Antifouling Paint Particles Research Articles

Metal contamination at recreational boatyards linked to the use of antifouling paints-investigation of soil and sediment with a field portable XRF.

The application of a field portable X-ray fluorescence spectrometer (FPXRF) to measure Cu, Zn, and Pb in soil and sediments at recreational boatyards by Lake Mälaren in Sweden was investigated. Confirmatory chemical analysis on freeze-dried samples shows that, ex situ, the FPXRF produces definitive level data for Cu and Zn and quantitative screening data for Pb, according to USEPA criteria for data quality. Good agreement was also found between the ex situ measurements and the in situ screening. At each of the two studied boatyards, >40 in situ soil measurements were carried out. Statistical differences in soil concentration based on land use were consequently found: the areas used for boat storage and maintenance were significantly higher in Cu and Zn than the areas used for car parking and transportation. The metal pollution in the boat storage areas is therefore shown to be directly linked to hull maintenance activities during which metal-containing antifouling paint particles are shed, end up on the ground, and consequently pollute the soil. In the boat storage areas, the Cu and Zn concentrations often exceeded the national guideline values for soil. In this study, they were also shown to increase with increasing age of the boatyard operation. Pb soil concentrations were only elevated at a few measurement points, reflecting the phasing out of Pb compounds from antifouling products over the past 2 decades. In the surface sediments, concentrations of Cu and Zn were 2–3 times higher compared to deeper levels. No decrease in metal concentration with time was found in the sediments, indicating that boat owners are not complying with the ban of biocide-containing paints in freshwater introduced over 20 years ago.

Environmental risks associated with booster biocides leaching from spent anti-fouling paint particles in coastal environments.

Boat maintenance facilities in coastal areas contribute a significant amount of antifouling paint particles (APP) to coastal environments. Very few studies have concentrated on the leaching of booster biocides embedded in old paint particles. Therefore, this study attempted to assess the leaching of Dichlofluanid and Irgarol 1051 from APP collected from Mayflower Marina in southwest England. They were analyzed by GC-MS. A leaching experiment revealed that a considerable amount of Dichlofluanid (ca. 24 μg/L) leached from 0.4 g/L of APP after the first hour, followed by a marked decline in the amount measured in the water over time, almost degrading after 24 h in seawater, affording less of an environmental threat to non-target organisms. Conversely, Irgarol 1051 appeared to be persistent and continuously leached from the 0.4 g/L of APP even after 10 days, yielding a concentration of 0.61 μg/L in seawater, potentially posing a significant threat to the aquatic environment through leaching from APP.

DGT-Induced Copper Flux Predicts Bioaccumulation and Toxicity to Bivalves in Sediments with Varying Properties

Many regulatory frameworks for sediment quality assessment include consideration of contaminant bioavailability. However, the "snap-shots" of metal bioavailability provided by analyses of porewaters or acid-volatile sulfide-simultaneously extractable metal (AVS-SEM) relationships do not always contribute sufficient information. The use of inappropriate or inadequate information for assessing metal bioavailability in sediments may result in incorrect assessment decisions. The technique of diffusive gradients in thin films (DGT) enables the in situ measurement of metal concentrations in waters and fluxes from sediment porewaters. We utilized the DGT technique to interpret the bioavailability of copper to the benthic bivalve Tellina deltoidalis in sediments of varying properties contaminated with copper-based antifouling paint particles. For a concentration series of copper-paint contaminated sandy, silty-sand, and silty sediment types, DGT-probes were used to measure copper fluxes to the overlying water, at the sediment-water interface, and in deeper sediments. The overlying water copper concentrations and DGT-Cu fluxes were shown to provide excellent exposure concentration-response relationships in relation to lethal effects occurring to the copper-sensitive benthic bivalve, T. deltoidalis. The study demonstrates the strength of the DGT technique, which we expect will become frequently used for assessing metal bioavailability in sediments.

Bioaccessibility of Trace Metals in Sediment, Macroalga and Antifouling Paint to the Wild Mute Swan, Cygnus olor

The bioaccessibilities of trace metals (Cd, Cr, Cu, Ni, Pb, Zn) in eelgrass, sediment and preparations thereof with and without antifouling paint particles have been assessed by undertaken a physiologically based extraction test (W-PBET) designed to mimic the chemistry of the gizzard and intestine of the mute swan, Cygnus olor. Because Cu- and Zn-based pigments are employed in contemporary antifouling paints, concentrations of these metals were greatest in the preparations containing paint particles. Moreover, relative to total metal, both Cu and Zn displayed the highest gizzard bioaccessibilities in these preparations (about 10%). In the intestine, where most nutrients are absorbed, the accessibility of Cu was maintained while that of Zn was dramatically reduced. These observations were qualitatively consistent with metal concentrations measured in source materials relative to those in swan faeces. We conclude that Cu poses the greatest threat to C. olor inhabiting coastal areas where boat repair takes place.

Bioaccessibility and mobilisation of copper and zinc in estuarine sediment contaminated by antifouling paint particles

Clean estuarine sediment amended with antifouling paint particles has been digested in biologically relevant reagents in order to evaluate the bioaccessibilities of Cu and Zn to deposit feeders in coastal environments where boat maintenance is important. Concentrations of Cu and Zn in the estuarine sediment of about 20 and 70 μg g −1, respectively, increased to about 930 and 330 μg g −1, respectively, on addition of 1.3% of a composite of fractionated paint particles collected from a boat repair facility. Seawater containing the vertebrate bile salt, sodium taurocholate, representative of surfactants in the digestive environment of deposit feeders, mobilised significantly greater quantities of metal (up to about 2 μg g −1 of both Cu and Zn) than seawater alone, presumably through complexation and exchange reactions. Seawater solutions of the protein, bovine serum albumin (BSA), a surrogate for proteinaceous material and amino acids encountered in the digestive tract, mobilised even greater quantities of metal (up to about 80 and 40 μg g −1 of Cu and Zn, respectively) via strong complexation, although addition of taurocholate reduced this capacity through interactions between the two reagents. Overall, and through feeding, burrowing and bioirrigation, infaunal invertebrates are predicted to greatly accelerate the rate of mobilisation and local dispersal of metals in sediment contaminated by antifouling paint particles.

Marine pollution from antifouling paint particles

Antifouling paint particles (APP) are generated during the maintenance of boats and are shed from abandoned structures and grounded ships. Although they afford a highly visible, colourful reflection of contamination in the vicinity of the source, little systematic study has been undertaken regarding the distribution, composition and effects of APP in the wider marine environment. This paper reviews the state of knowledge in respect of APP, with particular emphasis on those generated by recreational boatyards. The likely biogeochemical pathways of the biocidal and non-biocidal metals in current use (mainly Cu and Zn) are addressed in light of recent research and an understanding of the more general behaviour of contaminants in marine systems.Analyses of paint fragment composites from recreational facilities in the UK reveal chemical compositions that are similar to those representing the net signal of the original formulations; significantly, dry weight concentrations of Cu and Zn of up to about 35% and 15%, respectively, are observed and, relative to ambient dusts and sediment, elevated concentrations of other trace metals, like Ba, Cd, Cr, Ni, Pb and Sn, occur. These metals leach more rapidly from APP than a painted surface due to the greater surface area of pigments and additives exposed to the aqueous medium. In suspension, APP are subject to greater and more rapid environmental variation (e.g. salinity, pH, dissolved oxygen) than painted hulls, while settled APP represent an important source of persistent and degradable biocides to poorly circulating environments. Through diffusion and abrasion, high concentrations of contaminants are predicted in interstitial waters that may be accumulated directly by benthic invertebrates. Animals that feed non-selectively and that are exposed to or ingest paint-contaminated sediment are able to accelerate the leaching, deposition and burial of biocides and other substances, and represent an alternative vehicle for contaminant entry into the marine foodchain. Clearly, an extensive understanding of biocide behaviour on painted surfaces is not sufficient for predictive or management purposes regarding APP. Greater caution is required by boaters and boatyards during the removal and disposal of solid wastes, and more awareness or stricter enforcement of relevant codes of practice or legislation is recommended.

Accumulation of Cu and Zn in discarded antifouling paint particles by the marine gastropod, Littorina littorea

The short-term (5 day) accumulation of Cu and Zn in different tissues of the marine gastropod, Littorina littorea, has been studied in the presence of ∼10 mg l −1 of antifouling paint particles and pre- or simultaneously contaminated algal food ( Ulva lactuca). Accumulation of Cu was observed in the head–foot, digestive gland–gonad complex and gills to extents dependent on how and when food was contaminated and administered. However, retention of Zn was only observed in the gills and only when L. littorea and U. lactuca were simultaneously exposed to paint particles. Relative to the alga, faecal material was highly enriched in Zn, suggesting that the animal is able to rapidly eliminate this metal, most likely through the formation and egestion of insoluble phosphate granules. Thus, L. littorea is a useful biomonitor of marine contamination by antifouling applications in respect of Cu but not Zn.

Accumulation of Cu and Zn from antifouling paint particles by the marine macroalga, Ulva lactuca

The marine macroalga, Ulva lactuca, has been exposed to different concentrations of antifouling paint particles (4–200 mg L −1) in the presence of a fixed quantity of clean estuarine sediment and its photosynthetic response and accumulation of Cu and Zn monitored over a period of 2 days. An immediate (<2 h) toxic effect was elicited under all experimental conditions that was quantitatively related to the concentration of contaminated particles present. Likewise, the rate of leaching of both Cu and Zn was correlated with the concentration of paint particles added. Copper accumulation by the alga increased linearly with aqueous Cu concentration, largely through adsorption to the cell surface, but significant accumulation of Zn was not observed. Thus, in coastal environments where boat maintenance is practiced, discarded antifouling paint particles are an important source of Cu, but not Zn, to U. lactuca.

Bioaccessibility of metals in soils and dusts contaminated by marine antifouling paint particles

Fragments of antifouling paint and environmental geosolids have been sampled from the island of Malta and analysed for total and bioaccessible metals. Total concentrations of Ba, Cd, Cu, Pb, Sn and Zn were two to three orders of magnitude higher in spent antifouling composites relative to respective values in background soils and road dusts. Paint fragments were visible in geosolids taken from the immediate vicinity of boat maintenance facilities and mass balance calculations, based on Ba as a paint tracer, suggested that the most contaminated soils, road dusts and boatyard dusts contained about 1%, 7% and 9%, respectively, of antifouling particles. Human bioaccessibilities of metals were evaluated in selected samples using a physiologically based extraction technique. Accessibilities of Cd, Cu, Pb and Zn in the most contaminated solids were sufficient to be cause for concern for individuals working in the boat repair industry and to the wider, local community.

Trace metals in antifouling paint particles and their heterogeneous contamination of coastal sediments

Antifouling paint residues collected from the hard-standings of a marine leisure boat facility have been chemically characterised. Scanning electron microscopy revealed distinct layers, many containing oxidic particles of Cu and Zn. Quantitative analysis indicated concentrations of Cu and Zn averaging about 300 and 100 mg g −1, respectively, and small proportions of these metals (<2%) in organometallic form as pyrithione compounds. Other trace metals present included Ag, Cd, Cr, Ni, Pb and Sn, with maximum concentrations of about 330, 75, 1200, 780, 1800 and 25,000 μg g −1, respectively. Estuarine sediment collected near a boatyard contained concentrations of Cu and Zn an order of magnitude greater than respective concentrations in “background” sediment, and mass balance calculations suggested that the former sample was contaminated by about 1% by weight of paint particles. Clearly, antifouling residues represent a highly significant, heterogeneous source of metallic contamination in the marine environment where boating activities occur.

Leaching of copper and zinc from spent antifouling paint particles

Leaching of Cu and Zn from a composite of spent antifouling paint particles, containing about 300 mg g −1 and 110 mg g −1 of the respective metals, was studied in batch experiments. For a given set of simulated environmental conditions, release of Cu was independent of paint particle concentration due to attainment of pseudo-saturation, but Zn was less constrained by solubility effects and release increased with increasing particle concentration. Leaching of Cu increased but Zn decreased with increasing salinity, consistent with mechanisms governing the dissolution of Cu 2O in the presence of chloride and Zn acrylates in the presence of seawater cations. Because of complex reaction kinetics and the presence of calcium carbonate in the paint matrix, metal leaching appeared to be greater at 4 °C than 19 °C under many conditions. These findings have important environmental and biological implications regarding the deliberate or inadvertent disposal of antifouling paint residues.

Processing of antifouling paint particles by Mytilus edulis

Particles of spent antifouling paint collected from a marine boatyard were ground and subsequently administered to the filter-feeding bivalve, Mytilus edulis, maintained in static aquaria. Concentrations of Cu and Zn were measured in seawater throughout a 16 h feeding phase and a 24 h depuration phase, in rejected and egested particles collected during the respective phases, and in the organisms themselves at the end of the experiments. Concentrations and distributions of Cu and Zn in processed particles indicated that M. edulis was able to ingest paint particles, regardless of whether nutritionally viable silt was present, and no mechanism of particle discrimination was evident. Enrichment of Cu and Zn in the visceral mass of individuals and in the aqueous phase during depuration supported these assertions, although elevated concentrations in other compartments of the organism (e.g. shell, gill) suggested that biotic and abiotic uptake of aqueous metal was also important.

The effect of resuspending sediment contaminated with antifouling paint particles containing Irgarol 1051 on the marine macrophyte Ulva intestinalis

The effect of resuspending sediment contaminated with Irgarol 1051 based antifouling paint particles on the green macroalga Ulva intestinalis was examined. U. intestinalis was also exposed to sediment spiked with Irgarol 1051. The macroalga were exposed over 21 days to the resuspension of sediments containing 61.2 mg kg(-1) of antifouling paint particles containing Irgarol 1051 that provided aqueous Irgarol 1051 concentrations of approximately 0.3 microg l(-1), Irgarol 1051 and appropriate controls. The growth response was compared with that for 'clean' sediment. Resuspension of sediment was associated with reduced growth when compared to seawater alone. Resuspension of sediment spiked with Irgarol 1051 was associated with a greater reduction in growth, with growth being significantly reduced when sediment containing antifouling paint particles was resuspended. The data suggest that the prolonged disturbance of sediments containing antifouling paint particles in marinas represents a potential and as yet unquantified hazard to photosynthetic organisms.

Increased persistence of antifouling paint biocides when associated with paint particles

Current regulatory risk assessment procedures only assess the impact of antifouling paint biocides that are released through leaching from a painted surface. Hull cleaning activities can lead to particles of antifouling paint containing biocides to enter the environment. Comparative pseudo-first order anaerobic degradation rate constants and half-lives were determined for a selection of common antifouling paint booster biocides, their degradation products, and associated with paint particles. Anaerobic half-lives of <0.5 days were calculated for chlorothalonil, dichlofluanid, and SeaNine 211, between 1 and 3 days for DCPMU and DCPU, between 14 and 35 days for diuron and CPDU, and over 226 days for GS26575 and Irgarol 1051. Increased persistence was observed when the compounds were introduced to sediments associated with antifouling paint particles. When present as antifouling paint particles, an increased half-life of 9.9 days for SeaNine 211 and 1.4 days was calculated for dichlofluanid, no significant degradation was observed for diuron. It is suspected that this is due to much of the biocide being initially bound within the matrix of the paint particle that is slowly released through dissolution processes into the sediment pore water prior to degradation. The release of booster biocides associated with paint particles into marinas has the potential to lead to their accumulation unless activities such as hull cleaning are strictly regulated.

Antifouling Paint Booster Biocide Contamination in UK Marine Sediments

The proposed International Maritime Organization (IMO) ban on tributyltin (TBT) as an antifouling paint biocide, will raise the inevitability of the increased use of alternative paints containing copper and organic booster biocides. Although the fate of TBT in marine sediments has been extensively studied, very little work has been performed to assess the accumulation of organic booster biocides in sediments. A survey was conducted to determine concentrations of TBT, Irgarol 1051, the Irgarol 1051 metabolite GS26575 (2-(tert-butylamino)-4-amino-6-(methylthio)-1,3,5-triazine; also referred to as M1) and diuron in coastal and off-shore sediments. TBT was consistently determined at the highest concentrations and was detected in all sediments collected from Southampton Water, UK, along with the TBT degradation product dibutyltin (DBT). Irgarol 1051 was detected (0.01–0.11 μg/g) in some sediments collected from marinas, where high concentrations of these compounds have been measured in surface waters. The Irgarol 1051 metabolite 2-methylthio-4-tert-butylamino-6-amino-s-triazine (M1/GS26575) was only detected at a few locations at concentrations <0.001 μg/g, although higher concentrations were determined in surface waters (13–99 ng l −1 ). Diuron, thought to be present in the form of antifouling paint particles, was determined at a concentration of 1.4 μg/g in an enclosed marina. All analytes were found to be below the limit of detection in the sediments collected off-shore. The potential accumulation in sediments of the other two booster biocides currently used in the UK, zinc pyrithione and dichlofluanid, are also discussed.