title: Simultaneous determination of α-, β- and γ-hexabromocyclododecane diastereoisomers in water samples by isotope dilution mass spectrometry using (81)Br-labeled analogs.
abstract: This work describes the synthesis, characterization and application of three (81)Br-labeled diastereosiomers of hexabromocyclododecane (HBCD) for the accurate and precise determination of α-, β- and γ-HBCD in water samples by isotope dilution mass spectrometry. The synthesis of the labeled analogs was carried out by bromination of cis, trans, trans-1,5,9-cyclododecatriene with (81)Br-enriched bromine. After isolation and purification by semipreparative HPLC, each diastereoisomer was characterized in terms of concentration and isotopic enrichment. Then, they were added to the samples to simultaneously quantify the three HBCD diastereoisomers in a single LC-MS/MS injection without resorting to a methodological calibration graph. The results obtained here demonstrate that the use of (81)Br-labeled analogs provides accurate and precise determinations of α-, β- and γ-HBCD in real water samples. The limits of quantification obtained in real samples for α-, β- and γ-HBCD were 0.022, 0.073 and 0.015 ng L(-1), respectively, significantly lower than those required by the European Directive 2013/39/EC.
authors.affiliation: Department of Physical and Analytical Chemistry, Faculty of Chemistry, University of Oviedo, Julián Clavería 8, 33006 Oviedo, Spain.
authors.forename: Lourdes
authors.initials: L
authors.lastname: Somoano-Blanco
authors.affiliation: Department of Physical and Analytical Chemistry, Faculty of Chemistry, University of Oviedo, Julián Clavería 8, 33006 Oviedo, Spain. Electronic address: rodriguezpablo@uniovi.es.
authors.forename: Pablo
authors.initials: P
authors.lastname: Rodriguez-Gonzalez
authors.affiliation: ISC-Science, Innovative Solutions in Chemistry, S.L. Edificio Científico-Tecnológico Campus de "El Cristo", 33006 Oviedo, Spain.
authors.forename: Giusepe
authors.initials: G
authors.lastname: Centineo
authors.affiliation: ISC-Science, Innovative Solutions in Chemistry, S.L. Edificio Científico-Tecnológico Campus de "El Cristo", 33006 Oviedo, Spain.
authors.forename: Sergio García
authors.initials: SG
authors.lastname: Fonseca
authors.affiliation: Department of Physical and Analytical Chemistry, Faculty of Chemistry, University of Oviedo, Julián Clavería 8, 33006 Oviedo, Spain.
authors.forename: J Ignacio
authors.initials: JI
authors.lastname: Garcia Alonso
mesh_terms: D002138:Calibration; D002623:Chemistry Techniques, Analytical / Q000379:methods*; D002851:Chromatography, High Pressure Liquid; D054879:Halogenation; D006842:Hydrocarbons, Brominated / Q000032:analysis / Q000737:chemistry*; D053719:Tandem Mass Spectrometry
chemical_list: D006842:Hydrocarbons, Brominated; C089796:hexabromocyclododecane
keywords: (81)Br-labeled analogs; Hexabromocyclododecane diastereoisomers; Isotope dilution; Water samples