New insights into the cooperative adsorption behavior of Cr(VI) and humic acid in water by powdered activated carbon

Abstract

Chromium and humic acid often co-exist in wastewater and source waters, and the removal of chromium through sorption by activated carbon may be greatly influenced by humic acid. In this study, we systematically evaluated concurrent adsorption of humic acid (HA) and hexavalent chromium (Cr(VI)) in water by powdered activated carbon (PAC) and further, the effect on conversion to trivalent chromium (Cr(III)). Adsorption of both HA and Cr(VI) was significantly enhanced in the dual adsorbate system as compared to treatments with HA or Cr(VI) alone. The removal of HA increased by 16.0% in the presence of 80 mg/L Cr(VI), while the removal of Cr(VI) similarly increased with increasing levels of HA. However, the promotion effect of HA was found to decrease with increasing pH. With HA at 20 mg/L, removal of Cr(VI) increased from 40.09% to 70.12% at pH 3, which was about twice the increase at pH 10. The cooperative adsorption mechanism was explored using scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS), Raman spectroscopy, Fourier transform infrared spectrometer (FTIR), and X-ray photoelectron spectroscopy (XPS). Comprehensive analysis of spectra suggested that the mutual promotion between HA and Cr(VI) adsorption was attributable to the formation of Cr(VI)-HA and Cr(III)-HA complexes that were readily adsorbed on the PAC surfaces. The higher HA concentrations increased the reduction of Cr(VI) to Cr(III), which was likely due to the electron transfer provided by the functional groups such as -CO, -OH and -COOH in both PAC and HA. At pH 3, 99.1% of Cr adsorbed on the PAC surface was in the form of Cr(III). These findings imply that the interactions between Cr(VI) and HA in the process of water treatment by PAC provides additional and synergistic benefits, leading to a greater removal of chromium.

Keywords: Activated carbon; Adsorption; Chromium; Humic acid.