4.4 Article

Ferrihydrite Transformation Impacted by Adsorption and Structural Incorporation of Rare Earth Elements

Journal

ACS EARTH AND SPACE CHEMISTRY
Volume 5, Issue 10, Pages 2768-2777

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsearthspacechem.1c00159

Keywords

rare earth element; ferrihydrite; hematite; goethite; transformation; adsorption; substitution

Funding

  1. National Key R&D Program of China [2017YFC0602306]
  2. Key Research Program of the Institute of Geology & Geophysics, CAS [IGGCAS-201901]
  3. National Natural Science Foundation of China [41921003, 41773113]
  4. Science Research Program of Guangzhou, China [201804020037]
  5. Science and Technology Planning of Guangdong Province, China [2017B030314175, 2020B1212060055, 2020B1515020015, 2017GC010578]
  6. Guangdong Major Project of Basic and Applied Basic Research [2019B030302013]
  7. U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-06CH11357]

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The study found that heavy REEs tended to partition more in aged ferrihydrite during the transformation process, and the presence of REEs slowed down the transformation of ferrihydrite to goethite at pH 5. The structural substitution of heavy REEs such as Yb and Lu was identified as a critical factor in suppressing ferrihydrite transformation.
Understanding the association of rare earth elements (REEs) with iron (oxyhydr)oxides is of great interest in the recovery of REEs from regolith and weathered soils in the world. The objective of this study was to understand the effects of 1 mg L-1 REEs on the ferrihydrite transformation process. Ferrihydrite was synthesized at pH 5 and 7 in the presence of REEs, and the transformation products were characterized using X-ray diffraction, Fe Kedge X-ray absorption spectroscopy, and transmission electron microscopy. During the phase transformation process after 60-120 days, the retention of REEs varied with the REE atomic number. In general, heavy REEs preferably partitioned in aged (>= 90 days) ferrihydrite more than light REEs, especially at pH 5. At pH 5, the transformation of ferrihydrite to goethite was retarded by similar to 12% when REEs were present. The average structural substitution of REEs was as high as similar to 550 mg kg(-1), and the substitution of heavy REEs such as Yb and Lu was a critical factor to suppress the ferrihydrite transformation. At pH 7, the formation of hematite was retarded by similar to 10%, and the structural incorporation of REEs was more important than adsorbed REEs during the first 30 days. There was no REE-specific retention in aged iron (oxyhydr)oxides at pH 7. The results of this study may explain the association of REEs with iron (oxyhydr)oxides, especially heavy REEs in mildly acidic regolith and weathered soils. This study advanced our understanding of the aqueous geochemical behavior of REEs in iron (oxyhydr)oxide-rich supergene environments.

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