Despite their ban on small vessels in 1989 in the EU, organotin compounds (OTCs) are still being released into the environment due to their presence in historic paint layers on leisure boats. 23 paint samples scraped from recreational boats from three countries around the Baltic Sea were analyzed for total tin (Sn) and OTCs. Two antifouling paint products were also subjected to the same analyses. A new method for the detection of Sn in paint flake samples was developed and found to yield more accurate results compared to four different acid digestion methods. A new method was also developed for the extraction of OTCs from ground paint flakes. This endeavor revealed that existing methods for organotin analysis of sediment may not have full recoveries of OTCs if paint flakes are present in the sample. The hull paint samples had Sn concentrations ranging from 25 to 18,000 mg/kg paint and results showed that tributyltin (TBT) was detected in all samples with concentrations as high as 4.7 g (as Sn)/kg paint. TBT was however not always the major OTC. Triphenyltin (TPhT) was abundant in many samples, especially in those originating from Finland. Several other compounds such as monobutyltin (MBT), dibutyltin (DBT), tetrabutyltin (TeBT), monophenyltin (MPhT) and diphenyltin (DPhT) were also detected. These could be the result of degradation occurring on the hull or of impurities in the paint products as they were also identified in the two analyzed paint products. A linear correlation (r(2) = 0.934) was found between the total tin content and the sum of all detected OTCs. The detection of tin can therefore be used to indicate the presence of OTCs on leisure boats. (C) 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license.

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 Malaren 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.

Antifouling paints are environmentally risk assessed based on their biocidal release rates to the water phase. In situ release rates of copper (Cu) and zinc (Zn) were derived for five commercial paints in two recreational marinas with different salinities (5 and 14 PSU) using an X-Ray Fluorescence spectrometer (XRF). Salinity was found to significantly affect the Cu release, with twice the amount of Cu released at the higher salinity, while its influence on the Zn release was paint-specific. Site-specific release rates for water bodies with salinity gradients, e.g. the Baltic Sea, are therefore necessary for more realistic risk assessments of antifouling paints. Furthermore, the in situ release rates were up to 8 times higher than those generated using standardized laboratory or calculation methods. The environmental risk assessment repeated with the field release rates concludes that it is questionable whether the studied products should be allowed on the Swedish market.

The seasonal variations of dissolved and bioavailable copper (Cu) and zinc (Zn) were studied in two recreational marinas in Sweden and Finland. The time series from the two marinas were characterized by rising concentrations during the spring boat launching, elevated concentrations all through the peak boating season, and decreasing concentrations in autumn when boats were retrieved for winter storage. This pattern shows a clear link between Cu and Zn concentrations and boating activity, with antifouling paints as the principal source. The leaching from antifouling paints was also found to significantly alter the speciation of dissolved Cu and Zn in marina waters, with an increase of the proportion of metals that may be considered bioavailable. This change in speciation, which occurred without any change in dissolved organic carbon (DOC), further increases the environmental risk posed by antifouling paints. In the Swedish marina, dissolved Cu and Zn exceed both Environmental Quality Standards (EQS) and Predicted No Effect Concentrations (PNEC), indicating that the current Swedish risk assessment (RA) of antifouling paints is failing to adequately protect the marine environment. An evaluation of the RA performance showed the underlying cause to be an underestimation of the predicted environmental concentration (PEC) by factors of 2 and 5 for Cu and Zn, respectively. For both metals, the use of inaccurate release rates for the PEC derivation was found to be either mainly (Cu) or partly (Zn) responsible for the underestimation. For Zn, the largest source of error seems to be the use of an inappropriate partitioning coefficient (K-D) in the model. To ensure that the use of antifouling coatings does not adversely impact the sensitive Baltic Sea, it is thus recommended that the K-D value for Zn is revised and that representative release rates are used in the RA procedure.