Urinary biomonitoring of fuel ether oxygenates using a needle trap device packed with a novel molecularly imprinted...

This study introduces an innovative needle trap device (NTD) featuring a molecularly imprinted polymer (MIP) surface-modified Zeolite Y. The developed NTD was integrated with gas chromatography-flame ionization detector (GC-FID) and employed for analysis of fuel ether oxygenates (methyl tert‑butyl ether, MTBE, ethyl tert‑butyl ether, ETBE, and tert‑butyl formate, TBF) in urine samples. To optimize the key experimental variables including extraction temperature, extraction time, salt concentration, and stirring speed, a central composite design-response surface methodology (CCD-RSM) was employed. The optimal values for extraction in the study were found to be 51.2 °C extraction temperature, 46.2 min extraction time, 27 % salt concentration, and 620 rpm stirring speed. Under the optimized conditions, the calibration curves demonstrated excellent linearity within the range of 0.1-100 μg L^-1, with correlation coefficients (R²) exceeding 0.99. The limits of detection (LODs) for MTBE, ETBE, and TBF were obtained 0.06, 0.08, and 0.09 μg L^-1, respectively. Moreover, the limits of quantification (LOQs) for MTBE, ETBE, and TBF were obtained 0.18, 0.24, and 0.27 μg L^-1, respectively. The enrichment factor was also found to be in the range of 98-129.The NTD-GC-FID procedure demonstrated a high extraction efficiency, making it a promising tool for urinary biomonitoring of fuel ether oxygenates with improved sensitivity and selectivity compared to current methods.