Long-term monitoring of sulfonamides and tetracyclines in manure amended soils and leachate samples - A follow-up study.

Antibiotics can be detected in manure and digestate samples worldwide. As manure is a frequently used fertilizer, antibiotics are found in soil and leachate samples. Only little is known about the long-term fate of antibiotics in the soil environment. One shortcut is the lack of appropriate monitoring studies. Here we present the results of an unequalled soil monitoring study over 18 years from an agricultural field site in Lower Saxony (Germany). Sulfonamides and tetracycline are mainly fixed in the upper soil layer. Contents showed a sharp decrease below sampling depth of 30 cm (plough depth). Sulfaguanidine and sulfamethazine (SMZ) were detected down to 90 cm. Water samples taken below the field site revealed the transfer of sulfonamides into leachate. High variances were observed between sampling points emphasizing the need for sampling strategies for environmental studies. In addition, field lysimeters with defined input of sulfonamides enabled a long-term monitoring and mass balance of antibiotic transfer into leachate over 10 years. SMZ showed the highest mobility with concentrations up to 65 ng L-1. Less than 0.5% of the applied SMZ was transferred into the leachate. Data of lysimeter and field water samples support the theory of a steady state process with a continuous input of sulfonamides such as SMZ into leachate. Soils contaminated with antibiotics can be a long-term source for the input of antibiotic active compounds into deeper soil layers and groundwater.

Abiotic transformation products of tetracycline and chlortetracycline in salt solutions and manure.

Tetracyclines belong to the group of the most applied antibiotics in veterinary medicine worldwide. Due to their incomplete absorption and/or metabolism in the animal gut, tetracyclines are frequently detected in manure samples. Within the matrix, an elimination of these compounds has been reported in several studies. However, only little information about potential transformation products of tetracyclines in manure and the environment is available. Therefore, the fate of tetracycline (TC) and chlortetracycline (CTC) was investigated in aqueous solutions and manure. Abiotic incubation of TC in phosphate buffer led to a remarkable red-brown coloring of the solution. Subsequent compound isolation and structure elucidation by MS/MS and NMR techniques revealed the formation of seco-cycline A, a compound formerly described as a fungal biotransformation product of TC. For CTC, two comparable products were identified which were derived from its isomeric form isoCTC. All transformation products showed no antimicrobial activity for concentrations up to 500 mg L-1. When TC and CTC were incubated in cow manure for 7 d, the above mentioned three transformation products were also formed in this complex matrix (up to 5.1 mg kg-1). Manure, soil and leachate samples from Lower Saxony revealed the presence of seco-cycline A in manure and soil, but not in water. To obtain a better insight in the fate of tetracyclines in environmental matrices, future analytical and ecotoxicological studies dealing with this subject should include the analysis especially of seco-cycline A.

Transformation of Sulfonamides and Tetracyclines during Anaerobic Fermentation of Liquid Manure.

Liquid manure is frequently used as soil fertilizer due to its high nutrient content. It can also contain residues of pharmaceuticals, such as antibiotics, if farm animals are medicated. The anaerobic fermentation process in biogas plants is discussed as one way to reduce the input of antibiotics into the environment. Therefore, 10 worldwide-applied sulfonamides (sulfachloropyridazine, sulfadiazine, sulfadimethoxine, sulfaguanidine, sulfamerazine, sulfamethazine, sulfamethoxazole, sulfamethoxypyridazine, sulfapyridine, and sulfathiazole) and four frequently used tetracyclines (chlortetracycline, doxycycline, oxytetracycline, and tetracycline) were investigated concerning their elimination pattern during anaerobic fermentation. Batch fermenters with autoclaved and non-autoclaved inoculum were utilized to distinguish between biotic and abiotic elimination pathways. Overall, sulfadimethoxine, sulfamethoxypyridazine, and sulfamethoxazole showed the highest elimination, which was considerably reduced by autoclaving before inoculation. Structure elucidation via nuclear magnetic resonance and different mass spectrometry techniques revealed only minor structural modifications such as O-demethylation and hydrogenation, which did not result in a considerably reduced antimicrobial activity. These results show that, especially, sulfonamides are more persistent than expected. Future studies should deal with the elucidation of relevant process parameters for an enhanced compound degradation.