Optimal matrix identification of parabens, triclosan and triclocarban for biomonitoring: Comparative analysis in urine, whole blood, serum, and plasma.

Despite the risk of endocrine disruption, the choice of the optimal biological matrix for monitoring parabens, triclosan (TCS), and triclocarban (TCC) remains unresolved. This study addresses this gap by comprehensively comparing paired urine, whole blood, serum, and plasma samples from 70 Chinese participants. By integrating exposure assessment with methodological evaluation, we analyze matrix effects (ME), extraction recovery, precision, and contaminant distribution using liquid chromatography-tandem mass spectrometry. A multidimensional framework was developed, incorporating weighted correlations, discriminative ability, descriptive statistics, and methodological robustness, to identify the most suitable matrices. Key findings revealed that: (1) urine exhibited minimal matrix interference with polar parabens, with a 100 % detection rate (DR) for short-chain parabens and excellent discrimination ability; (2) serum achieved optimal recovery for moderately polar analytes through fibrinogen removal (TCS recovery: 116.3 %; median concentration: 2.94 μg/L); (3) plasma enabled reliable quantification of lipophilic compounds despite ionization enhancement (butylparaben DR: 100 % in plasma vs. 85.7 % in urine); and (4) whole blood showed significant signal suppression (TCC ME 40.8 %), requiring specialized pretreatment. Based on multidimensional assessment, the optimal matrices were determined as follows: urine for methylparaben and ethylparaben, whole blood for propylparaben, serum for benzylparaben and butylparaben, and plasma for TCS and TCC. Consequently, a standardized protocol was established: urine for routine parabens biomonitoring, plasma/serum for trace antimicrobial testing, and phospholipid removal for whole blood applications.