Some effects of certain metals on development and mortality within the moult cycle of crangon crangon (L.)

Crangon crangon (L.) (Crustacea: Decapoda) were subjected to three metals (Cd, Cu and Zn) at respective concentrations (0·35, 1·6 and 14·4mg/litre) that would induce 50% mortality in 5–6 days. Significantly different (P < 0·05) rates of mortality occurred in the three groups, although their ET₅₀'s were almost identical. No moultstage-dependent mortality was observed for Cd, but in Cu and Zn the post-moult stages (A and B) were more susceptible than either the intermoult (C_a and C_b) or premoult (D₀–D₄) stages.No significant (P> 0·05) sex- or size-dependent mortality was evident at the tested concentrations of these metals.Feeding and ecdysis were inhibited in all metals after day 3 and development from one moult-stage to the next was greatly reduced in Cd.Possible modes of toxicity have been discussed in terms of the physiological condition inferred from the moult-stage at the time of death.     

Cadmium in Mytilus spp.: Worldwide survey and relationship between seawater and mussel content

A worldwide literature survey of data on cadmium concentration in the soft tissue of the mussel, Mytilus spp., from 591 stations is presented. These stations are from 13 regions. Geometric means for the regions vary from 0·6 to 3·3 μg g⁻¹ (dry weight) for the Barents Sea and the Northeastern Pacific coast, respectively.The averages of seven of these regions, for which reliable cadmium concentrations in seawater were available, were used to calculate a relationship between cadmium concentrations in seawater and mussel soft tissue. The relationship was highly significant: (Cd) mussel (μg g⁻¹, dry weight) = 0·074 (Cd) water (ng litre⁻¹) + 0·39 (P ≤ 0·0005).This model has been successfully applied in the context of the contamination of the Gironde estuary (France). It can also be used to define a water quality criterion for mussel maturing parks consistent with the quality criterion defined for shellfish for human consumption.     

Relationship between metallothionein, copper and zinc in perch (Perca fluviatilis) environmentally exposed to heavy metals

Hepatic levels of Cu, Zn and metallothionein (MT) in perch, caught in a Cu/Zn gradient from a brassworks, reflected the water concentration of Cu (1·0–9·4 ppb) and Zn (0·56–59 ppb). Significant correlations were found between hepatic Cu and MT levels (r = 0·72), and between Zn and MT levels (r = 0·69). There was an increase of the amount of Cu and Zn in the cytosolic fraction of the liver with increased hepatic levels of the metals. When liver samples. from perch caught at the most contaminated location, were run on a gel filtration column (Sephadex G-75) 78% of the cytosolic Cu and 24% of the Zn in the cytosol eluted together with MT.     

Metal fluxes through the Strait of Gibraltar: the influence of the Tinto and Odiel rivers (SW Spain)

A large set of new data concerning dissolved metal concentrations has been acquired in the Gulf of Cadiz and in the Strait of Gibraltar from 1996 to 1999. These data, associated with models (hydrodynamic, tracer advection–dispersion and mixing), have been used to assess the influence of rivers draining the South Iberian Pyrite Belt on the Gulf of Cadiz and on the Atlantic inflow in the Strait of Gibraltar.Metal concentrations in surface waters from the Gulf of Cadiz are maximal near the mouth of the Tinto/Odiel rivers with values exceeding 50 nmol/kg (Mn), 5 nmol/kg (Ni), 30 nmol/kg (Cu), 100 nmol/kg (Zn), 0.9 nmol/kg (Cd) and 45 nmol/kg (As). From the Tinto/Odiel river, a plume of contamination follows the coast in the direction of the Strait of Gibraltar. The computation of a tracer advection–dispersion model confirms that the coastal currents carry the metals discharged from the Tinto and Odiel to the Strait of Gibraltar.From temperature–salinity and metal–salinity plots, four water masses can be recognised in the Gulf of Cadiz and in the Strait of Gibraltar: North Atlantic Surface Water (NASW), North Atlantic Central Water (NACW) and metal-enriched Spanish Shelf Waters from the Gulf of Cadiz (SSW). The Mediterranean Outflow Water (MOW) is also clearly seen at depths greater than 300 m.The chemical characteristics of these various water masses have been used in a mixing model to evaluate their relative contribution to the Atlantic inflow through the Strait of Gibraltar. These contributions are seasonally variable. In June 1997, the contribution was: 80±20%, 5±5% and 15±10% for NASW, NACW and SSW, respectively. In September, the SSW contribution was apparently negligible.Finally, these relative contributions allow the evaluation of the metal fluxes in the Strait of Gibraltar. The presence of SSW in the Strait increases the metal flux to the Mediterranean Sea by a factor of 2.3 (Cu), 2.4 (Cd), 3 (Zn) and 7 (Mn). It does not modify significantly As and Ni fluxes.     

Trace metal fronts in Scottish coastal waters

Dissolved cadmium and copper concentrations have been determined in 76 surface water samples in coastal and ocean waters around Scotland by anodic stripping voltammetry (ASV). A trace metal/salinity ‘front’ is observed to the west, north and north-east of Scotland separating high salinity ocean water (>35 × 10⁻³) with low concentrations of dissolved Cd and Cu from lower salinity (<35 × 10⁻³) coastal water containing higher concentrations of Cd and Cu. Mean Cd concentrations in ocean and coastal waters are 7 ng dm⁻³ (0·06 n ) and 11 ng dm⁻³ (0·10 n ) respectively; for Cu the respective levels are 60 ng dm⁻³ (0·95 n ) and 170 ng dm⁻³ (2·68 n ). The observed distribution is attributed principally to freshwater runoff and the advection of contaminated Irish Sea water into the study area.     

Cadmium accumulation by the blue crab, callinectes sapidus: Involvement of hemocyanin and characterization of cadmium-binding proteins

The accumulation of cadmium from seawater by the blue crab, Callinectes sapidus, was studied as a function of metal concentration and exposure time, with special emphasis on cadmium-binding proteins. Cadmium was found, in decreasing order of magnitude, in gills, digestive gland and hemolymph. When exposed to 0·5 ppm cadmium for 2–24h, virtually all of the cadmium in the cytosolic fraction of the gill was associated with a low molecular weight (LMW) cadmium-binding protein (MW 8000). However, after 48h of exposure only 50% of the cadmium in the cytosol was bound to this protein. The rest wasfound to be associated with proteins of a molecular weight of 300 000 and 60 000. This pattern of cadmium distribution did not change over a 12-day depuration period. Similar results were obtained upon exposure to 0·1 ppm cadmium. The pattern of cadmium accumulation in the cytosolic fraction of the digestive gland was in marked contrast to that observed for the gill. Initially, the cadmium was distributed over three low molecular weight fractions. During depuration the distribution of cadmium changed and all of the metal became bound to a low molecular weight protein (MW 9000). The cadmium concentrations in the gill and digestive gland remained essentially constant during depuration (12 days). The LMW cadmium-binding proteins were purified by a combination of gelpermeation and ion-exchange chromatography. Their molecular weight, spectral properties and amino acid composition are characteristic of the vertebrate metallothioneins. During exposure to cadmium the metal rapidly appeared in the hemolymph, mainly associated with hemocyanin. During depuration cadmium was transferred from the hemolymph to the digestive gland, demonstrating that hemocyanin acts as a carrier in trace metal transport.     

Interactions of cadmium with sulfhydryl-containing compounds in striped mullet (mugil cephalus L.)

Interactions between cadmium and sulfhydryl-containing compounds in striped mullet, Mugil cephalus, were examined. Exposure to 10 mg Cd/liter for up to 6 weeks caused an increase in the acid-soluble thiol (AST) content of the liver. Although the AST concentration was elevated at 1·4 weeks, increases in the glutathione and cysteine contents were not observed until after 4 weeks of exposure. Homogenates of livers were fractionated on a Sephadex G-75 column. A homogenate of livers of mullet injected with ¹⁰⁹Cd 2 days prior to sampling had an elution profile for thiols similar to controls. After 3 weeks exposure to 10 mg Cd/liter the 9400 MW thiol peak increased 3·6-fold and the peak with the same retention volume as glutathione increased 4·3-fold. Greater than 70% of the thiols in these two peaks were acid-soluble. In both experiments, almost all the cadmium was associated with the 9400 MW peak. The ratio in the 9400 MW peak declined from 14·1 (controls) to 3·2 after 3 weeks exposure. No cadmium was associated with glutathione in the bile.     

Chronic sublethal effects of the water soluble fractions of no. 2 fuel oils on the marine isopod, Sphaeroma quadridentatum

Two series of experiments were carried out to assess the long-term effects of the water soluble fractions (WSF) of fuel oils on the marine isopod, Sphaeroma quadridentatum. In one experiment, juvenile isopods (one month old) were exposed to sublethal concentrations (0·1% to 15% WSF) of a fuel oil (Baytown, Exxon) at room temperatures of 24 ± 1–6°C for nine months. These isopods survived to maturity and reproduced. However, growth rate was adversely affected at concentration ≥ 3% WSF and fecundity was depressed at concentrations ≥ 1% WSF. Survival of offspring in clean seawater was dependent to a large extent on the history of the previous generation. Offspring from groups exposed to ≥ 1% WSF experienced high mortality (> 70% within five weeks) even in clean seawater. This may imply that a population of Sphaeroma exposed to WSF as low as 0·2 ppm may eventually disappear, although animals can grow to maturity and reproduce at concentrations < 3 ppm.In another experiment, adult Sphaeroma (three months old) were subjected to the WSFs of four fuel oils (Baton Rouge, Baytown, Montana and New Jersey) for one month. Fecundity was depressed at a concentration > 15% WSF, regardless of the kind of fuel oil. On the other hand, the number of young produced bythe surviving females varied with the type of fuel oil for the same level of WSF. This may be attributed to different relative amounts of toxic components present in the WSF.     

Response of hematological and biochemical parameters to heavy metal exposure: Implications in environmental monitoring

The use of selected hematological and biochemical parameters as indicators of metal exposure in aquatic organisms was evaluated. The hematological and biochemical parameters examined include glucose, hematocrit and aminotransferase levels in golden shiners exposed to cadmium. Cadmium exposure produced significant alterations in the levels of glucose, aspartate aminotransferase and alanine aminotransferase; however, hematocrit was not altered by exposure to cadmium. In addition, the comparative activity of Na/K adenosine triphosphatase (ATPase) was evaluated in the fathead minnow, golden shiner and bluegill sunfish. Basal Na/K ATPase activity was lowest in golden shiner (1·01 μmol Pi/mg protein/h) and highest in bluegill sunfish (1·45 μmol Pi/mg protein/h). While a stimulation of Na/K ATPase activity was observed at an exposure concentration of 1 μg Cd/liter in the fathead minnow and bluegill sunfish, inhibition of enzymatic activity was observed at higher exposure concentrations (10 and 100 μg Cd/liter). Gill Na/K ATPase activity in golden shiner was not significantly influenced by cadmium exposure. The observed insensitivity of ATPase in shiner may, in part, be related to higher background and accumulated concentrations of cadmium in gill tissue.     

Mercury and the estuarine marsh clam, Rangia cuneata gray. II. uptake, tissue distribution and depuration

During a two-week period, Rangia rapidly accumulates mercury (as mercuric chloride) from dilute solution (0·03–0·05 ppm) with the majority being located in gill and mantle tissue. Initial depuration (5 h) in clean seawater is rapid in all tissues. From 10–192 h concentrations of mercury in gill, foot and adductor muscles remain stable while mantle, haemolymph and viscera levels continue to fluctuate in a manner suggesting internal redistribution of mercury. After eight days of depuration, the viscera contains the most mercury and appears to be the only tissue to increase its proportionate share of the total tissue mercury. After fifteen weeks of depuration, residual mercury in whole clams is about 20% of initial concentrations. Acute decreases in salinity (15% S to 2% S) enhance Rangia's ability to depurate mercury.     

The influence of salinity on the solubility of Zn and Cd sulphides in the Scheldt estuary

In the estuary of the river Scheldt, where an oxygen gradient exists in addition to the salinity gradient, redox processes will be of major importance for trace metal mobilisation. In this study, the influence of salinity and pH on the redox processes of dissolved Zn and Cd sulphides is investigated together with the effects on the ratio of the dissolved Zn and Cd concentrations. The speciation of these metals is calculated with the chemical equilibrium programme +. Zn sulphides are oxidised at lower oxygen concentrations than Cd sulphides, due to lower stability constants, causing a sudden increase or peak in the dissolved Zn/Cd ratio. The formation of dissolved Cd chloride complexes when oxidation occurs at high salinities (S=15) increases the mobility of Cd, causing a decrease in the Zn/Cd peak of the total dissolved concentrations. The peak is three to four times smaller at S=15 than when oxidation occurs at S=2. The simple model calculations compare very well with field data. The Scheldt estuary is suitable to illustrate these calculations. In the 1970s, the anoxic part of the estuary reached S=15–20, but since the early 1980s it has dropped to S=2–10. Historic data on metals in the estuary from 1978, 1987 and the 1990s were used to compare with the equilibrium calculations. The increase of the dissolved Zn/Cd peak at low salinity as a consequence, of the decreasing anoxic region is confirmed well by the data. The good agreement between model calculations and field data is a proof of the extreme importance of redox processes for the solubility of Zn and Cd sulphides in the estuary.     

Effect of oil and dispersants on the growth of Mussels

Mussels (Mytilus edulis L.) were exposed to North Sea crude oil, microencapsulated oil and dispersants, singly and in combination, and growth rates measured at 24–48 h intervals.Exposure to microencapsulated pure oil (2·0–2·1 mg litre⁻¹) and to microencapsulated mixtures of oil (2·2−2·5 mg litre^-1+5 % of the different dispersants (FINASOL OSR 5, COREXIT 9527, DISPOLENE 36 S) gave approximately the same reduction in growth rate (80–90%) within 170h.Oil chemically dispersed with DISPOLENE 36 S and a pure oil mechanically dispersed in water were significantly less toxic. In high concentrations (2 mg litre⁻¹) all disperants are toxic, DISPOLENE 36 S ssignificantly more than the others.Mussels exposed for 170 h to microencapsulated oil and to microencapsulated oil dispersant mixtures recovered to control growth within 300 h in clean seawater, while in those given pure oil-in-water suspension, the recovery was slower.It is concluded that the toxicity of oil is mainly related to size and concentration of oil particles, while the effect of 5% dispersants added is negligible.     

Behavioural and siphonal tissue responses of Scrobicularia plana (bivalvia) to zinc

The effects of zinc being added to sea water, to final concentrations of 0·1–20 ppm, have been studied on the heart rate, valve movements, mortality of Scrobicularia and on both isolated and in situ inhalant siphon preparations.The acute toxicity threshold for added zinc was determined to be about 10 ppm at 10°C. The median lethal times for 10 and 20 ppm zinc were 143·5 and 116·1 h respectively.The responses of Scrobicularia to zinc concentrations in sea water of between 0·1 and 10 ppm were tested by exposure for 6 h. Above 1 ppm, valve closure and bradycardia occur within 10–15 min. Below 5 ppm the valves subsequently opened and heart rate increased over the 6 h period, but in 10 ppm closure and pronounced bradycardia were maintained throughout.Addition of zinc, to final concentrations of 1, 5 and 10 ppm, had no effect on the isolated inhalant siphon in contrast to copper at 0·25 and 0·5 ppm which caused very marked siphonal contractions. However, when zinc (1–10 ppm) was added to an in situ inhalant siphon preparation, contractions occurred which were lost on removal of zinc from the bathing medium. Cutting the cruciform muscles medially resulted in the loss or delay of the response to zinc. This suggests the possibility of the cruciform muscle complex (muscle strands and associated sense organs) responding to zinc. This contrasts with the direct action of copper on the neuromuscular system of an isolated siphon.     

Semi-empirical equations for the partial molar volumes of some ions in water and in seawater

Partial molar volumes of the major salts of seawater found in diluted seawater and in pure water are experimentally determined at temperatures of 5°C, 15°C and 25°C. The range of salinity investigated, which is not purely oceanographic, is the link between pure water and seawater in the World Ocean.The partial molar volumes were determined by using the procedure of Poisson and Chanu (1976). An empirical relation is given, linking the partial molar volumes of the salts or major ions of seawater in pure water with those measured in seawater, within the salinity range 0–40 g kg⁻¹ and the temperature range 0–25°C.     

Inverse-estuarine Features of the Upper Gulf of California

The Upper Gulf of California is the shallow (depth <30 m), tidal area at the head of the Gulf of California. It is an inverse estuary, due to the high evaporation rate (E1·1 m year⁻¹) and almost nil freshwater input from rainfall and the Colorado River. Historical and recent hydrographic data show that the area is almost vertically well-mixed throughout the year, that the horizontal distribution of properties follows the bathymetry, and that the hydrography has a strong annual modulation. As in other negative estuaries, the year-round salinity increase toward the head causes the density to do likewise, despite the seasonally reversing temperature gradient. The pressure gradient thus formed leads to water-mass formation and gravity currents (speed 0·1 ms⁻¹), both in winter and in summer. In winter, the high salinity water sinks beyond 200 m, while in summer it only reaches a depth of 20–30 m. The gravity currents appear to be modulated by the fortnightly tidal cycle, with events in neap tides. This phenomenon causes the presence, at least during neap tides, of slight stratification (Δσ_t≈−0·2).     

The excretion of heavy metals by the salt marsh cord grass,Spartina alterniflora, and Spartina's role in mercury cycling

Excreted salts and leaves from the Salt Marsh Cordgrass Spartina alterniflora were collected from two different sites. One site, Piles Creek (PC), is near heavily industrialized Linden, New Jersey, USA. The other site, Big Sheepshead Creek (BSC), is located near non-industrialized Tuckerton, New Jersey, USA. PC soil concentrations of mercury were 18·17 ± 7·67 ppm, while BSC soil concentrations were 0·22 ± 0·04 ppm. Spartina leaves from PC contained 0·16 ± 0·07 ppm of mercury, and BSC leaves contained 0·02 ± 0·0 ppm. Laboratory studies showed that S. alterniflora from both sites was capable of excreting mercury. Field collected salts from PC Spartina plants contained 0·11 ± 0·02 ppm of mercury, 2·60 ± 0·52 ppm of cadmium and 11·98 ± 0·94 ppm of zinc. These levels of heavy metals were as much as five- and-a-half times the concentrations of these metals found in ambient sea salts.     

Outflow of trace metals into the Laptev Sea by the Lena River

Freshwater concentrations confirm the pristine character of the Lena River environment as already pointed-out in a previous study with a limited set of data (Martin et al., 1993). Total dissolved concentrations of the freshwater are 13.8 ± 1.6 nM, Cu, 4.4 ± 0.1 nM, Ni, 0.054 ± 0.047 nM, Cd, 642 ± 208 nM, Fe, 0.2–0.3 nM Pb and 1.2 ± 1.0 nM, Zn. For Zn and Pb, a simple mixing of the Lena River waters with the Arctic waters is observed. Relationships with salinity suggest that for Cu, Ni and Cd, there is a mobilization of the dissolved fraction from the suspended matter, with an increase of the dissolved concentration of 1.5, 3 and 6 times, respectively. For Fe, the total dissolved concentrations follow an exponential decrease in the mixing zone and 80% of the total “dissolved” Fe is removed from the solution. For Cu, Ni, Cd and Fe, the riverine end-members are 20 nM, 12 nM, 0.3 nM and 47 nM, respectively. When considering the input of total dissolved metals to the Arctic Ocean, the fraction attributed to the freshwaters from the Arctic rivers appears to be small (4% of the input of dissolved metal to the Arctic Ocean for Cd, 27% for Cu, 11 % for Ni and 2% for Zn). Metal concentrations in the Laptev Sea and Arctic Ocean are very similar, indicating a generally homogeneous distribution in the areas sampled.     

Effect of reproductive toxicants on lipovitellin in female blue crabs, Callinectes sapidus

Changes in the concentration of lipovitellin, a lipoprotein that is the major protein in mature oocytes of crustaceans, were determined during ovarian development in female blue crabs, Callinectes sapidus. To test the effects of reproductive toxins on vitellogenesis, crabs were fed food containing cadmium or injected with the juvenile hormone antagonist, precocene II. Monoclonal antibodies prepared against one of the lipovitellin peptides (peptide A—107 kDa) were used in an enzyme linked immunosorbent assay to determine lipovitellin concentrations. Recently molted female crabs fed food containing cadmium (0.02 mg/g) for 18 days had oocytes with the same lipovitellin concentration as controls, but after 24 days the oocytes in cadmium treated crabs had significantly lower lipoprotein contents than controls (30 ± 4 ng/oocyte—cadmium treated; 45 ± 4 ng/oocyte—control). Precocene II-treated crabs had significantiy lower lipovitellin concentrations after 18 and 24 days. Diameters of oocytes were the same in both treated and control crabs. The results suggest that some pollutants may affect reproduction by acting during secondary vitellogenesis i.e., period when there is a large increase in lipovitellin synthesis. Since lipovitellins serve many of the nutritional needs of recently emerged crab embryos, poor larval survival may occur as a result of lower lipovitellin content.     

Effects of dietary and water-borne oil exposure on larval pacific herring (Clupea harengus pallasi)

Pacific herring (Clupea harengus pallasi) larvae were exposed either directly to the water-soluble fraction (WSF) of crude oil or indirectly via oil-contaminated prey (OCP) (Artemia salina) for <- 28 days, to determine the relative effects of diet and water as routes of contamination. Larvae were affected rapidly by 0·9 ppm WSF, which caused high larval mortality, reduced swimming ability and rapid reductions in feeding rates. Larval length was significantly reduced by 0·7 ppm WSF in 7 days and by 0·3 ppm WSF within 14 days. The WSF exposure also caused similar reductions in larval weights. Highly contaminated prey (6 ppm prey exposure) caused significant mortality, but surviving larvae appeared robust. The OCP did not affect swimming, feeding, or growth. Exposure of larvae was not significantly extended by OCP, which rapidly depurated WSF in clean water (98% in 1 day). Therefore, OCP is probably not an important source of low molecular weight petroleum contamination to larval fish in the marine environment.     

Movement patterns and trajectories of ovigerous blue crabs Callinectes sapidus during the spawning migration

Female blue crabs (Callinectes sapidus Rathbun) migrate from low salinity estuarine regions to high salinity regions near the ocean to release larvae. During this migration, ovigerous females use ebb-tide transport, a vertical migratory behavior in which they ascend into the water column during ebb tides, to move seaward to larval release areas. In order to determine the relationship of ebb-tide vertical migrations to local currents and the influence of these vertical migrations on the horizontal transport of blue crabs in the estuary, ovigerous females with mature embryos (1–3 days from hatching) were tracked near Beaufort Inlet, North Carolina (USA), in July and August 2001 and 2002. Crabs were tagged and tracked using ultrasonic telemetry, and currents near the crabs were measured simultaneously with a shipboard acoustic Doppler current profiler.During the two seasons, eight crabs were successfully tracked for periods ranging from 3.9–37.0 h and for distances ranging from 1.9–10.6 km. All crabs migrated seaward during the tracking periods. Crabs moved episodically during all tidal phases with periods of movement on the order of minutes to an hour. They moved with local currents in terms of both speed and direction during ebb tides, consistent with ebb-tide transport, and moved down-estuary (seaward) in opposition to local currents during flood tides. The percentage of time that crabs were active was higher during night ebb tides than during day ebb tides or flood tides and increased with increasing ebb-tide current speed. Mean migratory speeds were 0.11, 0.04, 0.08 and 0.02 m s⁻¹ during night ebb, night flood, day ebb and day flood tides, respectively, and net migratory speeds were on the order of 5 km day⁻¹. Due to the episodic nature of the crabs' movements, the total distances that crabs traveled during ebb tides ranged from 10–40% of the distances that passive particles could have traveled under the same conditions.