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Sorption of tributyltin onto a natural quartz sand.

The aim of this study is to understand the sorption of tributyltin (TBT) onto natural quartz sand by classical batch experiments and spectroscopic surface analyses. At pH<6, the major species of TBT is the cation TBT(+). Due to the presence of both the cationic part and the butyl chains, TBT should present amphiphilic properties. For concentrations lower than 40 microM, TBT sorption occurs as a homovalent 1:1 cation exchange between either H(+) or Na(+) and TBT(+). The increasing affinity of TBT with respect to the different materials follows the series kaolinite<<natural sand<treated sand<pure quartz. From XPS analyses, where the chemical environment of Sn did not change, indicating possible complete reversibility of the TBT sorption, it seems that inner-sphere surface complexes could be formed due to the increase in the 3d-level binding energy. At TBT concentrations higher than 100 microM, we showed by flotation experiments and XPS analysis that the surface becomes hydrophobic. After one monolayer was formed, the TBT sorption could thus be due to hydrophobic interaction between the butyl chains of the sorbed TBT and those of the TBT still available from the bulk solution. This mechanism is consistent with surface condensation and the shape of the sorption isotherm.

Absorption↗

The effect of TBT on the structure of a marine sediment comunity--a Boxcosm study.

The effect of tri-n-butyl tin (TBT) on an intact marine sediment community after five months exposure was investigated. Changes in the structure of macro- and meiofauna communities were determined, as well as the functional diversity of the microbial community using BIOLOG microplates for Gram negative bacteria. Development of tolerance in the microbial community was investigated using Pollution Induced Community Tolerance (PICT) experiments with fluxes of nutrients as effect indicators. TBT affected the structure and recruitment of the macro- and meiofauna at nominal additions of 30-137 micromol TBT/m2 sediment. Number of species, diversity, biomass and community similarity was reduced at these concentrations compared to control. Species that molt seemed to be the most tolerant since they were predominant in boxes that had received the highest TBT addition and echinoderms were the most sensitive species. Renewed addition of TBT in PICT experiments with sediment from each boxcosm showed that TBT had an effect on individual nutrient fluxes from all sediments. Analyses of the flux patterns revealed a memory of previous TBT exposure, either due to induced tolerance or other community conditioning.

Adaptation, Physiological↗

The significance of imposex levels and TBT contamination in the red whelk, Neptunea antiqua (L.) from the offshore Irish Sea.

The extent to which open seas and oceanic waters have been contaminated by TBT is unclear since most sampling programmes have concentrated on inshore areas, particularly near harbours. Accordingly, the red whelk, Neptunea antiqua L. (Mollusca: Prosobranchia), a sublittoral and dioecious prosobranch species, was selected to investigate the potential effects of TBT-induced imposex in the central western Irish Sea. The presence of imposex was noted in > 90% of all female whelks that were examined on a monthly basis over a 12-month period. However, the proliferation of the vas deferens was not considered severe enough to affect the reproductive capabilities of the population. Low concentrations of butyltins were detected in the soft tissues of all whelks examined, ranging from 0.009 to 0.112 microg g(-1) Sn dry wt There was no significant correlation between the documented imposex stages and total butyltin contamination, indicating that the species is not a reliable bioindicator species of the effects of this contaminant.

Animals↗

Incidence of imposex in thais orbita from Port Phillip Bay (Victoria, Australia), following 10 years of regulation on use of TBT.

Imposex, the phenomenon in which induced male sex characteristics are superimposed on normal females, still occurs widely in the gastropod Thais orbita from Port Philip Bay, and its incidence is greatest in areas that have high boating and shipping activities. Compared to 1992, both the extent and severity of imposex has reduced. By inference, this means that pollution by tributyltin (TBT) in Port Phillip Bay has decreased and that the bans limiting its use to vessels greater than 25 m in length, in place since 1989, have been effective. However, TBT pollution is still an issue at locations that are adjacent to major ports, such as the Port of Melbourne, where TBT from large ships and ship maintenance activities continues to pollute fish habitats. It is anticipated that the incidence of imposex, and therefore TBT pollution, will continue to decrease in Port Phillip Bay as long as the bans currently in place continue to be observed. If the trends observed in the present study continue, then it is unlikely, with the notable exception of commercial ports, that TBT will pose a threat to the health of fish habitats in Port Phillip Bay.

Animals↗

Tributyltin along the coasts of Corsica (Western Mediterranean): a persistent problem.

Despite optimistic forecasts by various scientists after regulatory measures were taken in the 1980s, coastal tributyltin (TBT) contamination is still a major problem. The present study concerning Corsica (Western Mediterranean) shows that contamination is not limited to harbour areas, but extends along the coast, involving protected nature reserves. The concentrations measured in harbours, which can reach 200 ng TBT l(-1), tend to incriminate both pleasure craft and ferries providing regular service between the island and the continent. Contamination as high as 7 ng TBT l(-1) has been measured in waters of the Scandola nature reserve, which is quite excessive given the no effect concentrations (NOEC) for marine fauna are around 1-2 ng TBT l(-1). The inadequacy of current regulations and their application are a major factor in this situation.

Environmental Monitoring↗

Understanding ship-grounding impacts on a coral reef: potential effects of anti-foulant paint contamination on coral recruitment.

The 184 m cargo ship Bunga Teratai Satu collided with Sudbury Reef, part of the Great Barrier Reef and remained grounded for 12 days. The ship was re-floated only 3 days prior to the November 2000 mass coral spawning. No cargo or fuel was lost but the impact resulted in significant contamination of the reef with anti-foulant paint containing tributyltin (TBT), copper (Cu) and zinc (Zn). Larvae of the reef-building scleractinian coral Acropora microphthalma were exposed to various concentrations of sediment collected from the grounding site in replicated laboratory experiments. Two experiments were performed, both of which used varying ratios of contaminated and control site sediment in seawater as treatments. In the first experiment, the influence of contaminated sediment on larval competency was examined using metamorphosis bioassays. In the second, the effect of contaminated sediment upon larval recruitment on pre-conditioned terracotta tiles was assessed. In both experiments, sediment containing 8.0 mg kg(-1) TBT, 72 mg kg(-1) Cu and 92 mg kg(-1) Zn significantly inhibited larval settlement and metamorphosis. At this level of contamination larvae survived but contracted to a spherical shape and swimming and searching behaviour ceased. At higher contamination levels, 100% mortality was recorded. These results indicate that the contamination of sediment by anti-fouling paint at Sudbury Reef has the potential to significantly reduce coral recruitment in the immediate vicinity of the site and that this contamination may threaten the recovery of the resident coral community unless the paint is removed.

Animals↗

Spatial and temporal changes of TBT pollution along the Portuguese coast: inefficacy of the EEC directive 89/677.

Nucella lapillus imposex (superimposition of male characters onto prosobranch females) and organotin body burden were surveyed in the Portuguese coast in 1997 and 2000. Time comparisons of the available data on Nucella lapillus imposex in the Portuguese coast indicate a global increase of TBT pollution in recent years, revealing the inefficacy of the 1993 legislation that bans the use of TBT paints on small boats (<25 m). The absence or scarcity of the species inside harbours, which are the most polluted sites in Portugal, is probably a consequence of extinction due to female sterilisation by TBT.

Animals↗

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.

Animals↗

TBT toxicity on the marine microalga Nannochloropsis oculata.

Commercial antifouling formulations containing TBT are the major source of organotin contamination in coastal waters. In view of the persisting TBT residues (13 ng Sn l(-1)) in the coastal waters of South Korea, an attempt has been made to evaluate the growth response and biochemical composition of laboratory-cultured Nannochloropsis oculata to TBT toxicity. It is evident that the persisting concentration level of TBT is high enough to cause adverse effect on the microalgal species. The EC50 (24 h) was found to be at 0.89 nM level of TBT for this marine eustigmatophyte N. oculata. Photosynthetic pigment content was significantly affected. At elevated TBT concentrations of 1.0 nM, especially pronounced changes in biochemical composition was found. TBT tolerance of N. oculata and its growth as well as biochemical responses are discussed.

Eukaryota↗

Re-colonisation and recovery of populations of dogwhelks Nucella lapillus (L.) on shores formerly subject to severe TBT contamination.

Dogwhelks Nucella lapillus became locally extinct on some shores adjacent to areas of high shipping/boating activity during the period of high tributyltin (TBT) contamination in the 1980s and early 1990s. However, the species has now re-colonised sites at which extinction occurred on the Isle of Cumbrae, the northeast coast of England, the Shetland Isles and southwest England. There have also been substantial declines in the severity of imposex on adjacent shores where the species has persisted during this period. Re-colonisation and recovery can be attributed to two measures: regulations prohibiting the use of TBT-based paints on vessels < 25 m in length and the development of slow-releasing, self-polishing copolymer paints. Nevertheless, the International Maritime Organisation has now imposed a total ban on the use of TBT-based paints as antifoulants. This is almost certain to result in the use of paints containing alternative biocides and there is widespread concern that there is relatively little information on which to assess their likely environmental impacts. They could cause substantial environmental damage.

Animals↗

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.

Animals↗

Effects of antifouling paint components (TBTO, copper and triazine) on the early development of embryos in cod (Gadus morhua L.).

To assess the risk of antifoulant use to the commercially important cod (Gadus morhua L.), fertilised cod eggs were exposed to triazine, copper and TBTO singly or combined in laboratory tests with running seawater. At the highest tested concentrations (11.5 microg Cu l(-1); 5 microg TBTO l(-1)) larval mortality was increased. The highest concentration of triazine (40 microg l(-1)) did not cause any significant mortality. Fertilised eggs that had been exposed to all the three chemicals singly for five days showed a higher buoyancy than the controls. No synergistic or antagonistic effects were indicated. Embryos/larvae exposed to 0.004-0.8 microg TBTO l(-1) did not show any changed respiration compared to the controls after hatching. It is concluded that existing known field concentrations of the three antifoulants are hardly expected to cause detectable effects on fish embryonic/larval development.

Animals↗

Removal of tributyltin (TBT) by live and dead microalgal cells.

The removal of tributyltin (TBT) from artificial wastewater by dead and live cells of four microalgal species, Chlorella miniata, C. sorokiniana, Scenedesmus dimorphus and S. platydiscus was investigated. Dead cells were generally more efficient in removing TBT during three days exposure. More than 90% and 85% TBT were removed by dead cells of Scenedesmus and Chlorella, respectively. Although the removal percentages of live microalgae were smaller, TBT was continuously absorbed and degraded, and TBT removal percentages similar to respective dead cells were achieved at the end of 14 days treatment. Degradation products, DBT and MBT, were recorded mainly inside the cells, and intracellular MBT concentrations were significantly higher than DBT. In terms of TBT removal, Scenedesmus cells were more effective than Chlorella, probably due to larger cell sizes and biomass. However, TBT specific uptake and degradation by Chlorella was higher than in Scenedesmus. The highest specific TBT uptake values, as well as the highest degradation, were recorded in C. miniata, a Hong Kong isolate.

Adsorption↗

Economic and environmental impacts on ports and harbors from the convention to ban harmful marine anti-fouling systems.

The recent Diplomatic Conference held (1-5 October 2001) by the International Maritime Organization (IMO) in London adopted the Draft Convention prepared by The Marine Environmental Protection Committee (MEPC) of IMO for the "Control of Harmful Anti-fouling Systems for Ships." The convention has been developed to immediately ban the use of Tributyltin (TBT) globally in anti-fouling paints to "protect the marine environment". The ban on TBT has come about because TBT has detrimental effects on non-target marine organisms. In November 1999, IMO agreed that a treaty be developed by the MEPC to ensure a ban on the application of TBT based anti-fouling paints by 1 January 2003, and a ban on the use of TBT by 1 January 2008. At the meeting surious concern was expressed by some experts for the need to identify in the treaty the necessary regulatory language for: (1) the "safe" removal, treatment, and disposal of marine anti-foulants deemed "harmful" by the treaty and (2) who is liable for the future dredging and disposal of TBT-contaminated port and harbor sediments--to also "protect the marine environment". The requirement for "safe" removal and disposal was incorporated at MEPC 46 as Article 5 in the treaty, without it shipyards complying with existing national and local discharge regulations (most have none for discharge of TBT) could inadvertently release more TBT to ports and harbors in the five-year compliance period than has been leached from ships (hulls) in the past 40 years to the same waters. Virginia is the only State in the US that regulates the discharge to below 50 ng/l (50 parts per trillion). However, the liability for the future dredging and disposal costs of TBT-contaminated port and harbor sediments has not been addressed.

Commerce↗

Chronic effects of tributyltin on the caprellid amphipod Caprella danilevskii.

In order to examine the biological effects by TBT exposure, experiments involving the exposure of five levels of TBT concentrations (0, 10, 100, 1000 and 10,000 ngl(-1)) were conducted on the caprellid amphipod Caprella danilevskii, over a generation after hatching. Marked delays in growth and molting during the early developmental stage and maturation were found in both 100 and 1000 ng TBTCl l(-1) concentrations in spite of the sex. All specimens died in 10,000 ng TBTCl l(-1) within 4 days after hatching. Inhibition of maturation and reproduction such as delaying in the achievement of maturity and a decrease in the number of juveniles hatched was apparent in 10 and 100 ng TBTCl l(-1) concentrations. Furthermore, brood loss, and failure in egg formation and hatching were observed as the TBT concentration became higher. No significant changes in sex ratio were seen at any of the TBT exposure levels during hatching and maturation in the present study. This phenomenon was different from a previous study in which the proportion of females was increased with an increase in TBT concentrations in the embryonic exposure experiment. This suggests that sex disturbance is induced during the embryonic stage of the species. A drastic decrease in survival rate was observed at 10 ng TBTCl l(-1) (25%) which corresponds to the mean level in coastal waters. Therefore, the present encountering ambient TBT concentration may influence populations of C. danilevskii in the coastal environment.

Amphipoda↗

Imposex in the indigenous Nassarius kraussianus (Mollusca: Neogastropoda) from South African harbours.

Nassarius kraussianus populations in the Durban and Richards Bay harbours (along the eastern seaboard of southern Africa) and in the Knysna lagoon (southern Cape coast) showed imposex development, confirming bioavailability of tributyltin (TBT) in these waterways. Incidence of imposex (which ranged from 29% to 100%) and relative penis length of females (RPL; which ranged from 1.3% to 55.2%) were markedly variable among populations from different sites in each waterway, indicative of localised effects of TBT contamination. Shell length of the snails was apparently not correlated with contamination level, as assessed from imposex measurements. While population imposex features are easy to determine and often provide a sensitive biomarker of TBT exposure, the discussion outlines reservations when extrapolating these to general ecological situations. Additionally, this study represents the first published report on the topic for sub-Saharan, African harbours, some of which seem remarkably less affected than suggested for other world regions.

Animals↗