title: Simultaneous speciation of methylmercury and butyltin species in environmental samples by headspace-stir bar sorptive extraction-thermal desorption-gas chromatography-mass spectrometry.
abstract: In this work, making use of experimental designs, headspace-stir bar sorptive extraction (HS-SBSE) followed by thermal desorption (TD) coupled to a gas chromatography-mass spectrometry (GC-MS) for the simultaneous determination of mercury and tin organometallic compounds present in surface water, sediment and biological tissue was optimized. All solid samples require a previous extraction typically done with diluted HCl or KOH/methanol solutions, and the derivatization, in all the cases, of the organometallic compounds with NaBEt(4). As a consequence, the preconcentration step was carried out in a 0.1 mol L(-1) HOAc/NaOAc buffer solution, with 0.1% (m/v) of NaBEt(4), without the addition of NaCl as a salting out reagent, and with the stir bar (20 mm x 1 mm) located in the headspace (HS). In addition, the desorption step required the following conditions: 250 degrees C (desorption temperature), 15 min (desorption time), 14.1 psi (approximately 97.2 kPa) (vent pressure) and 75 mL min(-1) (vent flow). Finally, to assure the extraction of all the analytes under equilibrium, 5h are required. Inorganic mercury (Hg(2+)) and tripropyltin (TPrT) were used as internal standards to correct for variations in the extraction, derivatization and detection steps. The resulting method provides precise (4-17%) and accurate (against four certified reference materials) results in the ng L(-1) and pg g(-1) range concentrations with recoveries within 80-120% for water samples. The proposed methodology is currently applied in the speciation analysis of specimens obtained in different estuarine sites of the Basque Coast.
authors.affiliation: Kimika Analitikoa Saila, Euskal Herriko Unibertsitatea, 644 P.K., Bilbao, Spain. ailette.prieto@ehu.es
authors.forename: A
authors.initials: A
authors.lastname: Prieto
authors.forename: O
authors.initials: O
authors.lastname: Zuloaga
authors.forename: A
authors.initials: A
authors.lastname: Usobiaga
authors.forename: N
authors.initials: N
authors.lastname: Etxebarria
authors.forename: L A
authors.initials: LA
authors.lastname: Fernández
authors.forename: C
authors.initials: C
authors.lastname: Marcic
authors.forename: A
authors.initials: A
authors.lastname: de Diego
mesh_terms: D000818:Animals; D004777:Environment; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D006812:Humic Substances / Q000032:analysis; D008767:Methylmercury Compounds / Q000032:analysis*; D009947:Organotin Compounds / Q000302:isolation & purification*; D052616:Solid Phase Extraction; D014867:Water; D014874:Water Pollutants, Chemical / Q000032:analysis
chemical_list: D006812:Humic Substances; D008767:Methylmercury Compounds; D009947:Organotin Compounds; D014874:Water Pollutants, Chemical; D014867:Water; C048581:monotributyltin trichloride