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

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.

Highly-efficient fluoride retention in on-site solidification/stabilization of phosphogypsum: Cemented paste backfill synergizes with poly-aluminum chloride activation.

Phosphogypsum (PG) is a massively generated hazardous by-product in the phosphorus industry. Large-scale, efficient, profitable on-site recycling is an emerging topic for promoting sustainable phosphorus circularity and mitigating potential human exposure. In this work, we integrated a green and low-cost additive polymeric aluminum chloride (PAC) into the binder design of PG immobilization. The overall experimental results illustrate that the incorporation of PAC can efficiently promote the cement hydration reaction, with amorphous phases increased from 25.9 wt% (control group) to 27.5 wt% (with 2 g/L PAC). The macro-investigations indicate that the PAC optimized the porosity and mechanical properties of specimens, facilitating a mechanically stable solidified matrix for extrapolating its field engineering application. The detailed micrographs and elemental mapping demonstrate that apart from co-existing with the hydration products, the PAC agent plays a role in the immobilization of fluoride. Herein, the combined optimization enhanced the fluoride retention capacity due to the precipitated additional hydration products, comparable encapsulation, and high adsorption ability of PAC agents. Therefore our design of PAC-augmented binders can open up a new field of PG on-site solidification/stabilization application that ensures efficient fluoride retention in a technically feasible and financially profitable methodology.

Retention of phosphorus and fluorine in phosphogypsum for cemented paste backfill: Experimental and numerical simulation studies.

The solidification/stabilization of phosphogypsum using cemented paste backfill (OCPB) provides a low-cost and alternative in-situ technique for recycling phosphogypsum stockpiles. But the OCPB is far from obtaining steady states in which the pollutants would redistribute as a response to dynamic environmental conditions. Further, the associated chemical interactions and the mineralogy information of the solubility-controlling phases of contaminants (fluorine and phosphorus) have not been thoroughly studied or fully understood. In this study, a framework coupling the chemical, mineralogical, and morphological analyses is used to determine the fluoride and phosphate retention mechanisms of immobilized OCPB. Then the pH-dependent leaching tests and numerical simulation is applied as a useful tool to identify the minerals controlling stabilized OCPB leaching behavior. The overall findings proved that aluminate-rich calcium silicate hydrates play an essential role in fluoride and phosphate retention. Both experimental and simulational acid neutralization and leaching curves indicate that the cementitious matrix works as a strong buffering material ensuring high pH conditions that are necessary for fluorine and phosphorus retention. Although discrepancies were observed in absolute fluorine and phosphorus leaching values at highly acidic conditions, the simulations are able to describe highly amphoteric leaching behavior. The simulation suggests that the aluminum species and calcium phosphates governed the solubility of fluorine and phosphorus, respectively. The results of this work would have implications for predicting the leaching behavior of OCPB in detrimental and multiple environments.