Uranium incorporation into amorphous silica

Environ Sci Technol. 2014;48(15):8636-44. doi: 10.1021/es501064m. Epub 2014 Jul 11.

Abstract

High concentrations of uranium are commonly observed in naturally occurring amorphous silica (including opal) deposits, suggesting that incorporation of U into amorphous silica may represent a natural attenuation mechanism and promising strategy for U remediation. However, the stability of uranium in opaline silicates, determined in part by the binding mechanism for U, is an important factor in its long-term fate. U may bind directly to the opaline silicate matrix, or to materials such as iron (hydr)oxides that are subsequently occluded within the opal. Here, we examine the coordination environment of U within opaline silica to elucidate incorporation mechanisms. Precipitates (with and without ferrihydrite inclusions) were synthesized from U-bearing sodium metasilicate solutions, buffered at pH ∼ 5.6. Natural and synthetic solids were analyzed with X-ray absorption spectroscopy and a suite of other techniques. In synthetic amorphous silica, U was coordinated by silicate in a double corner-sharing coordination geometry (Si at ∼ 3.8-3.9 Å) and a small amount of uranyl and silicate in a bidentate, mononuclear (edge-sharing) coordination (Si at ∼ 3.1-3.2 Å, U at ∼ 3.8-3.9 Å). In iron-bearing synthetic solids, U was adsorbed to iron (hydr)oxide, but the coordination environment also contained silicate in both edge-sharing and corner-sharing coordination. Uranium local coordination in synthetic solids is similar to that of natural U-bearing opals that retain U for millions of years. The stability and extent of U incorporation into opaline and amorphous silica represents a long-term repository for U that may provide an alternative strategy for remediation of U contamination.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Adsorption
  • Ferric Compounds
  • Iron / chemistry
  • Oxides / chemistry
  • Silicates
  • Silicon Dioxide / chemistry*
  • Uranium / chemistry*
  • X-Ray Absorption Spectroscopy

Substances

  • Ferric Compounds
  • Oxides
  • Silicates
  • opoka
  • sodium metasilicate
  • Uranium
  • Silicon Dioxide
  • ferric oxyhydroxide
  • Iron