This study assessed the partitioning of 2,2',4,4'-tetrabromo diphenyl ether (BDE-47), 2,2',4,4',5-pentabromo diphenyl ether (BDE-99) and benzo[a]pyrene (BaP) among water, dissolved organic carbon (DOC: 4.93-8.72 mg/L), and particulate organic carbon (POC: 191-462 µg/L) along the salinity gradient (0-5.5‰) of the Baltic Sea off the coast of Finland. Equilibrium dialysis and two solid-phase extraction techniques using polyoxymethylene polymer (POM) were used to determine partitioning coefficients. Experiments using artificial coastal water (ACW) with Nordic fulvic (FAs) and humic acids (HAs) were used to assess the effect of salinity (0 and 5.5‰) on the DOC-water partitioning of the model compounds. All three compounds bound more (2.2-3.8-fold) to the HAs than to the FAs. Increasing salinity from 0 to 5.5‰ decreased sorption to dissolved humic substances in the ACW and Baltic Sea water samples. Along the salinity gradient, the sorption of compounds to organic material decreased when the salinity increased. Particulate organic matter sorbed model compounds per unit of carbon more than dissolved organic matter. Along the studied salinity gradient, the freely dissolved portion increased from 10 to 29% to 52 to 80% in the coastal water samples, mainly because of the increasing salinity and changes in DOC and quality of POC.
In this study, tetra- (#47), penta- (#99), and decabrominated (#209) diphenyl ethers were exposed (in isooctane) to summer sunlight at 60 degrees N, where their photochemical half-lives ranged from 0.6 to 203 h. Apparent quantum yields, ranging from 0.16 to 0.28, were applied to optical models to calculate the rates of direct photochemical decomposition at the surface (depth of 0 m) and in the mixing layer of the ocean. The calculated photolytic half-lives were 4-100 times as long in the mixing layer of the Baltic Sea and the North Atlantic Ocean as atthe surface of 0 m. Calculation of seasonal photochemical half-lives for the mixing layer of the North Atlantic Ocean from 0 degrees N to 60 degrees N showed that the solar photolysis effectively decomposes the congeners in the tropics. At mid- and high latitudes, where solar irradiances are lower outside summer, the photolysis rates for congeners #47 and #99 were often too low for their effective decomposition in the mixing layer. Although solar radiation can potentially decompose the congeners in the mixing layer of the ocean effectively, seasonal and latitudal variation in solar irradiance as well as optical and mixing properties of the ocean can make the direct photolytic decomposition ineffective at high latitude and the coastal ocean.
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