Determination of low level methyl tert-butyl ether, ethyl tert-butyl ether and methyl tert-amyl ether in human urine by HS-SPME gas chromatography/mass spectrometry

Licia Scibetta, Laura Campo, Rosa Mercadante, Vito Foà, Silvia Fustinoni

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14 Citations (Scopus)

Abstract

Methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE) and tert-amyl methyl ether (TAME) are oxygenated compounds added to gasoline to enhance octane rating and to improve combustion. They may be found as pollutants of living and working environments. In this work a robotized method for the quantification of low level MTBE, ETBE and TAME in human urine was developed and validated. The analytes were sampled in the headspace of urine by SPME in the presence of MTBE-d12 as internal standard. Different fibers were compared for their linearity and extraction efficiency: carboxen/polydimethylsiloxane, polydimethylsiloxane/divinylbenzene, and polydimethylsiloxane. The first, although highly efficient, was discarded due to deviation of linearity for competitive displacement, and the polydimethylsiloxane/divinylbenzene fiber was chosen instead. The analysis was performed by GC/MS operating in the electron impact mode. The method is very specific, with range of linearity 30-4600 ng L-1, within- and between-run precision, as coefficient of variation, -1 for all the analytes. The influence of the matrix on the quantification of these ethers was evaluated analysing the specimens of seven traffic policemen exposed to autovehicular emissions: using the calibration curve and the method of standard additions comparable levels of MTBE (68-528 ng L-1), ETBE (-1), and TAME (-1) were obtained.

Original languageEnglish
Pages (from-to)53-62
Number of pages10
JournalAnalytica Chimica Acta
Volume581
Issue number1
DOIs
Publication statusPublished - Jan 2 2007

Fingerprint

MTBE
ether
Gas chromatography
urine
Gas Chromatography-Mass Spectrometry
Mass spectrometry
gas chromatography
mass spectrometry
Urine
linearity
Gasoline
Ethers
Fibers
Calibration
competitive displacement
Electrons
tertiary-amyl methyl ether
ethyl tert-butyl ether
methyl tert-butyl ether
4-sulfophenylmethallyl ether

Keywords

  • Biomarkers
  • Ethyl tert-butyl ether
  • Methyl tert-butyl ether
  • Occupational exposure
  • Solid phase microextraction
  • tert-Amyl methyl ether
  • Urine

ASJC Scopus subject areas

  • Biochemistry
  • Analytical Chemistry
  • Spectroscopy
  • Environmental Chemistry

Cite this

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title = "Determination of low level methyl tert-butyl ether, ethyl tert-butyl ether and methyl tert-amyl ether in human urine by HS-SPME gas chromatography/mass spectrometry",
abstract = "Methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE) and tert-amyl methyl ether (TAME) are oxygenated compounds added to gasoline to enhance octane rating and to improve combustion. They may be found as pollutants of living and working environments. In this work a robotized method for the quantification of low level MTBE, ETBE and TAME in human urine was developed and validated. The analytes were sampled in the headspace of urine by SPME in the presence of MTBE-d12 as internal standard. Different fibers were compared for their linearity and extraction efficiency: carboxen/polydimethylsiloxane, polydimethylsiloxane/divinylbenzene, and polydimethylsiloxane. The first, although highly efficient, was discarded due to deviation of linearity for competitive displacement, and the polydimethylsiloxane/divinylbenzene fiber was chosen instead. The analysis was performed by GC/MS operating in the electron impact mode. The method is very specific, with range of linearity 30-4600 ng L-1, within- and between-run precision, as coefficient of variation, -1 for all the analytes. The influence of the matrix on the quantification of these ethers was evaluated analysing the specimens of seven traffic policemen exposed to autovehicular emissions: using the calibration curve and the method of standard additions comparable levels of MTBE (68-528 ng L-1), ETBE (-1), and TAME (-1) were obtained.",
keywords = "Biomarkers, Ethyl tert-butyl ether, Methyl tert-butyl ether, Occupational exposure, Solid phase microextraction, tert-Amyl methyl ether, Urine",
author = "Licia Scibetta and Laura Campo and Rosa Mercadante and Vito Fo{\`a} and Silvia Fustinoni",
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T1 - Determination of low level methyl tert-butyl ether, ethyl tert-butyl ether and methyl tert-amyl ether in human urine by HS-SPME gas chromatography/mass spectrometry

AU - Scibetta, Licia

AU - Campo, Laura

AU - Mercadante, Rosa

AU - Foà, Vito

AU - Fustinoni, Silvia

PY - 2007/1/2

Y1 - 2007/1/2

N2 - Methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE) and tert-amyl methyl ether (TAME) are oxygenated compounds added to gasoline to enhance octane rating and to improve combustion. They may be found as pollutants of living and working environments. In this work a robotized method for the quantification of low level MTBE, ETBE and TAME in human urine was developed and validated. The analytes were sampled in the headspace of urine by SPME in the presence of MTBE-d12 as internal standard. Different fibers were compared for their linearity and extraction efficiency: carboxen/polydimethylsiloxane, polydimethylsiloxane/divinylbenzene, and polydimethylsiloxane. The first, although highly efficient, was discarded due to deviation of linearity for competitive displacement, and the polydimethylsiloxane/divinylbenzene fiber was chosen instead. The analysis was performed by GC/MS operating in the electron impact mode. The method is very specific, with range of linearity 30-4600 ng L-1, within- and between-run precision, as coefficient of variation, -1 for all the analytes. The influence of the matrix on the quantification of these ethers was evaluated analysing the specimens of seven traffic policemen exposed to autovehicular emissions: using the calibration curve and the method of standard additions comparable levels of MTBE (68-528 ng L-1), ETBE (-1), and TAME (-1) were obtained.

AB - Methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE) and tert-amyl methyl ether (TAME) are oxygenated compounds added to gasoline to enhance octane rating and to improve combustion. They may be found as pollutants of living and working environments. In this work a robotized method for the quantification of low level MTBE, ETBE and TAME in human urine was developed and validated. The analytes were sampled in the headspace of urine by SPME in the presence of MTBE-d12 as internal standard. Different fibers were compared for their linearity and extraction efficiency: carboxen/polydimethylsiloxane, polydimethylsiloxane/divinylbenzene, and polydimethylsiloxane. The first, although highly efficient, was discarded due to deviation of linearity for competitive displacement, and the polydimethylsiloxane/divinylbenzene fiber was chosen instead. The analysis was performed by GC/MS operating in the electron impact mode. The method is very specific, with range of linearity 30-4600 ng L-1, within- and between-run precision, as coefficient of variation, -1 for all the analytes. The influence of the matrix on the quantification of these ethers was evaluated analysing the specimens of seven traffic policemen exposed to autovehicular emissions: using the calibration curve and the method of standard additions comparable levels of MTBE (68-528 ng L-1), ETBE (-1), and TAME (-1) were obtained.

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