Effective removal of Hg(II) and MeHg from aqueous environment by ball milling aided thiol-modification of biochars: Effect of different pyrolysis temperatures.

In order to synthesize biochar with the enhanced adsorption of inorganic mercury (Hg(II)) and organic mercury (Methylmercury, MeHg), biochars pyrolyzed at different pyrolysis temperatures (300, 500, and 700 °C) were ball milled with 3-trimethoxysilylpropanethiol (3-MPTS). Characterization results showed that 3-MPTS acted as an activator which further enlarged pores in biochars and ball-milling increased surface area of biochars. During ball milling, oxygen-containing functional groups increased which facilitated the loading of -SH group. The maximum adsorption capacities for Hg(II) adsorption in ball mill sulfhydryl modified biochars of 300, 500, and 700 °C were 401.8, 379.6 and 270.6 mg/g, respectively; simultaneously, the maximum adsorption capacity of MeHg was 108.16, 85.27 and 39.14 mg/g, respectively, which showed preferential increasing of 5.54 times on MeHg compared to the non-thiol modified biochar at low pyrolysis temperature of 300 °C. Results of kinetic adsorption experiments suggested that sorption data fitted well with Pseudo-second-order kinetic model, which proved that the mainly rate-limiting adsorption step was surface diffusion. Langmuir isotherm model fitting result showed that ligand exchange, surface complexation, surface adsorption and electrostatic attraction are dominant removal mechanisms. The 3-MPTS content and ball milling time are crucial during ball milling, and 2% 3-MPTS and 30 h of ball milling were found to be the most suitable conditions for both Hg(II) and MeHg adsorption. The result suggests that ball milling aided thiol-modification has great potential in synthesis of -SH modified biochar with prioritized MeHg adsorption.