Combined method of solid-phase extraction and GC-MS for determination of acidic, neutral, and basic emerging contaminants in wastewater (Poland)

Abstract

In this study an analytical procedure of solid-phase extraction (SPE) followed by gas chromatography mass spectrometry (GC-MS) was elaborated and validated for simultaneous determination of 11 acidic, neutral and basic emerging contaminants in wastewater. The most frequently used pharmaceuticals were studied, i.e. five anti-inflammatory drugs – ibuprofen, diclofenac, ketoprofen, naproxen and salicylic acid, an antiepileptic drug carbamazepine, clofibric acid, antibacterial triclosan, a plasticiser bisphenol A and two β-blockers – propranolol and metoprolol. Sample enrichment was performed using Oasis HLB sorbent. Sample pH and sorbent washing step during the solid-phase extraction were optimised on real wastewater samples. Recoveries of the most polar acidic compounds diminished substantially when the alkalinity of the sample loaded into the cartridge increased. Thus finally wastewater was extracted at pH 2.0. Before elution, sorbent was washed subsequently with 5% methanol in water and n-hexane, which resulted in best recoveries of most of the target compounds and reduced a co-elution phenomena with respect to β-blockers. The optimised method was successfully applied to influent and effluent samples from wastewater treatment plant, Krakow, Poland. All target compounds except propranolol were identified in wastewater at a concentration up to 12.8 µg L⁻¹.

Keywords:

• emerging contaminants
• gas chromatography-mass spectrometry
• GC-MS
• HLB sorbent
• solid-phase extraction
• SPE
• pharmaceuticals
• wastewater

Acknowledgements

This work was supported by the National Science Centre under grant no N N305 452340. The authors give special acknowledgments to the Krakow Municipal Water and Sewage Company and its personnel for the access to GC-MS system and for supplying wastewater samples.