Bentonite binding with mercury(II) ion through promotion of reactive oxygen species derived from manure-based dissolved organic matter

Abstract

This study reports the mercury binding by bentonite clay influenced by cattle manure-derived dissolved organic matter (DOM). The DOM (as total organic carbon; TOC) was reacted with bentonite at 5.2 pH to monitor the subsequent uptake of Hg²⁺ for 5 days. The binding kinetics of Hg²⁺ to the resulting composite was studied (metal = 350 µM/L, pH 5.2). Bentonite-DOM bound much more Hg²⁺ than original bentonite and accredited to the establishment of further binding sites. On the other hand, the presence of DOM was found to decrease the Hg²⁺ binding on the clay surface, specifically, the percent decrease of metal with increasing DOM concentration. Post to binding of DOM with bentonite resulted in increased particle size diameter (~ 33.37- ~ 87.67 nm) by inducing the mineral modification of the pore size distribution, thus increasing the binding sites. The XPS and FTIR results confirm the pronounced physico-chemical features of bentonite-DOM more than that of bentonite. Hydroxyl and oxygen vacancies on the surface were found actively involved in Hg²⁺ uptake by bentonite-DOM composite. Furthermore, DOM increased the content of Hg²⁺ binding by ~ 10% (pseudo-second-order q_e = 90.9-100.0) through boosting up Fe³⁺ reduction with the DOM. The quenching experiment revealed that more oxygen functionalities were generated in bentonite-DOM, where hydroxyl was found to be dominant specie for Hg²⁺ binding. The findings of this study can be used as theoretical reference for mineral metal interaction under inhibitory or facilitating role of DOM, risk assessment, management, and mobilization/immobilization of mercury in organic matter-containing environment.

Keywords: Bentonite binding; Manure DOM; Metal complex; Oxygen functional groups.