Polymer Inclusion Membranes with Condensed Phase Membrane Introduction Mass Spectrometry (CP-MIMS): Improved Analytical Response Time and Sensitivity

Condensed phase membrane introduction mass spectrometry (CP-MIMS) is an online, in situ analysis technique for low volatility analytes. Analytes diffuse through a hollow fiber membrane, where they are then dissolved by a liquid (condensed) acceptor phase flowing through the membrane lumen. Permeating analytes are entrained to an atmospheric pressure ionization source for subsequent measurement by a mass spectrometer. Larger analytes, with inherently lower diffusivities, suffer from lengthy response times and lower sensitivity, limiting the use of CP-MIMS for their online, real-time measurement. We present the use of a heptane cosolvent in a methanol acceptor phase in combination with a polydimethylsiloxane (PDMS) membrane. The heptane generates an in situ polymer inclusion membrane (PIM) with the PDMS. We report improved measurement response times and greater sensitivity across a suite of analytes studied (gemfibrozil, nonylphenol, triclosan, 2,4,6-trichlorophenol, and naphthenic acids), with detection limits in the low parts per trillion (ppt) range. These improvements are attributed to increasing analyte diffusivities, as well as increased analyte partitioning across the PIM. Response times are ∼3× faster for the larger analytes studied, and calibration sensitivity is improved by up to ∼3.5× using 0.046 mole fraction heptane in the methanol acceptor. We report the use of short sample exposure times and the use of non-steady-state signals to reduce the analytical duty cycle, and illustrate that the use of a PIM provides a simple and robust variant of CP-MIMS amenable to rapid screening of analytes in complex samples