Rapid identification of PS foam wastes containing HBCDD or its alternative PolyFR by X-ray fluorescence spectroscopy (XRF) Martin Schlummer a* , Jörg Vogelsang b , Dominik Fiedler a , Ludwig Gruber a , Gerd Wolz a a Fraunhofer Institute IVV, Recycling Plastics, 85354 Freising, Germany b BASF SE, , 67056 Ludwigshafen, Germany * corresponding author: martin.schlummer@ivv.fraunhofer.de Highlights: • Hexabromocyclododecane (HBCDD) has been added to Annex A of the list of persistent organic pollutants (POP) of the Stockholm Convention. • Recycling of HBCDD-containing PS foam waste will not further be allowed • A screening method is introduced to identify HBCDD in PS foams • HBCDD is released from PS foam by fast solvent extraction and detected by XRF analysis, using handheld XRF the method is applicable as onsite screening method to qualify PS foams in demolition waste for suitable end-of-life treatment. Abstract: The brominated flame retardant hexabromocyclododecane (HBCDD) was added to Annex A of the list of persistent organic pollutants (POP) of the Stockholm Convention. Thus, production and use of HBCDD will be banned, and the recycling of HBCDD-containing foam waste will be restricted. In reaction a special polymeric brominated flame retardant (PolyFR) was developed to replace HBCDD in PS foam for building and construction applications. In future, a decision has to be made whether PS foam waste is subjected to incineration (with HBCDD) or to recycling (without HBCDD). Therefore, an appropriate and rapid field method is required to distinguish between HBCDD containing and HBCDD-free foams. Here we present a screening method for identifying HBCDD containing EPS or XPS. The test principle is based on the fact that PolyFR (a brominated polymeric macromolecule) is not extractable whereas HBCDD (a low molecular substance) is. Following a rapid extraction of HBCDD the brominated flame retardant is identified and quantified via bromine analysis using a handheld XRF instrument. The method was applied successfully to 27 PS samples (foams and EPS raw materials), which were provided without any information on the applied flame retardant. The presence of HBCDD was confirmed for all HBCDDpositive samples in the test. A robustness test revealed a high correctness and a high repeatability of the test system: HBCDD equipped and HBCDD free samples were identified correctly with relative standard deviations of quantitative results below 14%. Moreover, XRF test results agree well with HBCDD determinations performed in a laboratory by GC-FID. Keywords: PS foam, EPS, XPS, HBCDD, PolyFR, demolition waste, analysis, POP This work has been published by Waste Management & Research: doi:10.1177/0734242X15589783