Determination of human and veterinary antibiotics in indirect potable reuse systems

Abstract

This paper reports the optimisation and validation of an analytical method for the determination of the residual concentration of the prescription antibiotics metronidazole, trimethoprim, sulfamethoxazole, azithromycin, clindamicyn, clarithromycin, erythromycin-H₂O, roxithromycin and tylosin in wastewater and advanced treated wastewater. The method applied was used in a study of removal efficiency of these compounds at a full scale operational water reclamation plant using microfiltration-reverse osmosis (MF-RO) (Kwinana, Western Australia). The analytical procedure involves off-line solid-phase extraction (SPE) followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) operated in multiple reaction monitoring mode. Method validation included determination of linearity, accuracy, precision, method limits of quantitation (MLQs), reproducibility and matrix effect. SPE recoveries were generally higher than 89% for both pre- and post-RO water, except for erythromycin which yielded approximately 50% recovery. The overall precision of the method was better than 16% RSD (relative standard deviation), for all compounds and matrices. MLQ ranged between 23–53 ng L⁻¹ and 2.5–31 ng L⁻¹ for pre- and post-RO water, respectively. In-house reproducibility expressed as RSD was generally better than 10%. Inter-laboratory tests revealed a generally good agreement between concentrations of antibiotics reported by all participants. Results demonstrate that MF/RO treatment is capable of removing antibiotics present at relevant environmental concentration in secondary effluent (from the low to mid ng L⁻¹ range) to below MLQs (2.5–31 ng L⁻¹), and more importantly, three to six orders of magnitude below the health guideline values developed for this project. Estimated RO rejections ranged between >91 and 99%.

Keywords:

• water reuse
• indirect potable reuse systems
• reverse osmosis
• PPCPs
• antibiotics
• LC-MS
• SPE
• wastewater

Acknowledgements

The authors would like to thank W. Giger, M. Suter, J. Hollander from EAWAG for their valuable advice on development and validation of analytical methods. J. Murby and O. Lord from NMI (Sydney and Perth) and F. Sacher and the staff at TZW (Karlsruhe) are also acknowledged for participating in the inter-laboratory trial and for advising on QA/QC protocols. J. Berry and K. Hall from Micromass and B. Greirson from Agilent are also acknowledged for their constant and valuable technical support on LC-MS instrumentation. This study was part of the Western Australian Premier's Collaborative Research Program ‘Characterising Treated Wastewater for Drinking Purposes Following Reverse Osmosis Treatment’. The authors would like to thank all project partners including Water Corporation of Western Australia, CSIRO Land and Water and Department of Health at UWA. Dr L. Berwick, Prof. U. Von Gunten and Dr K.L. Linge are also acknowledged for pre-reviewing the manuscript. We also acknowledge the contribution of two anonymous reviewers to revision and improvement of the manuscript.