title: Ice photolysis of 2,2',4,4',6-pentabromodiphenyl ether (BDE-100): laboratory investigations using solid phase microextraction.
abstract: Here, we report for the first time a laboratory investigation into the photochemical degradation of 2,2',4,4',6-pentabromodiphenyl ether (BDE-100) in ice solid samples using an artificial UV light source. Solid phase microextraction (SPME) was used as a sensitive extraction technique for monitoring trace amounts of the hydrophobic pollutant and its photoproducts. The results showed that ice photolysis kinetics for BDE-100 is similar to the one observed in the aqueous counterpart. The eight photoproducts identified consisted of brominated diphenyl ethers with lower bromine content and polybrominated dibenzofurans, suggesting two important photodegradation pathways for BDE-100 in ice solid samples: (i) stepwise reductive debromination and (ii) intramolecular elimination of HBr. Similarities in photochemical product arrays observed in the ice and water photolysis of BDE-100 were attributed to a similar mechanism for photochemical decomposition for both phases. Possible involvement of the water molecules in the reactions has been excluded by performing photolysis in D(2)O ice solid and water samples. Taking advantage of the high preconcentration factor obtained with SPME at low temperatures, a SPME fiber cooled with liquid carbon dioxide down to 0°C was used as a photoreaction support for BDE-100 allowing the identification of a greater number of photoproducts.
authors.affiliation: Department of Environmental Engineering, Technical University of Crete, GR-73100 Chania, Greece.
authors.forename: Lucia
authors.initials: L
authors.lastname: Sanchez-Prado
authors.forename: Konstantina
authors.initials: K
authors.lastname: Kalafata
authors.forename: Sanja
authors.initials: S
authors.lastname: Risticevic
authors.forename: Janusz
authors.initials: J
authors.lastname: Pawliszyn
authors.forename: Marta
authors.initials: M
authors.lastname: Lores
authors.forename: Maria
authors.initials: M
authors.lastname: Llompart
authors.forename: Nicolas
authors.initials: N
authors.lastname: Kalogerakis
authors.forename: Elefteria
authors.initials: E
authors.lastname: Psillakis
mesh_terms: D001572:Benzofurans / Q000737:chemistry; D001966:Bromine / Q000737:chemistry*; D017666:Deuterium Oxide / Q000737:chemistry; D008401:Gas Chromatography-Mass Spectrometry; D055768:Halogenated Diphenyl Ethers / Q000737:chemistry*; D007053:Ice / Q000032:analysis*; D007700:Kinetics; D044367:Phase Transition; D010782:Photolysis; D011075:Polybrominated Biphenyls / Q000737:chemistry*; D052617:Solid Phase Microextraction; D014466:Ultraviolet Rays
chemical_list: D001572:Benzofurans; D055768:Halogenated Diphenyl Ethers; D007053:Ice; D011075:Polybrominated Biphenyls; C517827:pentabrominated diphenyl ether 100; D017666:Deuterium Oxide; D001966:Bromine