Determination of persistent and mobile organic compounds in the river–groundwater interface of the Besòs river delta, Spain, using a wide extraction approach

Climate change impacts the Mediterranean region, transforming it from region with a semi-arid climate to a region with an arid climate. Under this situation, while groundwater is an essential hydric resource, its existence is in danger due to anthropogenic pressures. Persistent mobile organic compounds (PMOCs) have recently been recognised as an emerging problem; however, PMOCs in groundwater need to be better characterised. Here, we present a new analytical method to characterise the profile of PMOCs in groundwater based on two parallel solid-phase extraction (SPE), using weak anion exchange and weak cation exchange. Extracts were analysed by ultraperformance liquid chromatography (UPLC) using mix-mode chromatography for those compounds analysed under negative ionisation conditions and hydrophilic interaction liquid chromatography (HILIC) under positive conditions coupled to high-resolution mass-spectrometry (HRMS) using a Q-Exactive Orbitrap™ analyser. For the suspect screening of PMOCs in groundwater, the acquisition mode was in full scan (FS) by "independent scan of all ion fragmentation". For the tentative identification, different online databases such as Environmental and Food Safety (EFS) HRAM Compound database, PFAS NIST database, ChemSpider for chemical structural information, MzCloud as a mass spectral database, and an in-house list with 1280 PMOC structures have been used. The performance of the method was assessed with 29 representative PMOCs which were selected based on the previous literature. The recovery rates have been between 63 and 110 % for 90 % of the target compounds and method limits of quantification (MLQ) between 0.3 and 10.5 ng/L. The optimised approach was applied to assess PMOCs in the Besòs River aquifer, NE Spain, showing 148 tentatively identified structures at confidence levels 1-3. Among them, 66 suspects were tentatively identified at level 3, 54 at level 2, and 28 confirmed at level 1. Most of these compounds were polar and highly polar compounds which are difficult to retain with other extraction approaches. Major detected compounds were pharmaceuticals and personal care products (46), followed by perfluoroalkyl and polyfluoroalkyl substances (PFAS) (32), industrial additives (27), and pesticides (23), among other groups. Some compounds, such as ultrashort chain PFAS and fluorinated betaines, were detected for the first time in groundwaters in Spain.