Characterizing the removal of antibiotics in algal wastewater treatment ponds : a case study on tetracycline in HRAPs: a thesis presented in partial fulfilment of the requirements for the degree of Doctor of Philosophy in Environmental Engineering at Massey University, Turitea Campus, Palmerston, New Zealand

Abstract

Antibiotics are ubiquitous pollutants in wastewater, owing to their usefulness in both animal and human treatment. Antibiotic pollution is a growing concern because of the risk of encouraging antibiotic resistance in wastewater treatment (WWT) systems and downstream of effluent discharge. The aim of this thesis was to investigate the fate of antibiotics in algal WWT ponds, which have unique ecological and environmental characteristics (e.g. presence of algae; diurnal variation in pH, dissolved oxygen, and temperature) compared with conventional biological WWT. The research in this thesis focused on a case study of the fate of tetracycline (TET, an antibiotic) in high rate algal ponds (HRAP). Indoor lab scale HRAP studies were used to investigate the fate of TET under several operating conditions. Outdoor pilot scale studies (900 L and 180 L HRAPs) under Oceanic and Mediterranean climates were used to validate the lab scale findings. Results showed that high removal (85% to >98%) of TET was possible in the lab and pilot scale HRAPs with HRTs of 4 and 7 days. Sorption was consistently a low contributor (3-10% removal by sorption) during continuous HRAP studies, based on the amount of TET extracted from biomass. Batch experimentation was used to further distinguish mechanisms of TET removal. The majority of TET removal was caused by photodegradation. Indirect photodegradation of TET was dominant over direct photolysis, with 3-7 times higher photodegradation observed in wastewater effluent than for photodegradation in purified water during batch tests incubated in sunlight. Under dark conditions sorption was the dominant removal mechanism, and biodegradation was negligible in batch tests since aqueous TET removed was recovered (± 10%) by extraction of sorbed TET from the biomass. Irreversible abiotic hydrolysis was not observed during TET removal batch tests in purified (MQ) water. A kinetic model was developed and used to predict TET removal in the pilot HRAPs, based on parameters derived from batch experiments. The model predictions for aqueous TET concentrations were successfully validated against initial TET pulse tests in the 180 L pilot scale HRAP. However TET removal decreased in subsequent pulse tests in the pilot HRAP, resulting in over-prediction of TET removal by the kinetic model. This decrease in TET removal was associated with decrease in pH, dissolved oxygen concentrations, and biomass settleability, but causal relationships between TET removal and these variables could not be quantified. Until the predictive kinetic model is developed further, this model may serve as a preliminary estimate of TET fate in algal WWT ponds of different design and operation. Future research should also investigate the potential formation and toxicity (including antibiotic efficiency) of TET degradation products, but this was outside the scope of this thesis. Predictions from the model were sensitive to the daily light intensity, suggesting that TET removal would be reduced in the winter months