Issue 2, 2024

Effects of carbonate on ferrihydrite transformation in alkaline media

Abstract

Alkaline media widely exist in natural and engineered systems such as semiarid/arid areas, radioactive waste sites, and mine tailings. In these settings, the commonly occurring iron (oxyhydr)oxides differed in their ability to influence the fate of nutrients and contaminants. Due to the substantially increased atmospheric carbon dioxide (CO2) concentration, carbonate stands to increase in these media. However, how increasing carbonate affects the transformation of poorly crystalline iron (oxyhydr)oxides (e.g., two-line ferrihydrite) under alkaline conditions still remains unclear. Here, kinetics of ferrihydrite transformation were evaluated at pH ∼10 as a function of [carbonate] = 0–286 mM using synchrotron-based X-ray and vibrational spectroscopic techniques. The results showed that carbonate slowed down ferrihydrite transformation slightly and suppressed goethite formation, but promoted hematite formation regardless of its concentration. At low carbonate concentration (11.42 mM), the effect of carbonate on product formation was obvious due to the weak inner-sphere complex; however, at high carbonate concentration (80–286 mM), the effect was retarded because of the adsorption equilibrium of carbonate as well as the initial carbonate adsorption followed by desorption. Moreover, carbonate modified the morphology of hematite from rhombic to ellipsoidal to honeycomb and goethite from rod-like to needle-like to spindle-like due to the inner-sphere adsorption–desorption of carbonate and adsorption of hydroxyl ions on reactive sites of iron (oxyhydr)oxides in alkaline media. The results suggest that the concurrently increasing carbonate with enhanced atmospheric CO2 could control the transformation and occurrence of iron (oxyhydr)oxides in natural and engineered environments and have important implications for the biogeochemical cycles of iron and carbon.

Graphical abstract: Effects of carbonate on ferrihydrite transformation in alkaline media

Supplementary files

Article information

Article type
Paper
Submitted
24 Nhl 2023
Accepted
03 Sun 2024
First published
03 Sun 2024

Environ. Sci.: Processes Impacts, 2024,26, 288-297

Effects of carbonate on ferrihydrite transformation in alkaline media

Y. Li, C. Zhang, M. Yang, J. Liu, H. He, Y. Ma and Y. Arai, Environ. Sci.: Processes Impacts, 2024, 26, 288 DOI: 10.1039/D3EM00469D

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