Rejection of small and uncharged chemicals of emerging concern by reverse osmosis membranes: The role of free volume space within the active skin layer

Free-volume hole-radii of the active skin layer of one seawater and two low pressure reverse osmosis (RO) membranes namely SWC5, ESPAB, and ESPA2 respectively were evaluated using positron annihilation lifetime spectroscopy (PALS) with a slow positron beam. The results were related to the rejection of boric acid and eight N-nitrosamines to provide insights to the transport of these small solutes through RO membranes. At pH 8 (which is the experimental pH in this study), these solutes are uncharged. PALS analysis showed that the SWC5 has the smallest mean free-volume hole-radius (0.259 nm) among the three RO membranes investigated here. Correspondingly, the SWC5 membrane exhibited the highest rejection of boric acid and all N-nitrosamines. Results reported here also showed that the rejection of these chemicals increased in the order of increasing molecular volume. In addition, the difference in their rejection amongst the three RO membranes investigated here was most apparent for those (i.e., boric acid and N-nitrosodimethylamine (NDMA)) with a small molecular volume. The EPSA2 and ESPAB were determined to have mean freevolume hole-radius of 0.289 nm. However, the ESPAB membrane had lower water permeability and showed considerably higher rejection of boric acid and NDMA than the ESPA2 membrane. These results suggest that in addition to the mean free-volume hole-radius, other membrane parameters and properties such as the freevolume hole-radius distribution and thickness of the active skin layer can also play a role in governing the rejection of small and uncharged solutes by RO membranes.