Determination of Urinary Hydroxyl PAHs Using Graphene Oxide@Diatomite Based Solid-Phase Extraction and High-Performance Liquid Chromatography

A diatomite supported graphene oxide composite (GO@Dt–NH(2)) was fabricated and explored as a solid-phase extraction adsorbent coupled with high performance liquid chromatography to determine the trace hydroxyl polycyclic aromatic hydrocarbons (2-hydroxy-naphthalene, 2-hydroxy-fluorene, 1-hydroxy-phenanthrene, and 1-hydroxy-pyrene) in urine samples. The fabricated composites were characterized by X-ray powder diffractometry and scanning electron microscopy. GO@Dt–NH(2) offered enhanced adsorption affinity towards the analytes compared with the bare diatomite. The amount of graphene oxide and the factors affecting solid-phase extraction were investigated in detail. Under the optimized conditions, the method gave good linearity (0.30–200 ng/mL) and a low detection limit (0.10–0.15 ng/mL) for the hydroxyl polycyclic aromatic hydrocarbons. The average recovery for spiked urine samples with three levels ranged from 90.6% to 100%. The intra-day and inter-day relative standard deviations were in the range of 1.8–6.4% and 2.7–11.8%, respectively. Besides, the GO@Dt–NH(2) provided enrichment factors of 18–20 and superior purification ability. The developed method was successfully applied to the determination of hydroxyl polycyclic aromatic hydrocarbons in urine samples from smoking volunteers.