Urinary
1-hydroxypyrene (HP) is a widely used biomarker of polycyclic
aromatic hydrocarbon exposure relevant for biomonitoring the deleterious
health impacts from tobacco smoke and ambient air pollution, as well
as the hazards of certain occupations. Conventional methods for urinary
HP analysis based on liquid chromatography with native fluorescence
detection or tandem mass spectrometry (MS/MS) and gas chromatography–mass
spectrometry (GC–MS) are limited by low sample throughput and
complicated sample workup protocols that are prone to bias. Herein,
we introduce a high throughput method to directly analyze the intact
glucuronide conjugate of HP (HP-G) in human urine after a simple acidified
ether extraction procedure when using multisegment injection–capillary
electrophoresis–tandem mass spectrometry (MSI–CE–MS/MS).
Multiplexed analyses of 13 independent urine extracts are achieved
in a single run (<3 min/sample) with stringent quality control
while avoiding enzyme deconjugation and precolumn chemical derivatization.
Method validation demonstrates good technical precision (CV = 7.7%, n = 45) and accuracy with a mean recovery of (93 ±
3%) for urinary HP-G at three concentration levels with adequate detection
limits (7 ng/L, S/N = 3). An interlaboratory method
comparison of urine samples collected from firefighters deployed in
the 2016 Fort McMurray wildfire also confirms good mutual agreement
with an acceptable negative bias (mean bias = 15%, n = 55) when measuring urinary HP-G by MSI–CE–MS/MS
as compared to total hydrolyzed urinary HP by GC–MS due to
the low residual levels of free HP and its sulfate conjugate. This
multiplexed separation platform is optimal for large-scale biomonitoring
studies of air pollution relevant to global health as well as occupational
smoke exposures in firefighters susceptible to dermal PAH absorption
when using personal protective equipment.