Persistence of TBT and copper in excess on leisure boat hulls around the Baltic Sea

A handheld XRF-analyzer specially calibrated for measurements of metals on plastic boat hulls has been used on leisure boats in Denmark (DK), Finland (FI), and Germany (DE). The results on tin and copper are presented as μg metal/cm². Tin is a proxy for the occurrence of organotin compounds on the boat. Two or three sites were visited in each country and between 25 and 90 boats were measured at each site. Every boat was measured at six to eight places, and the results are presented both as mean and median values. Linear regression of mean to median values of the 377 data pairs shows high relationship with R²?=?0.9566 for tin and R² of 0.9724 for copper and thus both ways of calculation may be used. However, for regulative use, it is suggested that all individual measurements on each boat should be presented and used for decisions of removal or sealing of boat hulls. The results are compared with published data from different parts of Sweden, i.e., boats in fresh water, brackish water, and salt water. The results show that tin with mean values >?50 μg Sn/cm² is still found on 42, 24, and 23% of the boats in DK, FI, and DE, respectively. The corresponding percentages based on median values are 38, 22, and 18% for DK, FI, and DE, respectively. The variation among boats is high with a maximum mean value of 2000 μg Sn/cm². As comparison, one layer of an old TBT antifouling paint Hempels Hard racing superior, corresponds to 300 μg Sn/cm². The percentage of boats with tin >?400 μg Sn/cm² content based on mean values was 10% in DK, 5% in FI, and 1% in DE. The corresponding median values were 9, 6, and 1% for DK, FI, and DE. Copper, >?100 μg Cu/cm², was detected on all measured boats in DK and in DE and on all but 3% of the FI boats. One layer of Hempels MilleXtra corresponds to ? 4000 μg Cu/cm². The recommendation on the can is to apply two layers. The proportion of boats with higher mean copper values than 8000 μg Cu/cm² was 51, 56, and 61 for boats in DK, FI, and DE, respectively. The proportion based on median values >?8000 μg Cu/cm² was 50, 54, and 61% for DK, FI, and DE. The conclusion is that many leisure boats around the Baltic Sea still display or possess antifouling paints containing organotin compounds and that more than half of the boats have more copper than needed for one boat season according to the paint producers. Much of these known toxic compounds will probably be released into the environment and harm the biota. The calibrated XRF-method, intended for area measurements on boat hulls, is an easy and cheap way to detect boats with organotin compounds and high copper content. We recommend environmental authorities to use this method for identification of such boats and to use the results for requesting measures to minimize further leakage to the environment.

     

Bioassays and selected chemical analysis of biocide-free antifouling coatings

Over the years several types of biocide-free antifouling paints have entered the market. The prohibition of biocidal antifouling paints in special areas of some European countries such as Sweden, Denmark and Germany has favoured the introduction of these paints to the market.

Several types of biocide-free antifouling paints were subjected to bioassays and selected chemical analysis of leachate and incorporated substances. Both non-eroding coatings (silicones, fibre coats, epoxies, polyurethane, polyvinyl) and eroding coatings (SPCs, ablative) were tested to exclude the presence of active biocides and dangerous compounds. The paints were subjected to the luminescent bacteria test and the cypris larvae settlement assay, the latter delivering information on toxicity as well as on efficacy.

The following chemical analyses of selected compounds of dry-film were performed:

• leaching-rate of organotin compounds from silicones and of nonylphenol and bisphenol A from epoxy and vinyl based coatings,

• concentration and leaching rate of selected organic compounds in polyurethane,

• concentration of heavy metals in eroding coatings.

The results of the bioassays indicated that none of the coatings analysed contained leachable biocides. Nevertheless, some products contained or leached dangerous compounds. The analyses revealed leaching of nonylphenol (up to 74.7 ng/cm²/d after 48 h) and bisphenol A (up to 2.77 ng/cm²/d after 24 h) from epoxy resins used as substitutes for antifouling paints. The heavy metal, zinc, was measured in dry paint film in quantities up to 576 000 ppm in erodable coatings, not incorporated as a biocide but to control the rate of erosion. Values for TBT in silicone elutriates were mostly below the detection limit of 0.005 mg/kg. Values for DBT ranged between <0.005 and 6.28 mg/kg, deriving from catalysts used as curing agents. Some biocide-free paints contained leachable, toxic and dangerous compounds in the dry film, some of which may act as substitutes for biocides or are incorporated as plasticizers or catalysts. Implications to environmental requirements and legislation are discussed.