Magnetic metal-organic frameworks nanocomposites for negligible-depletion solid-phase extraction of freely dissolved polyaromatic hydrocarbons.

The bioavailability of a pollutant is usually evaluated based on its freely dissolved concentration (Cfree), which can be measured by negligible-depletion equilibrium extraction that is commonly suffered from long equilibration time. Herein, metal-organic framework (MOF) composites (Fe3O4@MIL-101), consists of a magnetic Fe3O4 core and a MIL-101 (Cr) MOF shell, is developed as sorbents for negligible-depletion magnetic solid-phase extraction (nd-MSPE) of freely dissolved polyaromatic hydrocarbons (PAHs) in environmental waters. The freely dissolved PAHs in 1000 mL water samples are extracted with 1.5 mg MOF composites, and desorbed with 0.9 mL of acetonitrile under sonication for 5 min. The MOF composites exclude the extraction of dissolved organic matter (DOM) and DOM-associated PAHs by size exclusion. Additionally, the combined interactions (hydrophobic, π-π and π-complexation) between PAHs and composites markedly reduced the extraction equilibration time to < 60 min for all the studied PAHs with logKOW up to 5.74. Moreover, the porous coordination polymers property of the MOFs makes the proposed nd-MSPE based on the partitioning of PAHs and thus excludes the competitive adsorption of coexisting substances. The developed nd-MSPE approach provides low detection limits (0.08-0.82 ng L-1), wide linear range (1-1000 ng L-1) and high precision (relative standard deviations (RSDs) (3.3-4.8%) in determining Cfree of PAHs. The measured Cfree of PAHs in environmental waters are in good agreement with that of verified method. Given the large diversity in structure and pore size of MOFs, various magnetic MOFs can be fabricated for task-specific nd-MSPE of analytes, presenting a prospective strategy for high-efficiency measuring Cfree of contaminants in environments.