Elucidating Phosphate and Cadmium Cosorption Mechanisms on Mineral Surfaces with Direct Spectroscopic and Modeling
Wantong Zhao1, Yun Xu1, Liting Gu1
1Key Laboratory of Arable Land Conservation (Middle and Lower Reaches of Yangtze River), Ministry of Agriculture and Rural Affairs, State Environmental Protection Key Laboratory of Soil Health and Green Remediation, Hubei Key Laboratory of Soil Environment and Pollution Remediation, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, China.
Abstract:
The simultaneous sorption of cations and anions at the mineral-water interface can substantially alter their individual sorption characteristics; however, this phenomenon lacks a mechanistic understanding. Our study provides direct spectroscopic and modeling evidence of the molecular cosorption mechanisms of the cadmium ion (Cd2+) and phosphate (P) on goethite and layered manganese (Mn) oxide of birnessite, through in situ attenuated total reflection Fourier-transform infrared (ATR-FTIR), P K-edge X-ray absorption near-edge structure (XANES) spectroscopy, and surface complexation modeling. Phosphate synergistically cosorbed with Cd on goethite predominantly through P-bridged ternary complexes (≡Fe-P-Cd) and electrostatic interactions at wide pH conditions. Likewise, P and Cd exhibited synergistic cosorption on birnessite by forming P-bridged ternary complexes (≡Mn-P-Cd) and weak competitive sorption at the layer edge sites. As pH and Cd loading increased, the surface P species transitioned from a binary complex to a ternary complex and/or Cd3(PO4)2 precipitate for both goethite and birnessite. Compared to that in solution at pH 8, the formation of Cd3(PO4)2 was inhibited by the presence of goethite and birnessite, ascribed to the specific adsorption of P and Cd, more pronounced in birnessite due to the stronger sorption of Cd at its vacant sites. The discovered cosorption mechanisms of P and Cd have important implications for understanding and predicting their mobility and availability in Cd-contaminated settings.
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