Tunable dual-ligand ZIF-8-90 effervescent tablet-assisted dispersive solid phase extraction for monitoring of both PAHs and their hydroxyl metabolites: from external to internal exposure analysis

Mixed-ligand metal organic frameworks have received great attentions as novel sorbents for sample preparation due to their fascinating structures and intriguing functionalities. Here, we report the fabrication of mixed-linker ZIF-8-90 s with tunable properties for effervescent tablet-assisted dispersive solid-phase extraction (ET-DSPE) of polycyclic aromatic hydrocarbons (PAHs) in environmental water before HPLC separation and hydroxyl metabolites of PAHs (OH-PAHs) in urine samples prior to LC-MS/MS. ZIF-8-90 s based effervescent tablets possessed the high affinity towards analytes via Zn-O bond and π-π interaction, and afforded a great excluding ability to interfering components from urine samples. ET-DSPE of PAHs from 15 mL water sample with ZIF-8 25 -90 75 gave enhancement factors of 122–155, linear ranges of 4-10 5 ng/L, detection limits ( S/N  = 3) of 1–8 ng/L, and recoveries of 81.1%-103%. For the determination of OH-PAHs, the proposed ET-DSPE method using ZIF-8 85 -90 15 allowed direct loading of 4 mL of crude human urine sample and provided the linearity range of 0.004-100 ng/mL, detection limits of 0.001–0.008 ng/mL, and recoveries of 82.1%-104%. In conclusion, ZIF-8-90-based ET-DSPE coupled with HPLC and LC-MS/MS were successfully applied to monitor both PAHs in environmental water and OH-PAHs in urine in a facile, efficient and reliable way. Graphical