title: Photodegradation study of decabromodiphenyl ether by UV spectrophotometry and a hybrid hard- and soft-modelling approach.
abstract: This work presents an exploratory study of the photochemical degradation process of decabromodiphenyl ether (decaBDE) and gives an interpretation of the kinetic pathway, species and effects of the key factors involved in the degradation process. Use of lowly brominated diphenyl ethers (PBDE) has been banned by the EU and there seems to be evidence of the photolytic degradation of highly brominated PBDEs into lowly brominated congeners. Hence, the importance of knowing the photodegradation process of decaBDE. The photodegradation was investigated under UV light by UV-spectrophotometric monitoring. A novel hybrid data analysis approach, based on the combination of hard- and soft-spectrophotometric multivariate curve resolution, was applied to elucidate the mechanism of the degradation process, to resolve kinetic profiles and pure spectra of the photodegradation products and to evaluate the rate constants. The photodegradation process could be described with a kinetic model based on three consecutive first-order reactions and a decrease of the degradation process was observed as solvent polarity increased. Complementary identification of photodegradation products by gas chromatography coupled to mass spectrometry using negative chemical ionization (GC-NCI-MS) is attempted. This work presents a novel attempt of describing in a comprehensive way the photochemical degradation process of decaBDE, with all successive steps and related rate constants. This study proves also the potential of the proposed hybrid data analysis methodology as a general strategy to interpret the evolution of these photochemical reactions.
authors.affiliation: Department of Environmental Chemistry, IIQAB-CSIC, Jordi Girona 18-26, 08034 Barcelona, Catalonia, Spain.
authors.forename: Sílvia
authors.initials: S
authors.lastname: Mas
authors.forename: Anna
authors.initials: A
authors.lastname: de Juan
authors.forename: Sílvia
authors.initials: S
authors.lastname: Lacorte
authors.forename: Romà
authors.initials: R
authors.lastname: Tauler
mesh_terms: D008401:Gas Chromatography-Mass Spectrometry / Q000295:instrumentation / Q000379:methods; D055768:Halogenated Diphenyl Ethers; D007700:Kinetics; D008956:Models, Chemical; D015999:Multivariate Analysis; D010647:Phenyl Ethers / Q000032:analysis / Q000737:chemistry* / Q000528:radiation effects; D010777:Photochemistry; D011075:Polybrominated Biphenyls / Q000032:analysis / Q000737:chemistry* / Q000528:radiation effects; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D013053:Spectrophotometry / Q000295:instrumentation / Q000379:methods; D013056:Spectrophotometry, Ultraviolet / Q000295:instrumentation / Q000379:methods; D013997:Time Factors; D014466:Ultraviolet Rays
chemical_list: D055768:Halogenated Diphenyl Ethers; D010647:Phenyl Ethers; D011075:Polybrominated Biphenyls; C010902:decabromobiphenyl ether