Quantifying PPCP interaction with dissolved organic matter in aqueous solution: Combined use of fluorescence quenching and tandem mass spectrometry

The documented presence of pharmaceuticals and personal care products (PPCPs) in water sources has prompted a global interest in understanding their environmental fate. Dissolved organic matter (DOM) can potentially alter the fate of these contaminants in aqueous systems by forming contaminant-DOM complexes. In-situ measurements were made to assess the interactions between three common PPCP contaminants and two distinct DOM sources: a wastewater treatment plant (WWOM) and the Suwannee River, GA (SROM). Aqueous DOM solutions (8.0 mg L−1 C, pH 7.4) were spiked with a range of concentrations of bisphenol-A, carbamazepine and ibuprofen to assess the DOM fluorophores quenched by PPCP interaction in excitation–emission matrices (EEM). Interaction effects on target analyte (PPCP) concentrations were also quantified using direct aqueous injection ultra high performance liquid chromatography tandem mass spectrometry (LC-MS/MS). At low bisphenol-A concentration, WWOM fluorescence was quenched in an EEM region attributed to microbial byproduct-like and humic acid-like DOM components, whereas carbamazepine and ibuprofen quenched fulvic acid-like fluorophores. Fluorescence quenching of SROM by bisphenol-A and carbamazepine was centered on humic acid-like components, whereas ibuprofen quenched the fulvic acid-like fluorophores. Nearly complete LC-MS/MS recovery of all three contaminants was obtained, irrespective of analyte structure and DOM source, indicating relatively weak PPCP-DOM bonding interactions. The results suggest that presence of DOM at environmentally-relevant concentration can give rise to PPCP interactions that could potentially affect their environmental transport, but these DOM-contaminant interactions do not suppress the accurate assessment of target analyte concentrations by aqueous injection LC-MS/MSMS.

► WWOM is composed of hydrophilic molecules; SROM of hydrophobic aromatics.
► Fluorescence quenching of OM reveals interaction with PPCPs.
► Quenching region depends on OM type.
► LC-MS/MS recovery of BPA, CBZ, and IBU – DOMs suggest weak interactions.