Concentrations of organotin compounds in blue mussels from the wharves of Tokyo Bay

Organotin compounds (tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), triphenyltin (TPT), diphenyltin (DPT), and monophenyltin (MPT)) were quantified in blue mussels, Mytilus edulis, in 1989 at 26 wharves along Tokyo Bay. Organotin compounds, other than DPT, were detected in all mussel samples (in case of DPT: 23 of 26). The concentration of DBT was highest among butyltin compounds and that of TPT was highest among phenyltin compounds. The results showed that relatively high concentrations of organotin compounds persist in blue mussels of Tokyo Bay, although the use of the paints containing these compounds has been limited for several years by regulations.     

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.     

Adsorption of tributyltin by tributyltin resistant marine Pseudoalteromonas sp. cells

The isolate, Pesudoalteromonas sp. TBT1, could grow to overcome the toxicity of tributyltin chloride (TBTCl) up to 30 microM in the absence of Cl(-) in the medium until the cells reached an exponential phase of growth. The viability, however, was reduced after the cells reached a stationary phase. The degradation products, such as dibutyltin (DBT) and monobutyltin (MBT), were not detected in the growth medium, indicating that the isolate has no ability to degrade TBT into less toxic DBT and MBT. Up to about 10(7.5) TBT molecules were adsorbed by a single cell. The observation of morphological changes with an electron microscope showed that the cell surface became wrinkled after exposure to the lethal concentration of 10 mM TBTCl. These results indicate that the resistance of the isolate toward the toxicity of TBTCl is not related to the unique cell surface, which seems to play an important role in preventing the diffusion of TBTCl into the cytoplasm.     

Assessment of organotin (butyltin species) contamination in marine biota from the Eastern Aegean Sea, Turkey

The marine environment continues to be adversely affected by tributyltin (TBT) release from maritime traffic. Therefore the concentrations of TBT, dibutyltin (DBT) and monobutyltin (MBT) were measured in barnacles, mussels and fish along the Eastern Aegean coastline. The average concentrations of TBT ng Sn g⁻¹ were found to be 235 in fish, 116 in mussels and 635 in barnacles. The highest concentrations of TBT, DBT and MBT were observed in the barnacles which had been sampled in marinas and harbors. All mussels sampled showed values of TBT + DBT, which were below the “tolerable average residue level (TARL)” as currently accepted. This indicates a lack of risk to the consumer. However, 7 out of the 15 fish sampled displayed TBT + DBT levels above the TARL, which indicates that a fish consumer group may be at risk. Barnacles have high potential as biomonitors for the presence of organotin in the Aegean Sea.     

Adsorption of tributyltin by tributyltin resistant marine Pseudoalteromonas sp. cells

The isolate, Pesudoalteromonas sp. TBT1, could grow to overcome the toxicity of tributyltin chloride (TBTCl) up to 30 μM in the absence of Cl⁻ in the medium until the cells reached an exponential phase of growth. The viability, however, was reduced after the cells reached a stationary phase. The degradation products, such as dibutyltin (DBT) and monobutyltin (MBT), were not detected in the growth medium, indicating that the isolate has no ability to degrade TBT into less toxic DBT and MBT. Up to about 10^7.5 TBT molecules were adsorbed by a single cell. The observation of morphological changes with an electron microscope showed that the cell surface became wrinkled after exposure to the lethal concentration of 10 mM TBTCl. These results indicate that the resistance of the isolate toward the toxicity of TBTCl is not related to the unique cell surface, which seems to play an important role in preventing the diffusion of TBTCl into the cytoplasm.     

Adsorption of tributyltin by tributyltin resistant marine Pseudoalteromonas sp. cells

The isolate, Pesudoalteromonas sp. TBT1, could grow to overcome the toxicity of tributyltin chloride (TBTCl) up to 30 μM in the absence of Cl⁻ in the medium until the cells reached an exponential phase of growth. The viability, however, was reduced after the cells reached a stationary phase. The degradation products, such as dibutyltin (DBT) and monobutyltin (MBT), were not detected in the growth medium, indicating that the isolate has no ability to degrade TBT into less toxic DBT and MBT. Up to about 10^7.5 TBT molecules were adsorbed by a single cell. The observation of morphological changes with an electron microscope showed that the cell surface became wrinkled after exposure to the lethal concentration of 10 mM TBTCl. These results indicate that the resistance of the isolate toward the toxicity of TBTCl is not related to the unique cell surface, which seems to play an important role in preventing the diffusion of TBTCl into the cytoplasm.     

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.     

Imposex in Morula Granulata as Bioindicator of Tributyltin (TBT) Contamination in the Dampier Archipelago, Western Australia

This study was undertaken to examine the use of imposex in the tropical neogastropod whelk Morula granulata as bioindicator of tributyltin (TBT) contamination. Samples were collected from sites throughout the Dampier Archipelago; both impact sites close to intensive shipping activity and remote control sites. TBT in this area originates mainly from commercial vessels using the Port of Dampier that are >25 m in length and exempt from legislation controlling the use of TBT in antifouling paints. A field survey was undertaken in July 1997; 100 M. granulata were taken at each of 18 sites with varying vessel activity, and examined for imposex. The level of TBT contamination in the Archipelago was low; ranging from <0.3 to 25 ng Sn l⁻¹ in water,<0.3 to 80 ng Sn g−¹ in oyster tissue (Saccostrea cuccullata – prey of M. granulata), and <0.3 to 33 ng Sn g⁻¹ in whelks. Percentage of imposex in M. granulata ranged from 0% to 57%, and was correlated with distance to vessel activity (r=0.646, p<0.05). The only significant relationship of imposex with butyltin concentrations was with TBT in oysters (r=0.826, p<0.05), and dibutyltin (DBT) in whelks (r=0.783, p<0.05). It is postulated that this is because of interspecies variation in ability to metabolize TBT to DBT and MBT (monobutyltin), as well as induction of imposex in earlier life stages, so that imposex in adults could be a reflection of prior contamination. M. granulata is a suitable bioindicator of TBT contamination in the Dampier Archipelago, which could be used throughout the Indo-Pacific given its abundance in the region.     

Baseline of butyltin pollution in coastal sediments within the Basque Country (northern Spain), in 2007-2008

Tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) were measured in surficial sediments at, the ports of Pasaia and Bilbao, together with other mid- and small-size harbours of the Basque Country (northern Spain), in 2007-2008. The highest values of the sum of the three measured butyltin species (3523-3640 ng g⁻¹, as Sn) were found at sampling stations near to shipyards located within the port of Pasaia. The highest value of TBT concentration (3143 ng g⁻¹, as Sn) was found at the marina of Getxo, in the port of Bilbao. The degree of TBT degradation varied greatly between sampling stations, being found to be generally higher in those sediments with higher values of redox potential and lower values of TBT concentration (normalized by organic matter content).     

Distribution of butyltins in the waters and sediments along the coast of India

Water and surface sediment samples were analyzed for butyltins (TBT, DBT, MBT) from various ports along the east and west coast of India. The total butyltin (TB) in water samples varied between ∼1.7 and 342 ng Sn l⁻¹, whereas for sediments it varied between below detection limit to 14861 ng Sn g⁻¹ dry weight of sediment. On an average Chennai port recorded the highest level of butyltins in the sediments while Paradip recorded the highest level of butylins in the waters. A fairly good relationship between the TB in the sediment and overlying water samples, as well as between organic carbon and TB, implicates the importance of adsorption/desorption process in controlling the levels of TBT in these port areas. In India the data on organotin pollution is very sparse; most of the port areas have been surveyed for butyltins for the first time during this study.     

Contamination by persistent organochlorines and butyltin compounds in the west coast of Sri Lanka

Concentrations of polychlorinated biphenyls (PCBs), dichlorodiphenyl trichloroethane and its metabolites (DDTs), isomers of hexachlorocyclohexane (HCHs), hexachlorobenzene (HCB), chlordane compounds (CHLs) and butyltin compounds (mono-, di- and tributyltin) were determined in biota and sediments collected from locations on the west coast of Sri Lanka. The PCB concentrations found in fish from the Kelani River mouth were higher than those from other Asian developing countries. The pattern of organochlorine accumulation was in the order of PCBs > DDTs > CHLs > HCHs > HCB, and resembled those reported for most developed countries. The accumulation pattern of butyltins in fish was in the order of TBT > DBT > MBT suggesting recent exposure to TBT sources. Total butyltin concentrations found in rabbit fish liver (11-38 micrograms/g wet wt), collected from the Colombo dockyard, could be the highest ever reported for fish in the world.     

Imposex in Three Marine Gastropod Species in Chile and Potential Impact on Muriciculture

A survey of imposex was conducted between the Bay of San Vicente, Concepción, Chile (36° 50′) and the Bay of Renocavi, Puerto Montt, Chile (41° 35′), to determine if imposex is occurring in an area of collection and cultivation of the gastropod, Chorus giganteus. Imposex was recorded in three chilean muricids C. giganteus, Xanthochorus cassidiformis and Nucella crassilabrum complex. Percentage of imposex in females sampled ranged from 0% to 100%. The degree of expression of imposex was not so severe as to elicit sterility in the individuals surveyed. Incidence of imposex was as high as 47% in areas of harvest of C. giganteus for reproductive and cultivation studies for commercial production of this species. A six percent incidence of imposex was observed in Nucella proximal to the facility for cultivation of C. giganteus. Gastropods of the genus Nucella are used in other countries to monitor incidence of imposex and have demonstrated sensitivity toward tributyltin (TBT), the associated causal agent. Since sex of individuals in muriciculture is determined by the presence or absence of a penis, imposex may lead to erroneous classification of males and females. The incidence and severity of imposex in C. giganteus and related species may have a negative impact on sustainable cultivation and harvest of gastropods in Chile.     

Organotins (TBT and DBT) in water, sediments, and gastropods of the southern Venice lagoon (Italy)

The release of tributyltin (TBT) from maritime traffic represents one of the main problems of direct, diffuse, and continued contamination of the marine environment. In the present survey, the concentrations of TBT and dibultytin (DBT) in brackish waters, sediments, and the gastropods Nassarius nitidus were evaluated in order to estimate the contamination of the southern part of the Venice lagoon. TBT and DBT were determined by GC-MS/MS. Recent contamination of TBT was found in brackish waters near marinas, whereas the highest concentrations of TBT and DBT were observed in surface sediments at dockyards and harbours. High content of organotin in the gastropods sampled near the dockyards, harbours, and marinas showed a mobilisation from the sediments through the food web. The present study allowed assessment of whether, despite the ban on the use of TBT paints, waters, sediments, and biota were still being contaminated by organotin compounds in the southern Venice lagoon.     

Organotin levels in Nazaré canyon (west Iberian Margin, NE Atlantic) and adjacent coastal area

Organotin compounds (OTs) are ubiquitous in the marine environment and high concentrations (μg g(-1) range) in sediments from different coastal areas around the world have been reported. However, few reports have described the OTs contamination status in the offshore and deep sea environment. This work investigated organotin levels in Nazaré canyon for the first time. Levels of monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), diphenyltin (DPT), triphenyltin (TPT), dioctyltin (DOT) and trioctyltin (TOT) were quantified in sediment samples from the upper flanks of the canyon and from the adjacent coastal area. TBT levels detected in the canyon flanks are about two to three orders of magnitude lower than those found in the coastal area. Nevertheless, when quantifiable, TBT levels in the canyon samples were higher than the Environmental Assessment Criteria set for TBT in sediments by the OSPAR Commission indicating that at those locations negative ecological impacts are likely to occur.     

Evaluation of butyltin compounds in Maryland waters of Chesapeake Bay

A monthly sampling programme for dibutyltin (DBT), tributyltin (TBT) and tetrabutyltin (TTBT) was initiated for a period of one year (July 1985–June 1986) in the Maryland waters of Chesapeake Bay. Concentrations of the above butyltin species were evaluated in the microlayer and water column of eight sampling stations representing two small and two large marinas, a large harbour, two major river systems and a heavily used shipping channel. DBT concentrations in the microlayer were generally higher in the four marinas when compared with the other stations. The highest DBT concentration reported in the microlayer was 1156 ng l⁻¹. Mean microlayer TBT concentrations ranged from 54–310 ng l⁻¹ in the four marinas. Three TBT concentrations ranging from 1049–1171 ng l⁻¹ were reported in the microlayer of the marinas. TBT concentrations of 41 and 29 mg l⁻¹ were detected in the microlayer of a heavily used shipping channel (C & D Canal) during May and June. TTBT concentrations were not detected in the microlayer at most stations during the 12 month sampling period.Mean DBT concentrations in the water column ranged from 23–145 ng l⁻¹ in the four marinas. DBT concentrations in the water column of the other stations were < 35 ng l⁻¹. Mean water column concentrations of TBT ranged from 51–408 ng l⁻¹ in all four marinas. Peak concentrations of TBT were reported in May and June for the various marinas. The highest TBT concentration reported in the water column was 998 ng l⁻¹. TBT concentrations of 20–24 ng l⁻¹ were reported in one of the river systems (Potomac River). TTBT concentrations were not detected in the water column at most of the stations.     

Decade-long monitoring reveals a transient distortion of baseline butyltin bioaccumulation pattern in gastropods

Worldwide measures to restrict tributyltin (TBT) in antifouling paints have been legislated for decades, and were upgraded to a total ban on September 2008. With a view to test the response of coastal biota to changing pollution, since 1996 we have determined the concentration of TBT and derivatives di- and mono-butyltin (DBT and MBT) in NW Spain populations of two gastropods of contrasting biology, the rock-snail Nucella lapillus (n = 18) and the mud-snail Nassarius reticulatus (n = 24). TBT pollution in the study area has decreased consistently and considerably over time. In addition, the baseline butyltin (BT) bioaccumulation patterns showed a marked but transient distortion. These field observations are consistent with BT desorption from sediments, a natural phenomenon that is now to be expected in developing countries recently subject to the global TBT ban.     

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.     

Integrative assessment of organotin contamination in a southern European estuarine system (Ria de Aveiro, NW Portugal): tracking temporal trends in order to evaluate the effectiveness of the EU ban

Organotin (OT) compounds have been used as biocide agents in antifouling paints since the mid 1960s and are now ubiquitous in the marine environment. Due to their high toxicity to non-target species they were banned from antifouling paints in the European Union in 2003 (2002/62/EC directive). The aim of the present work is to assess any obvious decline of the OT environmental levels at Ria de Aveiro (NW Portugal) after the ban. The organotins - monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), monophenyltin (MPT), diphenyltin (DPT), triphenyltin (TPT), monoctyltin (MOT), dioctyltin (DOT) and trioctyltin (TOT) - were quantified in the gastropod Nassarius reticulatus, in the mussel Mytilus galloprovincialis and in sediments. Imposex (imposition of male characters on females of gonochorist gastropods) in N. reticulatus was additionally used as a biomarker of TBT pollution. Time comparisons show a slight decrease of imposex between 2003 and 2005 probably as a consequence of the EU ban, though in some cases this trend seems to have started earlier since 2000. The fraction of TBT relatively to its metabolites has been decreasing over the last years but still remains high suggesting that there are still recent inputs of this compound into the study area.     

Continuing observation of disturbed reproductive cycle and ovarian spermatogenesis in the giant abalone, Haliotis madaka from an organotin-contaminated site of Japan

Histological examination of gonads as well as chemical analysis of organotin compounds in tissues of the giant abalone, Haliotis madaka, was conducted to evaluate continuing endocrine disruption in abalone populations in Japan. Abalone specimens were collected from two different areas, Tsushima as a reference site and Jogashima as a site representative of declining abalone populations where serious organotin contamination had been observed, each month from January 1998 to March 1999. Scores were given to the development stages of reproductive cells in the ovary and testis. The degree of sexual maturation was evaluated by calculating the mean value of a histogram of these scores for the reproductive cells of each abalone. The temporal variations in degree of sexual maturation showed that female and male abalone from Tsushima matured synchronously, while those from Jogashima did not, which were similar to results of the previous study during September 1995–November 1996. Approximately 19% of the female abalone from Jogashima were masculinized with an ovo-testis, which was also similar to the result of the previous study. The masculinization of female abalone is reported to be induced by tributyltin (TBT) and triphenyltin (TPhT) from antifouling paints. Concentrations of the sum of butyltins (TBT, dibutyltin (DBT) and monobutyltin (MBT): ΣBTs) and the sum of phenyltins (TPhT, diphenyltin (DPhT) and monophenyltin (MPhT): ΣPhTs) in the muscle of abalone from Jogashima (n = 73) of 7.8 ± 9.0 ng/g wet wt. and 4.5 ± 6.8 ng/g wet wt., respectively, were significantly higher than those from Tsushima (n = 87) of 4.7 ± 4.9 ng/g wet wt. and 0.8 ± 1.7 ng/g wet wt., respectively (p < 0.05 for ΣBTs; p < 0.001 for ΣPhTs), although concentrations of TBT and TPhT in the muscle of abalone from Jogashima (n = 73) of 2.2 ± 2.5 ng/g wet wt. and 5.8 ± 5.1 ng/g wet wt., respectively, were insignificantly and significantly higher than those from Tsushima (n = 87) of 0.4 ± 0.6 ng/g wet wt. and 0.5 ± 0.9 ng/g wet wt., respectively, (p > 0.05 for TBT; p < 0.001 for TPhT). Thus, endocrine disruption as well as contamination by organotins in the giant abalone from Jogashima is still persisting.     

Isolation of PAH-degrading bacteria from mangrove sediments and their biodegradation potential

Surface sediment samples were collected from seven mangrove swamps in Hong Kong SAR with different degrees of contamination. The total concentrations of 16 PAHs in these sediments ranged from 169.41 to 1058.37 ng g⁻¹ with the highest concentration found in Ma Wan and the lowest in Kei Ling Ha Lo Wai mangrove swamp. In each swamp, three bacterial consortia were enriched from sediments using phenanthrene (Phe) as the sole carbon and energy source, and individual bacterial colony showing Phe degradation was isolated and identified by 16S rDNA gene sequence. The consortia enriched from Sai Keng and Ho Chung sediments had highest ability to degrade mixed PAHs in liquid medium, with 90% Phe and Fla (fluoranthene) degraded in 7 days. On the other hand, Kei Ling Ha Lo Wai-enriched consortia degraded less than 40% Phe and Fla. Pyrene (Pyr) was hardly degraded by the consortia enriched from sediments. Bacterial isolates, namely Rhodococcus (HCCS), Sphingomonas (MWFG) and Paracoccus (SPNT) were capable to degrade mixed PAHs (Phe + Fla + Pyr). Their degradation percentages could be lower, comparable or even higher than their respective enriched consortia, depending on the consortium and the type of PAH compounds. These results suggest that PAH-degrading bacteria enriched from mangrove sediments, either as a mixed culture or as a single isolate could be used for PAHs bioremediation.