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Research on tributyltin in Australian estuaries
Abstract
Tributyltin (TBT) from marine antifouling paints has been shown to have a major impact on the oyster industry in eastern Australia. Current research projects are examining the impact of TBT on Australian estuaries, assessing the response of sensitive biota to recently imposed bans and determining whether a continuing use of TBT on large vessels is an environmental concern.
... Kogarah Bay, NSW Pre-ban 100 Batley et al. (1989a) Port Phillip Bay, Vic. Pre-ban 3-23 Batley and Scammell (1991) Southport, Qld Pre-ban 45 Batley and Scammell (1991) In the Georges River (NSW), an urban estuary, oysters (Saccostrea commercialis) in 1988 had copper concentrations exceeding the guideline concentration of 70 µg g-1. This was attributed to antifouling paints (Batley et al. 1992). ...
... Kogarah Bay, NSW Pre-ban 100 Batley et al. (1989a) Port Phillip Bay, Vic. Pre-ban 3-23 Batley and Scammell (1991) Southport, Qld Pre-ban 45 Batley and Scammell (1991) In the Georges River (NSW), an urban estuary, oysters (Saccostrea commercialis) in 1988 had copper concentrations exceeding the guideline concentration of 70 µg g-1. This was attributed to antifouling paints (Batley et al. 1992). ...
... As with heavy metals, the greatest concentrations of TBT are found in sediments. Data have been obtained for sites in Vic., Qld, SA, WA and NSW for their respective environmental authorities, and the results have been similar for each location (Batley & Scammell 1991;Witney 1991;EPAWA 1990). ...
... Tributyltin (TBT) is a highly toxic chemical that has been used worldwide in antifouling paints, mainly on ships and aquaculture facilities, to prevent the growth of marine organisms such as bacteria, mussels, and algae (Batley and Scammell, 1991;Cardwell et al., 1999;Ko et al., 1995;Murai et al., 2005). It is well known that TBT severely disrupts the endocrine systems of marine organisms, and impaired sexual development is among the typical and severe impacts of TBT on marine organisms (Horiguchi et al., 1997;Matthiessen and Gibbs, 1998;Shimasaki et al., 2003). ...
... TBT is a highly toxic chemical that had been used worldwide as antifouling paints mainly on ships and aquaculture facilities to prevent the growth of marine organisms such as bacteria, mussels and algae (Batley and Scammell, 1991;Cardwell et al., 1999;Ko et al., 1995;Murai et al., 2005). In addition, TBT is well known as a severe endocrine disruptor to marine organisms, and impaired sexual development by TBT is the typical and severe impact on marine organisms https://doi.org/10.1016/j.cbpc.2020.108785 ...
... Lasee (1991), however, reported that juveniles of Lampsilis cardium exposed to cadmium (Cd) concentrations as low as 0.01 mg/kg significantly reduced anterior shell growth. Shell curling, such as the individual in Figure 7 has been reported in marine mussels exposed to tributyltin (TBT -a compound found in marine anti-fouling paints) (see Batley and Scammell 1991). Other shell deformities have also been reported for other marine and estuarine bivalves exposed to heavy metals (Sunila and Lindström 1985;Nias et al. 1993;Yap et al. 2002). ...
... Some coatings, e.g. those containing tri-butyltin (TBT), have resulted in negative effects in cultured shellfish, such as reduced growth and shell thickening ( Batley and Scammell, 1991) and other species. Additionally, the metal compounds in such coatings often accumulate in the flesh of the bivalves, and cause concern for the food industry and public health officials (see McIntosh et al., 2005;Boyle et al., 2006;Milne, 2006). ...
Impacts of biofouling on molluscs (= shellfish) and aquaculture can be extreme and sometimes devastating. Biofouling affects all structures, both natural and artificial, immersed in the marine environment, although often in different ways (Glasby, 1999; Glasby and Connell, 1999; Railkin, 2004). Living organisms, such as gastropod and bivalve molluscs, can provide a massive amount of hard substratum that can be settled upon by larvae of marine organisms. In fact, in many benthic and intertidal areas, the surface area provided by shellfish may be equal to, or greater than, the inert substratum available (Railkin, 2004). Settling sedentary organisms generally recruit to both living and inert substrata (D'Antonio, 1985). Such biofouling of living substrata by both epibionts and endobionts is a major problem within the shellfish aquaculture sector, particularly with regard to the resultant increased labor costs and reduced value 13 Biofouling and the shellfish industry Abstract: The impacts of biofouling on shellfish and aquaculture can be extreme and sometimes devastating. Biofouling is a major problem within the shellfish aquaculture industry, particularly with regard to the resultant increased labor costs and reduced value of product. The chapter discusses the impacts of biofouling, economic costs involved during culture, processing, the value of the end product, and the techniques employed to mitigate and remove biofouling organisms. While biofouling can have drastic impacts on the quality of product, most issues are associated with marketing and reduced aesthetic value. Biofouling does not impact the safety of the product for human consumption.
... Proudfoot, 1990, unpublished results). Tributyltin-based paints are designed to leach at around 4 p~g cm -2 day -1 and this has been found to result in water concentrations ranging from 30 ng Sn 1-1 in estuaries to 300 ng Sn 1 -~ close to marinas (Batley & Scammell, 1991). Based on observations with TBT paints, predicted water concentrations of tetracycline, when used in this manner, could initially be of the order of 15 ~tg 1-1 in the vicinity of painted boats, falling below 0.4 ~tg 1-1 after just 24 h, if the degradation and removal rates were similar. ...
The banning of the use of tributyltin (TBT)-based antifouling paints on boats under 25 m in length, has lead to a search for replacement biocides. A recent yachting magazine article advocated the use of capsules of the antibiotic tetracycline to be added to cheap copper-based paints. The impact of such a paint on non-target bacteria, algae and oysters was investigated. Tetracycline was found to leach rapidly from painted surfaces and degrade quickly in seawater. The concentrations released were insufficient to cause any deleterious effects on marine organisms, including those responsible for fouling boat hulls.
... This is a characteristic shared with many other organic pollutants that promote their migration up the water column and results is their enrichment in the surface microlayer (SMIC), where total BT concentrations exceed many times that of bottom water and TBT largely predominate over DBT (e.g., Cleary, 1991). Thus, working with different oysters Batley and Scammell (1991) reported that, even if grown in similar TBT environments, there was a marked difference in the TBT content between intertidal and subtidal species that was ascribed to the SMIC exposure of the former as the tide rises and falls. Further on this line, in a field work disposing hexane-filled dialysis bags on the sediment and from 5 to 1000 mm above its surface to investigate in situ BT desorption, Stuer-Lauridsen and Dahl (1995) found that the mean concentration of total organic tin (TOT) was significantly lower in sediment bags that in those in the water column, along which TOT concentrations increased almost 3-fold from bottom to top. ...
Two monitoring surveys were repeated in Galicia (NW Spain): one in 2003 concerned the rocky shore gastropod Nucella lapillus (19 populations, the reference campaign in 1996), the other dealt in 2005 with the infaunal snail Nassarius reticulatus (25 sites, the previous one in 2000). Samples were subject to a standard protocol to determine the concentrations of butyltins (BTs) in tissues. Results show that pollution in most populations has considerably decreased over the last decade: for N. lapillus the mean descent ranged from 37% (for tributyltin -TBT-) to 66% (for monobutyltin -MBT-), and TBT concentrations were on average halved in N. reticulatus. However, derivatives generally increased in this latter species, to the extent that dibutyltin -DBT- in several 2005 samples exceeded the aggregate of all three BTs in 2000. As a consequence, a major change in the bioaccumulation patterns becomes evident, particularly when computing the butyltin degradation index [BDI: (DBT+MBT)/TBT]. This shift is most marked at sites where pollution has always been lowest, and it shows significant negative correlation between both gastropods. Since sources other than antifouling paints are not important in the area, it is proposed that observations are due to BT desorption from sediments through some interplay involving the different characteristics of the chemicals and the contrasting biology of the animals.
Environmental context This special issue is a tribute to Graeme Batley’s career and his many contributions to the field of environmental chemistry.
In this review we provide an overview of the Derwent estuary, Tasmania, Australia. The Derwent flows through the centre of Hobart, a city with a population of approximately 200,000 people. It provides a mechanism for trade and transport, and plays a key role in community recreation. There is significant metal contamination throughout the estuary as a result of historic industry practices, to the extent that the Derwent has an unenvied reputation as one of the most highly metal polluted estuaries in the world. The most recent sediment survey (2012) showed zinc, copper, lead, cadmium, arsenic and mercury levels as still particularly high; with levels in the mid-estuary exceeding 14000, 550, 1800, 120, 420 and 45 ug/g respectively. Zinc is the most abundant metal contaminant in the Derwent, with water column levels in the mid-estuary ranging between 30–60 ug/L. Considerable management and research efforts over the last 50 years have been focused on addressing these legacy issues. As a result, the Derwent Estuary Program was instigated and has proven to be a highly successful body for co-ordination of both remediation and research efforts in the estuary. Whilst the legacy issues have been a key focus for management to date, like other waterbodies worldwide, the estuary is also facing contemporary issues associated with increased urbanisation, changes in catchment usage and climate change. This review provides a comprehensive summary of management initiatives and research to date, and outlines those emerging issues.
The coastal marine environment is severely affected by vessel-repair operations especially from antifouling formulations containing organometals. Sediments from coastal areas were processed by direct aqueous-phase ethylation using tetraethylborate and analyzed on a GC using a FP Detector [detection limit for tributyltin ca 0.4 ng dm-1]. Significant levels of organotin pollution highlight the need for effective management of practices pertinent to the maritime industry.
The extremely toxic antifouling pesticide tributyltin (TBT) was regulated in many countries in the 1980s and 1990s. The regulations have been successful in reducing the toxic threat posed by TBT in many locations around the world. However, there are also many locations at which recovery has not been seen, even 10 years after regulation. Because of continuing concern about the environmental hazards of TBT, the International Maritime Organization proposes to prohibit all antifouling uses of TBT by 2003, and the presence of TBT on ship hulls by 2008. Canada has recently announced a prohibition on the use of organotin antifouling paints by January 1, 2003. This article reviews the persistence, bioaccumulation and toxicity of TBT in aquatic environments, and concludes that TBT meets all such criteria for designation as a Track 1 substance under Canada's Toxic Substances Management Policy, necessitating measures to virtually eliminate it from the Canadian environment. Because of the long persistence of TBT in sediment, there may be a 'legacy problem' in sediments in some locations in Canada for perhaps 20 to 30 years after a total ban.
A survey was conducted of water and sediment from across Canada in 1993-94 to assess the effectiveness of the 1989 regulation of antifouling uses of tributyltin (TBT) under the Canadian Pest Control Products Act. The survey was also designed to assess concentrations of 13 other organotin species in water and sediment, and in sewage treatment plant influents, effluents and sludges. The main conclusion is that the 1989 regulation has only been partially effective. It has had some effect in the reduction of TBT concentrations in fresh water, but not in sea water. It has had less effect in the reduction of TBT concentrations in sediment, probably because of the longer persistence of TBT in sediment than in water. In many locations the TBT concentration was high enough to cause acute and chronic toxicity to aquatic and benthic organisms. In some areas there may be potential for recycling TBT from contaminated sediments back into the water column. In addition, it appears that large harbours that handle ships legally painted with TBT-containing antifouling paints continued to experience ecotoxicologically significant TBT contamination. Other organotin species found appear to pose no acute or chronic hazards to fresh water or marine organisms, but nothing is known of their hazards to benthic organisms. The presence of monooctyltin and dioctyltin in sediments and sewage treatment plant influents, effluents and sludges is reported for the first time, and tripropyltin is quantified in sediments for the first time.
The toxicity of tributyltin (TBT) in sediment in fresh water was determined using spiked sediment bioassays for four benthic invertebrates, (the oligochaete worm Tubifex tubifex, the chironomid Chironomus riparius, the amphipod Hyalella azteca, and the mayfly Hexagenia). Although there was some degradation of spiked TBT into dibutyltin (DBT) and monobutyltin (MBT) in the sediment-water mixtures during the equilibration phase before toxicity testing, the contribution of these degradation products to the observed toxicity was assumed to be minimal based on evidence that TBT is up to orders of magnitude more toxic to many aquatic organisms than its degradation products. The results of this work indicated that Hexagenia was the most sensitive benthic organism to TBT of the four organisms tested (by factors up to about 7), with an IC50 (growth) value for TBT of 0.6 μg Sn/g dry weight. This value is about six times greater than mean concentrations of TBT observed in sediment in fresh water in surveys conducted across Canada before and after the regulation of antifouling uses of TBT in 1989. However, maximum TBT concentrations in sediment before and after regulation exceeded the IC50 (growth) value for Hexagenia, and were close to the lower limits of toxicity ranges for H. azteca and T. tubifex (cocoons/adult and young/adult). Consequently, at the time of surveys before and after the TBT regulation there was potential for adverse effects of TBT in some sediments to some freshwater benthic species.
Live speciments of the blue mussel Mytilus galloprovincialis were collected from the southwestern coastal region of Tokyo Bay and examined for seasonal, size-dependent and spatial variations in the concentrations of organochlorine compounds (OCs) such as PCBs (polychlorinated biphenyls), DDTs (DDT and its metabolites), CHLs (chlordane and related compounds), HCHs (hexachlorocyclohexane isomers) and HCB (hexachlorobenzene). Seasonal variations in OCs concentrations (fat weight base) appeared to reflect the levels in an ambient water rather than seasonal physiological changes of mussels. Neither shell size nor vertical habitation of mussels resulted in significant differences in their concentrations (fat weight base). These results suggest that the variable factors examined did not significantly affect the availability and suitability of mussels as bioindicators for monitoring of contamination with OCs.
An adsorptive stripping voltammetric (AdSV) procedure for the determination of monobutyltin in aqueous media at a silver liquid amalgam film-modified silver solid amalgam annular band electrode (AgLAFAgSAE) is described. Determination of monobutyltin proceeds in two steps. At the beginning monobutyltin ions (BuSn3+) are accumulated from 0.1 M NH4NO3 and 10 % ethanol solution at a potential of −0.2 V, than the BuSn0 film is preconcentrated at the working electrode surface at a potential of −0.7 V. After this step the DP AdSV voltammogram is recorded. The analytical parameters and the procedure of the electrode regeneration and activation were optimized. The calibration curve of monobutyltin in the range 0.02–0.30 mg L−1 is linear (r=0.9973). The detection limit for 5 s of preconcentration, calculated as 3σ of the blank was equal to 0.004 mg L−1, repeatability of the peak current was 1.8 % (n=5). Repeatability and sensitivity of monobutyltin determination depends strongly on the analyzed solution properties, measurement conditions and the working electrode quality. The proposed procedure was tested by means of monobutyltin determination in tap waters.
A method is described for leaching of nanogram amounts of monobutylin (MBT), dibutyltin (DBT) and tributyltin (TBT) and monophenyltin (MPT), diphenyltin (DPT) and triphenyltin (TPT) from sediments. The procedure is based on soaking the sediments in water-hydrogen bromide mixture (1: 1) with magnetic stirring for 30 min followed by extraction with 0.04% (w/v) tropolone solution in dichloromethane for 2 h. Organotins are determined by gas chromatography with a flame photometric detector (GC-FPD) after cleanup through a Florisil column and derivatization by Grignard pentylation. The method has been applied to the study of water and sediments in different areas of the south-west Spain. Predominant species are butyltins, especially TBT which rise critical levels in waters and sediments of fishering harbours. In this study it has been found a direct relation between organotin levels and distance to potential sources determined by boating activities. In addition, it has been verified the relative occurrence of DBT. and MBT together with TBT, possibly as a result of a degradation process, and the influence of sediment grain size and organic matter content on organotins accumulation.
The electrochemical reduction of tributyltin (Bu3Sn+) at mercury electrodes has been investigated in aqueous media with nitrate and chloride electrolytes using the techniques of cyclic voltammetry, differential pulse polarography, and differential pulse voltammetry. In contrast to previous studies in mixed aqueous—organic media, the electrochemical processes were found to be surface confined. At low concentrations, corresponding to less than monolayer coverage of the mercury electrode, the initial charge transfer process occurs after adsorption at approximately −0.8 V vs. the saturated calomel electrode (SCE) and is essentially reversible, the complete process being described by the reaction Bu3Sn(bulk)+→Bu3Sn(ads)+ + e− ⇌ Bu3Sn(ads).At more negative potentials (approximately − 1.3 V vs. SCE) a reversible tensammetric process is observed: Bu3Sn(ads).⇌u3Sn(desorb)In concentrated chloride media this tensammetric process has a well-defined counterpart: Bu3Sn(ads)+⇌ Bu3 Sn(desorb)+ at approximately − 0.06 V vs. SCE, showing that strong adsorption takes place over almost the entire potential range available at mercury electrodes.At higher concentrations, corresponding to more than monolayer coverage of the mercury electrode, the electrochemistry is more complex and additional processes are observed.
The electrochemical reduction of dilute aqueous solutions of monobutyltin containing nitrate and chloride electrolytes has been examined at mercury electrodes using the techniques of direct current polarography, cyclic voltammetry, differential pulse polarography and differential pulse voltammetry. In the present study, the processes were found to be much more reversible than reported in earlier investigations where more concentrated solutions were examined using direct current techniques. The primary charge transfer process is a reversible three-electron reduction step which occurs at approximately −0.5 V vs. Ag/AgCl (3 M KCl) and corresponds to the reaction At slightly more negative potentials, the reduction process at a stationary mercury electrode, but not significantly at a dropping mercury electrode, is inhibited by adsorption and polymerisation of the reaction product. However, at considerably more negative potentials, the exact value of which is strongly dependent on the solution conditions, product adsorption and electrode blockage by film formation ceases to occur. The electrochemistry of mixtures of monobutyltin, dibutyltin and tributyltin also has been examined. Interactions between the electrode processes implies that the direct and simultaneous voltammetric determination of these forms of butyltin compounds in aqueous samples is extremely problematic.
The effects of sublethal tributyltin (TBT) concentrations on the growth and development of Ruditapes decussatus larvae were studied. Veliger larvae of R.
decussatus were exposed to TBT nominal concentrations of 25, 50, 75 and 100 ng Sn l−1 in the water for a period up to 13 d. Larval growth and development were chosen as endpoints for evaluation of TBT toxicity. Growth of R.
decussatus larvae was severely affected by TBT concentrations (25–100 ng Sn l−1). A 3- to 6-fold reduction growth was observed in these early larval stages. Furthermore, R.
decussatus larvae exposed to TBT did not develop further than D-larvae while the unexposed ones reached the umbonated stage.
The electrochemical reduction of dibutyltin (Bu2Sn2+) at mercury electrodes has been investigated in aqueous media containing nitrate and chloride electrolytes using the techniques of direct current (DC) polarography, differential pulse (DP) polarography, DP voltammetry, and cyclic voltammetry. In 0.10 M nitrate media, the initial charge transfer process occurs at approximately –0.7 V (vs. Ag/AgCl) and is described by the equation
in which a reversible charge transfer occurs with completely surface-confined dibutyltin. However, when longer time domains at a hanging mercury drop electrode (HMDE) are used, the complexity of the electrochemistry increases, which is attributed to the occurrence of butyl exchange processes with the electrode mercury and consequent disruption of the film of adsorbed dibutyltin. In 0.50 M chloride media, the extent of adsorption is considerably less, and the processes, but not necessarily the postulated mechanism, correspond more closely to that described by previous workers for the reduction of dibutyltin compounds in ethanol-water mixtures.
A method is described for leaching of nanogram amounts of mono-, di and tri-butyltin compounds and mono-, di- and tri-phenyltin compounds from sediments. The procedure is based on soaking the sediments in a water–hydrogen bromide mixture (2:3) with magnetic stirring for 1 h followed by extraction with 0.02% (w/v) tropolone solution in pentane for 2 h. Organotins are determined by GF FPD after clean-up through a Florisil column and derivatization by Grignard pentylation. The method has been applied to the study of water and sediments in different areas of south-west Spain. Predominant species are butyltins, especially tributyltin (TBT), which has high values in waters and sediments of Puerto de Santa Maria and Cadiz Bay, as well as in sediments of the Sancti Petri Channel, which suggests a harmful action on biota. A direct relation has been found beween organotin levels and distance of potential focus determined by boating activities. In addition, the relative occurrence of dibutyltin (DBT) and monobutyltin (MBT) together with TBT has been noted, possibly as a result of a degractation process, and the influence of grain size of sediment and presence of organic matter on organotin accumulation has been studied.
Organotin concentrations were measured in water, sediments and clams (Ruditapes decussatus) from 11 sites in the Ria Formosa lagoon, Portugal, in 1992–93. Results showed a marked spatial pattern of tributyltin (TBT) and dibutyltin concentrations. The highest organotin concentrations were observed at Olhão (site 5), where the most important fishing harbour of the Southern coast of Portugal is located.
Results indicated that fishing vessels, moored in the harbour at Olhão (site 5), were the major source of organotin contamination to the lagoon. No significant seasonal trend was observed, suggesting a continuous input of organotin compounds throughout the year. In several areas of the lagoon the TBT burdens in R. decussatus could have deleterious developmental effects. Copyright
The tri(n-butyl)tin (TBT) moiety has been shown to have complex ecotoxicological effects on estuarine populations. In the Tagus the massive die-off of the Portuguese oyster (Crassostrea angulata Lmk), has been attributed to the introduction and use of this contaminant by shipyards. This paper reviews previous work by others and reassesses our results obtained in water and sediments of the Tagus estuary, as a contribution to the understanding of tin geochemistry and organotin speciation in this estuary. Contrary to earlier results, the latest surveys show that in the open waters of the Tagus measurable concentrations of all the three butyltin species occur, exhibiting peak concentrations at two locations that indicate two previously undetected sources of TBT. TBT also presents a peak concentration in sediments near the Lisnave shipyards, as previously suggested. The latest surveys still detected methylated forms of tin, particularly monomethyltin (Me Sn3+), in Tagus sediments, with maximum concentrations in the vicinity of urban effluent discharges. The concentrations for TBT and its degradation products found in the Tagus are potentially harmful to the populations of gastropods and endemic bivalves.
An analytical method for the simultaneous quantitative determination of organotin and triazine antifouling agents in sea water has been developed and optimized. The method involves extraction of organotin compounds and IRGAROL 1051 into dichloromethane with simultaneous derivatization of the organotins using sodium tetraethylborate. The extracts were analyzed without additional purification. Separation and determination of individual compounds, including tributyltin, triphenyltin (together with their degradation products) and IRGAROL 1051 were performed by capillary gas chromatography (cGC). Selected ion monitoring GC-mass spectrometry (GC-MS-SIM) was used to quantify both classes simultaneously, although cGC with flame photometric detection (cGC-FPD) and cGC with nitrogen phosphorus detection (cGC-NPD) were also used separately to analyze the same extract of organotins and triazine, respectively. Recoveries of the individual spiked triazines and the organotin chlorides (at concentrations of approximately 100ng l−1) were higher than 70% (with a RSD lower than ± 13%. The detection limits of the procedure (for 750 ml water samples) range between 0.5 and 1.4 ng 1−1 for the various organotin species and between 0.5 and 2.2 ng 1−1 for IRGAROL 1051 (dependent upon which GC detector is used).
Six organotin species -tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), triphenyltin (TPT), diphenyltin (DPT) and monophenyltin (MPT)- have been determined in seawater and sediments collected from some representative enclosed areas of the southwest Spain. No phenyltin species were found in waters showing the absence of recent inputs of these species. However, butyltin species were present in all the stations along the Huelva coast. The highest TBT levels were found in sediments (up to 195 ng g−1 as Sn, dry weight basis) and seawater (up to 100 ng L−1) in harbours and marinas, closely related with boating activity and decreasing according to the distance from the potential sources. Results make possible to establish conclusions about the critical ecological consequences of organotin presence in this area, where shell-fish farms, fishery activity and migrating birds might be at risk. Different TBT degradation rates were found in sediments collected in winter (Cadiz coast) and in summer (Huelva coast).
Concentrations of butyltin residues were determined in muscle tissue of fish collected from local markets and sea food shops in India, Bangladesh, Thailand, Indonesia, Vietnam, Taiwan, Australia, Papua New Guinea and the Solomon Islands. Contamination levels were determined in the Asia-Pacific region and human exposure was estimated. Similarly, corresponding liver samples of fish muscle collected in Australia, Papua New Guinea and the Solomon Islands were analyzed to obtain information on partitioning of butyltin compounds between muscle and liver tissues. Butyltin compounds were detected in most of the samples which suggested widespread contamination in Asia and Oceania. The concentrations of butyltin compounds were, on average, an order of magnitude higher in liver than in muscle. Residue concentration of Σbutyltin in liver was found to be correlated significantly (p < 0.02) with those in muscle. Intensive ship-scrapping activities, sewage disposal and antifouling paints are considered the major sources of butyltins in this region. Increased proportions of MBT over DBT and TBT in samples from most locations indicated degradation of TBT to MBT in fish tissues during storage at 4°C in the dark over 1–2 years. The possibility that fish have been subject to increased exposure to MBT and that TBT degrades to MBT quite rapidly in tropical environments are also considered. Butyltin concentrations in fish from Asia and Oceania were lower than those reported for Japan, Canada and the USA. Although the number of samples analyzed from each country was small, it is tentatively suggested that intake of butyltins by humans via consumption of fish in these countries was < 25% of the tolerable daily intake of 250 ng kg bw−1 day−1. To our knowledge, this is the first study reporting on butyltin pollution in developing Asian countries.
Marine biofouling, or the growth of marine organisms on surfaces immersed in the sea, can have a significant operational and economic impact on vessels and other marine structures. Biofouling is potentially diverse, and develops sequentially from an initial conditioning layer of adsorbed organic and inorganic matter, through microbial film formation, to a community of macroscopic plants and animals. Up until now, prevention of fouling on underwater substrates has depended on the creation of surfaces which continuously release biocide to kill or deter the settlement of potential foulers, commonly by the application of antifouling paints. However, environmental concerns about a number of antifouling biocides have brought this practice under close scrutiny. Alternative approaches are now actively being sought, which include more environmentally acceptable biocides or biocide delivery systems, non-toxic fouling release coatings, and natural antifouling agents and processes.
Two years after the banning in New South Wales (Australia) of tributyltin (TBT)-based antifouling paints for vessels under 25 metres in length, the impact on the Sydney rock oyster, Saccostrea commercialis, has been assessed. Reduced growth and shell deformities present before banning were found to be absent and healthy oysters contained TBT at concentrations close to the detection limit of 0.2 micrograms Sn kg-1. High tissue concentrations of both copper and zinc, prior to banning were also significantly reduced. This behaviour was predicted by field experiments which showed that TBT had a synergistic effect on the uptake of copper. The distribution of both TBT and copper in the various organs of the oyster were examined in an attempt to explain this synergism.
Antifoulant concentrations were determined in marine sediments collected from commercial harbours, marinas, mooring locations on mid-shelf continental islands, and outer reef sites in four regions within the Great Barrier Reef World Heritage Area in 1999. Highest copper concentrations were present in sediments collected from commercial harbour sampling sites (28-233 microg Cu g(-1) dry wt.). In contrast, copper concentrations in sediments collected from boat mooring sites on mid-shelf continental islands and outer reef sites were at background concentrations (i.e. <20 pg Cu g(-1) dry wt.). Butyltin was only detectable in four of the 42 sediments sampled for analysis, and was only present in sediments collected from commercial harbours (18-1275 ng Sn g(-1) dry wt.) and from marinas (4-5 ng Sn g(-1) dry wt.). The detection of tributyltin at marina sites implies that this antifoulant may continue to be used illegally on the hulls of smaller recreational vessels. Sediment samples were also collected opportunistically from the site of a 22,000 t cargo ship grounding in May 1999 at Heath Reef, in the far northern Great Barrier Reef. Butyltin concentrations were grossly elevated (660-340,000 ng Sn g(-1) dry wt.) at the grounding site. The impact of residual antifoulants at large ship grounding sites should be recognised as a significant, long-term environmental problem unless antfoulant clean-up strategies are undertaken.
Tributyltin (TBT) concentrations have been measured in the tissue of the Sydney rock oyster Saccostrea commercialis sampled from estuaries in New South Wales, Australia. Background TBT levels of below 2 ng Sn g-1 contrasted with values between 80 and 130 ng Sn g-1 in oysters exposed to high boat densities or poor tidal flushing. Shell deformities and reduced tissue weights were associated with all samples displaying elevated TBT levels. Specimens of the Pacific oyster, Crassostrea gigas, growing on the same racks displayed 2-3 times the TBT concentrations of S. commercialis.
Water from 23 sites in Sydney Harbour and the Georges River estuary (N.S.W.) have been analysed for tributyltin (TBT) using gas chromatography with electron capture detection, after solvent extraction as the hydride. Analytical data for TBT in Sydney waters are consistent with other data reported for overseas estuaries, with the majority of samples containing less than 45 ng Sn L-1 as TBT. Samples from areas of high boating activity such as Rushcutters Bay and Garden Island gave the highest TBT concentrations at 90-190 ng Sn L-1. The mean ambient TBT concentration in each estuary was computed using a tidal prism model. Despite the broad assumptions made, calculated results agreed well with those measured at sites with no obvious local point source of TBT.
Inorganic tin and methyl- and n-butyltin compounds were speciated by volatilization from water samples by hydride generation, separation by a chromatographic packing material, and detection by atomic absorption spectrophotometry in an electrothermal quartz furnace at the 224.61-nm wavelength. Absolute detection limits of 20-50 pg (3sigma) as Sn and linearity of calibration curves up to 30 ng as Sn avoid preconcentration by extraction and allow direct determination of methyl- and n-butyltin compounds from environmental waters. Reproducibility for 15 ng as Sn is less than 15% for most alkyltin compounds. This study discusses optimization of parameters and results from natural waters. 26 references, 4 figures, 3 tables.
A method is described for the speciation of n-butyltin compounds. The compounds are volatilized from aqueous solution, trapped on a chromatographic packing material contained in a teflon column, and separated on the basis of differing boiling points. The column is attached directly to an electrothermal quartz furnace of an atomic absorption spectrometer for detection at 224.61 nm. Absolute detection limits (3σ) are 11–45 pg as tin, calibration curves are linear to 13 ng, and reproducibility at the 2-ng level ranges from 5% for mono-n-butyltin to 18% for tri(n-butyl)tin.
A survey of the gastropod Nucella lapillus around the south-west peninsula of England has revealed that the incidence of ‘imposex’, the induction of male sex characters in the female, is widespread, that all populations are affected to some degree and that the phenomenon is most prevalent along the south (Channel) coast. Populations close to centres of boating and shipping activity show the highest degrees of imposex, especially those within the vicinities of the Helford, Fal, Salcombe and Dart estuaries and in Plymouth Sound and Tor Bay. Within Plymouth Sound the degree of imposex increased markedly between 1969 and 1985, coinciding with the introduction and increasing usage of antifouling paints containing tributyltin (TBT) compounds.
Comenta que el tributyltin es un compuesto organico utilizado como biocida en la pintura de botes, barcos y espigones y para evitar la viscosidad del agua en las torres de enfriamiento. Actua como fungicida bactericida, insecticida y preservante para madera, textiles, papel, cuero y equipo electrico. Debido al creciente dano al ambiente ocasionado por este compuesto quimico en los Estados Unidos se esta restringiendo su uso en las pinturas. Revisa la literatura sobre este tema y ofrece una bibliografia de 119 referencias que comprende de 1960 a la fecha
The presence of butyltin and methyltin species is reported for the first time in lakes, rivers and harbors in Ontario. Concentrations of methyltin and dimethyltin are high in Kingston Harbor and Whitby Harbor and in industrial areas such as Lake St. Clair.-from Authors
The tributyltin species, the active ingredient in some antifouling paint formulations, is perhaps the most acutely toxic chemical to aquatic organisms ever deliberately introduced to water. It has been demonstrated to have an adverse effect on shellfish in France and England, and as a consequence the use of tributyltin-containing antifouling paints has been restricted in these countries. Other countries have banned the use of tributyltin-containing antifouling paints or are contemplating restrictions. This article reviews such environmental aspects of tributyltin as methods of analysis, toxicity, environmental occurrence, persistence and fate. Tributyltin concentrations in many locations may be high enough to cause chronic toxicity or harmful effects in some aquatic organisms, and in some locations the tributyltin concentrations may be high enough to be acutely toxic to some organisms. Biological degradation of tributyltin in water and sediment appears to be the most important factor limiting the persistence of tributyltin in aquatic environments. To some degree, then, the persistence of tributyltin in aquatic environments depends upon the nature of the ecosystem. Tributyltin exhibits low-to-medium persistence in water and moderate persistence in sediment. A summary is given of the regulatory status of tributyltin in some countries, and recommendations are made for further research.
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