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Published:
Journal of Analytical Toxicology,
ISSN 0146-4760,
Volume 32, Number 4, May,
pp.273-280
Quantification
of Fuel Oxygenate Ethers in Human Blood using Solid-Phase Microextraction
Coupled with Gas Chromatography–High-Resolution Mass Spectrometry
Lalith K. Silva1, Clayton R. Wilburn2,
Michael A. Bonin1, Mitchell M. Smith1, Katherine
A. Reese3, David
L. Ashley1, and Benjamin C. Blount1
1Division of Laboratory Sciences, National Center for Environmental
Health, Centers for Disease Control and Prevention, Atlanta, Georgia
30341;
2Department of Clinical Pharmacology, Vanderbilt Center
for Bone Biology, Nashville, Tennessee 37232; and
3Children’s
Healthcare of Atlanta at Egleston, Atlanta, Georgia 30322
Widespread use of fuel oxygenates, coupled with
their high water solubility and slow degradation rate, have led
to an increase in the potential for human exposure. We developed
an accurate, precise, sensitive, and high-throughput analytical
method to simultaneously quantify trace levels (low parts-per-trillion)
of four fuel oxygenates in human blood: methyl tert-butyl
ether (MTBE), ethyl tert-butyl ether (ETBE), di-isopropyl
ether (DIPE), and tert-amyl methyl ether (TAME). The
analytes were extracted from the head space above human blood
samples, using solid-phase microextraction, desorbed into the
heated injector, and chromatographically resolved by capillary
gas chromatography. Analytes were detected by high-resolution
mass spectrometry with multiple ion monitoring, and quantified
against known standard levels by use of stable isotope-labeled
internal standards for recovery correction. The low limits of
detection (0.6 ng/L) allowed for measurement of MTBE, ETBE, DIPE,
and TAME in parts- per-trillion levels with excellent precision
(coefficient of variation ranging from 1.7 to 5.4%) and accuracy
(96–100%). This method provides a
means to assess fuel oxygenate exposure and study the potential
relationship between exposure and adverse health outcomes.
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