Department of Environmental Science and Analytical Chemistry, ACES, Stockholm University, Stockholm, Sweden.
Laboratory for Aquatic Research, Limnomar, Hamburg, Germany.
Environ Sci Pollut Res Int. 2018 May;25(15):14595-14605. doi: 10.1007/s11356-018-1614-1. Epub 2018 Mar 12.
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/cm. 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 R = 0.9566 for tin and R 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/cm 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/cm. As comparison, one layer of an old TBT antifouling paint Hempels Hard racing superior, corresponds to 300 μg Sn/cm. The percentage of boats with tin > 400 μg Sn/cm 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/cm, 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/cm. The recommendation on the can is to apply two layers. The proportion of boats with higher mean copper values than 8000 μg Cu/cm was 51, 56, and 61 for boats in DK, FI, and DE, respectively. The proportion based on median values > 8000 μg Cu/cm 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.
一款专门针对塑料船壳金属测量而校准的手持式 XRF 分析仪已在丹麦 (DK)、芬兰 (FI) 和德国 (DE) 的休闲船中使用。本文呈现了锡和铜的测量结果,单位为μg 金属/cm。锡是船壳上有机锡化合物存在的替代物。每个国家都有 2 到 3 个地点被访问,每个地点测量了 25 到 90 艘船。每艘船在 6 到 8 个位置进行测量,并呈现了平均值和中位数。377 对数据的平均值与中位数的线性回归显示出高度相关性,锡的 R 值为 0.9566,铜的 R 值为 0.9724,因此两种计算方法均可使用。然而,为了进行监管使用,建议报告每艘船上所有的个体测量值,并根据需要决定是否去除或密封船壳。结果与来自瑞典不同地区的已发表数据进行了比较,即淡水、半咸水和咸水船只中的数据。结果表明,丹麦、芬兰和德国分别仍有 42%、24%和 23%的船只上锡的平均值大于 50μg Sn/cm。基于中位数的相应百分比分别为 38%、22%和 18%。船只之间的差异很大,最大平均值为 2000μg Sn/cm。相比之下,一层旧的 TBT 防污漆 Hempels Hard racing superior 对应 300μg Sn/cm。基于平均值,锡含量大于 400μg Sn/cm 的船只百分比为 10%的船只在丹麦,5%的船只在芬兰,1%的船只在德国。相应的中位数分别为 9%、6%和 1%,在丹麦、芬兰和德国。铜含量大于 100μg Cu/cm 的船只在丹麦和德国的所有测量船只上均有检测到,在芬兰的所有船只中除了 3%以外的船只上也有检测到。一层 Hempels MilleXtra 对应约 4000μg Cu/cm。该产品的推荐用量为两层。铜含量平均值大于 8000μg Cu/cm 的船只比例分别为 51%、56%和 61%,在丹麦、芬兰和德国。基于中位数值大于 8000μg Cu/cm 的船只比例分别为 50%、54%和 61%,在丹麦、芬兰和德国。结论是,波罗的海周边的许多休闲船只仍显示或含有含有有机锡化合物的防污漆,而且根据油漆生产商的说法,超过一半的船只一个船季的铜含量都超过了所需的水平。这些已知的有毒化合物很可能会释放到环境中,对生物区系造成危害。校准后的 XRF 方法旨在对船壳进行区域测量,是一种检测含有有机锡化合物和高铜含量船只的简便廉价方法。我们建议环境主管部门使用该方法识别此类船只,并根据结果要求采取措施,最大限度地减少对环境的进一步泄漏。