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Title: Determining Individual Mineral Contributions To U(VI) Adsorption In A Contaminated Aquifer Sediment: A Fluorescence Spectroscopy Study

The adsorption and speciation of U(VI) was investigated on contaminated, fine grained sediment materials from the Hanford 300 area (SPP1 GWF) in simulated groundwater using cryogenic laser-induced U(VI) fluorescence spectroscopy combined with chemometric analysis. A series of reference minerals (montmorillonite, illite, Michigan chlorite, North Carolina chlorite, California clinochlore, quartz and synthetic 6-line ferrihydrite) was used for comparison that represents the mineralogical constituents of SPP1 GWF. Surface area-normalized Kd values were measured at U(VI) concentrations of 5x10-7 mol L-1 and 5x10-6 mol L-1, respectively, that displayed the following affinity series: 6-line-ferrihydrite > North Carolina chlorite ≈ California clinochlore > Michigan chlorite ≈ quartz > montmorillonite ≈ illite ≈ SPP1 GWF. Both time-resolved spectra and asynchronous two-dimensional (2D) correlation analysis of SPP1 GWF at different delay times indicated that two major adsorbed U(VI) species were present in the sediment that resembled U(VI) adsorbed on quartz and phyllosilicates. Simulations of the normalized fluorescence spectra confirmed that the speciation of SPP1 GWF was best represented by a linear combination of U(VI) adsorbed on quartz (90%) and phyllosilicates (10%). However, the fluorescence quantum yield for U(VI) adsorbed on phyllosilicates was lower than quartz and, consequently, its fractional contribution to speciation may be underestimated. Spectral comparisonmore » with literature data suggested that U(VI) exists primarily as inner-sphere U(VI) complexes with surface silanol groups on quartz while U(VI) on phyllosilicates was consistent with the formation of surface U(VI) tricarbonate complexes.« less
Authors:
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Publication Date:
OSTI Identifier:
1012515
Report Number(s):
PNNL-SA-75951
Journal ID: ISSN 0016-7037; 34494; KP1702030; TRN: US201110%%129
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Geochimica et Cosmochimica Acta; Journal Volume: 75; Journal Issue: 10
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; ADSORPTION; AFFINITY; AQUIFERS; CHLORINE COMPOUNDS; CRYOGENICS; FLUORESCENCE; FLUORESCENCE SPECTROSCOPY; ILLITE; MONTMORILLONITE; OXYGEN COMPOUNDS; QUARTZ; SEDIMENTS; SPECTRA Environmental Molecular Sciences Laboratory