# The pH-Driven Distribution and Migration of Phosphate, Fluoride and Metals/Metalloids in Phosphogypsum Stacks: Insights from Southwest China

## TL;DR

This study examines how pH affects the movement of pollutants like phosphate, fluoride, and metals in phosphogypsum stacks in Southwest China, offering insights for pollution control.

## Contribution

The paper introduces a pH-controlled conceptual model explaining the source-to-sink behavior of pollutants in phosphogypsum stacks.

## Key findings

- Under acidic conditions, pollutants migrate vertically and enrich in deeper layers of phosphogypsum stacks.
- A membrane–soil composite covering is most effective at inhibiting surface diffusion of TP and F−.
- A pH increase leads to calcium-mediated precipitation, fixing pollutants in solid phases.

## Abstract

The long-term accumulation of phosphogypsum (PG) stacks has caused combined pollution of total phosphorus (TP), fluoride (F−), metals and metalloids (MMs), posing a severe threat to regional ecological security. To clarify the migration characteristics of pollutants in PG stacks, water leaching experiments and environmental risk assessment were conducted in 21 typical PG stacks in Southwest China. The spatial differentiation and vertical migration characteristics of pollutants under various coverage measures (high-density polyethylene (HDPE) film covering, soil covering, a composite of film–soil covering, and open-air storage) at different pH conditions were systematically analyzed. Results indicated that under open-air stockpiling conditions, the surface accumulation of TP and F− was the most significant among all covering measures, corresponding to the highest environmental risk. In contrast, the membrane–soil composite covering exhibited the optimal inhibitory effect on the surface diffusion of TP and F−, but was less effective for metal and metalloid enrichment. Under acidic conditions (pH < 6), the vertical migration capacity of TP, F−, and MMs (Cu, Cd, Cr, Pb, and Zn) increased, leading to enrichment in the deep layers of the stack. With the increase in pH, the calcium-mediated precipitation–adsorption effect created a “geochemical barrier”, facilitating the solid-phase fixation of pollutants. A significant positive correlation among pollutants indicates synergistic release and fixation behaviors. In addition, a pH-controlled P-F-MM source-to-sink conceptual model was established, outlining the dissolution, precipitation, adsorption, fixation and re-enrichment pathway from fresh stock to leachate. This work provides insights for optimizing cover designs and pollution control strategies.