A novel hollow-fibre microporous membrane liquid-liquid extraction for determination of free 4-isobutylacetophenone concentration at ultra trace level in environmental aqueous samples

In this study, a method was developed for determination of the free concentration of 4-isobutylacetophenone, a toxic degradation product of ibuprofen, in river and sewage water samples from Sweden. Sample preparation and analysis were performed by a hollow-fibre microporous membrane liquid-liquid extraction (HF-MMLLE) set-up and gas chromatography-mass spectrometry (GC-MS), respectively. In this novel approach, only the liquid in the membrane pores is utilised for non-depleting extraction. Several parameters were studied, including: type of organic solvent, sample pH, and salt and humic acid content. The optimised method allowed the determination of the analyte at the ng L-1 level in river and sewage water. A linear plot gave a correlation coefficient better than 0.992 and resulted in a limit of detection of 7 and 14 ng L-1 for river and sewage water, respectively. The enrichment factor was over 2000 in the fibre and over 300 after dilution. The repeatability and reproducibility were better than 5% and 10%, respectively. For the first time, 4-isobutylacetophenone was found at free concentrations of 40 ng L-1 or below in sewage waters, while it could not be quantified in a river downstream from a municipal sewage treatment plant.