Relationship Between Pb2+ Adsorption and Average Mn Oxidation State in Synthetic Birnessites

Abstract

AbstractThe relationship between vacant Mn structural sites in birnessites and heavy-metal adsorption is a current and important research topic. In this study, two series of birnessites with different average oxidation states (AOS) of Mn were synthesized. One birnessite series was prepared in acidic media (49.6–53.6 wt.% Mn) and the other in alkaline media (50.0–56.2 wt.% Mn). Correlations between the Pb2+ adsorption capacity and the d110 interlayer spacing, the AOS by titration, and the release of Mn2+, H+, and K+ during adsorption of Pb2+ were investigated. The maximum Pb2+ adsorption by the birnessites synthesized in acidic media ranged from 1320 to 2457 mmol/kg with AOS values that ranged from 3.67 to 3.92. For birnessites synthesized in alkaline media, the maximum Pb2+ adsorption ranged from 524 to 1814 mmol/kg, with AOS values between 3.49 and 3.89. Birnessite AOS values and Pb2+ adsorption increased as the Mn content decreased. The maximum Pb2+ adsorption to the synthetic birnessites calculated from a Langmuir fit of the Pb adsorption data was linearly related to AOS. Birnessite AOS was positively correlated to Pb2+ adsorption, but negatively correlated to the d110 spacing. Vacant Mn structural sites in birnessite increased with AOS and resulted in greater Pb2+ adsorption. Birnessite AOS values apparently reflect the quantity of vacant sites which largely account for Pb2+ adsorption. Therefore, the Pb2+ adsorption capacity of birnessite is mostly determined by the Mn site vacancies, from which Mn2+, H+, and K+ released during adsorption were derived.