Aliphatic and aromatic hydrocarbons in marine biota and coastal sediments from the Gulf and the Gulf of Oman

The composition and spatial distribution of aliphatic and polycyclic aromatic hydrocarbons (PAHs) were investigated in biota and coastal sediments from four countries surrounding the Gulf (Bahrain, Qatar, United Arab Emirates and Oman). The levels of total petroleum hydrocarbons (TPH), aliphatic unresolved mixture and PAHs in sediments and biota were relatively low compared to world-wide locations reported to be chronically contaminated by oil. Only in the case of the sediments collected near the BAPCO oil refinery in Bahrain, having concentrations of 779 μg g⁻¹ total petroleum hydrocarbon equivalents and 6.6 μg g⁻¹ ∑PAHs, can they be categorized as chronically contaminated. Some evidence of oil contamination was also apparent in sediments and bivalves around Akkah Head and Abu Dhabi in the UAE, and near Mirbat in Oman. Contaminant patterns in sediments and biota indicated that the PAHs were mainly from fossil sources, with the exception of the high PAH concentrations in sediments near the BAPCO refinery that contained substantial concentrations of carcinogenic PAH combustion products.     

Hydrocarbons in surface sediments from the Changjiang (Yangtze River) Estuary, East China Sea

Sedimentary aliphatic (AH) and polycyclic aromatic hydrocarbons (PAHs) were studied in the Changjiang Estuary and the adjacent East China Sea. Total AH ranged from 2.20 to 11.82 μg g⁻¹ and consisted of n-alkanes and a dominant petroleum-related unresolved complex mixture (UCM). Within the n-alkanes, terrestrial plant wax compounds prevailed at nearly all stations. Of the PAHs, biogenic perylene dominated at stations receiving riverine inputs. Anthropogenic PAHs originating from combustion/pyrolysis processes varied from 17 to 157 ng g⁻¹, while fossil PAH concentrations ranged from 42 to 187 ng g⁻¹. Both biogenic and anthropogenic hydrocarbons are primarily derived from riverine discharges and accumulate at shallow-water stations. Distinct phase associations lead, nevertheless, to different sedimentation patterns. Fossil PAHs are enhanced at offshore stations where they are introduced directly by shipping activities. Biomarker fingerprints ascribe their source to Chinese crude oils. The overall levels of anthropogenic hydrocarbons are low compared to relevant areas worldwide and reveal a low/moderate level of hydrocarbon pollution.     

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.     

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.     

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.     

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.     

Organochlorine micropollutants in the Jiulong River Estuary and Western Xiamen Sea, China

Organochlorine contaminants including 12 polychlorinated biphenyl (PCB) congeners and 18 insecticides were determined in water, pore water and sediments of the Jiulong River Estuary and Western Xiamen Sea, China. The results showed that the levels of the total PCBs ranged from non-detectable to 1500 ng l⁻¹ in water, from 209 to 3870 ng l⁻¹ in pore water, and from 2.78 to 14.8 ng g⁻¹ dry weight in sediments. Total organochlorine insecticide concentrations were from below the limit of detection to 2480 ng l⁻¹ in water, from 267 to 33400 ng l⁻¹ in pore water, and from 4.22 to 46.3 ng g⁻¹ dry weight in sediments. Concentrations of PCBs and insecticides in pore water were significantly higher than those in surface water, due to the high affinity of these hydrophobic compounds for sediment phase. The PCB congeners with the highest concentrations were CB153, CB180 and CB194, which together accounted for 68–87% of total PCBs in water, pore water and sediment. Among the hexachlorocyclohexane (HCH) compounds, beta-HCH was found to be a major isomer. Analysis of 1,1,1-trichloro-2,2-bis-chlorophenyl-ethane (DDT) and its metabolites showed that 1,1-dichloro-2[o-chlorophenyl]-2[p-chlorophenyl]-ethylene (DDE) was dominant in the group. In comparison to a 1998 study in the Western Xiamen Sea, levels of organochlorines were enhanced due probably to recent inputs and changes in sediments.     

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.     

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.     

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.     

Clam burrowing behaviour: Inhibition by copper-enriched sediment

Burrowing behaviour is adaptive and allows clams to escape predation; yet the effects of potentially toxic metals on such behaviour have not been adequately investigated. In natural marine sediment contaminated with copper the time for littleneck clams (Protothaca staminea) to achieve complete burial was recorded. Above a threshold of 5.8 μg g⁻¹ Cu added to dry sediment, the time for 50% of the clams to burrow (ET₅₀) increased logarithmically with increasing sediment copper concentration according to:

logET₅₀ = 0.15 (CU) - 1.37 (n = 4, r² = 0.98)

where ET₅₀=time in hours for 50% of clams to burrow and Cu=μg g⁻¹ Cu in dry sediment. Previously exposed clams had both a lower threshold to Cu and a longer reburrowing time (ET₅₀). Clams exposed to sediment mixed with Chelex-100®-sorbed copper showed no significant change in burrowing time. Bioassays based on claim burrowing behaviour can measure both bioeffectiveness of sediment-sorbed metals and a sublethal effect with ecological meaning.     

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.     

Pesticides in Sediments From Queensland Irrigation Channels and Drains

Pesticide concentration in sediment from irrigation areas can provide information required to assess exposure and fate of these chemicals in freshwater ecosystems and their likely impacts to the marine environment. In this study, 103 sediment samples collected from irrigation channels and drains in 11 agricultural areas of Queensland were analysed for a series of past and presently used pesticides including various organochlorines, synthetic pyrethroids, benzoyl ureas, triazines and organophosphates. The most often detected compounds were endosulphans (, β and/or endosulphan sulphate) which were detectable in 78 of the 103 samples and levels ranged from below the limit of quantification (0.1 ng g⁻¹ dw) up to 840 ng g⁻¹ dw. DDT and its metabolites were the second most often detected pesticide investigated (74 of the 103 samples) with concentrations up to 240 ng g⁻¹ dw of ∑DDTs. Mean ∑endosulphan and ∑DDT concentrations were 1–2 orders of magnitude higher in sediments from the irrigation areas which are dominated by cotton cultivation compared to those which are dominated by sugarcane cultivation. In contrast to these insecticides, the herbicides diuron, atrazine and ametryn were the compounds which were most often detected in sediments from irrigation drains in sugarcane areas with maximum concentrations in areas of 120, 70 and 130 ng g⁻¹ dw, respectively. In particular during flood events, when light is limiting, transport of these photosynthesis inhibiting herbicides from the sugarcane cultivation areas to the marine environment may result in additional stress of marine plants.     

Distribution and Fate of Organochlorine Pollutants in the Pearl River Estuary

Samples of surface sediment and suspended particulate matter (SPM) were collected from the Pearl River estuary, China, and the distribution and concentration of hexachlorocyclohexanes (HCHs), DDTs and polychlorinated biphenyls (PCBs) were extensively studied. The concentration ranges of HCHs, DDTs and PCBs in the sediments were 0.28–1.23 ng g⁻¹, 1.36–8.99 ng g⁻¹ and 0.18–1.82 ng g⁻¹, respectively. The concentrations of HCHs, DDTs and PCBs in the SPM varied both with the sampling locations and the season of collection. Higher concentrations were recorded in the SPM as compared with sediments. The distribution pattern of such organochlorine compounds (OCs), in the Pearl River estuary, showed that sources were some major river mouths and input from Shenzhen Bay. The concentrations of OCs were, however, low as compared with other estuaries and seas. The environmental fate of the OCs during estuarine mixing was determined, in part, by physicochemical and biochemical properties. The absorption and sedimentation of SPM were also considered important factors. Marine sediments may, therefore, be regarded as an important reservoir of hydrophobic and persistent OCs.     

Calcium alginate immobilized marine microalgae: experiments on growth and short-term heavy metal accumulation

Growth of 11 calcium alginate immobilized marine microalgal species belonging to eight taxonomical groups has been checked in the present work. Cellular densities inside the calcium alginate beads were monitored during 17 days. Good growth and maintenance of the structure of the beads were both found for some of the assayed species. One of those species (Tetraselmis chui, Prasinophyceae) was selected in order to perform a short term (up to 24 h) heavy metal accumulation experiment. Beads of calcium alginate containing (or not) cells of T. chui were exposed to 820 μg L⁻¹ Cu and 870 μg L⁻¹ Cd separately during a 24 h period, and accumulation of heavy metals in the beads was measured after this time and compared. Concentration of each metal in the supernatants was monitored at 5, 10, 60 min and 24 h from the beginning of the experiment. After 24 h, practically all Cu was removed by the beads. Beads with immobilized algae removed around 20% of total Cd, while beads without algae removed half of that percentage.     

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.     

Coprostanol as sewage tracer in McMurdo Sound, Antarctica

Sediment cores from the vicinity of sewage outfalls off McMurdo Station as well as surface grab samples from different locations in the McMurdo Sound, Antarctica were analysed for coprostanol (5β-cholestan-3β-ol) and epicoprostanol (5β-cholestan-3-ol) to assess the degree of sewage addition to the Sound. Sediment samples close to the point source contain as much as 3 mg g⁻¹ dry sediment of coprostanol, whereas samples farther from the source, for example from New Harbour and Granite Harbour, contain only trace levels to 40 ng g⁻¹. Coprostanol in the sediments of latter locations most likely originates from seals rather than from sewage outfalls. It appears that sewage particles are very quickly incorporated into the sediment layers close to the discharge point in the eastern Sound. However, significant levels (930 ng g⁻¹) of fecal sterols were detected in Cape Armitage surface sediments, indicating that the sewage plume could also have reached the seawater intake station, situated in between the outfall and Cape Armitage sampling site. These results suggest the need for a sound environmental monitoring and assessment of the existing wastewater practices in the region.     

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.     

Geographical distribution and accumulation features of organochlorine residues in bivalves from coastal areas of South Korea

As a part of Mussel Watch Program in Korea, the contamination levels and accumulation features of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed for 82 bivalve samples collected from 66 sites along the entire coast of Korea. The dry weight based ∑PCBs and ∑OCPs ranged from 4.4 ng g⁻¹ to 422.0 ng g⁻¹ (geometric MEAN=36.9 ng g⁻¹) and from 9.95 ng g⁻¹ to 131.37 (34.88) ng g⁻¹, respectively. PCB was predominant in Korean coast, followed by DDTs, HCHs, and Chlordanes. From the observed log normal distribution of PCB and each OCP, low- and high-levels were defined as geometric mean ±1 S.D., respectively. The levels at the sites near urban and/or industrial areas often exceeded the high-levels and the spatial distributions of ∑DDTs and ∑CHLs were correlated with that of ∑PCBs, indicating terrestrial input pathways. Even distribution of ∑HCHs suggested a possibility of atmospheric input pathway of HCHs. The observed isomer ratios of DDTs, HCHs, and CHLs indicated that aging has occurred.     

Organochlorines and other environmental contaminants in muscle tissues of sportfish collected from San Francisco Bay

Edible fish species were collected from 13 locations throughout San Francisco Bay, during the spring of 1994, for determination of contaminant levels in muscle tissue. Species collected included white croaker, surfperch, leopard and brown smoothhound sharks, striped bass, white sturgeon and halibut. 66 composite tissue samples were analysed for the presence of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (P0CBs), pesticides, trace elements and dioxin/furans. The US EPA approach to assessing chemical contaminant data for fish tissue consumption was used for identifying the primary chemicals of concern. Six chemicals or chemical groups were found to exceed screening values (SVs) established using the US EPA approach. PCBs (as total Aroclors) exceeded the screening level of 3 ng g⁻¹ in all 66 muscle tissue samples, with the greatest concentrations (638 ng g⁻¹) found near San Francisco's industrial areas. Mercury was elevated (> 0.14 μg g⁻¹) in 40 of 66 samples with the greatest concentrations (1.26 μg g⁻¹) occurring in shark muscle tissues. Concentrations of the organochlorine pesticides dieldrin, total chlordane and total dichlorodiphenyltri-chloroethane (DDT) exceeded screening levels in a number of samples. Dioxin/furans (as toxic equivalent concentrations (TEQ's)) were elevated (> 0.15 pg g⁻¹) in 16 of the 19 samples analysed. Fish with high lipid content (croaker and surfperch) in their muscle tissue generally exhibited higher organic contaminant levels while fish with low lipid levels (halibut and shark) exhibited lower organic contaminant levels. Tissue samples taken from North Bay stations most often exhibited high levels of chemical contamination. The California Office of Health Hazard Assessment is currently evaluating the results of this study and has issued an interim Health Advisory concerning the human consumption of fish tissue from San Francisco Bay.