A review and assessment of tributyltin contamination in the North Sea,based on surveys of butyltin tissue burdens and imposex/intersex in four species of neogastropods

It is evident from measures of butyltin tissue burdens and imposex or intersex in neogastropods that tributyltin (TBT) contamination of coastal waters and open parts of the North Sea is now low. It has been declining for at least the past decade. This is probably due to two measures. First, regulations prohibiting the use of TBT-based paints on small boats and fish farms have reduced inputs of TBT from these sources so that they are now negligible (except possibly where the regulations are flaunted). Second, there is evidence from sites, where commercial vessels are the sole source of TBT, that the adoption of TBT SPC paints has been effective in reducing environmental levels of these contaminants. However, poor dockyard practices, allowing TBT-contaminated wastes, including paint flakes, to accumulate in sediments have left a legacy of hot-spots of contamination in some ports. The impact is localised so that TBT contamination is low in coastal areas immediately adjacent to ports.     

Medium-term assessment of the effects of the Prestige oil spill on estuarine benthic communities in Cantabria (Northern Spain, Bay of Biscay)

A specific monitoring program was implemented in the estuaries of Cantabria (northern Spain) in order to assess the medium-term effects (2003-2005) of the Prestige oil spill (POS) on benthic macroinvertebrate communities. A control-impact design was adopted, examining four unaffected and five oil-affected estuaries. High mortalities and significant differences in overall richness and diversity between the control and impacted estuaries were not detected. Some changes in the temporal evolution of species abundance were observed for some key species, but these could not be related to the spillage event. It was not possible to ensure that low magnitude effects had not occurred, due to the high range of natural variability of benthic communities, the confounding effects of other contamination sources and the absence of previous reference conditions.     

A survey of imposex in muricids from 1996 to 2000 and identification of optimal indicators of tributyltin contamination along the east coast of Phuket Island,Thailand

The present investigation is the most extensive survey of imposex in gastropods from the west coast of Thailand. Imposex in Thais distinguenda increased significantly (p < 0.001; Chi Square test for trend) from 1996 to 2000 at 21 stations in Phangna Bay, Thailand. Females with imposex increased, extending from 3.5 km in 1996 to 10 km from the harbour areas in 1999 and 2000. Increasing intensity of imposex was also observed for Thais bitubercularis from 1996 to 2000. The less sensitive species: Morula musiva, Morula granulata, Morula margariticola and Thais rufotincta only developed imposex at the three main areas of intense shipping activities. T. bitubercularis and T. distinguenda are recommended as indicators of tributyltin (TBT) in Southeast Asia because of their sensitivity and wide distribution in the region. The results suggest that TBT contamination is worsening, against global trends, because regulations prohibiting the use of TBT-based paints, do not exist in Thailand.     

TBT-pollution in the Gulf of Thailand: A re-inspection of imposex incidence after 10 years

Imposex in neogastropods was used to determine the relative TBT distribution in the Gulf of Thailand in 2006. To identify the imposex prevalence, 8757 specimens, belonging to 22 species from five families of neogastropods, were collected at 56 sites in 13 sample areas. These areas were located between the Bight of Bangkok in the north and the Malaysian border in the south. A contamination model was developed to compensate for differences in TBT sensitivity among species and to make comparisons among areas. At every area imposex was found in neogastropods. The highest incidence was in the east side of the Bight of Bangkok off Si Racha and Pattaya and in the southern part around Pattani. The same areas showed the highest frequency of imposex in 1996. While the frequency of imposex appeared to have slightly decreased in these areas, increases were found elsewhere. In Pattani Province this could be related to dumping of highly polluted harbour sediments in the shallow coastal area. The overall frequency of imposex in the Gulf of Thailand significantly increased from 1996 to 2006.     

Modelling of hydrodynamics and cohesive sediment transport in Tanshui River estuarine system,Taiwan

A laterally averaged two-dimensional numerical model is used to simulate hydrodynamics and cohesive sediment transport in the Tanshui River estuarine system. The model handles tributaries as well as the main stem of the estuarine system. Observed time series of salinity data and tidally averaged salinity distributions have been compared with model results to calibrate the turbulent diffusion coefficients. The overall model verification is achieved with comparisons of residual currents and salinity distribution. The model reproduces the prototype water surface elevation, currents and salinity distributions. Comparisons of the suspended cohesive sediment concentrations calculated by the numerical model and the field data at various stations show good agreement. The validated model is applied to investigate the tidally averaged salinity distributions, residual circulation and suspended sediment concentration under low flow conditions in the Tanshui River estuarine system. The model results show that the limit of salt intrusion in the mainstem estuary is located at Hsin-Hai bridge in Tahan Stream, 26 km from the River mouth under Q75 flow. The null point is located at the head of salt intrusion, using 1 ppt isohaline as an indicator. The tidally averaged sediment concentration distribution exhibits a local maximum around the null point.     

Seasonal changes in imposex and tissue burden of butyltin compounds in Thais clavigera populations along the coastal area of Mirs Bay, China

We assessed the current status of tributyltin (TBT) contamination of Thais clavigera (Gastropoda) along the coastal area of Mirs Bay, China for the first time. The snail samples were collected from 10 different sites in the summer (June) and winter (December) of 2006, respectively. They were analyzed for imposex status, i.e. relative penis size index (RPSI) and vas deferens sequence index (VDSI), followed by quantification of butyltins in their tissues. Most of the collected females suffered from imposex, but the level of butyltin contamination varied with the distance from Yantian Port, which is currently the fourth busiest container port in the world. The tissue concentration of TBT varied with season. For a particular site, the winter samples in general contained much higher concentration of TBT than the summer samples. RPSI, VDSI and organotin concentrations were higher in T. clavigera collected from sites closer to the Port, such as the Seafood Street and Kat O. Both RPSI and VDSI were positively correlated with the tissue burden of tributyltin. VDSI exhibited little seasonal variability, whereas RPSI showed marked seasonal variability, with lower values in the summer samples. The current results will serve as an important reference for long-term monitoring of butyltin contamination in this area.     

Toxicity of tributyltin in the marine mollusc Mytilus edulis

Our previous studies have demonstrated that tributyltin (TBT) is genotoxic to the early life stages of marine mussels and worms. Here, the toxicity of TBT to adult organisms was determined using a suite of biomarkers designed to detect cytotoxic, immunotoxic and genotoxic effects. Exposure of adult mussels, Mytilus edulis, to environmentally realistic concentrations of TBTO for 7 days resulted in a statistically significant decrease in cell viability at concentrations of 0.5 μg/l and above. TBT had no effect on phagocytic activity or antioxidant capacity (FRAP assay). There was a statistically significant increase in DNA damage detected using the comet and micronucleus assays between the controls and 0.5, 1 and 5 μg/l of TBTO (P > 0.0005). Furthermore there was a strong correlation between DNA strand breaks (comet assay) and formation of micronuclei (P = 0.0005; R² = 61.5%). Possible mechanisms by which TBT could damage DNA either directly or indirectly are discussed including the possibility that TBT is genotoxic due to its ability to disrupt calcium homeostasis.     

Observations on the biota of an estuarine beach at Hardys Bay (NSW, Australia) following a spillage of aldrin

An industrial accident resulted in a spillage of aldrin onto an estuarine beach at Hardys Bay, New South Wales. Samples of water and sediment were taken 3 weeks later to measure the level of contamination resulting from the spill. The abundances of some intertidal biota were also determined at the site of the spillage and in other uncontaminated areas.

Three weeks after the spill, samples of water were not contaminated by aldrin but samples of sediment from the surface in the vicinity of the drain contained aldrin. In comparison to uncontaminated locations the abundances of crustacea were greatly reduced in the vicinity of the drain but abundances of polychaetes were not significantly different. The field data on the relative susceptibility of the two groups of animals agrees well with laboratory derived LC50 data for crustacea and polychaetes.

The study suggests that degree of contamination of water and sediment may not always be an accurate reflection of acute impact on biota, and that different components of the biota can show different reactions to the presence of a toxic chemical.     

Status of butyltin pollution along the coasts of western Japan in 2001, 11 years after partial restrictions on the usage of tributyltin

Restrictions on the use of tributyltin (TBT) in aquaculture and on boats in coastal regions, except for ocean-going vessels, have been in place in Japan since 1990 due to the strong toxic effects of TBT on marine organisms. However, TBT pollution along the Japanese coasts has been reported after this legislation was enacted. In order to elucidate the present status of contamination by butyltin (BT) compounds, we measured the levels of BTs [monobutyltin (MBT), dibutyltin (DBT) and TBT] in seawater and Caprella spp. samples obtained from the western part of Seto Inland Sea, Uwa Sea and Uranouchi Bay in western Japan during March to September, 2001. Butyltins were detected in more than 90% of the seawater samples (n = 59), with average concentrations of 8.2 ± 9.2 (SD) ng MBT L⁻¹, 3.3 ± 3.0 ng DBT L⁻¹ and 9.0 ± 7.0 ng TBT L⁻¹. Among 41 stations situated on coastal lines, a sufficient number of Caprella organisms for chemical analysis could be collected from only 16 stations. The butyltin concentrations in seawater and Caprella samples from Uwa Sea and Uranouchi Bay, in which the dominant industry in both waters is aquaculture, showed significantly higher than or no significant differences from those samples from the western part of Seto Inland Sea, a major heavy-industry area in Japan. As the TBT concentration in seawater increased, the number of Caprella organisms collected decreased. The mean TBT concentration among the seawater samples was above the estimated lowest observable effect concentration (LOEC) that reduces the survival rate of Caprella danilevskii. Thus, the present study indicates that TBT is still a potential ecological hazard to the survival of marine invertebrates inhabiting coasts along western Japan, even 11 years after the partial ban on TBT usage was implemented.     

Bowhead whales feed on plankton concentrated by estuarine and tidal currents in Academy Bay,Sea of Okhotsk

Academy Bay in the Sea of Okhotsk is an important summertime feeding ground for pelagic-feeding Bowhead whales (Balaena mysticetus) in the western subarctic North Pacific. The present work combines satellite observations with physical (CTD, currents, tides) and biological (zooplankton sampling) measurements. Data obtained aboard the RV Lugovoe in August–September 2003 and July–August 2004 show dense populations of zooplankton (such as copepods Calanus glacialis, Pseudocalanus sp., pteropods Limacina helicina, and chaetognaths Sagitta sp.) that are concentrated by physical mechanisms within this critically important ecosystem. We show that near-bottom, cold water intrusions from the northern Sea of Okhotsk associated with the estuarine circulation advect arctic herbivorous calanoids (Calanus glacialis) and mollusks Limacina helicina into the region.     

Seasonal variation in the transverse and layered structure of estuarine circulation in Ariake Bay, Japan

Seasonal variation in the transverse and layered structure of estuarine circulation in Ariake Bay, Japan was investigated by box model analysis using monthly salinity data from 1990 to 2000. Two-layered gravitational estuarine circulation was intensified from autumn to spring (vertically well mixed season) accompanied by a small river discharge. Two-layered circulation was weakened accompanying the transversely segregated cyclonic circulation in the upper layer during summer (stratified season) with a large river discharge. Such seasonal variation in the transverse and layered structure of estuarine circulation is because the bay width of Ariake Bay (20 km) is narrower than the external Rossby deformation radius (235 km) but wider than the internal Rossby deformation radius (3–5 km).     

Toxicity of tributyltin in the marine mollusc Mytilus edulis

Our previous studies have demonstrated that tributyltin (TBT) is genotoxic to the early life stages of marine mussels and worms. Here, the toxicity of TBT to adult organisms was determined using a suite of biomarkers designed to detect cytotoxic, immunotoxic and genotoxic effects. Exposure of adult mussels, Mytilus edulis, to environmentally realistic concentrations of TBTO for 7 days resulted in a statistically significant decrease in cell viability at concentrations of 0.5 μg/l and above. TBT had no effect on phagocytic activity or antioxidant capacity (FRAP assay). There was a statistically significant increase in DNA damage detected using the comet and micronucleus assays between the controls and 0.5, 1 and 5 μg/l of TBTO (P > 0.0005). Furthermore there was a strong correlation between DNA strand breaks (comet assay) and formation of micronuclei (P = 0.0005; R² = 61.5%). Possible mechanisms by which TBT could damage DNA either directly or indirectly are discussed including the possibility that TBT is genotoxic due to its ability to disrupt calcium homeostasis.     

Differences in the acute toxicities of tributyltin between the Caprellidea and the Gammaridea (Crustacea: Amphipoda)

Tests for the acute toxicity of tributyltin (TBT) were conducted on amphipod crustaceans collected from Otsuchi Bay, Japan. Five species of caprellids and three species of gammarids, which belong to a closely related ecological niche, were used for the exposure experiments at seven test concentrations (0, 0.001, 0.01, 0.1, 1, 10 and 100 microg TBTCl/l) for 48 h at 20 degrees C. The 48-h LC50 values of the caprellids were 1.2-6.6 microg TBTCl/l, and these were significantly lower than those of the gammarids (17.8-23.1 microg TBTCl/l). This suggests that caprellids are more sensitive to TBT than gammarids. Furthermore, the proportions of TBT and its derivatives, dibutyltin (DBT) and monobutyltin (MBT), were measured in the amphipods collected from Otsuchi Bay. In the caprellids, TBT was the predominant compound, accounting for 72% of the total butyltin which reflected the butyltin ratio in seawater, while in the gammarids, TBT's breakdown products (DBT and MBT) predominated, accounting for 75% of the total butyltin. This difference suggests that caprellids may have lower metabolic capacity to degrade TBT than gammarids. Therefore, the difference in sensitivity to TBT among the amphipods is thought to be related to the species-specific capacity to metabolize TBT.     

Erosion rather than plant dieback as the mechanism of marsh loss in an estuarine marsh

Coastal marsh loss in Louisiana is attributed to plane dieback caused by processes that stress vegetation, and a common landscape pattern is broken marsh that expands at the expense of surrounding unbroken marsh. We tested the hypothesis that vegetation is more stressed in broken marsh than in adjacent unbroken marsh, as indicated by vegetation aboveground biomass, species diversity and soil Eh, on transects that extended from broken marsh to unbroken marsh at Marsh Island, Louisiana. Soil Eh, vegetation above-ground biomass and species diversity did not differ between broken marsh and unbroken marsh, and above-ground biomass was similar to that reported from other marshes. Thus, we rejected the hypothesis that marsh loss is related to vegetation stress. Two factors were related to vegetation vigour: soil drainage and soil bulk density. Surprisingly, significant soil drainage occurred in broken marsh but not in unbroken marsh. Above-ground biomass of the dominant plant, Spartina patens (Aiton) Muhl., was lowest where soil bulk density was less than 0-08 gcm⁻³, which illustrated the importance of mineral matter accumulation in submerging coastal marshes. The mechanism of marsh loss appeared to be erosion below the living root zone, as indicated by the vertical and often undercut marsh-water interface, and by the separation of sod clasts. This is different from more rapid marsh loss associated with plant stress which we observed in other Louisiana marshes only 135 km away, indicating that marsh loss mechanisms can vary spatially even within a relatively small region.     

An idealized model study of flocculation on sediment trapping in an estuarine turbidity maximum

Flocculation has an important impact on particle trapping in estuarine turbidity maximum (ETM) through associated increases in particle settling velocity. To quantify the importance of the flocculation processes, a size-resolved flocculation model is implemented into an ocean circulation model to simulate fine-grained particle trapping in an ETM. The model resolves the particle size from robust small flocs, about 30 μm, to very large flocs, over 1000 μm. An idealized two-dimensional model study is performed to simulate along-channel variations of suspended sediment concentrations driven by gravitational circulation and tidal currents. The results indicate that the flocculation processes play a key role in generating strong tidal asymmetrical variations in suspended sediment concentration and particle trapping. Comparison with observations suggests that the flocculation model produces realistic characteristics of an ETM.     

Tidal effects on estuarine circulation and outflow plume in the Chesapeake Bay

The response of the Chesapeake Bay to river discharge under the influence and absence of tide is simulated with a numerical model. Four numerical experiments are examined: (1) response to river discharge only; (2) response to river discharge plus an ambient coastal current along the shelf outside the bay; (3) response to river discharge and tidal forcing; and (4) response to river discharge, tidal forcing, and ambient coastal current. The general salinity distribution in the four cases is similar to observations inside the bay. Observed features, such as low salinity in the western side of the bay, are consistent in model results. Also, a typical estuarine circulation with seaward current in the upper layer and landward current in the lower layer is obtained in the four cases. The two cases without tide produce stronger subtidal currents than the cases with tide owing to greater frictional effects in the cases with tide. Differences in salinity distributions among the four cases appear mostly outside the bay in terms of the outflow plume structure. The two cases without tide produce an upstream (as in a Kelvin wave sense) or northward branch of the outflow plume, while the cases with tide produce an expected downstream or southward plume. Increased friction in the cases with tide changes the vertical structure of outflow at the entrance to the bay and induces large horizontal variations in the exchange flow. Consequently, the outflow from the bay is more influenced by the bottom than in the cases without tide. Therefore, a tendency for a bottom-advected plume appears in the cases with tide, rather than a surface-advected plume, which develops in the cases without tide. Further analysis shows that the tidal current favors a salt balance between the horizontal and vertical advection of salinity around the plume and hinders the upstream expansion of the plume outside the bay.     

Effects of an estuarine plume-associated bloom on the carbonate system in the lower reaches of the Pearl River estuary and the coastal zone of the northern South China Sea

We observed a phytoplankton bloom downstream of a large estuarine plume induced by heavy precipitation during a cruise conducted in the Pearl River estuary and the northern South China Sea in May–June 2001. The plume delivered a significant amount of nutrients into the estuary and the adjacent coastal region, and enhanced stratification stimulating a phytoplankton bloom in the region near and offshore of Hong Kong. A several fold increase (0.2–1.8 μg Chl L⁻¹) in biomass (Chl a) was observed during the bloom. During the bloom event, the surface water phytoplankton community structure significantly shifted from a pico-phytoplankton dominated community to one dominated by micro-phytoplankton (>20 μm). In addition to increased Chl a, we observed a significant drawdown of pCO₂, biological uptake of dissolved inorganic carbon (DIC) and an associated enhancement of dissolved oxygen and pH, demonstrating enhanced photosynthesis during the bloom. During the bloom, we estimated a net DIC drawdown of 100–150 μmol kg⁻¹ and a TAlk increase of 0–50 μmol kg⁻¹. The mean sea–air CO₂ flux at the peak of the bloom was estimated to be as high as ∼−18 mmol m⁻² d⁻¹. For an average surface water depth of 5 m, a very high apparent biological CO₂ consumption rate of 70–110 mmol m⁻² d⁻¹ was estimated. This value is 2–6 times higher than the estimated air–sea exchange rate.     

The estuarine chemistry and isotope systematics of U in the Amazon and Fly Rivers

Natural concentrations of ²³⁸U and δ²³⁴U values were determined in estuarine surface waters and pore waters of the Amazon and Fly (Papua New Guinea) Rivers to investigate U transport phenomena across river-dominated land–sea margins. Discharge from large, tropical rivers is a major source of dissolved and solid materials transported to the oceans, and are important in defining not only oceanic mass budgets, but also terrestrial weathering rates.On the Amazon shelf, salinity-property plots of dissolved organic carbon, pH and total suspended matter revealed two vastly contrasting water masses that were energetically mixed. In this mixing zone, the distribution of uranium was highly non-conservative and exhibited extensive removal from the water column. Uranium removal was most pronounced within a salinity range of 0–16.6, and likely the result of scavenging and flocculation reactions with inorganic (i.e., Fe/Mn oxides) and organic colloids/particles. Removal of uranium may also be closely coupled to exchange and resuspension processes at the sediment/water interface. An inner-shelf pore water profile indicated the following diagenetic processes: extensive (1 m) zones of Fe(III)—and, to a lesser degree, Mn(IV)—reduction in the absence of significant S(II) concentrations appeared to facilitate the formation of various authigenic minerals (e.g., siderite, rhodocrosite and uraninite). The pore water dissolved ²³⁸U profile co-varied closely with Mn(II). Isotopic variations as evidenced in δ²³⁴U pore waters values from this site revealed information on the origin and history of particulate uranium. Only after a depth of about 1 m did the δ²³⁴U value approach unity (secular equilibrium), denoting a residual lattice bound uranium complex that is likely an upper-drainage basin weathering product. This suggests that the enriched δ²³⁴U values represent a riverine surface complexation product that is actively involved in Mn–Fe diagenetic cycles and surface complexation reactions.In the Fly River estuary, ²³⁸U appears to exhibit a reasonably conservative distribution as a function of salinity. The absence of observed U removal does not necessarily imply non-reactivity, but instead may record an integration of concurrent U removal and release processes. There is not a linear correlation between δ²³⁴U vs. 1/²³⁸U that would imply simple two component mixing. It is likely that resuspension of bottom sediments, prolonged residence times in the lower reaches of the Fly River, and energetic particle–colloid interactions contribute to the observed estuarine U distribution. The supply of uranium discharged from humid, tropical river systems to the sea appears to be foremost influenced by particle/water interactions that are ultimately governed by the particular physiographic and hydrologic characteristics of an estuary.