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Antifouling paint residues may contribute to high concentrations of metals in sediments. This study aims at assessing seasonal variations of labile metals (Cu, Zn, Pb, Cr and Ni) in surficial sediments (<63 µm) of port, marina and shipyard locations in southern Brazil under the influence of antifouling paints for vessels. The highest concentrations of Cu and Zn in the sediment of shipyard areas were consistent with the composition of the most used antifouling paints, which were analyzed for the first time. The extended El Niño effect on the region caused a decrease in concentrations of labile metals in the sediment. A high correlation between Cu and Zn in the sediment could indicate that they may have the same source, antifouling paints. Levels of Pb were correlated to concentrations of Cu and Zn, and these, to Cr and Ni to a lesser extent. Data were compared with concentrations of trace metals in marine sediment established by the National Oceanic and Atmospheric Administration (NOAA) Screening Quick Reference Tables which indicate the toxicity levels of the sediment. Labile Cu, Zn and Pb levels at shipyard and marine areas exceeded the NOAA values, thus, showing that these areas need attention regarding the waste input of antifouling paints, marine diesel oil and lubricants. [ABSTRACT FROM AUTHOR]

The incrustation of marine organisms (biofouling) affect several submerged metallic structures, like ship hulls. Biofouling frequently induces metal corrosion, reduces the speed of displacement, increases fuel consumption, and increases the frequency of dry-dock operations. Antifouling paints which have the capacity to prevent the marine organisms from contacting the painted surface (by means of biocide release), have been developed in order to mitigate these deleterious effects. Static tests of antifouling paints include immersing painted panels (attached to floating structures), and periodically evaluating its performance. Before conducting these static tests, it is important to characterize the local maritime environment by determining the range of values of the most significant physical, chemical and biological variables. A complete characterization of the sea water in the zone of Mamonal (Cartagena Bay) was conducted; variables such as solar irradiation, light availability, dissolved oxygen, temperature, pH, redox potential, alkalinity, and salinity were measured. In addition, the determination and quantification of the main biological entities present in the samples was also carried out.

After the Tributyltin world ban, Irgarol 1051 and Diuron have been the most commonly used biocides in antifouling paints. When adsorbed to suspended particulate matter or introduced as paint particles, these compounds accumulate in marine sediments and potentially cause ecological damage to benthic organisms. Therefore, a microcosm experiment was designed to evaluate the effects of Irgarol 1051 and Diuron, individually, on a meiofaunal community with emphasis on the dominant nematode assemblages. The experiment tested two factors: “Treatment” (two types of controls and three environmentally relevant concentrations of each contaminant) and “Exposure time” (5, 15 and 30 days). Significant declines in meiofauna density, nematode species richness and diversity, and changes in multivariate community structure were observed for both biocides at all exposure levels when compared to controls. Decreases occurred early on, within five days of exposure, which suggests that mortality, and not sub-lethal effects, has befallen upon the organisms. Sediment chlorophyll a and pheopigment concentrations, and redox potential were monitored to verify any indirect effects to the fauna through changes in the environment and results gave no indications of such mediated effects pointing to a direct toxic effect of both Irgarol and Diuron on the meiofauna. Although contaminated treatments showed a significant decline in the relative abundances of a particular functional group represented by the larger, longer-lived species, we did not observe the typical expected switch to smaller, more opportunistic taxa. Indeed, differences between controls and contaminated treatments were mainly due to an overall reduction in densities of the most abundant species in contaminated treatments. The high mortality (ca. 50% decline in total abundances), changes in community structure and species loss observed at biocide levels frequently encountered in the field suggest Irgarol and Diuron as a threat to benthic communities. Such severe effects contrast to other studies that have detected lower impacts, suggesting the free-living nematodes as potential indicators of marine pollution and the microcosm approach using natural communities as an impending tool for ecotoxicological studies. [ABSTRACT FROM AUTHOR]

Twelve organotins (methyl-, octyl-, butyl-, and phenyl-tin), and eight tin-free antifouling paints and their degradation products were measured in marine sediments from the Korean coastal area, and Busan and Ulsan bays, the largest harbor area in Korea. The total concentration of tin-free antifouling paints was two- to threefold higher than the total concentration of organotins. Principal component analysis was used to identify sites with relatively high levels of contamination in the inner bay area of Busan and Ulsan bays, which were separated from the coastal area. In Busan and Ulsan bays, chlorothalonil and DMSA were more dominant than in the coastal area. However, Sea-Nine 211 and total diurons, including their degradation products, were generally dominant in the Korean coastal area. The concentrations of tin and tin-free compounds were significantly different between the east and west coasts. [ABSTRACT FROM AUTHOR]

Despite the ban of applying TBT coatings on leisure boats in the late 80s, recent studies show an ongoing spread of TBT from leisure boats, particularly during hull cleaning events. Therefore, countries in EU have adopted expensive measures to clean this wash water. A more cost-efficient measure is to focus directly on the source, i.e. identify leisure boats with high concentrations of TBT and prescribe boat owners to remove the paint. We have developed a new antifouling paint application for a handheld X-ray fluorescence (XRF) analyzer to be used for identifying boats with high area concentrations (µg/cm 2 ) of Sn (indication that the hull contains TBT paint residues). Copper and zinc are also included in the application since these metals are used in the vast majority of today's paints. A blind test with up to four layers of TBT-, copper- and zinc-based paints showed good correlation between XRF-measured area concentrations and chemically analyzed concentrations. Future usage of the applications involves identification of boat hulls in particular with high Sn concentrations and also with high Cu and Zn concentrations. This method has the potential to become a useful tool in regulatory management of existence and use of toxic elements on boat hulls. [ABSTRACT FROM AUTHOR]

Ciliate assemblages are often overlooked, but ubiquitous components of microbial biofilms which require a better understanding. Ciliate, diatom and bacterial colonisation were evaluated on two fouling-release (FR) coatings,viz. Intersleek 970 and Hempasil X3, and two biocidal antifouling (AF) coatings,viz. Intersmooth 360 and Interspeed 5640, in Port Phillip Bay, Australia. A total of 15 genera were identified during the 10 week deployment. Intersleek 970 displayed the most rapid fouling by ciliates, reaching 63.3(± 5.9) cells cm−2. After 10 weeks, all four coatings were extensively fouled. However, the toxicity of the AF coatings still significantly inhibited microbial fouling compared to the FR coatings. On all treatments, colonies of sessile peritrichs dominated the ciliate assemblage in the early stage of succession, but as the biofilm matured, vagile ciliates exerted more influence on the assemblage structure. The AF coatings showed selective toxic effects, causing significant differences in the ciliate species assemblages among the treatments. [ABSTRACT FROM AUTHOR]

Cuprous oxide is the most commonly used biocide in antifouling paints. However, copper has harmful effects not only on the fouling community but also on non-target species. In the current study, we investigated the use of thymol, eugenol and guaiacol in this role combined with small quantities of copper. Phenolic compounds were tested for anti-settlement activity against cyprid larvae of the barnacle Balanus amphitrite and for their toxicity to nauplius larvae. Thymol, eugenol and guaiacol were active for anti-settlement but guaiacol had the disadvantage of being toxic to nauplius larvae. However, all of them showed therapeutic ratio>1. Antifouling paints with thymol (low copper content/thymol, LCP/T), eugenol (low copper content/eugenol, LCP/E) and guaiacol (low copper content/guaiacol, LCP/G) combined with small copper content were formulated for field trials. After 12 months exposure in the sea, statistical analysis revealed that LCP/T and LCP/E paints were the most effective combinations and had similar performances to control paints with high copper content (traditional cuprous oxide based paints). In contrast, LCP/G paint was only partially effective in preventing and inhibiting biofouling and was colonized by some hard and soft foulers. However, this antifouling paint was effective against calcareous tubeworm Hydroides elegans . In the light of various potential applications, thymol, eugenol and guaiacol have thus to be considered in future antifouling formulations. [ABSTRACT FROM AUTHOR]

Development of non-toxic or less toxic paints has become a target for researchers due to the awareness of the impacts from the use of toxic antifouling paints. One of the modern alternatives to produce an environmental friendly paint is by using natural products. This study investigated the mangrove, Rhizophora apiculata tannin derivatives (zinc tannate) for antifouling properties by incorporating the powdered extract with different amount in epoxy paint formulation. The antifouling activity of zinc tannate was proved by antifouling crystal violet assay and the specimens have been exposed in seawater environment. The initial and final weights of mild steel were recorded to obtain the mass accretion which indicates the weight of biofouling settlement over the specimen surface. The effectiveness of this antifouling agent depends on the amount of zinc tannate in the paint and their leaching rate in seawater. Low concentration of zinc tannate (2.736 mg/ml) was found sufficient to inhibit the growth of bacteria, Bacillus cereus . [ABSTRACT FROM AUTHOR]

Purpose - The purpose of this paper is to reduce the amount of copper in antifouling paints by using eugenol as an additive. Biofouling leads to deterioration of any submerged material. The most widespread method for control is the application of cuprous oxide antifouling paints which are toxic. First of all, the paper describes the effect of eugenol on larvae of Balanus amphitrite (fouling organism) under laboratory conditions and then the preparation, application and performance of different types of antifouling paints in field trials. Design/methodology/approach - Three types of soluble matrix antifouling paints were prepared with different pigments. The first one containing 16 per cent v/v copper, the second with 1.6 per cent copper and the third with 1.6 per cent copper + 2 per cent eugenol. Findings - After 12 months of immersion in Mar del Plata harbour paints containing 1.6 per cent copper + eugenol and 16 per cent copper were the most effective. Although these formulations showed a similar performance, copper + eugenol-based paint contains 90 per cent lesser copper than a traditional copper-based formulation. Originality/value - The use of antifouling paints with copper + eugenol combination as pigment is a promising alternative due to its performance, low cost and reduction in copper leaching to environment. [ABSTRACT FROM AUTHOR]

Although aquaculture is considered the fastest growing food production industry, nevertheless there is little information regarding pollutant levels in cultured fish. Samples of cultured sea bass –Dicentrarchus labrax(Linnaeus, 1758), sea bream –Sparus aurata(Linnaeus, 1758), and sharpsnout sea bream –Diplodus puntazzo(Walbaum, 1792) from three fish farms located in the Eastern Mediterranean which utilized antifouling paints on the nets were analyzed for quantitative determination of zinc (Zn), chrome (Cr), and copper (Cu) in the gills, the liver, and the muscle separately for each tissue and fish. The results show that the highest levels of zinc (up to 29.6 mg kg−1dry wt) were found in the gills of all samples of sea bream and sharpsnout sea bream while in the samples of sea bass, the highest levels of zinc and chrome were found in the liver (up to 39.3 and 13.8 mg kg−1dry wt, respectively). Insofar, as copper is concerned the highest exposure was found in the liver of sharpsnout sea bream (up to 5.49 mg kg−1dry wt). The results indicate that the use of antifouling paints in aquaculture practices are a significant source of chemical pollution in cultured fish and poses a risk to the exposed organisms. [ABSTRACT FROM AUTHOR]

Release of copper (Cu) from antifouling paints on marine vessels is pollution concern globally. Estimates of the total amount of Cu released from antifouling paints are fairly well constrained; however, less is known about the dispersal of this dissolved Cu. To help improve our understanding of the fate of Cu releases from antifouling paints, a study was carried out in Crane Creek and the adjacent Indian River Lagoon, FL. Dissolved Cu released from antifouling paints accounted for >90% of the total dissolved Cu input to the creek. The maximum concentration of dissolved Cu in the creek, 2.2 μg/L, was ~16%above the U.S. EPA chronic value of 1.9 μg/L. Potential adverse impacts from Cu were likely reduced by uptake of dissolved Cu on suspended particles. Mass balance calculations for Cu showed that about one-third of the dissolved, anthropogenic Cu released from antifouling paint was transported from the creek into the adjacent lagoon. About two-thirds of the anthropogenic Cu was independently shown to be deposited in creek sediments. Copper values for creek sediments were as high as 201 μg/g, well above an effects range-low of 70 μg/g. [ABSTRACT FROM AUTHOR]

Organotin compounds are industrial chemicals used as biocides, polyvinyl chloride stabilizers and industrial catalysts for the manufacture of silicone and polyurethane foams. Despite multiple applications, organotin notoriety is due to tributyltin, a potent biocide used in antifouling paints. Because of the intensive use of tributyltin for the protection of ships' hulls, tributyltin has been largely released into waters, resulting in adverse and even bizarre effects on aquatic organisms, such as imposex in gastropods. However, organotins include other compounds such as tributyltin derivatives, phenyltins and octyltins. Organotin use in plastics, silicone and foams results in their occurrence almost everywhere, e.g., clothes, toys, wallpaper, food containers, household piping and medical devices. Hence, humans are exposed to organotins not solely through ingestion of contaminated seafood but also through direct contact with treated products and by inhalation and ingestion of dust. As a consequence, organotins have been detected in human samples. Toxicity data reveal that organotins are endocrine disruptors, immunotoxicants, carcinogens and obesogens. Here, we review the levels, fate and effects of organotin compounds toward wildlife and humans, starting with a description of organotin applications, with particular incidence in antifouling paints. The global contamination of the marine environment and the deleterious effects of tributyltin onto nontarget organisms are addressed, with particular attention to the imposex phenomenon. The restrictions on tributyltin use in antifouling paints are also described alongside with the new regulations for organotins in consumer products. The sources and pathways of organotins in the environment are discussed, studies in human exposure are presented, and future research is proposed. [ABSTRACT FROM AUTHOR]

Abstract: Biofouling control involves the application of paints containing toxic substances to the marine ecosystem. One of the most promising alternative technologies to antifouling paints based on heavy metals is the development of coatings whose active ingredients are compounds naturally occurring in marine organisms. This study investigated the antifouling activity of organic extracts from some epibiont-free Colombian Caribbean Sea sponges (Agelas tabulata, Myrmekioderma gyroderma, Oceanapia peltata, Aplysina lacunosa, Neopetrosia sp.) and a sea-cucumber (Holoturia glaberrima). Extracts were incorporated into hard stable gels and into soluble matrix antifouling paints and exposed in the sea (Colombia and Argentina). After 45 and 90 days, significant differences in fouling cover percentages between painted panels and controls were found (p < 0.05). It was demonstrated that the greatest antifouling activity was contained in extracts of A. tabulata and Holoturia glaberrima in both study sites. This study successfully identified potential new sources of natural antifouling compounds. [Copyright &y& Elsevier]

Biofouling is an important aspect to consider in the protection of a structure submerged in sea water. In fact, besides causing deterioration of the entire protective system (e. g., corrosion protection), biofouling increases roughness and weight in ships and other structures therefore affecting their operation. Antifouling paints, having the capacity to exclude the marine organisms that tend to adhere to the surface, have been developed in order to mitigate these adverse effects. In order to formulate and evaluate a potential paint it is necessary to have knowledge of the marine environment, and to be able to conduct both laboratory and field tests so representative and applicable results are obtained. The recommended steps to follow in such a study are described in this paper. The methodology proposed has been recently developed and applied with promising results.

Abstract: We studied if the levels of copper released from antifouling treated nets used in finfish mariculture could affect the immune defense mechanism and/or induce oxidative stress in Dicentrarchus labrax, after short term exposure in laboratory experiments. Dissolved copper concentration released from the treated nets, copper bioavailability and a set of biomarkers responses were measured. Biomarkers included hemoglobin concentration, activities of lysozyme, total complement, respiratory burst, glutathione S-transferase and acetycholinesterase and concentration of thiobarbituric acid reactive substances. Results indicated elevated copper concentration in seawater (184μgL−1) but low concentration in muscle (1.5μgg−1) and liver (117μgg−1). Copper bioavailability was independent of copper complexes with dissolved organic carbon. However, formation of copper complexes with other matrices could neither be excluded nor justified. The released copper from the treated nets did not induce oxidative stress but affected the immediate immune defense mechanism of the exposed fish making them more easily vulnerable to diseases. Consequently, copper-based antifouling treated nets could be a risk factor for D. labrax health. [Copyright &y& Elsevier]

Abstract: Liver butyltin concentrations (monobutyl, dibutyl and tributyltin (TBT)) in harbour porpoises (n =410) have been determined during 1992–2005, and again in 2009 following a ban on the use of tributyltin-based antifouling paints on ships. The aim was to assess the effectiveness of the regulation, which was implemented during 2003–2008. Since the ban was put in place summed butyltin concentrations have declined. Also, the percentage of animals in which TBT was detected has fallen sharply, indicating the cessation of fresh inputs. In 1992, 1993 and 1995, TBT was detected in 100% of samples analysed. In 2003–2005, once the implementation of the ban had begun, this fell to 61–72%, and in 2009, following the completion of the ban, had reduced to 4.3% (i.e. in only 1 of 23 samples analysed). Thus we conclude that the ban has proved effective in reducing TBT inputs to the seas from vessels. [Copyright &y& Elsevier]

The growth of fouling communities on ships' hulls causes economic losses due to increased fuel consumption and to the deterioration of the metallic substrate by corrosion. Antifouling paints are formulated to avoid the settlement of these organisms and may contain biocides as active compounds. The objective of this research was to evaluate the antifouling performance of paints formulated with a 'quebracho' tannin derivative (zinc 'tannate') and 'boosters' (secondary biocides). The 'boosters' used in this study were bismuth lactate, a zeolite exchanged with silver cations, and the same zeolite modified with silver chloride. Bioassays with 'boosters' solutions were carried out employing Artemia persimilis. Soluble matrix antifouling paints were formulated and their action was assessed in a natural sea water environment. Results showed that the bismuth lactate resulted in a coating with almost triple service life of the antifouling paints with zinc 'tannate.' Paints formulated with the silver composites behaved slightly better than the control paint. [ABSTRACT FROM AUTHOR]

Abstract: The southern Venice lagoon has been affected by an increase of several anthropogenic activities (dockyards, harbours and marina) which have contributed to enrich sediments with metals in the recent years. The contamination of metals in the surface sediments along with their accumulation in the gastropod Nassarius reticulatus were investigated. Highest metal concentrations of Cu, Zn, Pb and Cr found in the dockyards and marina sites suggest their possible past and recent use as biocides in the antifouling paints. The enrichment factor (EF) showed highest values (EF>10) near the dockyards, harbour and marina sediments for Cu, where the use of the antifouling tin free paints has been more relevant. High levels of metals were also found in the target gastropods. Biota-Sediment-Accumulation-Factor and correlation analyses pointed out a significant mobilization of metals, particularly Cu, from sediments and their accumulation in the gastropods. [Copyright &y& Elsevier]

The aim of this study was to investigate the efficiency of (1) chemical precipitation by calcium oxide, (2) coagulation/flocculation by ferric chloride (FC), and (3) the combination these two methods in reducing the toxicity of wastewater generated by boat pressure washing. All three methods gave satisfactory results in the removal of colour, turbidity, Cr, Fe, Cu, Zn, and Pb. The concentrations of heavy metals were lowered below national limits with 1 g of CaO, 2.54 mg of Fe3+ in the form of FeCl3x6H2O, and the combination of 0.25 g of CaO and 5.08 mg of Fe3+ per 50 mL of wastewater. Both CaO (1.50 g per 50 mL of wastewater) and FC proved efficient, but their combination yielded a significantly better performance: 99.41%, 100.00 %, 97.87 %, 99.09 %, 99.90 %, 99,46 % and 98.33 % for colour, turbidity, Cr, Fe, Cu, Zn, and Pb respectively. For colour, Cr, Cu, Zn, and Pb removal efficiencies increased in the following order: FC

The evaluation of new antifouling paints is usually performed through long and expensive field tests (raft-tests), often depending on the season of exposure. Particularly in the Mediterranean Sea, these tests are representative only if carried out during spring or summer. Therefore, it is strategically important to develop laboratory methods that are able to test and select, during winter, the best formulations to submit to raft-test during the summer. For this reason, an acute toxicity bioassay using larvae (Stage II nauplii) of Amphibalanus amphitrite on paint leaching products obtained with an accelerated ageing system was tested as a tool for the indirect evaluation of antifouling efficacy. Seven experimental paint formulations were selected on the basis of previous obtained field efficacy performances, and were subjected to both laboratory bioassays and to a 12-month raft-test. The data show how paint behaviour (expressed as fouling coverage percentage) after 12 months of immersion in the field could be predicted by the results of laboratory bioassays, expressed as immobilisation percentage of larvae exposed for 48 h to leaching products of artificially aged paints. [ABSTRACT FROM PUBLISHER]

This paper provides the information on the optimum conditions of the treatment process of the boat pressure washing wastewater (BPWW) by the combination of the ozonation and electrochemical (EC) methods developed on the laboratory and pilot plant scale. The initial effluent was highly enriched in heavy metals and elevated levels of organic contaminants. The concentrations of V, Cr, Fe, Cu, Zn, TOC, and COD exceeded the upper permissible limits of 22, 20, 6, 112, 17, 4, and 2 times, respectively. The main mechanisms of the organic matter destruction were the ozone oxidation and the indirect oxidation with chlorine/hypochlorite formed by the anodic oxidation of chloride already present in the wastewater. The heavy metal removal was forced by the coagulation/flocculation using Fe2+, Fe3+, and Al3+ ions released into the treated solution by electrochemical corrosion of the sacrificial stainless steel and aluminum electrodes. At the optimum conditions obtained with the pilot plant, the removal efficiencies of the parameters V, Cr, Fe, Ni, Cu, Zn, Pb, TOC, and COD were 100.00 %, 99.35 %, 99.51 %, 87.31 %, 99.83 %, 99.65 %, 100.00 %, 88.46 %, and 76.28 %, respectively. All the parameters in the final effluent were in agreement with regulated values. The advantages of this system compared to its physico-chemical counterparts are as follows: (1) no need for the external addition of flocculating agents since they are electrochemically generated inside the treatment tank; (2) minimal pH changes during the treatment process not requiring pH adjustment by acids/basis; (3) a significantly lower amount of sludge since only Fe and Al ions were released in the solution; (4) flocs formed by the electrocoagulation can be easily separated by the filtration due to their higher stability, lower content of the bound water and larger surface compared to chemical flocs; (5) the final EC effluent is clear, colourless and odourless, containing the less total dissolved solids and organics, thence more suitable for the reuse compared to the one obtained by the standard chemical treatment. [ABSTRACT FROM AUTHOR]

Diatoms are primary colonizers of both antifouling and fouling-release ship hull coatings. There are few published studies which report on diatom community development on modern ship hull coatings. This study reports diatom communities on eight commercial marine ship hull coatings exposed at three static immersion sites along the east coast of Florida, viz. Daytona, Sebastian, and Miami. The coatings tested were three ablative copper systems (Ameron ABC-3, International BRA-640, and Hempel Olympic 76600), two copper-free biocidal systems (E-Paint SN-1, Sherwin Williams HMF), and three fouling-release (FR) systems (International Intersleek 700, International Intersleek 900, and Hempel Hempasil). One hundred and twenty-seven species comprising 44 genera were identified, including some of the more commonly known foulers, viz. Achnanthes, Amphora, Cocconeis, Entomoneis, Licmophora, Melosira, Navicula, Nitzschia, Synedra, and Toxarium. A significant difference was seen among sites, with the more estuarine site, Sebastian, having lower overall diatom abundance and higher diversity than Daytona and Miami. Copper coatings were primarily fouled by Amphora delicatissima and Entomoneis pseudoduplex. Copper-free coatings were fouled by Cyclophora tenuis, A. delicatissima, Achnanthes manifera, and Amphora bigibba. FR surfaces were typified by C. tenuis, and several species of Amphora. The presence of C. tenuis is new to the biofouling literature, but as new coatings are developed, this diatom may be one of many that prove to be problematic for static immersion. Results show coatings can be significantly influenced by geographical area, highlighting the need to test ship hull coatings in locations similar to where they will be utilized. [ABSTRACT FROM PUBLISHER]

Abstract: Special microcontainers for producing self-healing and antifouling paints for corrosive and biocorrosive environment were elaborated. Our work aimed to improve the efficiency of anticorrosion paints in cases of abrasion and scratching with application of microcapsules filled with film former and corrosion inhibitor and, as well as of antifouling paints in underwater environment with application of slow-release polymeric microspheres filled with antifouling agent. First the preparation and characterization of microcapsules/spheres were in the focus, then application in paints in order to see their anticorrosion and antifouling efficiency. The preparation of microcapsules and microspheres has been carried out by emulsion polymerization by traditional techniques. The characterization of microcontainers with different shells and cores were done by complementary techniques. The morphology and the shell-thickness was visualized and measured by scanning and transmission electron microscopy (SEM, TEM), by fluorescence and optical microscopy (FM, OM). The presence and the amount of encapsulated corrosion inhibitor and antifouling agent was measured by inductively coupled plasma spectrometer (ICP). The efficiency of coatings with microcapsules and microspheres was checked on sandblasted mild steel and on glass in natural water. [Copyright &y& Elsevier]

Abstract: This study investigated butyltin contamination in Hong Kong waters using the rock shell Thais clavigera as a biomonitor. We collected rock shells from nine coastal sites in both winter 2005 and summer 2006 to examine the spatial and seasonal patterns. The relative penis size index (RPSI) and vas deferens sequence index (VDSI) were determined following a standard protocol, while the tissue concentrations of butyltins (i.e., mono-, di- and tri-butyltin) were measured using gas chromatography. The results showed that imposex was particularly severe in T. clavigera collected from Victoria Harbour, Pak Sha Wan and Sai Kung Pier where shipping activities were frequent. Both imposex indices had a positive correlation with tissue concentration of tributyltin in T. clavigera. While VDSI exhibited little seasonal variation, RPSI of winter specimens was significantly higher than that of summer specimens. Thus, sampling season should be standardised when using RPSI as a biomarker. [Copyright &y& Elsevier]

Antifouling (AF) paints are used to prevent the attachment of living organisms to the submerged surfaces of ships, boats and aquatic structures, usually by the release of biocides. Apart from copper, organic booster biocides are the main active components in AF paints, but their use can have a negative impact on the marine environment. The direct effects of biocides on marine bacteria are poorly known. This work investigates the impact of two biocides, viz. diuron and tolylfluanid, on the growth and the viability of marine microorganisms and on their ability to form biofilms. The biocides in solution were found to inhibit growth of two strains of marine bacteria, viz. Pseudoalteromonas and Vibrio vulnificus, at a high concentration (1000 μg ml-1), but only a small effect on viability was observed. Confocal laser scanning microscopy (CLSM) showed that the booster biocides decreased biofilm formation by both bacteria. At a concentration of 10 μg ml-1, the biocides inhibited cell attachment and reduced biofilm thickness on glass surfaces. The percentage of live cells in the biofilms was also reduced. The effect of the biocides on two diatoms, Fragilaria pinnata and Cylindrotheca closterium, was also evaluated in terms of growth rate, biomass, chlorophyll a content and attachment to glass. The results demonstrate that diuron and tolylfluanid are more active against diatoms than bacteria. [ABSTRACT FROM AUTHOR]

Abstract: Background: Organotin compounds (OTCs) are a large class of synthetic chemicals with widely varying properties. Due to their potential adverse health effects, their use has been restricted in many countries. Humans are exposed to OTCs mostly through fish consumption. Objectives: The aim of this study was to describe OTC exposure through fish consumption and to assess the associated potential health risks in a Finnish population. Methods: An extensive sampling of Finnish domestic fish was carried out in the Baltic Sea and freshwater areas in 2005–2007. In addition, samples of imported seafood were collected in 2008. The chemical analysis was performed in an accredited testing laboratory during 2005–2008. Average daily intake of the sum of dibutyltin (DBT), tributyltin (TBT), triphenyltin (TPhT) and dioctyltin (DOT) (ΣOTCs) for the Finnish population was calculated on the basis of the measured concentrations and fish consumption rates. Results: The average daily intake of ΣOTCs through fish consumption was 3.2ng/kgbwday−1, which is 1.3% from the Tolerable Daily Intake (TDI) of 250ng/kgbwday−1 set by the European Food Safety Authority. In total, domestic wild fish accounted for 61% of the ΣOTC intake, while the intake through domestic farmed fish was 4.0% and the intake through imported fish was 35%. The most important species were domestic perch and imported salmon and rainbow trout. Conclusions: The Finnish consumers are not likely to exceed the threshold level for adverse health effects due to OTC intake through fish consumption. [Copyright &y& Elsevier]

Recent research suggests anthropogenic disturbance may disproportionately advantage non-indigenous species (NIS), aiding their establishment within impacted environments. This study used novel laboratory- and field-based toxicity testing to determine whether non-indigenous and native bryozoans (common within marine epibenthic communities worldwide) displayed differential tolerance to the common marine pollutant copper (Cu). In laboratory assays on adult colonies, NIS showed remarkable tolerance to Cu, with strong post-exposure recovery and growth. In contrast, native species displayed negative growth and reduced feeding efficiency across most exposure levels. Field transplant experiments supported laboratory findings, with NIS growing faster under Cu conditions. In field-based larval assays, NIS showed strong recruitment and growth in the presence of Cu relative to the native species. We suggest that strong selective pressures exerted by the toxic antifouling paints used on transport vectors (vessels), combined with metal contamination in estuarine environments, may result in metal tolerant NIS advantaged by anthropogenically modified selection regimes. [Copyright &y& Elsevier]

To evaluate the effects of antifouling paints and biocides on larval settlement and metamorphosis, newly hatched swimming larvae of the compound ascidian Botryllus schlosseri, a dominant species of soft-fouling in coastal communities, were exposed to (i) substrata coated with seven antifouling paints on the market containing different biocidal mixtures and types of matrices and (ii) sea water containing various concentrations of eight biocidal constituents. All antifouling paints showed high performance, causing 100% mortality and metamorphic inhibition, with ≥75% not-settled dead larvae. All antifouling biocides prevented the settlement of larvae. The most severe larval malformations, i.e., (i) the formation of a bubble encasing the cephalenteron and (ii) the inhibition of tail resorption, were observed after exposure to metal and organometal compounds, including tributyltin (TBT) at 1 μM (325.5 µg L−1), zinc pyrithione (ZnP) at 1 μM (317.7 µg L−1), and CuCl at 0.1 μM (98.99 µg L−1), and to antimicrobials and fungicides, including Sea-Nine 211 at 1 μM (282.2 µg L−1) and Chlorothalonil at 1 μM (265.9 µg L−1). The herbicides seemed to be less active. Irgarol 1051 was not lethal at any of the concentrations tested. Diuron at 250 μM (58.2 mg L−1) and 2,3,5,6-tetrachloro-4-(methylsulphonyl)pyridine (TCMS pyridine) at 50 μM (14.8 mg L−1) completely inhibited larval metamorphosis. These results may have important implications for the practical use of different antifouling components, highlighting the importance of their testing for negative impacts on native benthic species. [ABSTRACT FROM AUTHOR]

Tributyltin (TBT)-based antifouling paints have been successfully used for over 40years to protect a ship's hull from biofouling. However, due to its high toxicity to marine organisms, the International Maritime Organization (IMO), in 1990, adopted a resolution recommending governments to adopt measures to eliminate antifouling paints containing TBT. High concentrations of TBT are detected in the vicinity of ports and shipyards. TBT is also usually detected in the sediment, in which it accumulates. This study reviews recent literature for the best management practices (BMPs) in order to minimize the environmental effects of TBT. The paper focuses on the evaluation of the available techniques for the removal of TBT from shipyard wastes and from the sediment. The most effective treatment methods are highlighted. BMPs include recycling of abrasive materials, use of cleaner abrasive materials, reuse of spent abrasive materials, substitution of hydroblasting by vacuum blasting or containment or ultra-high-pressure water blasting and confinement of pollution by enclosure and containment systems. The treatment of the TBT wastes by conventional biological wastewater treatment processes is probably not suitable, because the concentrations of TBT found in shipyards’ wastewaters are toxic to microorganisms. Advanced technologies such as activated carbon adsorption and dissolved air floatation, in combination with filtration and coagulation-clarification, photodegradation and electrochemical treatment, are required to remove TBT. However, advanced methods should be further optimized to meet the regulatory limit of 200ng/L. To date, only one published work examines the efficiency of incineration for the treatment of solid sandblast wastes. Regarding the treatment of sediment, land deposition of the less polluted fraction of sediment is a feasible option. Such treatment must take into account the risk of contamination of groundwater and the surroundings, and it requires... [Copyright &y& Elsevier]

Organotin compounds are widely used in almost all sectors of industry. Antifouling paints, which were applied to ship hulls to protect from fouling organisms, are the main source of TBT and TPhT derivatives loaded into the sea. The global ban on the use of these compounds in antifouling systems was introduced by the IMO in 2001. However, the ban did not solve the problem of the use of alternatives to TBT in the ship industry. Moreover, the issue of storing the organotins-containing dredged spoils at sea still remains unresolved. The pollution load deposited in port sediments may become an additional threat to the organisms that dwell in a given water basin. In such cases, it is necessary to establish appropriate norms for the quality classification of dredged spoils. Unfortunately, detailed guidelines concerning the disposal of dredged spoils are still lacking. [ABSTRACT FROM AUTHOR]

Some samples of sea shell animals stuck and multiplied on the bottom (beneath the seawater) coated with antifouling paints were collected at some domestic maritime spaces, and the content of heavy metals was detected through Inductively Coupled Plasma-Mass Spectroscopy. Meanwhile, comparison with sea shell animals was made on market for edible use. It shows that the content of heavy metals in internal organs of these marine animals is very high due to the large amount of copper and zinc contained in the antifouling paints, and this also does severely harm to sea environment and ecology. To study and develop the novel antifouling paints without copper(l) oxide is an imperative task which brooks no delay. [ABSTRACT FROM AUTHOR]

Abstract: Thirteen areas around the Chinese Bohai coast, individuals including ten kinds of bivalves and two kinds of snails were collected during the period of 2002–2005 for the investigation of spatial distribution and temporal variations of butyltin compounds (BTs). BTs including tributyltin (TBT) and its derivates, dibutyltin (DBT) and monobutyltin (MBT) were quantified by gas chromatography/flame photometric detection after extraction and Grignard derivatization. BTs compounds were widely existed in the samples and TBT was the dominant composition, indicating recent TBT input along Bohai coast. As a whole, BTs concentration remained high during the sampling years except a slightly decreased in samples from several sites in 2005. The contamination characteristics of BTs in different sampling sites were analyzed using principal component analysis (PCA) method, and the species specific bioaccumulation of BTs was also identified using cluster analysis. [Copyright &y& Elsevier]

Maritime transport is a primary vector for many marine invaders. For the past two decades, most commercial vessels have used tributyltin (TBT) antifouling (AF) paint, whereas recreational vessels have been restricted to alternatives, most commonly containing copper. Settlement plates painted with a collar of copper or TBT AF paint, and unpainted control plates, were deployed in commercial and recreational embayments in Port Jackson, Australia, and sampled photographically after 5 and 10 months. Copper enhanced early recruitment of several non-indigenous species (NIS), whereas recruitment of indigenous species was typically reduced by copper. TBT limited the recruitment of NIS for just 5 months and indigenous species, for the entire study. The results suggest that the use of toxic AF paints, and the possible accumulation of AF biocides in embayments, may be negatively affecting indigenous epibiota. Conversely, copper antifoulants on recreational vessels may be facilitating the transport and establishment of copper tolerant NIS into disturbed estuarine habitats. [ABSTRACT FROM AUTHOR]

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. [Copyright &y& Elsevier]

Abstract: Single and joint effects of two antifouling booster biocides, irgarol 1051 (2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine) and diuron (1-(3,4 dichlorophenyl)-3,3 dimethyl urea), their metabolites, M1 (2-methylthio-4-tert-butylamino-s-triazine), DCPMU (1-(3,4-dichlorophenyl)-3 methyl urea), DCPU (1-(3,4 dichlorophenyl urea) and DCA (3,4-dichloroaniline), respectively, as well as copper were examined. Two phytoplanktonic microorganisms, the green alga Dunaliella tertiolecta and the diatom Navicula forcipata were exposed to various concentrations of the aforementioned compounds both alone and in binary mixtures during a period of 96h. Estimation of EC50 values was performed by daily cell number counting of the tested microorganisms. The toxicity of the six compounds and the metal, applied singly, was found to be, in decreasing order, irgarol 1051>diuron>M1>DCPMU>DCA>Cu>DCPU and irgarol 1051>diuron>M1>DCA for the green alga and the diatom, respectively. Diatoms were found to be more sensitive in the presence of all the tested compounds, except diuron. Co-existence of irgarol 1051 and M1 revealed additive effects on both microorganisms. Same results were observed owing to the joint action of copper with either irgarol 1051 or M1 for almost all the examined mixtures. Combined effects of diuron with its metabolites DCPMU and DCA resulted in synergism in almost all cases, for both species of phytoplankton. On the contrary, antagonistic effects were observed owing to the joint action of copper with either diuron or one of its metabolites. [Copyright &y& Elsevier]

Copper is currently the most common biocide in antifouling paints. Levels of this metal were measured in the water, particulate matter and sediments from a shellfish farming area in the Sacca di Goro (Northern Adriatic Sea) over one year. With respect to the 1980s, copper environmental level increased twofold. The release of copper from shellfish farmers’ boats was also estimated to be >250kgCuy−1. Clams Tapes philippinarum were collected in the same area and seasonally exposed to a sublethal (10μgCul−1) concentration of copper. Physiological traits were significantly affected by copper exposure (scope for growth declined as a result of reduced clearance rate, increased oxygen consumption and a generally lower absorption efficiency). The results of this study are cause for concern for shellfish farming activities at least in Northern Adriatic, where shellfish farming is a monoculture of T. philippinarum. A strict interpretation of the precautionary principle might suggest that more rigorous regulatory action to control copper inputs in the field would be justified. [Copyright &y& Elsevier]

Systematic measurements of both Tributyltin (TBT) and Dibutyltin (DBT) in sediments along different locations in the inner zone of Bahía Blanca estuary were done. Two samples were taken near the main dry dock facility, at Puerto Belgrano naval base, in Argentina. TBT concentrations from non-detected to 170.3 ng Sn g−1 were measured in the inner region of the estuary, and higher one of 3,288 ng Sn g−1 near the dry dock at Puerto Belgrano. DBT values ranging between non-detected and 75.2 ng Sn g−1 were obtained along the principal channel, but extreme concentration of 1,645 ng Sn g−1 was measured at Puerto Belgrano. These values show that this estuary is affected by organotin pollution, mainly in areas of heavy shipyard activities. [ABSTRACT FROM AUTHOR]

Abstract: The authors present a general overview of marine paints, paying particular attention to the case of antifouling paints. After locating these paints in the anticorrosive protection systems used on the underwater parts of ships and/or other moving structures, a summary is made of the main types of antifouling products used through history up to the present time. This is complemented by a systematic assessment of the main types of living organisms that fix themselves to the underwater parts of ships. Consideration is also briefly made of the main basic mechanisms by which the different types of antifouling paints work. Finally a number of current research lines on antifouling technologies are mentioned. [Copyright &y& Elsevier]

Abstract: Two major antifouling biocides used worldwide, Irgarol 1051 and diuron, and their degradation products in Shoreham Harbour and Brighton Marina, UK were studied during 2003–2004. The highest concentrations of Irgarol 1051 were 136 and 102 ng L−1 in water and 40 and 49 ng g−1 dry weight in sediments for Shoreham Harbour and Brighton Marina, respectively. As the degradation product of Irgarol 1051, M1 was also widespread, with the highest concentration of 59 ng L−1 in water and 23 ng g−1 in sediments in Shoreham Harbour, and 37 ng L−1 in water and 5.6 ng g−1 in sediments in Brighton Marina. The target compounds showed enhanced concentrations during the boating season (May–July), when boats were being re-painted (January–February), and where the density of pleasure crafts was high. Overall, the concentration of Irgarol 1051 decreased significantly from late 2000 to early 2004, indicating the effectiveness of controlling its concentrations in the marine environment following restricted use. Diuron was only detected in 14% of water samples, and mostly absent from sediment samples. [Copyright &y& Elsevier]

Formation of biofouling communities on the surfaces of steel panels coated with two different TBT-free copper-based and one TBT-based antifouling paint was examined following submersion for periods of 3, 6, 9 and 12 months in Kastela Bay, Croatia. Test panels coated with Shopprimer and anticorrosive paint were used as control panels. Thirty five taxa of benthic algae and 32 taxa of benthic animals were found. Diatomeae dominated by frequency and abundance on test panels coated with antifouling paints, while the animal species Serpula vermicularis, Mytilus galloprovincialis and Balanus amphitrite amphitrite dominated the fouling communities on control panels. On panels protected by antifouling paints, low values of biomass were found compared to the very high values associated with control panels. [ABSTRACT FROM AUTHOR]