Sanjay Kay Sagar, Sabrina Sorlini, Satesh Kumar Devrajani, Athanasia K. Tolkou
Coagulation-based technologies are increasingly recognized as key for controlling fluoride and hexavalent chromium in urban water and wastewater. Combined geogenic and industrial sources often drive chronic exposure and create an underrecognized public health burden. This review synthesizes current knowledge on the occurrence, speciation, and toxicology of F− and Cr(VI) in urban systems, links regulatory targets to health outcomes, and critically examines conventional, advanced, and electrochemical coagulation processes for their removal under realistic water-quality conditions. Mechanistic sections describe how aluminum-, iron-, magnesium- and zirconium-based coagulants, including pre-polymerized and composite formulations (e.g., IPC-type coagulants, PSiFAC-Mg, ZrCl4), remove fluoride via Al–F complexation, Al–F–OH co-precipitation, ion exchange, and sweep flocculation, while Cr(VI) control relies on Fe(II)-mediated reduction to Cr(III), followed by adsorption and co-precipitation with metal hydroxides. The review assesses how water chemistry and operating conditions affect single- and multi-contaminant removal, highlighting competition among fluoride, Cr(VI), nutrients, and other oxyanions. Performance data from bench-, pilot-, and selected full-scale studies show that optimized coagulation and electrocoagulation can substantially reduce fluoride and Cr(VI) (to drinking-water-relevant levels) in diverse urban waters, but also reveal persistent issues of sludge generation and stability, residual metals, process robustness, and cost. The review identifies priorities, including long-term urban-scale assessments, low-toxicity green coagulants, life-cycle and health impact assessments, and real-time coagulation control for fluoride and Cr(VI).