Urinary biomonitoring of fuel ether oxygenates using a needle trap device packed with a novel molecularly imprinted polymer surface modified Zeolite Y

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 minutes 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.