Influence of pH on the adsorption-desorption of doxycycline, enrofloxacin, and sulfamethoxypyridazine in soils with variable surface charge

Abstract

In this research, the adsorption/desorption of the antibiotics doxycycline (DC), enrofloxacin (ENR), and sulfamethoxypyradazine (SMP) was studied in 6 agricultural soils with predominance of variable charge, both before and after removing organic matter by calcination. DC adsorption was high at acidic pH, and decreased at pH values above 8. Removal of organic matter with calcination caused just a slight decrease in adsorption, and even in some soils adsorption was similar to that in non-calcined samples. The adsorption coefficients (K_d) were higher for the DC^- species compared to DC⁺, DC⁰ and DC^2-. Regarding DC desorption, the values were very low throughout the pH range covered in the study (2-12), both in the calcined samples and in those not subjected to calcination. ENR showed a similar behavior to DC regarding the effect of pH, since ENR adsorption also decreased at basic pH, but the effect of removing organic matter was different, as it caused a clear decrease in ENR adsorption. The species with the highest K_d was in this case ENR⁰, although ENR⁺ is also quantitatively important as regards K_d value in calcined samples. For this antibiotic, no differences in desorption were observed between calcined and non-calcined samples. Finally, SMP adsorption also decreased as pH increased, and, in addition, similarly to what happened with ENR, in general, there was a strong decrease in SMP adsorption when organic matter was removed. The species with the highest K_d in this case was SMP⁺ in non-calcined samples, but SMP⁰ and SMP^- become more relevant in calcined samples. The percentages of SMP desorption were higher than those for the other two antibiotics, and an increase occurs at intermediate pH values, being higher for calcined samples. These results can be considered relevant in terms of increasing the knowledge as regards the possible evolution and fate of the three antibiotics studied. Specifically, for different pH conditions and with different organic matter contents, when they reach soils and other environmental compartments after being discharged as contaminants. This could have important repercussions on public health and the overall environment.

Keywords: Antibiotics; Doxycycline; Enrofloxacin; Sulfamethoxypyridazine; pH adsorption; pH desorption.