Release characteristics of heavy metals from electrolytic manganese residue under varying environmental factors

High levels of manganese (Mn) and other heavy metals from electrolytic manganese residue (EMR) stockpiled would be released into the environment under natural conditions. A batch-leaching test was carried out to investigate the release characteristics of heavy metals from EMR with different storage times under simulated environmental conditions such as acid rain with different pH (3.0, 4.5, 5.6, and 7.0) at contact times of 1, 2, 4, 6, and 12 h; liquid to solid ratio (L/S) (5:1, 10:1, 20:1, and 30:1); and temperature (15, 25, 35, and 45 °C). The results showed that low pH (3.0 and 4.5) and high temperature (35 and 45 °C) could significantly promote heavy metal leaching from EMRs and increasing the L/S ratio above 20:1 mL/g significantly decreased heavy metal leachate concentrations due to dilution effect. Cr, Mn, and Pb concentrations in leachate increased almost continuously throughout the leaching process, while Zn decreased slightly at the 12th hour. Meanwhile, heavy metal concentrations in EMR1 (fresh EMR) were higher than in EMR2 (out stockpiled for more than 3 months). The concentrations of Mn, Pb, and Zn in leachates from EMRs at pH 3.0 and 4.5 leaching far exceeded the allowable maximum discharge concentrations for pollutants of the integrated wastewater discharge standard in China (GB8978-1996) by 57.5-59.0, 1.3-4.3, and 1.1-1.8 and 53.5-56.0, 3.04-7.25, and 1.0-1.91 times, respectively. Additionally, the Mn concentrations from both EMR leachates at pH 7.0 were above the national safe emission threshold. The morphological structure of EMRs changed after leaching, and XRD analysis showed the disappearance of MnO₂, SiO₂, FeS₂, and CaSO₄. The XPS revealed that Cr, Mn, Pb, and Zn existed as Cr³⁺, MnO, PbSO₄, and ZnSiO₃, respectively, after leaching. The study concluded that Mn, Pb, and Zn from EMRS leached by acid rain might pose a high potential environmental risk. Therefore, developing appropriate disposal techniques for EMR is necessary to prevent heavy metal pollution.