Mathematical modeling of PCB bioaccumulation in Perna viridis

In the present work, we built a mathematical model of polychlorinated biphenyl (PCB) bioaccumulation in Perna viridis, namely, a one-compartment model with a time dependent incorporation rate R (μg g⁻¹ lipid per ppb water per day), with positive substrate cooperativity as the underlying physical mechanism. The temporal change of the PCB concentration Q (μg g⁻¹ lipid) in the soft tissues of the mussel depends on the competition of the input rate RW and the output rate kQ, where W is the concentration of PCB in water (ppb water) and k is the elimination rate (per day). From our experimental data, k=0.181±0.017 d⁻¹. The critical concentration in water W_c for positive substrate cooperativity was found to be 2.4 ppb. Below W_c, R is a constant. For a water concentration of 0.5 ppb Aroclor 1254, R=24.0±2.4 μg g⁻¹ lipid ppb⁻¹ d⁻¹. Above W_c, positive substrate cooperativity comes into effect and R becomes a function of time and dependent on the concentration Q in a form R=γQ/(Q+δ). This is the case for a water concentration of 5 ppb Aroclor 1254, where γ=15.1 μg g⁻¹ lipid ppb⁻¹ d¹ and δ≈200 μg g⁻¹ lipid. From this model, the uptake is exponentially increasing when the PCB concentration in the mussel is small compared to 200 μg g⁻¹ lipid, and hyperbolically increasing when the concentration is large compared to 200 μg g⁻¹ lipid, which are consistent with the experimental data. The model is useful for understanding the true processes taking place during the bioaccumulation and for risk assessment with higher confidence. Future experimental data which challenge the present model are anticipated and in fact desirable for improvement and perfection of the model.     

Effects of copper exposure on the scope for growth of the clam Ruditapes decussatus from southern Portugal

The clam Ruditapes decussatus L. was collected from Ria Formosa, Faro, southern Portugal, and exposed to a sublethal copper concentration of 0.01 mg l⁻¹ for 20 days. Physiological measurements, respiration rates, clearance rates and absorption efficiency, were undertaken initially and after 2, 5, 9, 14 and 20 days and used to calculate Scope for Growth. Copper accumulation rate was calculated through the analysis of copper in the tissues at the same sampling times. The experiment showed two phases. Initially, copper was rapidly accumulated (1.95 μg Cu g⁻¹ dw day⁻¹ in the first 48 h), clearance rates declined markedly (lowest value 13.5% of control) and respiration rates increased (116% of control), resulting in a rapid decline of Scope for Growth, which showed a negative value after 5 days. In the second phase, (from day 9 on), the rate of copper uptake declined to 0.55 μg Cu g⁻¹ day⁻¹ and physiological responses were more stable. After 20 days, copper concentration in the tissues was 38.4 μg Cu g⁻¹ dw (bioconcentration factor 3840). Clearance rates were 50% of control rates and respiration rates were still high, 145% of control rates. Therefore, Scope for Growth and performance of the clams was still greatly affected (ca. 23% of the control values), indicating that though animals partially recovered through detoxifying mechanisms, excess copper caused sustained impairment of physiological functions. This experiment confirms that the physiological energetics approach and the integrated Scope for Growth measurement is a sensitive methodology to detect deviations from normal performance and assess stress at environmental realistic copper concentrations.     

Tin and organotin in water, sediments, and benthic organisms of Poole Harbour

Tributyltin (TBT) concentrations in waters of Poole Harbour ranged between 2–139 ng l⁻¹ (as Sn) and increased to 234–646 ng l⁻¹ within marinas. Seasonal trends in contamination coincided with boat usage patterns and peaked during summer months. A combination of poor tidal flushing and removal of TBT to particulates restricts high levels of contamination to areas closest to marinas and moorings; TBT concentrations in benthic sediments decreased from 0.52 μg g⁻¹ near such sites to 0.02 μg g⁻¹ at the harbour mouth. Organotin accumulations in several benthic invertebrates including polychaetes (Nereis diversicolor), snails (Littorina littorea) and clams (Scrobicularia plana, Mya arenaria) reflect the distribution of contamination in the environment, though concentration factors (relative to water) vary considerably between species and were highest in sediment dwelling clams, notably Mya (1.3×10⁵). Compared to organotins, biological availability of inorganic tin is low.

Levels of TBT in parts of Poole Harbour exceed Environmental Quality Targets designed to protect marine life and may be responsible for poor recruitment, particularly in bivalves, at heavily contaminated sites.     

The Effect of Copper on the Settlement Success of Larvae from the Scleractinian Coral Acropora tenuis

This study examined the effect of copper on the settlement success of planula larvae of the reef-building coral Acropora tenuis during 1994 and 1996 at Magnetic Island, Great Barrier Reef. Copper concentrations of 2, 10, 20 μg l⁻¹ did not inhibit larval settlement after 48-h exposure. However, copper concentrations of 42 μg l⁻¹ and 81 μg l⁻¹ significantly reduced settlement success of A. tenuis larvae after 48-h exposure compared with controls using normal seawater. At 200 μg l⁻¹ copper, all larvae died. EC₅₀ values for the effect of copper on A. tenuis larval settlement were calculated from the 1996 results using measured copper concentrations. The 48-h EC₅₀ was 35 μg l⁻¹ with an upper and lower 95% confidence limit of 37 μg l⁻¹ and 32 μg l⁻¹, respectively. The 48-h NOEC value for both experiments was 20 μg l⁻¹ copper. These experiments provide some of the first data on sub-lethal effects of trace metals on tropical marine organisms, and demonstrate that relatively low copper concentrations impair or inhibit settlement of coral larvae.     

The toxicity of marine sediments in Victoria Harbour, Hong Kong

When the toxicity of marine sediment in Hong Kong was evaluated, it was found that the seven sediments collected within Victoria Harbour were severely contaminated with heavy metals, at concentrations many times higher than those in sediments collected from outside the harbour. The highest metal content was recorded in site VS14 (located near the airport runway and the industrialized area), with copper, zinc, lead and chromium values of 3789, 610, 138 and 601 mg kg⁻¹ dry wt, respectively. This site also had the greatest alkaline phosphatase activities (15 fluorescent intensity unit g⁻¹ wet wt), the largest number of total coliforms (910 CFU g⁻¹ wet wt) and sulphate-reducing bacteria (8.5 × 10⁴ cells g⁻¹ wet wt), implying that site VS14 was also contaminated with organic matter and nutrients. Sediment bioassays, Microtox and algal tests, demonstrated that sediment elutriates obtained from site VS14 were of greatest toxicity. The EC₁₀ value in Microtox tests was 17% elutriate, and the 96-h IC₅₀ values using Skeletonema costatum and Dunaliella tertiolecta were 40 and 79% elutriate, respectively. No toxic effects were found in sediment samples collected from the control site outside Victoria Harbour. Significant correlations were found between the results of the algal toxicity test (using S. costatum) and the coliform count and metal content of the sediments. The Microtox test was less sensitive than the algal bioassay, and no sediment elutriate, even from the site mostly contaminated by heavy metals, caused more than 50% inhibition of the light-emitting activity of the bacteria. In this study, S. costatum (the diatom) provided a more sensitive and reliable test species than D. tertiolecta (the flagellate) in differentiating the toxicity of marine sediments.     

The potential role of mucus in the depuration of copper from the mussels Perna viridis (L.) and Septifer virgatus (Wiegmann)

Experiments were conducted to measure the mucus secretion rate in two common mussels in Hong Kong, Perna viridis (L.) and Septifer virgatus (Wiegmann), when chronically exposed to Cu (50 μg l⁻¹). After a 3-month exposure period, the mucus production rate of P. viridis at 25°C in the metal treatment was 2.65 times that of the control (10.7 vs 4.0 mg g⁻¹ dry wt h⁻¹), while S. virgatus showed a 1.85 times difference (4.41 vs 2.38 mg g⁻¹ dry wt h⁻¹). Mucus secretion by P. viridis under acute Cu exposure (0.5 mg l⁻¹) was significantly higher in the metal treatment than the control (13.43 vs 9.16 mg g⁻¹ dry flesh wt). Metal contents of the mucus secreted was about 18 times those in the control and 6 times in the soft tissues. Therefore, mucus appears to be an effective agent for Cu depuration in the mussel. The significance of these results to the local distribution and abundance of the mussels is discussed.     

Burrowing responses of the short-neck clam Ruditapes philippinarum to sediment contaminants

The burrowing responses of a common tropical bivalve, the short-neck clam Ruditapes philippinarum, to cadmium (Cd)-spiked sediment, variations of sediment grain size and natural sediments collected from 15 locations in Hong Kong's inshore waters were investigated through a series of laboratory tests. Results showed that the burrowing response exhibited a negative relationship with an increase in Cd concentration in the spiked sediments. The level of Cd was also found to be directly proportional to the percent mortality of the clam. However, there was no significant difference (p>0.05) in the time elapsed for the clam to burrow into sediments with different grain size composition. The elapsed time for 50% of the test clams to burrow into the sediment (ET₅₀) over a period of 48 h was calculated for the sediment samples collected from the 15 locations. Results of ANOVA showed significant difference (p<0.05) among the sediment samples. Tukey's multiple comparison test revealed two groups of sediments: group 1 containing 3 sediment samples collected from Victoria Harbour and group 2 containing 12 samples obtained from other coastal areas of Hong Kong. The ET₅₀ value for group 1 sediments was found to be greater than 2880 min whilst the ET₅₀ for group 2 sediments had a mean of 173.9 min. Agglomerative classification of the sediment samples, based on metal content (As, Cd, Cr, Cu, Ni, Pb, Zn), also showed two similar groups, suggesting that the ET₅₀ values were correlated with the metal level of the sediment samples. Group 1 sediments collected from Victoria Harbour had greater concentrations of Cd, Cr, Cu, Ni and Zn as compared to that in group 2. The present study demonstrated that high metal content in the sediment tends to inhibit the burrowing responses of the clam and that there is potential to develop the burrowing responses of R. philippinarum as a sublethal sediment toxicity test.     

A case study on fuel oil contamination in a mangrove swamp in Hong Kong

Mangroves commonly found along tropical and subtropical coastlines are susceptible to oil pollution. In December 2000, around 500 1 m tall Kandelia candel saplings at the age of 3–5 years old located at the foreshore region of Sheung Pak Nai swamp, Hong Kong SAR, were found to be damaged by oil pollution. More than 80% of the saplings were either dead or washed away and leaving less than 5% healthy saplings with dense green leaves. Elevated concentrations of light n-alkanes (ranging from n-C₁₄ to n-C₂₀), pristane and phytane were recorded in surface sediments collected in December 2000. The ratio between light and total n-alkanes was 0.4. The total petroleum hydrocarbons (60–80 μg g⁻¹ TPH) and unresolved complex mixtures (60–70 μg g⁻¹ UCM) were higher than the background values of other mangrove sediments in Hong Kong, which were 40 and 20 μg g⁻¹, respectively. In certain root zone sediments, TPH concentrations were above 1000 μg g⁻¹. These results suggest that surface sediments in Sheung Pak Nai were contaminated by petroleum oil, most likely by illegal discharge of fuel oil which occurred between 1998 and 2002. One year later, in December 2001, unhealthy saplings had recovered and re-grown. The concentrations of TPH and UCM in sediments declined to around 40 μg g⁻¹, pristane and phytane dropped by 80%, and the ratio of light to total n-alkanes was 0.15, suggesting that residual oil in sediments was weathered leading to a remarkable recovery of the unhealthy saplings.     

Toxic effects of copper on larval development of the barnacle Balanus amphitrite

Experiments were conducted to assess the effects of copper on larval development in the barnacle Balanus amphitrite. In the first experiment, we compared the sensitivity of three naupliar stages to copper stress. Molting inhibition occurred at copper concentrations ranging from 32 μg l⁻¹ in nauplius II to 128 g l⁻¹ in nauplius VI. EC₅₀ for molting ranged from 97 μg l⁻¹ in nauplius II to 129 g l⁻¹ in nauplius VI. Decreased survival occurred at 128 μg Cu l⁻¹ in all of the naupliar stages tested, with LC₅₀ ranging from 145 in nauplius II to 213 μg l⁻¹ in nauplius VI. In the second experiment, we examined effects of copper on the development from nauplius II to cyprid. The larvae reached cypris stage only in treatments of 16 μg Cu l⁻¹. Our study therefore showed that molting was a more sensitive endpoint than survival, nauplius II was the most sensitive naupliar stage, and that whole larval development assay was more sensitive than assays using a particular larval stage. The results were discussed with respect to the use of this species in toxicity tests.     

Effects of Animal Size on Concentrations of Metallothionein and Metals in Periwinkles Littorina littorea Collected from the Firth of Clyde, Scotland

Different sizes of Littorina littorea were collected from four areas in the Firth of Clyde, Scotland. Their metallothionein (MT) and heavy metal concentrations were analysed using the Silver Saturation Method and Atomic Absorption Spectrophotometry, respectively. Concentrations of MT, Cd and Zn (as μg g⁻¹ dry soft-body weight) generally decreased with an increase in size of L. littorea. MT concentrations were better correlated with Cd than with Zn or Cu concentrations. Nevertheless, MT and the metals in periwinkles (as μg individual⁻¹) increased significantly with increasing size. Concentrations of MT and the metals among the sampling areas were compared at a standardised soft-body weight (10 mg). The results from Discriminant Analysis based on all metal concentrations indicate that Largs is different from the other areas and characterised by high Fe concentrations in L. littorea. The problems and differences in using either soft-body weight or shell length as independent variable for size-standardisation are discussed.     

Hydrocarbon and coprostanol levels in seawater, sea-ice algae and sediments near Davis station in eastern Antarctica: A regional survey and preliminary results for a field fuel spill experiment

A survey of hydrocarbons and the sterol coprostanol, together with a hydrocarbon degradation experiment, was conducted in a coastal marine environment in East Antarctica. Aliphatic hydrocarbon levels in sea-ice algae were 1.9–12.5 mg m⁻² and in seawater particulate matter 0.07–0.17 μg l⁻¹. Sea-ice algae contained the diatom biomarker, the highly branched isoprenoid (ip) diene ipC_25:2, and Southern Ocean seawater particulate matter samples were distinguished from near shore samples by the presence of nC_21:6. Sea-ice algae and seawater particulate matter samples showed a predominance of even chain n-alkanes. Hydrocarbon levels in sediment samples from anoxic fjord basins were high (45–48 μg g⁻¹) compared to a sub-tidal marine sample (0.7 μg g⁻¹), and were predominantly of bacterial origin. Contaminants detected were linear alkyl benzenes in sewage effluent from Davis station, and polycyclic aromatic hydrocarbons (PAH) which were present in very low levels (parts per trillion) throughout the environment. High levels of 2,6-dimethylnaphthalene were found in anoxic sediment from Ellis Fjord and may arise from a novel bacterial source. Coprostanol concentrations in sediments ranged from 67 to 1280 ng g⁻¹. A dual origin is proposed from marine mammalian faeces and, at several sites, from conversion of algal-derived sterols by anaerobic bacteria. Future studies examining the impact of human sewage from scientific bases or other ventures should use care in interpreting results when such high baseline values, from marine mammalian input, may occur naturally around the Antarctic coast. The potential exists, however, for the technique to distinguish between human and mammalian inputs through measurement of the coprostanol to epicoprostanol ratio, particularly if undertaken with appropriate comparative sampling. Results for a hydrocarbon degradation experiment where a light fuel was applied to an Antarctic beach, showed loss of up to 99% of the fuel within 2 months, mainly by volatilization.     

Levels of heavy metals along the Libyan coastline

A coastal survey off the east part of the Libyan coastline which has no river inputs was initiated to measure the existing level and distribution of selected heavy metals (Cu, Zn, Cd, Ni, and Mn) in surface sediments along Benghazi Bay. In order to place the finding of this survey in proper perspective and for practical terms a Pollution Load Index (PLI) was used. The results establish that of the sites examined only the harbour site exhibited relatively high levels particularly in the cases of cadmium and copper indicating a detectable anthropogenic input. The range of concentrations were 1.03%–1.96% μg g⁻¹ (dry wt) for organic content and 64.7%–93% for calcium carbonate while the range of heavy metals concentrations (μg g⁻¹ dry wt) were 8.7–42 for Cu, 2.3–27.3 for Zn, 5.7–19 for Ni, 37–76.7 for Mn, and below the detection limit-1.73 for Cd. A PLI score of 2.93 was obtained at the harbour site and a range of 6.11–7.63 for the other sites. The PLI score for the control site was 9.51 and the score for the overall studied area was 7.51 indicating a very clean environment. The index would be, with some modification, a step in the right direction from the management point of view in Libya due to the absence of environmental expertise.     

PAH contamination of western Irish Sea sediments

Concentrations of the sum of 15 PAHs in 22 surficial sediment samples from the western Irish Sea ranged from below 100 ng g⁻¹ in sandy sediments to a maximum of 1422 ng g⁻¹ in the centre of the mud basin. The concentrations are typical of coastal shelf sediments, but greater than those observed for aquatic sediments remote from known anthropogenic sources. Organic C and the % sediment <15 μm were positively correlated with ΣPAH. ΣPAH was normalised to organic C and particle size (i.e. expressed as ΣPAH/C^org and ΣPAH/%<15 μm) and significant relationships were still observed with organic C and %<15 μm. The results are discussed in the context of using organic C to normalise concentrations of PAHs to assess contamination levels in sediments.     

Physiological and biochemical changes in shrimp larvae (Penaeus vannamei) intoxicated with organochlorine pesticides

Shrimp larvae (Penaeus vannamei) collected from an uncontaminated area were challenged with sublethal concentrations of organochlorine pesticides. The effects of treatment with lindane, lorsban, chlordane and DDT, were a 5, −12, 13 and 21% increase in the larval respiratory rate, respectively. Glycogen synthesis decreased from the 0.471 μg g⁻¹ h⁻¹ of the control, to 0.455, 0.415, 0.400 and 0.365 μg g⁻¹ h⁻¹, for larvae submitted to DDT, chlordane, lindane and lorsban. In addition, we measured decreases in nucleic acid content, from 20.4 and 34.9% in larvae challenged by chlordane and lorsban, respectively, and values close to 25% for two other pesticides tested. These results indicate drastic metabolic changes, which may impinge on the commercial fishery and culture of this organisms.     

Accumulation of butyltins in muscle tissue of chinook salmon reared in sea pens treated with tri-n-butyltin

Muscle tissue of chinook salmon, Oncorhyncus tshawytscha, reared for 3 to 19 months in sea pens treated with an antifouling biocide, tri-n-butyltin (TBT), contained organotin concentrations of 0.28–0.90 μg g⁻¹ (as TBT). Organotins are present in some pen-reared salmon sold in the United States: eleven of 15 salmon advertised as aquaculture products and purchased from public markets contained organotin concentrations of 0.081–0.20 μg g⁻¹. Most common cooking practices do not effectively destroy or remove butyltins from salmon muscle tissue. We believe this is the first evidence of entry of organotins into the human diet in the United States.     

The comparative effects of oil dispersants and oil/dispersant conjugates on germination of the marine macroalga Phyllospora comosa (Fucales: Phaeophyta)

Germination inhibition of the marine macrophyte Phyllospora comosa was utilized as a sub-lethal end-point to assess and compare the effects of four oil dispersants and dispersed diesel fuel and crude oil combinations. Inhibition of germination by the water-soluble fraction of diesel fuel increased following the addition of each of the dispersants; the nominal 48-h EC₅₀ concentration of diesel fuel declined from 6800 to approximately 400 μl l⁻¹ nominal for each dispersed combination. This contrasted with crude oil, where the addition of two dispersants resulted in an enhanced germination rate and an increase in nominal EC₅₀ concentrations from 130 μl l⁻¹ for the undispersed crude to 4000 and 2500 μl l⁻¹. The results indicate that, while germination inhibition of P. comosa may be enhanced by the chemical dispersal of oil, the response varies with type of both oil and oil dispersant.     

Clam burrowing behaviour and mortality related to sediment copper

Gravel sediment freshly enriched with over 4.4 μg Cu g^?1 significantly increased the burrowing and reburrowing times of Littleneck marine clams (Protothaca staminea). Abnormal burrowing behaviour was observed with time-lapse video. Aged (1 day) copper-enriched sediment did not affect clam burrowing time. Copper in sediment porewater declined three days after sediment enrichment to background levels without change in total sediment copper. In a long-term experiment, clams with increased burrowing time into copper-enriched sediment had up to 25% mortality after 12–29 days burial in the sediment. The majority of clam mortality was found in clams burrowing within the first 48 h. Over 7 weeks there was blackening of sediment and clam shells proportional to sediment copper enrichment.     

Organochlorines in Hong Kong Fish

Muscle samples from 15 species of fish (n=1) purchased from markets in Hong Kong and 10 liver samples of tilapia (Tilapia mossambica) collected from the Shing Mun River were analysed for organochlorines (polychlorinated biphenyls, ΣDDTs, hexachlorobenzene, hexachlorocyclohexanes, chlordanes, mirex and dieldrin). Polychlorinated biphenyls (PCBs) were detected in 15 market fish samples but the levels were very low (around 1 ng g⁻¹). PCB levels in tilapia livers collected from Tai Wai (29.3–65.1 ng g⁻¹) were higher than those from Fo Tan (3.5–23.2 ng g⁻¹) suggesting that there may be some local point soucres. ΣDDTs were detected in all samples, ranging from 3.3 to 75.6 ng g⁻¹ in the market fish and from 7.1 to 88.8 ng g⁻¹ in tilapia. The DDE/DDT ratios in the market fish (0.12–0.75) showed higher variability than those of tilapia (0.30–0.46), suggesting that some of the market fish may have been collected from areas where DDT was recently used. Results of this preliminary study show that organochlorine levels in Hong Kong market fish are low and do not cause any concern for human consumption. An on-going monitoring program, however, is recommended.     

Histopathological effects of petroleum hydrocarbons and heavy metals on the American oyster (Crassostrea virginica) from Tabasco, Mexico

Oyster tissues may be affected by the concentration of ions in the water (i.e. salinity) and by contaminants such as petroleum hydrocarbons and heavy metals. Oyster populations from three coastal lagoons (Mecoacan, Camen and Machona) in the Mexican state of Tabasco, in the southern Gulf of Mexico, were sampled for pollution studies during June, September and November 1992 and May 1993. No statistically significant relationships were found between the concentration of contaminants in the body tissues of organisms and their shell length, soft tissue weight and particulate matter; however, a significant correlation was found between condition index and salinity (r = −0.72). Generally, the lowest weights, shell lengths and indices of condition were found in Mecoacan. The concentrations of cadmium and zinc were inversely related to salinity (r = −0.52 and r = −0.32, respectively), so a riverine input is suspected. On average, 63% of the individual oysters showed histopathological lesions, which can be related to salinity and to the concentrations of cadmium and the unresolved fraction of hydrocarbons (UCM). The response of each of the tissues analysed was different. The percentage of individuals with damage in the digestive diverticulum increased linearly with UCM (r = 0.71), but in a saturation-response fashion (Y = B₀ − B₀/(1 + X^B1) r = 0.66) with cadmium. The percentage of individuals with damage in the gills increased linearly with weight (r = 0.68), cadmium (r = 0.60) and UCM (r = 0.60). The lesions in the connective tissue decreased linearly (r = −0.82) with salinity, but increased in a saturation-response way (r = 0.83) with cadmium. Finally, the percentage of individuals with lesions in the digestive tube decreased linearly with salinity (r = −0.59). Only the damage to the gills and digestive diverticula were dependent on gonadal maturity, while damage to the connective tissue was dependent on the sex of the individual.     

Cadmium content, accumulation and toxicity in dog whelks collected around the Welsh coastline

The concentration of cadmium in sexually mature Nucella lapillus was investigated around the coast of Wales. Higher concentrations of cadmium were found in whelks located in the Bristol Channel compared with Cardigan Bay Nucella. Accumulation and toxicity of cadmium were investigated at 50–600 μg Cd l⁻¹ over a period of 21 days. At the lower concentrations of 50–100 μg Cd l⁻¹ all Nucella survived the 21 days of experimentation. The rate of cadmium uptake after exposure to cadmium was inconsistent and not related to the degree of site contamination. At all sites the concentration of cadmium in Nucella, after treatment with 50–600 μg Cd l⁻¹ for 21 days, was significantly different from controls, but after 7 days it varied with the site and cadmium concentration. Only samples collected at Fishguard, Dale, and Swansea survived 21 days at 600 μg Cd l⁻¹. Tissue cadmium concentrations did not significantly effect the whole body concentration of zinc.