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Title: Oxyanion Surface Complexes Control the Kinetics and Pathway of Ferrihydrite Transformation to Goethite and Hematite
The rate and pathway of ferrihydrite (Fh) transformation at oxic conditions to more stable products is controlled largely by temperature, pH, and the presence of other ions in the system such as nitrate (NO3–), sulfate (SO42–), and arsenate (AsO43–). Although the mechanism of Fh transformation and oxyanion complexation have been separately studied, the effect of surface complex type and strength on the rate and pathway remains only partly understood. We have developed a kinetic model that describes the effects of surface complex type and strength on Fh transformation to goethite (Gt) and hematite (Hm). Two sets of oxyanion-adsorbed Fh samples were prepared, nonbuffered and buffered, aged at 70 ± 1.5 °C, and then characterized using synchrotron X-ray scattering methods and wet chemical analysis. Kinetic modeling showed a significant decrease in the rate of Fh transformation for oxyanion surface complexes dominated by strong inner-sphere (SO42– and AsO43–) versus weak outer-sphere (NO3–) bonding and the control. The results also showed that the Fh transformation pathway is influenced by the type of surface complex such that with increasing strength of bonding, a smaller fraction of Gt forms compared with Hm. These findings are important for understanding and predicting the role of Fh in controlling the transport and fate of metal and metalloid oxyanions in natural and applied systems.  more » « less
Award ID(s):
1652237
PAR ID:
10467706
Author(s) / Creator(s):
; ; ; ;
Publisher / Repository:
ACS Environmental Science and Technology
Date Published:
Journal Name:
Environmental Science & Technology
Volume:
56
Issue:
22
ISSN:
0013-936X
Page Range / eLocation ID:
15672 to 15684
Subject(s) / Keyword(s):
ferrihydrite oxyanion transformation arsenate sulfate nitrate oriented attachment dissolution/recrystallization
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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