Occurrence of tetracyclines and their transformation products in manure-based organic fertilizers
Manure-based organic fertilizers are important sources of pollution of antibiotic and transformation products in farmland soil.To study the residues of tetracyclines and transformation products in manure-based organic fertilizers,55 organic fertilizer samples were collected from eight provinces in China.Ultra-performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS)was used to analyze the distribution characteristics of tetracycline,doxycycline,chlortetracycline,oxytetracycline and their transformation products in organic fertilizers.The results showed that tetracycline,doxycycline,chlortetracycline and oxytetracycline were detected in 55 organic fertilizer samples,and the concentrations were 1.63-4348 μg·kg-1,ND—11451 μgkg-1,ND—30300 μg·kg-1,7.11-55008 μg·kg-1,respectively.Among the 10 transformation products,the 4-epimers were the main transformation products.There were significant differences in the contents of tetracyclines and their transformation products in organic fertilizers produced from manure of different animal species.The concentrations and detection rates of tetracyclines and their transformation products in swine manure fertilizers were higher than those in chicken manure fertilizers,cattle manure fertilizers and sheep manure fertilizers.The treatment model of resource utilization of livestock manure might also affect the contents of tetracyclines in organic fertilizers.The concentrations of tetracyclines and their transformation products in organic fertilizers produced by the model of combination of farming and animal husbandry were significantly higher than those produced by the mode of centralized treatment.The pollution characteristics of tetracyclines and their transformation products in manure-based organic fertilizers and fertilized soil in typical areas were further studied.The results showed that the 4-epimers were still the main transformation products in the fertilized soil.Therefore,the residues of tetracyclines and their transformation products in manure-based organic fertilizers and fertilized soil cannot be ignored.