In constructed wetlands, micropollutants can be removed from water by phytoremediation. However, micropollutant uptake and metabolism by plants here is poorly understood due to the lack of good analytical approaches. Reported herein is the first methodology developed and validated for the multi-residue determination of 81 micropollutants (pharmaceuticals, personal care products and illicit drugs) in the emergent macrophyte Phragmites australis. The method involved extraction by microwave-accelerated extraction (MAE), clean-up using off-line solid phase extraction and analysis by ultra-high-performance liquid chromatography tandem mass spectrometry. Development of the MAE method found the influence of studied variables on micropollutant recovery to be: extraction temperature > sample mass > solvent composition. Validation of the developed extraction protocol revealed that method recoveries were in the range 80-120% for the majority of micropollutants. Method quantitation limits (MQLs) were generally < 5 ng g-1 dry weight, demonstrating the sensitivity of the methodology. Application of the method to P. australis from a constructed wetland used to treat trickling filter effluent found 17 micropollutants above their MQL, up to concentrations of 200 ng g-1. Other than uptake, the presence of several metabolites (carbamazepine 10,11 epoxide, desvenlafaxine, 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine, N-desmethyltramadol and norketamine) indicated that metabolism within the plant may also occur. This new analytical methodology will enable a process mass balance of the constructed wetland to be attained for the first time, and thus help understand the role of phytoremediation in micropollutant removal by such systems.
PETRIE, B., SMITH, B.D., YOUDAN, J., BARDEN, R. and KASPRZYK-HORDERN, B. 2017. Multi-residue determination of micropollutants in Phragmites australis from constructed wetlands using microwave assisted extraction and ultra-high-performance liquid chromatography tandem mass spectrometry. Analytica chimica acta [online], 959, pages 91-101. Available from: https://doi.org/10.1016/j.aca.2016.12.042