Fluoride removal using membrane capacitive deionization: The role of pH-dependent dissolved inorganic carbon

[Display omitted] •pH-dependent DIC species affect F- removal in CDI and MCDI.•Integrating AEMs enhances SAC for F- and DIC but reduces F- selectivity.•Higher applied voltages improve SAC but cause severe Faradaic reactions.•DIC species and pH changes interrelate during CDI and MCDI processes.•DIC species impact pH variations at different applied voltages. Defluorination technology is crucial for ensuring the safety of accessible water. The application of capacitive deionization (CDI) technology faces challenges due to competitive adsorption of fluoride ions within complex natural fluoride-rich brackish water matrices, which often contain high levels of dissolved inorganic carbon (DIC) species (mainly HCO3– and CO32–). These DIC species are pH-dependent, playing a significant role in the selective removal of fluoride by the CDI process. Thus, there is a knowledge gap in understanding the effects of membranes in membrane capacitive deionization (MCDI) on fluoride removal. In this study, we examined the key operating parameters in CDI and MCDI, including applied constant voltages and different types of anion-exchange membranes (AEMs), on the desalination performance in F- and dissolved inorganic carbon water matrices. The application of AEMs significantly improve the salt adsorption capacity (SAC) for both F- and DIC species, and reduced energy consumption. However, it simultaneously results in a notable decrease in F- selectivity as membranes control mass transfer. Higher applied voltages enhance the SAC performance for F- and DIC species, but also induce more severe Faradaic reactions, leading to increased energy consumption and lower energy efficiency. Additionally, ion species and pH changes during CDI and MCDI processes are interrelated, indicating that stability tests of CDI electrodes in batch mode are not reliable when using the same testing solution repeatedly. The diverse valence states of ions in the solution impact pH variations under different voltages in the CDI/MCDI process. These findings provide valuable insights into the development of water purification and desalination technology, particularly for the application and further advancement of selective fluoride removal by the CDI process.