Occurrence and Risk Assessment of Tetracyclines and Their Transformation Products in Organic Amendments.

Background/Objectives: The application of organic soil amendments constitutes an important source of antibiotic residues in agricultural soils. However, studies have mainly focused on a few parent tetracyclines, whereas information on their transformation products (TPs) in organic amendments remains scarce. Therefore, this study assessed the occurrence and environmental risk of six tetracyclines and seven TPs in organic amendments. Methods: Processed livestock manures applied in the European Union (horse, poultry, and bovine manure), as well as fresh and treated sewage sludge, were analyzed using matrix solid-phase dispersion (MSPD) combined with online SPE-LC-MS/MS. Environmental risk was assessed using risk quotients (RQs) based on predicted environmental concentrations in soil (PECsoil) calculated from the maximum measured concentrations and predicted no-effect concentrations in soil (PNECsoil) obtained either directly from terrestrial ecotoxicity data or derived from aquatic ecotoxicity data using the equilibrium partitioning method and soil-water distribution coefficients. Results: Tetracyclines and their TPs were widely detected in both sample types, although concentrations varied according to matrix type and treatment. Overall, sludge showed higher detection frequencies and concentrations than manure. Doxycycline and tetracycline were the predominant parent compounds, reaching concentrations up to 2838 ng g-1 dry weight (dw) in manure and 2892 ng g-1 dw in sludge. Epimerized TPs were frequently detected and sometimes exceeded the concentrations of their parent compounds, especially epitetracycline and epioxytetracycline. Among the sludge types and treatment conditions investigated, anaerobically digested sludge showed the highest tetracycline concentrations, whereas the composted sludge sample presented the lowest concentrations. Individual RQs indicated insignificant to low ecotoxicological risk, whereas cumulative RQ (ΣRQ) values, used as conservative estimates of co-exposure to all evaluated tetracyclines and their TPs, fell within the medium-risk category for bovine manure and anaerobically digested sludge, with the composted sludge sample showing the lowest ΣRQ. Conclusions: These findings highlight the importance of including TPs in environmental monitoring and the differences in tetracycline occurrence and environmental risk to soil among the processed manure types and sludge treatment conditions investigated.