Humic Acid Enhances Ciprofloxacin Sorption in a Typical Loess Soil: Implications for the Fate of Veterinary Antibiotics in Soil–Water Systems

Studies have shown that natural organic matter can regulate pollutant behavior through multiple pathways; however, research on the environmental behavior of veterinary antibiotics (VAs) in typical alkaline calcareous loess soil under the influence of exogenous organic matter remains limited. This study investigated the influence of humic acid (HA), as a representative of natural organic matter, on the sorption behavior of ciprofloxacin (CIP) in sierozem—a typical alkaline calcareous loess soil. Using the batch equilibrium method, we examined how HA affects CIP sorption under various environmental conditions to better understand the environmental fate of VAs in soil–water systems with low organic matrix content. Results showed that CIP sorption onto sierozem involved both fast and slow processes, reaching equilibrium within 2 h, with sorption capacity increasing as HA concentration increased. Kinetic data were well described by the pseudo-second-order model regardless of HA addition, suggesting multiple mechanisms governing CIP sorption, such as chemical sorption reaction, intraparticle diffusion, film diffusion, etc. Sorption decreased with increasing temperature both before and after HA amendment, indicating an exothermic process. Isotherm analysis revealed that both the Linear and Freundlich models provided excellent fits (R2 ≈ 1), implying multilayer sorption dominated by hydrophobic distribution. In ion effect experiments, cations at concentrations above 0.05 mol/L consistently inhibited CIP sorption, with inhibition strength following the order: Mg2+ > K+ > Ca2+ > NH4+, and intensifying with increasing ionic strength. However, HA addition significantly mitigated this inhibition, likely due to complexation between HA’s functional groups (e.g., carboxyl and hydroxyl) and cations, which reduced their competitive effect and enhanced CIP sorption. pH-dependent experiments indicated stronger CIP sorption under acidic conditions. HA addition increased soil acidity, further promoting CIP retention. In summary, HA enhances CIP sorption in sierozem by providing additional sorption sites and modifying soil surface properties. These findings improve our understanding of how exogenous organic matter influences the behavior of emerging contaminants such as antibiotics in soil–water systems, offering valuable insights for environmental risk assessment in semi-arid agricultural regions.