Strategic optimization of phase-selective thermochemically amended terra-firma originating from excavation-squander for geogenic fluoride adsorption: a combined experimental and in silico approach.

An inimitable adsorbent "FI-TM-BWCC," emanated from meta-phase-selective thermochemical modulation of excavation-squander (mine waste)-derived terra-firma (blackish white china clay, i.e., BWCC), is explored in the present work for fluoride (F) adsorption purpose. FI-TM-BWCC portrayed an excellent adsorption efficiency (95% removal capacity and Q: 99 mg/g, at initial adsorbate dose: 10 mg/L, pH: 7±0.5, adsorbent dosage: ~600 mg, exposure time: 60 min). At identical experimental conditions, the F scavenging phenomenon was superior than two analogous adsorbents: (i) biopolymer chitosan and glutaraldehyde cross-linked BWCC (CG@BWCC, wherein F removal efficiency: 74%) and (ii) meta-phase-selective thermally moduled BWCC (TM-BWCC, removal efficiency: 75%). BWCC predominantly comprises kaolinite and a trace amount of anatase along with prime elemental compositions: 41.71% AlO, 49.80 % SiO, 4.25% FeO, and 3.93% TiO, as revealed by PXRD and XRF analyses. The thermochemical modulation pathway significantly escalated the BET surface area of BWCC (~11.92 m/g, avg. pore radius: 23.64 Å, i.e., mesoporous in nature) to FI-TM-BWCC (216.95 m/g, avg. pore radius: 31.41 Å). The fluoride-adsorbed F•••FI-TM-BWCC species revealed a reduced surface area of 21.5 m/g, which was explained in the light of ion exchange pathway on FI-TM-BWCC's non-uniform surface (surface roughness/S of 1597 nm, reduced to 1179 nm after F uptake). The spontaneous F•••FI-TM-BWCC interaction (ΔG = -6.25 kJ) occurred following chemisorption-controlled ion exchange (CCIE) pathway as appearance of a F1s band at 685.5 eV was rationalized for Si-F bond formation; corroborating pseudo second-order (PSO) kinetics and resembling Freundlich isotherm. The usefulness of FI-TM-BWCC was diversified through field validation with natural groundwater specimens and proposition of a gravity-fed defluoridation unit. The flow rate was documented to be ~11 liters per hour (LPH) by implementing viscous turbulence fluent model. The experimental findings certainly followed the premise conventions of sustainability metrics upholding socio-economic equipoise.