The importance of element-selective detection with inductively
coupled plasma mass spectrometry (ICPMS) has been significantly increased
in recent years following the introduction of tandem ICPMS (ICPMS/MS),
which unlocked access to nonmetal speciation analysis. However, nonmetals
are ubiquitous, and the feasibility of nonmetal speciation analysis
in matrices with complex metabolomes is yet to be demonstrated. Herein,
we report the first phosphorous speciation study by HPLC-ICPMS/MS
in a human sample, namely, urine, involving the determination of the
natural metabolite and biomarker phosphoethanolamine. A simple one-step
derivatization procedure was employed to enable the separation of
the target compound from the hydrophilic phosphorous metabolome in
urine. The challenge of eluting the hydrophobic derivative under ICPMS-compatible
chromatographic conditions was addressed by employing hexanediol,
a novel chromatographic eluent recently described in our previous
work but has not yet been exploited in a real-world application. The
developed method features fast chromatographic separation (<5 min),
no need for an isotopically labeled internal standard, and an instrumental
LOD of 0.5 μg P L–1. The method was evaluated
for recovery (90–110%), repeatability (RSD ±5%), and linearity
(r2= 0.9998). The method accuracy was
thoroughly examined by comparing with an independently developed method
based on HPLC-ESIMS/MS without derivatization, where agreement was
found within ±5–20%. An application is presented to gain
first insight into the variability in the human excretion of phosphoethanolamine,
which is key for the interpretation of its levels as a biomarker,
by repeated urine collection from a group of volunteers over 4 weeks.