Multi-residue determination of micropollutants in Phragmites australis from constructed wetlands using microwave assisted extraction and ultra-high-performance liquid chromatography tandem mass spectrometry.
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 method recoveries were in the range 80-120% for the majority of micropollutants. Method quantitation limits (MQLs) were generally <5 ng g-1dry 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 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.
Department of Chemistry, University of Bath, Bath, BA2 7AY, UK; Water Innovation & Research Centre (WIRC), University of Bath, Bath, BA2 7AY, UK.
Bruce
B
Petrie
Department of Chemistry, University of Bath, Bath, BA2 7AY, UK.
Benjamin D
BD
Smith
Wessex Water, Bath, BA2 7WW, UK.
Jane
J
Youdan
Wessex Water, Bath, BA2 7WW, UK.
Ruth
R
Barden
Department of Chemistry, University of Bath, Bath, BA2 7AY, UK; Water Innovation & Research Centre (WIRC), University of Bath, Bath, BA2 7AY, UK. Electronic address: b.kasprzyk-hordern@bath.ac.uk.
Barbara
B
Kasprzyk-Hordern
D001673:Biodegradation, Environmental; D002851:Chromatography, High Pressure Liquid; D008872:Microwaves; D006109:Poaceae / Q000737:chemistry*; D052616:Solid Phase Extraction; D053719:Tandem Mass Spectrometry; D014874:Water Pollutants, Chemical / Q000032:analysis*; D053833:Wetlands
D014874:Water Pollutants, Chemical
Constructed wetland; Microwave assisted extraction; Pharmaceutical; Reeds; Wastewater