Fluorides immobilization through calcium aluminate cement-based backfill: Accessing the detailed leaching characterization under torrential rainfall

Abstract

Urbanization and economic development have increased the demand for fertilizers to sustain food crop yields. Huge amounts of by-products, especially phosphogypsum (PG), are generated during the wet processing of rock phosphate to produce fertilizers. Chronic exposure to fluoride in phosphogypsum in groundwater as a result of the weathering of fluoride-containing waste poses a significant health risk to millions of people. We propose a method for using calcium aluminate cement (CAC) to remediate high fluoride contents in solid waste. Column leaching tests under harsh rainfall conditions confirmed the efficient fluoride immobilization capacity of a CAC binder. Although the fluoride concentrations in leachates during the first 1–2 days (1.25 mg/L) slightly exceeded the threshold of 1.00 mg/L, the concentrations over 3–28 days (ranging from 0.98 to 0.83 mg/L) consistently remained well within the acceptable range. Furthermore, our characterization and geochemical modeling revealed the fluoride retention mechanisms of CAC-stabilized PG under laboratory-simulated conditions of torrential rainfall. During leaching, physical encapsulation prevents fluoride from contacting leachate. However, an unfavorable pH value can cause the release of fluoride from the cement matrix, which is subsequently captured by aluminate hydrate through adsorption or co-precipitation. We quantified the carbon footprint of CAC for immobilizing 1 mg of fluoride in PG, obtaining a remarkably low value of 4.4 kg of CO2, in contrast to the emissions associated with the use of ordinary Portland cement (OPC). The findings suggest a unique opportunity for extensive PG remediation. This opportunity extends the horizons of achieving zero-waste emissions in the phosphorus industry and has practical significance in the context of reducing carbon emissions.