Behaviour of nonsteroidal anti-inflammatory drugs and eight of their metabolites during wastewater treatment studied by hollow fibre liquid phase microextraction and liquid chromatography mass spectrometry

In this work hollow fibre liquid phase microextraction combined with liquid chromatography mass spectrometry was applied for the determination of the nonsteroidal anti-inflammatory drugs (NSAIDs) ketoprofen, naproxen, diclofenac and ibuprofen as well as eight of their known human metabolites in wastewater samples. Extraction time and addition of tri-n-octylphosphine oxide (TOPO) to the liquid membrane were evaluated resulting in a method with an optimal extraction time of 5h and 5% (w/V) TOPO addition to the membrane liquid (di-n-hexyl ether). With the optimized method, enrichment factors ranged between 778 and 4830. The method was applied for analysis of samples collected from Källby wastewater treatment plant in the city of Lund, Sweden. Samples were collected from the influent, water entering as well as exiting the conventional activated sludge treatment and the effluent to study the behaviour of these compounds during the treatment process. All twelve substances were found in the influent and for all four drugs, higher concentrations were detected of the metabolites than the parent compounds. Highest concentrations were detected of o-desmethylnaproxen, 2-hydroxyibuprofen and carboxyibuprofen (average influent concentrations of 45, 35 and 63 μg/L respectively). The study showed only partial removal during the primary treatment whereas both parent compounds and metabolites were efficiently removed during the activated sludge process. In the effluent all analytes were detected in concentrations below 1 μg/L thus showing that either the investigated metabolites do not belong to the NSAID transformation products formed during the activated sludge treatment or they are also quickly further transformed within the treatment.