Transformation of veterinary ionophore antibiotics under conditions related to water-soil-litter systems
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Veterinary pharmaceuticals are routinely used in livestock production to treat diseases, prevent infections, and promote growth. However, the potential release of pharmaceuticals from agricultural activities has raised concerns because they may pose detrimental effects to the ecosystems and human health, for example fostering the evolution of antibiotic-resistant bacteria in the natural environment. A better understanding of the environmental fate of veterinary pharmaceuticals is critical to properly assess and mitigate their risks. This dissertation focuses on a major group of veterinary pharmaceuticals, ionophore antibiotics (IPAs), which is sold at over 4 million kilograms per year and constitutes more than one third of the total antibiotic consumption by the livestock industry in the U.S. Despite the extensive usage of IPAs, their environmental fate was not well-understood. Therefore, this study aimed at achieving a comprehensive understanding of the occurrence, persistence, and transformation of IPAs from poultry litter before and after applications to the agricultural lands. Three of the most commonly used members of IPAs were investigated in this study: monensin (MON), salinomycin (SAL), and narasin (NAR). Based on the common management practices of poultry litter, the potential abiotic and biotic transformation reactions of IPAs were examined under varying conditions relevant to the water-soil-litter systems. This dissertation consists of three sections. First, a robust analytical method was developed to quantify IPAs in various environmental compartments, especially in high organic-containing matrices such as poultry litter, and soil and runoff from litter-fertilized lands. Efforts were made to optimize the analytical method with respect to improving extraction recovery, reducing matrix effects, and validating a surrogate standard. Second, lab-scale experiments were set up to determine the chemical properties of IPAs in aqueous environments and to study the abiotic transformation of IPAs, including hydrolysis and photolysis. The results showed that IPAs are prone to hydrolytic transformation in acidic environments, which are likely to be encountered in acidic soils, alum-amended litter (alum: Al₂(SO₄)₃•12H₂O), and acidic runoff. Multiple transformation pathways were proposed based on the identified hydrolysis products. It is also noteworthy that the hydrolysis products of MON still exhibited a toxic effect on the selected microorganism (Bacillus subtilis). SAL and NAR were found to undergo direct photolysis under both UV light and sunlight irradiation. In natural water matrix, IPAs were also degraded by indirect photolysis with hydroxyl radicals generated by light-excited nitrate. Dissolved organic matter can shield IPAs from light and slow down their photolysis. Third, the biodegradation potential of IPAs was first tested in litter and soil microcosms. Factor analysis was conducted to delineate the interaction of water and temperature on IPA degradation in the litter. Litter-fertilized and non-fertilized soil microcosms were compared on the degradation of MON and SAL. Furthermore, the inhibition and biotransformation potential of IPAs were assessed under different redox conditions with litter-enriched cultures. Inhibition tests focused on examining IPAs’ impact on microbial community functions, including denitrification, sulfate-reduction, and methane production. Biodegradation tests were conducted with different electron acceptors, including oxygen, nitrate, sulfate, and organic carbons, with efforts to elucidate primary biotransformation products. On the basis of the results obtained in this study, several recommendations on litter management and IPA selection were made to help mitigate the release and transport of IPAs, as well as enhance their degradation. Overall, this study significantly improved the understanding of the environmental fate of IPAs and the obtained knowledge can aid proper selection of IPAs and management strategies in future applications to minimize the risks of antibiotic micropollutants in the environment.