Discrimination of hexabromocyclododecane from new polymeric brominated flame retardant in polystyrene foam by nuclear magnetic resonance.
Hexabromocyclododecane (HBCDD) is a brominated flame retardant (BFR) and major additive to polystyrene foam thermal insulation that has recently been listed as a persistent organic pollutant by the Stockholm Convention. During a 2013/2014 field analytical survey, we measured HBCDD content ranging from 0.2 to 2.4% by weight in 98 polystyrene samples. Liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) analyses indicated that expandable (EPS) and extruded (XPS) polystyrene foams significantly differed in the α/γ HBCDD isomer ratio, with a majority of α and γ isomers in XPS and EPS, respectively. Interestingly, this technique indicated that some recent materials did not contain HBCDD, but demonstrated bromine content when analysed with X-ray fluorescence (XRF). Further investigation by Nuclear Magnetic Resonance (NMR) was able to discriminate between the BFRs present. In addition to confirming the absence or presence of HBCDD in polystyrene samples, high-field NMR spectroscopy provided evidence of the use of brominated butadiene styrene (BBS) as copolymer in the production of polystyrene. Use of this alternative flame retardant is expected to cause fewer health and environmental concerns. Our results highlight a trend towards the use of copolymerized BFRs as an alternative to HBCDD in polystyrene foam boards. In addition to providing a rapid NMR method to identify polymeric BFR, our analytical approach is a simple method to discriminate between flame-retardants in polystyrene foam insulating materials.
Département de chimie organique, Université de Genève, 30 quai Ernest Ansermet, 1211 Genève 4, Switzerland. Electronic address: damien.jeannerat@unige.ch.
Damien
D
Jeannerat
Département de chimie organique, Université de Genève, 30 quai Ernest Ansermet, 1211 Genève 4, Switzerland.
Marion
M
Pupier
Service de Toxicologie de l'Environnement Bâti, 23 avenue de Sainte Clotilde, Case postale 78, 1211 Genève 8, Switzerland.
Sébastien
S
Schweizer
Département de chimie organique, Université de Genève, 30 quai Ernest Ansermet, 1211 Genève 4, Switzerland; Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev str., bl 9, 1113 Sofia, Bulgaria.
Yavor Nikolaev
YN
Mitrev
Service de Toxicologie de l'Environnement Bâti, 23 avenue de Sainte Clotilde, Case postale 78, 1211 Genève 8, Switzerland.
Philippe
P
Favreau
Service de Toxicologie de l'Environnement Bâti, 23 avenue de Sainte Clotilde, Case postale 78, 1211 Genève 8, Switzerland.
Marcel
M
Kohler
D002853:Chromatography, Liquid; D004784:Environmental Monitoring / Q000379:methods*; D004785:Environmental Pollutants / Q000032:analysis*; D005411:Flame Retardants / Q000032:analysis*; D006842:Hydrocarbons, Brominated / Q000032:analysis*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D011137:Polystyrenes / Q000032:analysis*; D013052:Spectrometry, X-Ray Emission; D053719:Tandem Mass Spectrometry
D004785:Environmental Pollutants; D005411:Flame Retardants; D006842:Hydrocarbons, Brominated; D011137:Polystyrenes; C089796:hexabromocyclododecane
Brominated butadiene styrene; HBCDD; LC-MS/MS; NMR; Polystyrene insulation foam; XRF