Quantification of tributyltin in seawater using triple isotope dilution gas chromatography-inductively coupled plasma mass spectrometry achieving high accuracy and complying with European Water Framework Directive limits

Tunç M., Ay Ü., Can S. Z., Bingöl D., Ün İ.

JOURNAL OF CHROMATOGRAPHY A, vol.1637, 2021 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 1637
  • Publication Date: 2021
  • Doi Number: 10.1016/j.chroma.2020.461847
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, PASCAL, Analytical Abstracts, Aqualine, Aquatic Science & Fisheries Abstracts (ASFA), BIOSIS, CAB Abstracts, Chemical Abstracts Core, Chimica, Compendex, EMBASE, Environment Index, Food Science & Technology Abstracts, MEDLINE, Pollution Abstracts, Veterinary Science Database
  • Keywords: Tributyltin, Triple isotope dilution, Gas chromatography, Inductively coupled plasma mass spectrometry, Environmental quality standard, Water framework directive, MICROEXTRACTION
  • Kocaeli University Affiliated: Yes


A triple isotope dilution GC-ICPMS method for the determination of tributyltin (TBT) was developed and validated to meet the European Water Framework Directive (WFD) requirements. The validation procedure involved the evaluation of trueness, precision (repeatability, intermediate precision), limit of detection (LOD) and limit of quantification (LOQ), stability, measurement uncertainty and traceability studies. The method is one of the most sensitive methods published to date with good accuracy, 103% average recovery in the range with %RSDs of 2.8-6.7%. A LOD value of 0.015 ng L-1 for the TBT cation was achieved with a sample volume of 12 mL seawater. TBT was derivatized using 20 mu L sodium tetraethylborate solution (0.05% NaBEt4) to make volatile for GC-ICPMS. Measurement uncertainty was in the range of 4.813% which was achieved through dissolution of tributyltinchloride (TBTCl) in 1-propanol, a low-volatility solvent combined with the use of a triple isotope dilution (ID) calibration technique. Isotope dilution calibration was performed by adding Sn-117 isotopically enriched TBT to the seawater samples. The stability test results showed that TBT concentration was stable for three months in seawater samples after passing through a 0.2 mu m filter and stored in amber glass bottles at 4 degrees C. The response surface methodology (RSM) approach was successfully implemented to provide optimal conditions for large volume injection (LVI) to obtain the maximum analytical signal. The key variables selected in the experimental design were evaporation time, evaporation temperature, carrier flow, and injection speed. This method was applied to seawater samples collected from the Bay of Izmit, Kocaeli, Turkey, where TBT pollution has not been measured yet. (C) 2020 Elsevier B.V. All rights reserved.