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Brominated flame retardants have widely been used for more than 50 years and have been frequently detected in environmental samples as surface water and fish. Leaching from construction products was identified as one possible source. The use of substances as e.g. hexabromocyclododecane (HBCCD) was restricted recently due to increasing concern about negative impacts on the environment and human health caused by the persistent, bio accumulative and toxic properties. New polymeric brominated flame retardants have been developed to replace HBCCD in expanded polystyrene (XPS), which is used for insulation of buildings. It is assumed that the release from the polymer is much smaller in comparison to release of small molecules as HBCCD. The release from the polymer may include monomers or small fragments of different size. Thus, a sum parameter is needed. According to Schlummer et al. it is possible to detect brominated molecules using X-ray fluorescence spectroscopy by determination of brome content in XPS extracts. As only small brominated compounds can be extracted it also allows for the differentiation between the two classes of compounds. This method was applied to verify the presence of different kinds of flame retardants in XPS samples and to evaluate the leaching behavior.