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.     

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.     

Chemical contamination of a coral reef by the grounding of a cruise ship in Bermuda

Bulk metal analyses of surficial sediments collected around the Norwegian Crown cruise ship grounding site in Bermuda indicated significant but localized contamination of reef sediments by copper and zinc, caused by the stripping of the tri-butyltin (TBT)-free antifouling (AF) paint (Intersmooth 460) from the underside of the hull. Highest copper and zinc values were found in heavily compacted and red-pigmented sediments inside the impact scar and were comparable to levels found close to slip ways of local boat yards where AF paints from hull stripping and cleaning processes are washed into the sea. The re-distribution of AF contaminated sediments by storms and deposition on nearby reefs constitutes a significant ecological risk that could delay recovery processes and reduce the effectiveness of remediation efforts. Whilst the ecotoxicological effects of AF paint particles interspersed with sediment is unknown, and in need of further study, it is argued that the significance of AF paint contamination of grounding sites has been overlooked.     

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.     

Quantification and classification of ship scraping waste at Alang-Sosiya, India

Alang–Sosiya located on the Western Coast of Gulf of Cambay, is the largest ship recycling yard in the world. Every year on average 365 ships having a mean weight (2.10 × 10⁶ ± 7.82 × 10⁵ LDT) are scrapped. This industry generates a huge quantity of solid waste in the form of broken wood, rubber, insulation materials, paper, metals, glass and ceramics, plastics, leather, textiles, food waste, chemicals, paints, thermocol, sponge, ash, oil mixed sponges, miscellaneous combustible and non-combustible. The quantity and composition of solid waste was collected for a period of three months and the average values are presented in this work. Sosiya had the most waste 15.63 kg/m² compared to Alang 10.19 kg/m². The combustible solid waste quantity was around 83.0% of the total solid waste available at the yard, which represents an average weight of 9.807 kg/m²; whereas, non-combustible waste is 1.933 kg/m². There is not much difference between the average of total solid waste calculated from the sampling data (96.71 MT/day) and the data provided by the port authorities (96.8 MT/day).     

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.     

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.     

Marine debris surveys at Volunteer Beach, Falkland Islands, during the summer of 2001/02

This survey evaluated the monthly accumulation rate of marine debris and the types of objects washed ashore at Volunteer Beach on East Falkland between October 2001 and March 2002. The mean (±SD) accumulation rate of marine debris was 77 ± 25 items/km/month, of a mean weight of 17.3 ± 12 kg. Forty different objects were collected and the five most frequent items were cotton fabric, string, polystyrene packing sheet, plastic packing tape and broken plastic pieces. The debris on Volunteer Beach was dominated by fishing debris; 42% of the items were discarded fishing equipment, while 39% of the items were of a packaging or associated nature. The mostly likely source of this household waste was fishing vessels, with Falkland Islands Government (FIG) fisheries observers seeing 27 of the 40 items of debris collected from Volunteer Beach being discarded from fishing vessels. It is suggested that, although further marine debris research is warranted, more effective at-sea ship waste disposal regulations are required in Falkland waters to reduce environmental and economic threats both at the local and international level.     

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.     

Improving the Efficiency of Wastewater Biological Treatment at Chemical Plants

The potential for improving the efficiency of wastewater biological treatment by using carbonate slime (heat power engineering waste) as a secondary material resource is illustrated by the case of Kazan Synthetic Rubber Works. The details of interaction between carbonate slime and activated-sludge microorganisms with inorganic components of plant wastewater are considered. The authors came to the conclusion that adsorption material should be used and developed a process flow chart for wastewater biosorption treatment.     

Induction of tributyltin-binding protein type 2 in Japanese flounder, Paralichthys olivaceus, by exposure to tributyltin-d27

In this study, individual Japanese flounder were intraperitoneally injected with 2 μg tributyltin-d27 (TBT-d27) fish⁻¹. Blood samples were collected on day 7 after injection. TBT-binding protein types 1 and 2 (TBT-bp1, -bp2) in the blood serum were quantified by western blotting analysis. As a result, the concentration of TBT-bp2 in TBT-d27 treated group increased to 220% of that in the solvent control, whereas the TBT-bp1 concentration decreased to 65% of that in the solvent control. Additionally, a positive relationship between the concentrations of TBT-bp2 and TBT was observed in blood sera of wild and cultured flounder. We suggest that TBT-bp2 is produced in response to TBT exposure and may play an important role in fish physiology.     

Optimisation of the Operation of an Electrochemical Process To Treat TBT‐contaminated Sediments on a Pilot Scale

Since at least three decades tributyltin had been commonly used in paint formulations to protect ship hulls and submersed surfaces from fouling. This has resulted in negative and Technology, effects to the marine environment due to its high toxicity towards non‐target organisms and to its accumulation in sediments, especially near point sources of pollution. Even if a ban of TBT for its application in anti‐fouling paints is enforced the problem of TBT‐contaminated sediments will remain for the coming years due to the low degradation rates of organotin in sediments. In this work an electrochemical process at a pilot scale to destroy TBT in sediments was investigated. Previous experiences at a laboratory and technical scale have demonstrated the potential of this process to electrolytically degrade organotin species in sediments. This article deals with the optimisation of the pilot plant performance in terms of organotin degradation and operation costs monitoring additionally the effect of the electrochemical treatment on other pollutants such as heavy metals, PCBs, and PAHs. The aim was to investigate by means of a parametric study the range of operating conditions required to destroy TBT down to concentrations lower than 100 μg/kg; to determine the influence of those parameters on the performance of the process; and to evaluate the operation costs associated to the process. It was determined that it was possible to destroy TBT down to 100 μg/kg at current densities in the range of 4.4 to 6.6 mA/cm² and chloride concentrations of least of 0.2 mol/L with operation costs of 13 to 18 EUR/m³.     

Magnetic characteristics of sediment grains concurrently contaminated with TBT and metals near a shipyard in Busan,Korea

Bottom sediments near shipyards are often susceptible to receiving accidental spills of TBT and metals or their degradation products from hull scraping of antifouling system paints applied prior to 2008, when the AFS Convention 2001 was not in force. We investigated TBT and metal contamination of sediments near the shipyards of a small marina located in Busan, Korea and found that they were highly contaminated with TBT, Cu, and Zn. To better understand the environmental impacts and to make an optimal remediation plan, we characterized individual antifouling fragments in terms of metal and TBT contents, magnetic properties, and grain-size. Coarse-sized individual antifouling fragments exhibited simultaneously high levels of TBT, metals and high magnetic susceptibility, and appeared to be a major source of pollution in the sediment. Therefore, magnetic separation in combination with size-separation appears to be a cost-effective remediation method to remove the TBT and metals from contaminated shipyard sediments.     

Determination of Polycyclic Aromatic Hydrocarbons in Soil by Miniaturized Ultrasonic Extraction and Gas Chromatography‐Mass Selective Detection

A miniaturized ultrasonic extraction procedure was developed for the determination of polycyclic aromatic hydrocarbons (PAHs) in soil by gas chromatography‐mass spectrometry. After determination of the most suitable extraction solvent with 5 min sonication time, several other parameters (sample amount, solvent volume and number of extraction times) were optimized using a 2³ factorial experimental design. Recoveries of PAHs from spiked soil samples were over 90% for three different fortification levels between 50 and 300 μg/kg, and relative standard deviations of the recoveries were in the range of < 1–15%. The limits of detection ranged from 0.002 to 1.87 μg/kg. The performance of the developed procedure was also compared with other traditional Soxhlet, shake flask and large scale ultrasonic extraction procedures on real soil samples, and extraction methods showed comparable efficiencies. The proposed procedure required small volumes of solvent and sample. It was practicable, rapid and easy to use for analysis of PAHs in soils.     

Toxicity-directed Fractionation of Tannery Wastewater Using Solid-phase Extraction and Luminescence Inhibition in Microtiter Plates

A four-step solid-phase extraction (SPE) method is presented for toxicity-directed fractionation of industrial wastewater. This fractionation procedure serves as a key step for identifying unknown organic toxicants in complex samples. Toxicity was determined as luminescence inhibition of Vibrio fischeri using microtiter plates. This method was compared to standard tests in glass cuvettes using both 37 standard chemicals and 24 wastewater fractions with EC₅₀ values covering five orders of magnitude. Results of both methods correlated well. 22 tannery wastewater samples were sequentially extracted using C₁₈e and polystyrene-divinylbenzene phases in combination with pH-changes. Final solid-phase filtrates showed low inhibition, so toxicity of inorganics could be neglected. Using 1/EC₅₀ values, the SPE eluates showed clearly different toxicity patterns. Even in eluates of the fourth extraction step, high toxic effects could be observed. In several cases, luminescence inhibition was increasing at the anaerobic treatment step compared to the corresponding untreated samples. After aerobic treatment, toxicity of most wastewater fractions was greatly diminished. HPLC/DAD analyses of the wastewater fractions showed a fair separation concerning compound polarity. However, the samples were still too complex to identify single compounds responsible for the detected toxicity. Therefore, a further clean-up step accompanied with toxicity testing is needed.     

Removal of Organic Pollutants from Wastewater Using Wood Fly Ash as a Low‐Cost Sorbent

In this study, untreated and treated wood fly ash (WA) was used as a low‐cost sorbent in batch sorption tests to investigate the removal of organic pollutants from a real wastewater generated by cleaning/washing of machinery in a wood‐laminate floor industry in Sweden. The experiments focused on the effect of the WA dosage and particle size on the removal efficiency for organic compounds. With a WA dosage of 160 g L^?1 and a particle size less than 1 mm, the reductions of chemical oxygen demand (COD), biologic oxygen demand, and total organic carbon were 37 ± 0.4, 24 ± 0.4, and 30 ± 0.3%, respectively. Pre‐treatment of WA with hot water improved the COD removal efficiency by absorption from 37 ± 0.4 to 42 ± 1.6% when the same dosage (160 g L^?1) was applied. Sorption isotherm and sorption kinetics for COD using untreated WA can be explained by Freundlich isotherm and pseudo‐second‐order kinetic models. Intra‐particle diffusion model indicates that pore diffusion is not the rate‐limiting step for COD removal. Based on the experimental data, WA could be used as an alternative low‐cost sorption media/filter for removal of organic compounds from real industrial wastewater.     

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.     

Accumulation of Butyltins in Sediments and Lipid Tissues of the Asian Clam,Potamocorbula amurensis,Near Mare Island Naval Shipyard,San Francisco Bay

Studies of butyltin compounds in soil, benthic sediments and the Asian clam Potamocorbula amurensis were conducted at the former Mare Island Naval Shipyard, and nearby Mare Island and Carquinez Straits in San Francisco Bay, California. Soils from a sandblast abrasives dump site at the shipyard contained low concentrations of mono-, di- and tributyltin (0.3–52 ng/g, total butyltin). Similarly, concentrations of total butyltin in benthic sediments from nearby Mare Island and Carquinez Straits ranged from 1.3 to 8.1 ng/g. In contrast, clams accumulated much greater concentrations (152–307 ng/g, total butyltin). Tributyltin (TBT) and dibutyltin (DBT) made up from 54–85% to 15–46%, respectively, of the total butyltin body burden of the clams. Biota Sediment Accumulation Factors (BSAFs) for butyltins in Potamocorbula were in reasonable agreement with literature values; they are greater than those of neutral hydrophobic compounds, suggesting that partitioning and binding processes may be involved in bioaccumulation. Tributyltin is a potent endocrine disrupting chemical. There is potential for long-term chronic effects of TBT in San Francisco Bay.     

Ecological impacts of tributyltin on estuarine communities in the Hastings River, NSW Australia

Oyster (Saccostrea commercialis) biomonitoring, assessment of oyster and gastropod (Bembicium auratum) abundance, and gastropod imposex were used to measure the significance of tributyltin (TBT) contamination in an intertidal mangrove forest. We studied the bioavailable levels of TBT in oysters approximately 1 km downstream and 2 km upstream from a TBT waste disposal site. We found observable declines in the abundance of oysters and gastropods correlated with the bioavailable TBT and these findings were confirmed by mapping oyster beds. Oyster cover near the disposal site ranged from 0% to 5% while downstream and upstream populations ranged in cover from 25–50% to 5–25%, respectively. Similarly, gastropod abundances at the disposal site were only 7% of the downstream population and 17% of the upstream population. Imposex was present in 90% of female B. auratum from populations near the disposal site but this effect declined more sharply than the population level effects.     

Biomonitoring of TBT contamination and imposex incidence along 4700 km of Argentinean shoreline (SW Atlantic: From 38S to 54S)

The imposex incidence and TBT pollution were investigated along 4,700 km of Argentinean coast, including city harbors and proximal zones without marine traffic. We analyzed 1805 individuals from 12 gastropod species, including families Volutidae, Muricidae, Nassariidea, Calyptraidae, Marginellidae, and Buccinidae, and found the imposex phenomenon for the first time in six species. In high marine traffic zones, TBT pollution was registered and the percentage of imposex was high, while these occurrences were null in areas without boat traffic. The species that best reflect the degree of imposex were those inhabiting sandy/muddy or mixed bottoms. TBT determination and imposex incidence indicate that pollution was focused only in ports with high marine traffic or in areas where ship hulls are painted. This is the first report of an imposex-sediment approach to evaluate organotin contamination along the coast of a South American country.