The micro-scale synthesis of (117)Sn-enriched tributyltin chloride and its characterization by GC-ICP-MS and NMR techniques.
Organotin compounds (OTCs) are among the most toxic substances ever introduced to the environment by man. They are common pollutants in marine ecosystems, but are also present in the terrestrial environment, accumulated mainly in sewage sludge and landfill leachates. In investigations of the degradation and methylation processes of OTC in environmental samples, the use of enriched isotopic tracers represents a powerful analytical tool. Sn-enriched OTC are also necessary in application of the isotope dilution mass spectrometry technique for their accurate quantification. Since Sn-enriched monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT) are not commercially available as single species, "in house" synthesis of individual butyltin-enriched species is necessary. In the present work, the preparation of the most toxic butyltin, namely TBT, was performed via a simple synthetic path, starting with bromination of metallic Sn, followed by butylation with butyl lithium. The tetrabutyltin (TeBT) formed was transformed to tributyltin chloride (TBTCl) using concentrated hydrochloric acid (HCl). The purity of the synthesized TBT was verified by speciation analysis using the techniques of gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS) and nuclear magnetic resonance (NMR). The results showed that TBT had a purity of more than 97%. The remaining 3% corresponded to DBT. TBT was quantified by reverse isotope dilution GC-ICP-MS. The synthesis yield was around 60%. The advantage of this procedure over those previously reported lies in its possibility to be applied on a micro-scale (starting with 10mg of metallic Sn). This feature is of crucial importance, since enriched metallic Sn is extremely expensive. The procedure is simple and repeatable, and was successfully applied for the preparation of (117)Sn-enriched TBTCl from (117)Sn-enriched metal.
Department of Environmental Sciences, Jožef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia.
Kelly
K
Peeters
Laboratory of Organic and Bioorganic Chemistry, Department of Physical and Organic Chemistry, Jožef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia; Centre of Excellence for Integrated Approaches in Chemistry and Biology of Proteins (CIPKeBiP), Jamova 39, 1000 Ljubljana, Slovenia.
Jernej
J
Iskra
Department of Environmental Sciences, Jožef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia.
Tea
T
Zuliani
Department of Environmental Sciences, Jožef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia.
Janez
J
Ščančar
Department of Environmental Sciences, Jožef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia. Electronic address: radmila.milacic@ijs.si.
Radmila
R
Milačič
D060326:Chemistry Techniques, Synthetic / Q000379:methods*; D004355:Drug Stability; D004785:Environmental Pollutants / Q000032:analysis / Q000138:chemical synthesis* / Q000737:chemistry*; D008401:Gas Chromatography-Mass Spectrometry; D007554:Isotopes; D009682:Magnetic Resonance Spectroscopy; D009947:Organotin Compounds / Q000737:chemistry; D015203:Reproducibility of Results; D014001:Tin / Q000737:chemistry*; D014220:Trialkyltin Compounds / Q000032:analysis / Q000138:chemical synthesis* / Q000737:chemistry*
D004785:Environmental Pollutants; D007554:Isotopes; D009947:Organotin Compounds; D014220:Trialkyltin Compounds; C102881:tetrabutyltin; C011559:tributyltin; D014001:Tin
(117)Sn-enriched tributyltin chloride; Characterization; Gas chromatography–inductively coupled plasma mass spectrometry; Micro-scale synthesis; Nuclear magnetic resonance; Tracer in environmental studies