An in situ XAS study of ferric iron hydrolysis and precipitation in the presence of perchlorate, nitrate, chloride and sulfate

被引：32

作者：

Collins, Richard N. ^{[1
]}

Rosso, Kevin M. ^{[2
]}

Rose, Andrew L. ^{[3
]}

Glover, Chris J. ^{[4
]}

Waite, T. David ^{[1
]}

机构：

[1] UNSW Australia, Sch Civil & Environm Engn, UNSW Water Res Ctr, Sydney, NSW 2052, Australia

[2] Pacific NW Natl Lab, Environm Mol Sci Lab, Richland, WA 99336 USA

[3] So Cross Univ, So Cross Geosci, POB 157, Lismore, NSW 2480, Australia

[4] Australian Synchrotron Co Ltd, Xray Absorpt Spect Beamline, 800 Blackburn Rd, Clayton, Vic 3168, Australia

来源：

GEOCHIMICA ET COSMOCHIMICA ACTA | 2016年 / 177卷

基金：

澳大利亚研究理事会;

关键词：

RAY-ABSORPTION-SPECTROSCOPY; REVISED STRUCTURAL MODEL; PAIR DISTRIBUTION FUNCTION; DENSITY-FUNCTIONAL THEORY; ACID-MINE DRAINAGE; FE K-EDGE; AQUEOUS-SOLUTIONS; MU-OXO; FE(II)-CATALYZED TRANSFORMATION; IRON(III) HYDROLYSIS;

D O I：

10.1016/j.gca.2016.01.021

中图分类号：

P3 [地球物理学]; P59 [地球化学];

学科分类号：

0708 ; 070902 ;

摘要：

Using a novel combination of in situ potentiometric experiments and quick-scanning XAS we present Fe K-edge XAS spectra (to k = 12 angstrom(-1)) during Fe-III hydrolysis and precipitation in 0.33M Fe(ClO4)(3), Fe(NO3)(3), FeCl3 and Fe-2(SO4)(3) solutions up to pH 4.8. Edge-sharing Fe-III polymers appeared almost immediately upon hydrolysis with strong evidence for a mu-oxo dimer species forming in the Fe(ClO4)(3), Fe(NO3)(3) and FeCl3 solutions. The effects of SO4 on hydrolysis and polymerization pathways included inhibition of both the formation of the mu-oxo dimer and double corner Fe-III bonding, ultimately resulting in the precipitation of schwertmannite. As such, under these experimental conditions, double corner Fe-III bonding appears to be critical to the formation of ferrihydrite. The spectral trends indicated that the decomposition/transformation of the dimer was sudden and broadly coincident with shortening average Fe-O bond distances, increased Fe neighbors at similar to 3.43 angstrom and a pre-edge energy transformation suggestive of decreased ligand field strength as well as increasing proportions of tetrahedral Fe-III. This result suggests that the incorporation of tetrahedral Fe-III into ferrihydrite occurs only at the latter stages of extended polymerization. (C) 2016 Elsevier Ltd. All rights reserved.

引用

页码：150 / 169

页数：20

共 96 条

[91] DFT-based thermodynamics of fenton reactions rejects the 'pure' aquacomplex models [J].

Zakharov, I. I. ;

Kudjukov, K. Yu. ;

Bondar, V. V. ;

Tyupalo, N. F. ;

Minaev, B. F. .

COMPUTATIONAL AND THEORETICAL CHEMISTRY, 2011, 964 (1-3) :94-99

[92] STRUCTURE OF A NANOPHASE IRON-OXIDE CATALYST [J].

ZHAO, J ;

HUGGINS, FE ;

FENG, Z ;

LU, FL ;

SHAH, N ;

HUFFMAN, GP .

JOURNAL OF CATALYSIS, 1993, 143 (02) :499-509

[93]

ZHAO JM, 1994, CLAY CLAY MINER, V42, P737, DOI 10.1346/CCMN.1994.0420610

[94] Precipitation pathways for ferrihydrite formation in acidic solutions [J].

Zhu, Mengqiang ;

Frandsen, Cathrine ;

Wallace, Adam F. ;

Legg, Benjamin ;

Khalid, Syed ;

Zhang, Hengzhong ;

Morup, Steen ;

Banfield, Jillian F. ;

Waychunas, Glenn A. .

GEOCHIMICA ET COSMOCHIMICA ACTA, 2016, 172 :247-264

[95] In Situ Structural Characterization of Ferric Iron Dimers in Aqueous Solutions: Identification of μ-Oxo Species [J].

Zhu, Mengqiang ;

Puls, Brendan W. ;

Frandsen, Cathrine ;

Kubicki, James D. ;

Zhang, Hengzhong ;

Waychunas, Glenn A. .

INORGANIC CHEMISTRY, 2013, 52 (12) :6788-6797

[96] Early Stage Formation of Iron Oxyhydroxides during Neutralization of Simulated Acid Mine Drainage Solutions [J].

Zhu, Mengqiang ;

Legg, Benjamin ;

Zhang, Hengzhong ;

Gilbert, Benjamin ;

Ren, Yang ;

Banfield, Jillian F. ;

Waychunas, Glenn A. .

ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2012, 46 (15) :8140-8147

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