Groundwater antibiotic pollution and its relationship with dissolved organic matter: Identification and environmental implications.

The occurrence of veterinary antibiotics and hydro-chemical parameters in eleven natural springs in a livestock production area is evaluated, jointly with the characterization of their DOM fingerprint by Orbitrap HRMS. Tetracycline and sulfonamide antibiotics were ubiquitous in all sites, and they were detected at low ng L-1 concentrations, except for doxycycline, that was present at µg L-1 in one location. DOM analysis revealed that most molecular formulas were CHO compounds (49 %-68 %), with a remarkable percentage containing nitrogen and sulphur (16 %-23 % and 11 %-24 %, respectively). Major DOM components were phenolic and highly unsaturated compounds (~90 %), typical for soil-derived organic matter, while approximately 11 % were unsaturated aliphatic, suggesting that springs may be susceptible to anthropogenic contamination sources. Comparing the DOM fingerprint among sites, the spring showing the most different profile was the one with surface water interaction and characterized by having lower CHO and higher CHOS formulas and aliphatic compounds. Correlations between antibiotics and DOM showed that tetracyclines positively correlate with unsaturated oxygen-rich substances, while sulfonamides relate with aliphatic and unsaturated oxygen-poor compounds. This indicates that the fate of different antibiotics will be controlled by the type of DOM present in groundwater.