Sulfur-modified rice husk biochar: A green method for the remediation of mercury contaminated soil

Mercury (Hg) contamination of surface soils has increased by ~86Giga grams due to anthropogenic activities. There is an urgent need to find new, effective and preferably 'green' remediation technologies to protect human health and the environment. Sulfur-modification of sorbents can greatly enhance Hg sorption capacity - by forming low solubility HgS (cinnabar). However, S-modified sorbents are not considered suitable for soil remediation due to the economic cost and secondary environmental impacts of sorbents such as granulated activated carbon (GAC), and the toxicity of S-modifiers such as thiol compounds. It was previously found that if biochar is used as an alternative to GAC then the overall environmental impact can be significantly reduced. However, due to a lack of experimental evidence, the practicality of S-modified biochar remains uncertain. The present study was undertaken to provide a proof-of-concept for the 'green' remediation of Hg contaminated soils with rice husk biochar modified with non-toxic elemental S. It was found that the S modification process increased the biochar S content from 0.2% to 13.04% via surface deposition or volume pore filling. This increased the biochar's Hg²⁺ adsorptive capacity (Q_max) by ~73%, to 67.11mg/g. To assess the performance of S-modified rice husk biochar for soil remediation it was applied to a high 1000mg/kg Hg²⁺ contaminated soil. Treatment dosages of 1%, 2% and 5% (dry wt.) were found to reduce freely available Hg in TCLP (toxicity characterization leaching procedure) leachates by 95.4%, 97.4% and 99.3%, respectively, compared to untreated soil. In comparison, unmodified rice husk biochar reduced Hg concentrations by 94.9%, 94.9% and 95.2% when applied at the same treatment dosage rates, respectively. This study has revealed that S-modified rice husk biochar has potential to stabilize Hg as a 'green' method for the remediation of contaminated soils.