Automatic Mesofluidic System Combining Dynamic Gastrointestinal Bioaccessibility with Lab-on-Valve-Based Sorptive Microextraction for Risk Exposure of Organic Emerging Contaminants in Filter-Feeding Organisms.

An automatic mesofluidic system combining dynamic oral bioaccessibility with lab-on-valve (LOV)-based sorptive microextraction is herein proposed for the first time for exploring the kinetics of leaching of incurred rather than spiked organic emerging contaminants (viz., methyl paraben, butyl paraben, diclofenac, and triclosan) from exposed mussels on the basis of the Versantvoort's fed-state physiological extraction test. Our method capitalizes on programmable flow analysis, in which gastrointestinal extracts are obtained online by pumping a simulated biorelevant gastrointestinal fluid across a large-bore column (maintained at 37.0 ± 2.0 °C) loaded with 250 mg of freeze-dried and powdered mussel onto a polyvinyldiene difluoride filter membrane. The physiologically relevant extracts are then cleaned up, and the analytes are preconcentrated onto a dedicated reversed-phase solid-phase extraction (Oasis PRIME-HLB) microcolumn that is captured into the channels of an LOV mesofluidic platform. The aim behind this is to obtain analyte-laden eluates with ACN/MeOH (90:10, v/v) in unsupervised mode for direct injection into LC-MS. The LOV minicolumn (≤25 mg) is automatically disposed of and renewed for every individual fraction on account of the strong retention of (phospho)lipids by the copolymeric sorbent. The proposed dynamic bioaccessibility test features a significant shortening of the extraction time against the batch method (28 vs 240 min) while avoiding overestimation of potentially bioavailable fractions. The trueness of the online gastrointestinal extraction method was confirmed using mass-balance validation following ultrasonic-assisted solid-liquid extraction of the original mussel sample and the residual (nonbioaccessible) fraction of emerging contaminants.