Determination of veterinary drugs in microalgae biomass from photobioreactors fed with piggery wastewater

Abstract

Concentration data of veterinary drugs in microalgae biomass collected from photobioreactors fed with piggery wastewaters are presented for the first time in this work. To this aim, a QuEChERS methodology and an ultrasound-assisted solid-liquid extraction have been assessed as sample preparation procedures with the purpose of determining 20 veterinary drugs, mainly antibiotics of different physico-chemical properties in addition to dexamethasone, fenbendazole and progesterone. Some critical operation parameters of the QuEChERS procedure were optimized by an experimental design but tetracycline, oxytetracycline, doxycycline, marbofloxacin and ciprofloxacin were not detected by the QuEChERS sample preparation. The use of a longer and thorough approach, a solid-liquid extraction with water/methanol in presence of primary secondary amine as a clean-up agent followed by solid-phase extraction on Oasis HLB cartridges, is recommended to monitor all intended analytes. The determination in extracts is carried out by ultra-high performance liquid chromatography-tandem mass spectrometry in selected reaction monitoring mode. Limits of detection about 0.2-42 ng per g of lyophilized microalgae sample, and repeatabilities about 6-46% (n = 5, RSDs) are reached. The solid-liquid extraction method was applied to microalgae biomass samples collected from a photobioreactor. Nine drugs were detected in the samples at relatively low concentration and a proportional relationship between the found concentrations and the octanol/water partition coefficients of the drugs has been outlined. Moreover, a linear ratio between the concentrations measured in biomass and effluent has been observed for most of the drugs.

Keywords: Adsorption; Analytical methods; Microalgae biomass; Photobioreactors; Swine manure; Veterinary drugs.