Trace-level quantification of N-nitrosopiperazine in treated wastewater using supported liquid extraction and hydrophilic interaction chromatography mass spectrometry

Abstract

Regenerable amine-based solvents used for post-combustion CO2 capture, primarily monoethanolamine and piperazine, are known to undergo degradation and secondary reactions over time forming, amongst other species, N-nitrosamines. These carcinogenic species can eventually make their way from treated wastewater into environmental waters. The United States Environmental Protection Agency (US EPA) recommends that the concentration of N-nitrosamines in surface water not exceed 1.24 μg/L. We have developed a straightforward method to quantify N-nitrosopiperazine in treated wastewater by hydrophilic interaction liquid chromatography – mass spectrometry (HILIC–MS) after sample preparation by supported liquid extraction (SLE). To achieve the best extraction recovery and method limits of quantification (MLOQ), standards were prepared in a high-salt synthetic matrix to mimic the treated wastewater effluent. To further improve the MLOQ, the drying steps after extraction were optimized. HILIC separation of the highly polar analytes was achieved using an ethylene-bridged hybrid amide stationary phase. Detection was achieved using a triple quadrupole mass spectrometer operated in positive electrospray ionisation and multiple reaction monitoring mode, providing a final MLOQ of 0.25 μg/L for N-nitrosopiperazine. Validation of the method was carried out to ensure good confidence in the data obtained for a treated wastewater sample from a post-combustion CO2 capture facility. In addition, N-nitrosopiperazine was quantified with the developed SLE-HILIC–MS method in eight degraded carbon capture samples that had not yet undergone wastewater treatment.