi, M. J. (Eds) (1988). EnvironmentalManagement of Port Valdez. Alaska: Scientific Basis and Practical Results. SpringerVerlag, New York. Shaw, D. G., Cheek, L. M. & Paul, A. J. (1977). Uptake and release of petroleum by intertidal sediments at Port Valdez, Alaska. Estuar. Coast. Mar Sci. 5,429-436. Staccy, B. M. & Marcotte, B. M. (1987). Chronic effect of No. 2 fuel oil on population dynamics of harpacticoid copepods in experimental

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Marine Pollution Bulletin, Volume 21, No. 3, pp. 137-143, 1990. Printed in Grea~ Britain.

0025-326X/90 $3.00+0.00 © 1990 Pergamon Press plc

Mediterranean Pollution from a Ferro-nickel Smelter: Differential uptake of metals by some gastropods A NICOLAIDOU* and J. A. NOTT +

*Zoological Laboratory, University of Athens, Panepistimiopolis, GR-15784 Athens, Greece *Plymouth Marine Laboratory, Citadel Hill, Plymouth, Devon PLI 2PB, UK

Cadmium, Co, Cr, Cu, Fe, Mn, Ni, and Zn were measured by atomic absorption spectroscopy in the digestive gland of the marine gastropods Cerithium vulgatum, Monodonta spp., Murex trunculus, Conus mediterraneus, and Patella coerulea, sampled during different seasons at four sites near a ferro-nickel smelting plant and two control sites on the east coast of Greece. Near the smelter there were higher concentrations of all metals in Cerithium (except Cu) and Murex, and of Ni and Co in Monodonta, compared with the control sites, which indicated that the plant contaminated the environment. The animals from the contaminated area showed marked differences in concentrations which were associated both with the genera and the sites, while there were no consistent seasonal variations.

This plant processes locally-mined laterite and imported coal. It produces ferro-nickel granules and ingots together with metalliferous slag. Spillages and dust derived from these materials enter the marine environment. A preliminary analysis of plants, animals and

At Larymna, in the Northern Evoikos Gulf, there is a small bay which is dominated by a ferro-nickel smelter.

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1 Maps showing the location of Larymna on the east coast of

Greece and the position of the sampling sites and smelter in the bay.

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