Study of the Reactions Controlling the Mobility of Uranium in Ground and Surface Water Systems in Contact with Apatite
The objective of this project was to define the mechanisms, equilibria, kinetics, and extent of sorption of aqueous uranium onto hydroxyapatite (Ca{sub 5}(PO{sub 4}){sub 3}(OH)) for a range of pH, ionic strength, aqueous uranium concentration, dissolved carbon/air CO{sub 2}, and mineral surface area. We conducted chemical modeling, batch and flow-through experiments, chemical analysis, x-ray absorption and diffraction measurement, and electron microscopy. Our motivation was the need to immobilize U in water and soil to prevent it's entry into water supplies and ultimately, biological systems. Applying hydroxyapatite to in-situ treatment of uranium-bearing ground water could be an effective, low cost technology. We found that hydroxyapatite quickly, effectively, and reversibly sorbed uranium at a high capacity by inner-sphere complexation over a wide range of conditions. Our results indicate that at aqueous uranium concentrations below 10-20 ppb: (1) equilibrium sorption of uranium to hydroxyapatite occurs in hours, regardless of pH; (2) in ambient and CO{sub 2}-free atmospheres, over 98% of initial uranium is sorbed to hydroxyapatite, (3) in waters in equilibrium with higher air CO{sub 2} concentrations, sorption removed over 97% of aqueous uranium, except above pH 9, where aqueous uranium concentrations were reduced by less than 40%, and (4) at near-neutral pH, bicarbonate alkalinities in excess of 500 slightly retarded sorption of uranium to hydroxyapatite, relative to lower alkalinities. Uranium sorption and precipitation are reversible and are not appreciably affected by ionic strength. The reversibility of these reactions requires that in situ treatment be carefully monitored to avoid breakthrough and de-sorption of uranium unto ground water. At typical surface conditions, sorption is the only mode of uranium sequestration below 20-50 ppb U - above this range, precipitation of uranium phosphate minerals begins to dominate sequestration processes. We verified that one m{sup 2} of hydroxyapatite can sorb over 7.53 X 10{sup -6} moles or 1.8 mg of uranium in agreement with calculations based on phosphate and calcium oxide sites on the unit cell. Our work is significant because small masses of hydroxyapatite can sorb appreciable masses of uranium quickly over a wide range of chemistries. Preliminary work with ground water containing 260 ppb of uranium and cow bone char indicates that its sorptive capacity is appreciable less than pure hydroxyapatite. Pure crystalline hydroxyapatite sequestered 2.9 mg of uranium per m{sup 2} as opposed to 0.083 mg of uranium sequestered per m{sup 2} of cow bone char, or 27% versus 3.5% by surface area, respectively. Extended x-ray adsorption fine structure (EXAFS) spectroscopy defined mono- and bidentate sorption of uranium to phosphate and calcium oxide groups on the hydroxyapatite surface. The EXAFS data indicate that up to several thousand parts U per million parts hydroxyapatite, surface complexation, and not precipitation, is the predominant process. Above this uranium: hydroxyapatite mass ratio, precipitation of meta-autunite (H{sub 2}(UO{sub 2})2(PO{sub 4}){sub 2} x 10H{sub 2}0) dominates the sequestration process.
- Research Organization:
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- W-7405-ENG-48
- OSTI ID:
- 15014139
- Report Number(s):
- UCRL-TR-203891; TRN: US0802061
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
54 ENVIRONMENTAL SCIENCES
12 MANAGEMENT OF RADIOACTIVE WASTES AND NON-RACIOACTIVE WASTER FROM NUCLEAR FACILITIES
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
APATITES
CALCIUM OXIDES
CHEMICAL ANALYSIS
ELECTRON MICROSCOPY
FINE STRUCTURE
GROUND WATER
PRECIPITATION
SORPTION
SURFACE AREA
SURFACE WATERS
URANIUM
URANIUM PHOSPHATES
WATER