From Mineral Salts to Smart Hybrids: Coagulation–Flocculation at the Nexus of Water, Energy, and Resources—A Critical Review

Coagulation–flocculation, historically reliant on simple inorganic salts, has evolved into a technically sophisticated process that is central to the removal of turbidity, suspended solids, organic matter, and an expanding array of micropollutants from complex wastewaters. This review synthesizes six decades of research, charting the transition from classical aluminum and iron salts to high-performance polymeric, biosourced, and hybrid coagulants, and examines their comparative efficiency across multiple performance indicators—turbidity removal (>95%), COD/BOD reduction (up to 90%), and heavy metal abatement (>90%). Emphasis is placed on recent innovations, including magnetic composites, bio–mineral hybrids, and functionalized nanostructures, which integrate multiple mechanisms—charge neutralization, sweep flocculation, polymer bridging, and targeted adsorption—within a single formulation. Beyond performance, the review highlights persistent scientific gaps: incomplete understanding of molecular-scale interactions between coagulants and emerging contaminants such as microplastics, per- and polyfluoroalkyl substances (PFAS), and engineered nanoparticles; limited real-time analysis of flocculation kinetics and floc structural evolution; and the absence of predictive, mechanistically grounded models linking influent chemistry, coagulant properties, and operational parameters. Addressing these knowledge gaps is essential for transitioning from empirical dosing strategies to fully optimized, data-driven control. The integration of advanced coagulation into modular treatment trains, coupled with IoT-enabled sensors, zeta potential monitoring, and AI-based control algorithms, offers the potential to create “Coagulation 4.0” systems—adaptive, efficient, and embedded within circular economy frameworks. In this paradigm, treatment objectives extend beyond regulatory compliance to include resource recovery from coagulation sludge (nutrients, rare metals, construction materials) and substantial reductions in chemical and energy footprints. By uniting advances in material science, process engineering, and real-time control, coagulation–flocculation can retain its central role in water treatment while redefining its contribution to sustainability. In the systems envisioned here, every floc becomes both a vehicle for contaminant removal and a functional carrier in the broader water–energy–resource nexus.