Arsenic Oxidation and Removal from Water via Core–Shell MnO2@La(OH)3 Nanocomposite Adsorption

Arsenic (As(III)), more toxic and with less affinity than arsenate (As(V)), is hard to remove from the aqueous phase due to the lack of efficient adsorbents. In this study, a core–shell structured MnO2@La(OH)3 nanocomposite was synthesized via a facile two-step precipitation method. Its removal performance and mechanisms for As(V) and As(III) were investigated through batch adsorption experiments and a series of analysis methods including the transformation kinetics of arsenic species in As(III) removal, FTIR, XRD and XPS. Solution pH could significantly influence the removal efficiencies of arsenic. The adsorption process of As(V) occurred rapidly in the first 5 h and then gradually decreased, whereas the As(III) removal rate was relatively slower. The maximum adsorption capacities of As(V) and As(III) were up to 138.9 and 139.9 mg/g at pH 4.0, respectively. For As(V) removal, the inner-sphere complexes of lanthanum arsenate were formed through the ligand exchange reactions and coprecipitation. The oxidation of As(III) to the less toxic As(V) by δ-MnO2 and subsequently the synergistic adsorption process by the lanthanum hydroxide on the MnO2@La(OH)3 nanocomposite to form lanthanum arsenate were the dominant mechanisms of As(III) removal. XPS analysis indicated that approximately 20.6% of Mn in the nanocomposite after As(III) removal were Mn(II). Furthermore, a small amount of Mn(II) and La(III) were released into solution during the process of As(III) removal. These results confirm its efficient performance in the arsenic-containing water treatment, such as As(III)-contaminated groundwater used for irrigation and As(V)-contaminated industrial wastewater.