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 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.     

Burial, crawling and drifting behaviour of the bivalve Macomona liliana in response to common sediment contaminants

To investigate the effect of sediment contamination on the tellinid bivalve Macomona liliana, juvenile shellfish (about 1.3 mm long) were exposed to copper- and zinc-dosed sand, and sediments collected from several contaminated sites. The behavioural responses measured included burial rate, crawling and drifting. In copper-dosed sediment, a significant reduction in the number of shellfish burying after 10 min occurred at 25 mg Cu kg⁻¹ (dry wt). After a 96-h exposure, shellfish crawled away from sediment with 10 mg Cu kg⁻¹ (dry wt), and when a weak current was provided they left this 10 mg Cu kg⁻¹ (dry wt) sediment by drifting. Zinc-dosed sediment slowed burial at 80 mg Zn kg⁻¹ (dry wt), and stimulated crawling and drifting at 40 mg Zn kg⁻¹ (dry wt). Some of the field-collected contaminated sediments slowed burial and stimulated drifting, but none affected crawling. It appears that juvenile drifting induced by sediment contamination could play a role in determining M. liliana distributions.     

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.     

Persistent organochlorine residues in green mussels from coastal waters of South India

Green mussels (Perna viridis) collected from nine locations along the South Indian coast were used as bioindicator to assess the organochlorine contamination (HCHs, DDTs, and PCBs) in the coastal environment of South India. Concentrations of ΣHCH and ΣDDT were found to be similar, ranging from 3 to 39 ng g⁻¹ on wet wt basis. On the other hand, PCB levels were apparently lower, varying from <1.0 to 7.1 ng g⁻¹ wet wt. The residue pattern of organochlorines in mussels are principally similar to those in Indian human samples, reported earlier. The coastal marine pollution by HCH in India ranks among the highly contaminated areas in the world.     

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.     

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.     

Aspects of Assaying Sediment Toxicity in Irish Estuarine Ecosystems

The toxicity of surface sediments collected from eight estuarine sites around the Irish coast was assessed in March 1997 using a whole sediment bioassay. Two molluscan species, Tapes semidecussatus (1 + age class) and Scrobicularia plana (unknown age) were exposed to test sediments for 21 days. Survival, morphometric, behavioural and histochemical measurements were taken during the 21 day bioassay. 100% mortality occurred in both species in sediments from one site in Dublin Bay within 18 days of initial exposure. 100% survival of T. semidecussatus was observed in all but four of the test sediments to which it was exposed during this study. The animal condition and wet tissue weight of T. semidecussatus decreased for all sediments during the bioassay. 95% survival of S. plana was observed after 21 days exposure to Youghal (reference) sediment. Condition and wet tissue weight of S. plana increased in all test sediments during the bioassay, however, there was significant variation in wet tissue weight of this species on day 25 of the bioassay in all test sediments. There was significant variation in the burrowing behaviour of S. plana during the bioassay. Lipofuscin accumulation was observed in the digestive diverticula of T. semidecussatus exposed to all test sediments with the exception of Youghal (reference). The potential for both species as bioassay organisms is discussed.     

Fate of polycyclic aromatic hydrocarbon (PAH) contamination in a mangrove swamp in Hong Kong following an oil spill

The fate of polycyclic aromatic hydrocarbon (PAH) contamination in a mangrove swamp (Yi O) in Hong Kong after an oil spill accident was investigated. The concentrations and profiles of PAHs in surface sediments collected from five quadrats (each of 10 m×10 m) covering different degrees of oil contamination and the most contaminated mangrove leaves were examined in December 2000 (30 days after the accident) and March 2001 (126 days later). The concentrations of total PAHs in surface sediments ranged from 138 to 2135 ng g⁻¹, and PAHs concentrations decreased with time. In the most contaminated sediments, total PAHs dropped from 2135 (30 days) to 1196 ng g⁻¹ (120 days), and the decrease was smaller in less contaminated sediments. The percentage reduction in sediment PAHs over three months (44%) was less significant than that in contaminated leaves (85%), indicating PAH in or on leaves disappeared more rapidly. The PAH profiles were very similar in sediments collected from quadrats Q1 and Q2 with benzo[a]anthracene and pyrene being the most abundant PAH compounds, but were different in the other three quadrats. The proportion of the light molecular weight PAHs to total PAHs increased after three months, especially phenanthrene. Results suggest that physical and photo-chemical weathering (tidal washing and photo-oxidation) of crude oil in surface sediments and on plant leaves were important processes in the first few months after the oil spill. The PAH contamination in Yi O swamp came from both petrogenic and pyrolytic sources. The petrogenic characteristic in the most contaminated sediment was confirmed with high values of phenanthrene to anthracene ratio (>10) and low values of fluoranthene to pyrene ratio (0.3–0.4).     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Impacts of domestic sewage effluent on phytoplankton from Bedford Basin, eastern Canada

The impact of domestic sewage effluent (SE) on the dynamics of phytoplankton assemblages from Bedford Basin was evaluated in the laboratory. Phytoplankton production and chlorophyll a increased proportionally with SE enrichment. Phytoplankton species composition also changed. The potentially harmful diatoms, Pseudonitzschia spp., present initially in small numbers (600 cells 1⁻¹) in Bedford Basin seawater, and became dominant (3–5×10⁶ cells 1⁻¹) when the seawater was enriched with 0.5–5% untreated SE. With higher proportions of SE, other harmful species such as Fragilaria spp. and Euglena spp. became dominant (7−15×10⁶ and 2.2×10⁴ cells 1⁻¹, respectively). Treatment of SE with UV light or activated charcoal seems to favour growth of benign species, such as Chaetoceros socialis, Skeletonema costatum and Thalassiosira spp., but not harmful species such as Pseudonitzschia spp. Further research on UV treatment of domestic sewage is recommended.     

Levels and patterns of polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls in surface sediments from the western Baltic Sea (Arkona Basin) and the Oder River estuarine system

Surface sediment samples were collected from the western Baltic Sea (Arkona Basin) and the Oder River estuarine system in May and August 1995 and analysed for polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls. Contents of PCDF (sum) and PCDD (sum) varied from 2.5 to 820.0 pg g⁻¹ dw and from 12.7 to 2991.0 pg g⁻¹ dw, respectively. PCB contents (sum of 23 congeners) ranged between < 130.0 and 16267.0 pg g⁻¹ dw. Only slight variations in PCDF/D and PCB contents on dry weight basis were found between the Oder River estuarine system and the open Baltic Sea. TOC-normalization of the data showed an approximately homogen PCDF/D distribution in the study area. The distribution pattern for PCDF/D and PCB may be attributed to high sediment dynamics combined with transport processes from the temporary sedimentation basin (Oderhaff) to the deeper parts of the Baltic Sea.     

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.     

The West Falmouth oil spill after 20 years: Fate of fuel oil compounds and effects on animals

The barge Florida spilled No. 2 fuel oil into Buzzards Bay, Massachusetts on 29 September 1969. Sediments from five of the original stations were sampled in August 1989 and analysed for fuel oil hydrocarbons. Two subtidal and one intertidal marsh station showed no evidence of fuel oil. One subtidal mud core had traces of biodegraded fuel oil at 10–15 cm. One marsh core contained 10⁻⁶ g g⁻¹ dry wt of weathered and biodegraded fuel oil aromatic hydrocarbons and cycloalkanes at 5–10 cm with lesser concentrations at 0–5 and 10–15 cm. Although present in trace concentrations, these hydrocarbons appear to be slightly inducing cytochrome P4501A in marsh fish (Fundulus heteroclitus).