Journal of Chromatography A, 1071 (2005) 125–129 Short communication Determination of bromophenols as dioxin precursors in combustion gases of fire retarded extruded polystyrene by sorptive sampling-capillary gas chromatography–mass spectrometry Koen Desmet, Marc Schelfaut, Pat Sandra ∗ Laboratory of Separation Sciences, Department of Organic Chemistry, Ghent University, Krijgslaan 281 S4, B-9000 Ghent, Belgium Available online 25 December 2004 Abstract Extruded polystyrene (XPS) is often treated with hexabromocyclododecane (HBCD) as fire retardant (FR). Because of its aliphatic struc- ture, HBCD is not suspected to cause formation of polybrominated dioxins upon combustion. Precursors of polybrominated dioxins, namely bromophenols, were detected during tubular furnace combustion experiments of FR-XPS in combination with sorptive enrichment on poly- dimethylsiloxane followed by on-line thermal desorption-capillary GC/MS. The highest concentration of mono- and tribromophenols detected were 85.9 and 3.7 mg kg -1 , respectively, at a temperature of 700 ◦ C, while a temperature of 500 ◦ C yielded the highest concentration of di- bromophenols namely 10.4 mg kg -1 . At a combustion temperature of 900 ◦ C no bromophenols were detected. © 2004 Elsevier B.V. All rights reserved. Keywords: Sorptive sampling; Extruded polystyrene; Brominated flame retardant; Bromophenols; Dioxin precursors 1. Introduction For several decades, flame-retardants (FRs) are added to consumer products for several decades in a successful effort to reduce fire-related injury and property damage. Brominated flame-retardants (BFRs) are presently most fre- quently used, because of their low cost and high perfor- mance efficiency. Concerns for this emerging class of chem- icals have, however, risen because of their occurrence in the environment and in human biota. In addition, forma- tion of hazardous products upon thermal degradation of these substances has been stated. In particular, fires involving polymeric materials containing BFRs, with aromatic moi- eties, are suspected to lead to the formation of brominated polyaromatic compounds such as polybrominated dioxins [1–3]. There are five major classes of BFRs namely brominated bisphenols, diphenyl ethers, cyclododecanes, phenols and ph- talic acid derivatives. The first three classes represent the ∗ Corresponding author. Tel.: +32 92 644462; fax: +32 92 644998. E-mail address: pat.sandra@ugent.be (P. Sandra). highest production volumes. In fact the five overwhelming BFRs on the market at the moment are tetrabromobisphe- nol A (TBBPA), hexabromocyclododecane (HBCD) and three commercial mixtures of polybrominated diphenylethers (PDBEs). At present, the use of BFRs in general is highly dynamic because of the ongoing debates in many countries concerning their risk to wildlife and humans and whether their use should be phased out [1,4,5]. The present research was concentrated to HBCD. HBCD is a non-aromatic, brominated cycloalkane used primarily as an additive flame retardant in plastic materials, textiles and electronics. HBCD has to some extent replaced the usage of PDBEs in several applications. Its total production was about 15,900 ton in 1999 and Europe accounts for 56% of the total global use. This makes HBCD a relatively minor contributor to the total BFR economy. The European market share for HBCD is, however, significantly higher than for other BFRs, where Europe only accounts for about 10–15% of the global consumption. Extruded polystyrene (XPS), mainly used as an insulating building material, is the main product, that is flame retarded with HBCD. All European XPS contains about 1–2% HBCD [4]. 0021-9673/$ – see front matter © 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.chroma.2004.12.019