Elucidating Phosphate and Cadmium Cosorption Mechanisms on Mineral Surfaces with Direct Spectroscopic and Modeling Evidence

Zhao, Wantong; Xu, Yun; Gu, Liting; Zhu, Mengqiang; Yang, Peng; Gu, Chunhao; Liu, Zhe; Feng, Xionghan; Tan, Wenfeng; Huang, Qiaoyun; Wang, Xiaoming

doi:10.1021/acs.est.4c08847

Title: Elucidating Phosphate and Cadmium Cosorption Mechanisms on Mineral Surfaces with Direct Spectroscopic and Modeling Evidence

Journal Article · 31 October 2024 · Environmental Science and Technology

DOI: https://doi.org/10.1021/acs.est.4c08847 · OSTI ID:2478333

Zhao, Wantong ^[1]; Xu, Yun ^[1]; Gu, Liting ^[1];

^[2];

^[3]; Gu, Chunhao ^[4]; Liu, Zhe ^[1];

^[1]; Tan, Wenfeng ^[1];

^[1];

^[1]

Huazhong Agricultural University, Wuhan (China)
Univ. of Maryland, College Park, MD (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Univ. of Delaware, Newark, DE (United States)

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. Finally, 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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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2478333

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 45 Vol. 58; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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