Degradation of polyamide nanofiltration membranes by free chlorine and halide ions: Kinetics, mechanisms, and implications

The kinetics of polyamide membrane degradation by free chlorine and halide ions (Br- and Cl-) were innovatively evaluated based on physicochemical properties and filtration performance, using water/solute permeability coefficient in addition to bromide incorporation as important indicators. The reaction rate constants for the reduced water and H3BO3 permeability coefficient were 1-2 orders of magnitude higher at 0-1 h than 1-10 h. N-bromination and bromination-promoted hydrolysis are dominant degradation mechanisms at 0-1 h (reflected by the breakage of hydrogen bond, the increased Ca binding content, and the increased charge density), and ring-bromination further occurs at 1-10 h (reflected by the disappearance or weakening of aromatic amide band and the nearly constant hydrogen bond). The more reactive but less abundant brominating agents (Br2O, BrOCl, BrCl, and Br-2) played significant roles in membrane degradation, contradicting the conventional belief that HOBr is the only reactive species. BrCl at pH 4.0 and BrOCl and Br2O at pH 7.0 made significantly higher contributions to membrane degradation than HOBr (>76 % vs. <13 %). The increased contribution of BrCl and Br-2 with the increased [Cl-] and [Br-](ex) (the excess bromide, defined as [Br-](o) - [HOCl](o) when [Br-](o) > [HOCl](o)), respectively, was responsible for the greater reduction of water permeability coefficient. The innovative and simple approach developed in this study provides important insights to evaluate and predict membrane degradation.