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Title: Influence of Oxalate on Ni Fate during Fe(II)-Catalyzed Recrystallization of Hematite and Goethite

Abstract

During biogeochemical iron cycling at redox interfaces, dissolved Fe(II) induces the recrystallization of Fe(III) oxides. Oxalate and other organic acids promote dissolution of these minerals and may also induce recrystallization. These processes may redistribute trace metals among the mineral bulk, mineral surface, and aqueous solution. However, the impact of interactions among organic acids, dissolved Fe(II), and iron oxide minerals on trace metal fate in such systems is unclear. As such, the present study explores the effect of oxalate on Ni release from and incorporation into hematite and goethite in the absence and presence of Fe(II). When Ni is initially structurally incorporated into the iron oxides, both oxalate and dissolved Fe(II) promote the release of Ni to aqueous solution. When both species are present, their effects on Ni release are synergistic at pH 7 but inhibitory at pH 4, indicating that cooperative and competitive interactions vary with pH. In contrast, oxalate suppresses Ni incorporation into goethite and hematite during Fe(II)-induced recrystallization, decreasing the proportion of Ni substituting in a mineral structure by up to 36%. These observations suggest that at redox interfaces oxalate largely enhances trace metal mobility. In such settings, oxalate, and likely other organic acids, may thus enhance micronutrientmore » availability and inhibit contaminant sequestration.« less

Authors:
 [1]; ORCiD logo [1]
  1. Washington Univ., St. Louis, MO (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC)
OSTI Identifier:
1459013
Grant/Contract Number:  
EAR-1056480; DGE-1745038; AC02-06CH11357; ECS-0335765
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Environmental Science and Technology
Additional Journal Information:
Journal Volume: 52; Journal Issue: 12; Journal ID: ISSN 0013-936X
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Oxides; Anions; Metals; Hematite; Minerals

Citation Formats

Flynn, Elaine D., and Catalano, Jeffrey G. Influence of Oxalate on Ni Fate during Fe(II)-Catalyzed Recrystallization of Hematite and Goethite. United States: N. p., 2018. Web. doi:10.1021/acs.est.8b00641.
Flynn, Elaine D., & Catalano, Jeffrey G. Influence of Oxalate on Ni Fate during Fe(II)-Catalyzed Recrystallization of Hematite and Goethite. United States. doi:10.1021/acs.est.8b00641.
Flynn, Elaine D., and Catalano, Jeffrey G. Mon . "Influence of Oxalate on Ni Fate during Fe(II)-Catalyzed Recrystallization of Hematite and Goethite". United States. doi:10.1021/acs.est.8b00641. https://www.osti.gov/servlets/purl/1459013.
@article{osti_1459013,
title = {Influence of Oxalate on Ni Fate during Fe(II)-Catalyzed Recrystallization of Hematite and Goethite},
author = {Flynn, Elaine D. and Catalano, Jeffrey G.},
abstractNote = {During biogeochemical iron cycling at redox interfaces, dissolved Fe(II) induces the recrystallization of Fe(III) oxides. Oxalate and other organic acids promote dissolution of these minerals and may also induce recrystallization. These processes may redistribute trace metals among the mineral bulk, mineral surface, and aqueous solution. However, the impact of interactions among organic acids, dissolved Fe(II), and iron oxide minerals on trace metal fate in such systems is unclear. As such, the present study explores the effect of oxalate on Ni release from and incorporation into hematite and goethite in the absence and presence of Fe(II). When Ni is initially structurally incorporated into the iron oxides, both oxalate and dissolved Fe(II) promote the release of Ni to aqueous solution. When both species are present, their effects on Ni release are synergistic at pH 7 but inhibitory at pH 4, indicating that cooperative and competitive interactions vary with pH. In contrast, oxalate suppresses Ni incorporation into goethite and hematite during Fe(II)-induced recrystallization, decreasing the proportion of Ni substituting in a mineral structure by up to 36%. These observations suggest that at redox interfaces oxalate largely enhances trace metal mobility. In such settings, oxalate, and likely other organic acids, may thus enhance micronutrient availability and inhibit contaminant sequestration.},
doi = {10.1021/acs.est.8b00641},
journal = {Environmental Science and Technology},
issn = {0013-936X},
number = 12,
volume = 52,
place = {United States},
year = {2018},
month = {5}
}

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