Santana-Barros, KayoMartí-Calatayud, Manuel CésarVelizarov, SvetlozarPérez-Herranz, Valentín2025-10-072025-10-072025-080076-6356PURE: 131469795PURE UUID: 92d5cf54-fcee-43f6-a427-d5e84202cd6eScopus: 105014314977ORCID: /0000-0002-9446-0897/work/193715015http://hdl.handle.net/10362/189115Funding Information: This research was funded by the European Union NextGenerationEU, grant number PRTR-C17.I1, formed part of the ThinkInAzul programme, and was supported by MCIN. This research was also funded by Generalitat Valenciana, grant number GVA-THINKINAZUL/2021/013; principal investigator: V. P\u00E9rez-Herranz, Universitat Polit\u00E8cnica de Val\u00E8ncia, and by national funds from FCT\u2014Funda\u00E7\u00E3o para a Ci\u00EAncia e a Tecnologia, I.P., grant number UID/50006/2023 of the Associate Laboratory for Green Chemistry\u2014LAQV REQUIMTE. Publisher Copyright: © 2025 by the authors. Licensee MDPI, Basel, Switzerland.This study investigates the behavior of phosphate ion transport through two structurally distinct anion-exchange membranes—AMV (homogeneous) and HC-A (heterogeneous)—in an electrodialysis system under both static and stirred conditions at varying pH levels. Chronopotentiometric and current–voltage analyses were used to investigate the influence of pH and hydrodynamics on ion transport. Under underlimiting (ohmic) conditions, the AMV membrane exhibited simultaneous transport of H2PO4− and HPO42− ions at neutral and mildly alkaline pH, while such behavior was not verified at acidic pH and in all cases for the HC-A membrane. Under overlimiting current conditions, AMV favored electroconvection at low pH and exhibited significant water dissociation at high pH, leading to local pH shifts and chemical equilibrium displacement at the membrane–solution interface. In contrast, the HC-A membrane operated predominantly under strong electroconvective regimes, regardless of the pH value, without evidence of water dissociation or equilibrium change phenomena. Stirring significantly impacted the electrochemical responses: it altered the chronopotentiogram profiles through the emergence of intense oscillations in membrane potential drop at overlimiting currents and modified the current–voltage behavior by increasing the limiting current density, reducing electrical resistance, and compressing the plateau region that separates ohmic and overlimiting regimes. Additionally, both membranes showed signs of NH3 formation at the anodic-side interface under pH 7–8, associated with increased electrical resistance. These findings reveal distinct ionic transport characteristics and hydrodynamic sensitivities of the membranes, thus providing valuable insights for optimizing phosphate recovery via electrodialysis.2450249engelectroconvectionelectrodialysismembrane potential dropnutrient recoveryphosphoruswater dissociationChemical Engineering (miscellaneous)Process Chemistry and TechnologyFiltration and Separationjournal article10.3390/membranes15080230https://www.scopus.com/pages/publications/105014314977