Removal mechanisms of organic and inorganic solutes in raw, upland drinking water by nanofiltration: influence of solute-solute and solute-membrane interactions

Nanofiltration (NF) membranes have been applied successfully for the removal of inorganic and organic pollutants, including micropollutants, from drinking water for the past two decades. However, a complete and quantitative understanding of NF removal mechanisms has yet to be achieved. Quantifying the factors governing solute transport and retention by NF is necessary in order to achieve higher treatment efficiency at a lower cost. The aim of this research was to contribute to the current state of the knowledge of the mechanisms of solute retention and transport by NF membranes. The focus was on evaluating the contribution of solute-solute interactions and solute-membrane interactions on solute removal and transport mechanisms. To the knowledge of the author, at the start of this research there was a lack of understanding of the simultaneous impacts of both interactions on the performance of NF membranes, which renders this research novel. To highlight challenges faced by modern membrane plants and identify inorganic and organic pollutants of interest, a study of water quality in Scotland was carried out. Experiments were performed in dead-end stirred cells using two commercial NF membranes, TFC-SR2 and TFC-SR3 provided by Koch, which were extensively characterized. Radiolabeled Endosulfan (ES, 10 μg/L), manganese (5-1,500 mg/L) and Humic Acids (HA, 5-250 mgC/L) were spiked in synthetic water with background electrolyte (1 mM NaHCO3 and 20 mM NaCl). Calcium (Ca, 2.5 mM) was employed in fouling experiments. The influence of the complexation of solutes with HA on solute retention by NF was for the first time quantified for the solute concentrations employed in this study. It was found that manganese retention was influenced by membrane pore size and charge (solute-membrane interactions) and solute speciation (solute-solute interactions). Complexation of manganese and HA (solute-solute interactions) occurred at alkaline conditions but did not enhance manganese retention. At high pH manganese precipitated as solid MnCO3 and these precipitates achieved high retention (99%), even without the presence of HA. ES retention by NF membrane was controlled by size exclusion (solute-membrane interactions). For the tighter TFC-SR3, whose pore size are smaller than the size of ES, ES retention increased in the presence of HA, while for the looser TFC-SR2, whose pores are bigger than ES diameter, ES retention decreased in the presence of HA. For TFC-SR3 increase of ES retention in the presence of HA was due to size exclusion (solute-membrane interactions) and formation of ES-HA complexes (solute-solute interactions). For TFC-SR2 HA-membrane interactions were dominant with respect to solute-solute interactions, increasing membrane molecular weight cut-off (MWCO) and in turn passage of ES. The influence of pressure (5-15 bar) on ES retention in the presence of HA was systematically investigated. Results showed that ES transport through TFC-SR2 and TFC-SR3 was dominated by convection. For the tighter TFC-SR3 lower permeate flux was responsible for the increase of retention with pressure, while for the looser TFC-SR2 higher permeate flux increased concentration polarisation, decreasing retention with pressure. The presence of HA lowered the permeate flux, resulting in a less pronounced variation of retention with pressure for TFC-SR2 and in constant retention for TFC-SR3. The impact of manganese scaling on the performance of NF membranes was investigated at neutral pH. The effects of inorganic precipitates on flux and solute retention by NF have been so far scarcely studied and the impact of inorganic scaling on micropollutant retention by NF is unknown. Findings from this research indicated that manganese deposits did not foul the membranes but on the contrary enhanced their flux and prevented fouling by HA and Ca. The retention of ES, manganese and HA by membranes through which manganese was previously filtered was found to decrease with respect to solute retention by virgin membranes. Manganese filtration was shown to increase membrane MWCO and hydrophilicity. It was proposed that manganese-membrane interactions caused swelling of the membrane active layer by increasing the membrane free volume. The findings of this research indicated the importance of investigating simultaneously the impacts of solute-solute interactions and solute-membrane interactions to understand and explain transport and removal mechanisms of organic and inorganic contaminants by NF