Immobilization of heavy metals in tannery sludge by the formation of tobermorite in subcritical water treatment with rice husk silica

Abstract

Tannery sludge, heavy metals (HMs) enriched hazardous solid waste, is produced extensively in many regions of the world. Even though the sludge is hazardous, it can be considered a material resource, if organic matter and HMs in the sludge can be stabilized to minimize its negative environmental impacts. This research aimed to evaluate the efficacy of using subcritical water (SCW) treatment for tannery sludge treatment through immobilization and thus reduction of HMs to mitigate their potential environmental risk and toxicity. HMs in the tannery sludge were analyzed by inductively coupled plasma mass spectrometry (ICP-MS) and the average concentration of HMs (mg kg⁻¹) was found in the following decreasing order of Cr (12 950) > Fe (1265) > Cu (76) > Mn (44) > Zn (36) > Pb (14) with very high Cr concentration. The result of toxicity characteristics leaching procedure and sequential extraction procedure tests revealed that the raw tannery sludge leachate contained 11.24 mg L⁻¹ Cr, which classified the raw tannery sludge into a very high-risk category. After SCW treatment, the concentration of Cr in leachate was reduced to 1.6 mg L⁻¹ indicating risk reduction to a low-risk category. The eco-toxicity levels of other HMs also decreased considerably after SCW treatment. X-ray diffractometry (XRD) and scanning electron microscopy (SEM) analysis were employed to identify the effective immobilizing substances formed in the SCW treatment process. The favorable formation of immobilizing orthorhombic tobermorite (Ca₅Si₆O₁₆(OH)₂·4H₂O) at 240 °C in the SCW treatment process was confirmed by XRD and SEM analysis. The results confirmed that the formation of 11 Å tobermorite is capable of strongly immobilizing HMs in the SCW treatment process. Further, both orthorhombic 11 Å tobermorite and 9 Å tobermorite were successfully synthesized by SCW treatment on a mixture of tannery sludge including rice husk silica and Ca(OH)₂ with water under rather mild conditions. Hence, it can be concluded that SCW treatment of tannery sludge with supplementary silica from rice husk can effectively immobilize the HMs and significantly reduce their environmental risk through tobermorite formation.