Determination of Antibiotics and Other Veterinary Drugs in the Solid Phase of Pig Manure

The presence of residues of veterinary pharmaceuticals in farm wastewaters such as pig slurry represents a problem that needs to be tackled to avoid further contamination of environmental waters and the development of resistant bacteria. For their monitoring and control, it is necessary the existence of reliable analytical tools. The present paper describes for the first time the development and optimization by statistical experimental design of a specifically designed analytical method for the analysis of 21 veterinary drugs, including 18 antibiotics of several families (β-lactams, tetracyclines, fluoroquinolones, sulfonamides, macrolides, among others), 1 antiparasitic, 1 analgesic and 1 hormone, in a complex environmental matrix such as the fresh solid phase of pig slurry. The resulting method, consisted of an ultrasound assisted extraction (UAE) combined with in-situ dispersive solid phase extraction (d-SPE) from a 0.3 g of freeze-dried sample aliquot followed by a preconcentration step by compact solid phase extraction (c-SPE) and subsequent instrumental analysis by ultra-high-performance-liquid-chromatography (UHPLC) coupled to mass spectrometry in tandem (MS/MS) by a triple quadrupole, was successfully validated as a very sensitive (method limit of quantification in the low ng g) and reliable method (relative recoveries around 100% and method repeatability featured by a general relative standard deviation below 20%). Provided raw data was intended to be processed by matrix-matched quantification approach. The resulting methodology was applied to the characterization of several pig manures from different Spanish farms sampled across breeding season between 2018 and 2019. Sample precedence showed to have a high impact in the positives, its frequency and concentration.