Structural Characterization of Poorly-Crystalline Scorodite, Iron (III)-arsenate Co-precipitates and Uranium Millneutralized Raffinate Solids using X-ray Absorption Fine Structure Spectroscopy

Journal Article · Thu Jan 01 04:00:00 EST 2009 · Geochimica et Cosmochimica Acta

DOI:https://doi.org/10.1016/j.gca.2009.02.019· OSTI ID:980517

Chen, N; Jiang, D; Cutler, J; Kotzer, T; Jia, Y; Demopoulos, G; Rowson, J

X-ray absorption fine structure (XAFS) is used to characterize the mineralogy of the iron(III)-arsenate(V) precipitates produced during the raffinate (aqueous effluent) neutralization process at the McClean Lake uranium mill in northern Saskatchewan, Canada. To facilitate the structural characterization of the precipitated solids derived from the neutralized raffinate, a set of reference compounds were synthesized and analyzed. The reference compounds include crystalline scorodite, poorly-crystalline scorodite, iron(III)-arsenate co-precipitates obtained under different pH conditions, and arsenate-adsorbed on goethite. The poorly-crystalline scorodite (prepared at pH 4 with Fe/As = 1) has similar As local structure as that of crystalline scorodite. Both As and Fe K-edge XAFS of poorly-crystalline scorodite yield consistent results on As-Fe (or Fe-As) shell. From As K-edge analysis the As-Fe shell has an inter-atomic distance of 3.33 {+-} 0.02 A and coordination number of 3.2; while from Fe K-edge analysis the Fe-As distance and coordination number are 3.31 {+-} 0.02 A and 3.8, respectively. These are in contrast with the typical arsenate adsorption on bidentate binuclear sites on goethite surfaces, where the As-Fe distance is 3.26 {+-} 0.03 A and coordination number is close to 2. A similar local structure identified in the poorly-crystalline scorodite is also found in co-precipitation solids (Fe(III)/As(V) = 3) when precipitated at the same pH (pH = 4): As-Fe distance 3.30 {+-} 0.03 A and coordination number 3.9; while at pH = 8 the co-precipitate has As-Fe distance of 3.27 {+-} 0.03 A and coordination number about 2, resembling more closely the adsorption case. The As local structure in the two neutralized raffinate solid series (precipitated at pH values up to 7) closely resembles that in the poorly-crystalline scorodite. All of the raffinate solids have the same As-Fe inter-atomic distance as that in the poorly-crystalline scorodite, and a systematic decrease in the As-Fe coordination is observed when pH is progressively increased; the basic poorly-crystalline scorodite structural feature remains in the raffinate solid up to pH 7.

• Research Organization: Brookhaven National Laboratory (BNL) National Synchrotron Light Source
• Sponsoring Organization: Doe - Office Of Science
• DOE Contract Number: AC02-98CH10886
• OSTI ID: 980517
• Report Number(s): BNL--93435-2010-JA
• Journal Information: Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Vol. 73; ISSN GCACAK; ISSN 0016-7037
• Country of Publication: United States
• Language: English

Related Subjects

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS
ABSORPTION
ADSORPTION
ARSENATES
CANADA
COORDINATION NUMBER
DISTANCE
FEED MATERIALS PLANTS
FINE STRUCTURE
GOETHITE
IRON
LAKES
MINERALOGY
PH VALUE
SASKATCHEWAN
SHELLS
SOLIDS
SPECTROSCOPY
SURFACES
URANIUM
YIELDS
national synchrotron light source