• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.7 no.4
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• pp.219-227
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• 2009

The effect of organic acids on the adsorption of U(VI) onto oxide surfaces ($TiO_2)$(anatase), $SiO_2$(amorphous) and $Al_2O_3$(amorphous)) has been investigated. Two different organic acids, salicylic and picolinic acids, were used. Changes of adsorption ratio of U(VI), which depend on the existence of organic acids in a sample, were measured as a function of pH. Quantities of adsorbed organic acids, which depend on the existence of U(VI) in a sample, were also measured as a function of pH. It is confirmed that the soluble complex formation of U(VI) with organic acids can deteriorate the adsorption of U(VI) onto $TiO_2$ surface. It is noteworthy that salicylic acid does not affect the adsorption of U(VI) onto $SiO_2$ surface, however, picolinic acid enhances the adsorption of U(VI) onto $SiO_2$ surface. The latter effect can be understood by considering the formation of a ternary surface complex on $SiO_2$ surface, which was confirmed by the co-adsorption of picolinic acid with U(VI) and the change in a fluorescence spectra of U(VI) on surface, In the case of $Al_2O_3$, organic acids themselves were largely adsorbed onto a surface without deteriorating the adsorption of U(VI). This would support the possibility of a ternary surface complex formation on the $Al_2O_3$ surface, and an additional spectroscopic study is required.

• Economic and Environmental Geology
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• v.45 no.2
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• pp.205-215
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• 2012

Metal ions, toxic or potentially toxic to biota and human beings, can be immobilized by sorption onto the mineral surfaces in soils and sediments. This article briefly explains theories regarding the chemical properties of mineral surfaces to sorb metal ions and processes of extended X-ray absorption fine structure (EXAFS) analysis for sorption study, and reviews atomic-scale findings on metal sorption on mineral surfaces. The theoretical understanding on the chemistry of mineral surfaces and metal sorption is fundamental to the proper analysis of the atomic-scale spectroscopy to determine the sorption phases. Atomic-scale findings on metal sorption phases discussed here include co-precipitation, ternary complexation, aging effects, and desorption possibilities, as well as outer-sphere complexation, inner-sphere complexation, and surface precipitation.

• Economic and Environmental Geology
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• v.42 no.5
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• pp.495-500
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• 2009

Actinide sorption to the geological materials can reduce the mobility and bioavailability of radionuclides released to the environment through the development of nuclear weapons and nuclear energy. Under circumneutral pH conditions, actinide sorption can be enhanced by phosphate anions sorbed on oxide mineral surfaces as indicated by the sorption of trivalent lanthanide ions ($Ln^{3+}$), the chemical analog for trivalent actinide ions ($Ac^{3+}$). In this paper, we examined a ternary sorption system of trivalent europium ions ($Eu^{3+}$) sorbed onto boehmite (${\gamma}$-AlOOH) surfaces pre-sorbed with phosphate anions (${PO_4}^{3-}$), using extended X-ray absorption fine structure (EXAFS) spectroscopy. In the Eu-$PO_4$-boehmite ternary sorption system, $EuPO_4$ surface precipitates were formed as implicated by Eu $L_{III}$-edge EXAFS spectroscopy. Phosphorus K-edge EXAFS fingerprinting indicated a bidentate mononuclear surface complex formation of phosphate sorbed on boehmite surfaces as well as $EuPO_4$ surface precipitate formation.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.17 no.2
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• pp.127-137
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• 2019

Zr electrorefining is demonstrated herein using Zirlo tubes in a chloride-fluoride mixed molten salt in the presence of $AlF_3$. Cyclic voltammetry reveals a monotonic shift in the onset of metal reduction kinetics towards positive potential and an increase in intensity of the additional peaks associated with Zr-Al alloy formation with increasing $AlF_3$ concentration. Unlike the galvanostatic deposition mode, a radial plate-type Zr growth is evident at the top surface of the salt during Zr electrorefining at a constant potential of -1.2 V. The diameter of the plate-type Zr deposit gradually increases with increasing $AlF_3$ concentration. Scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDX) and X-ray photoelectron spectroscopy (XPS) analyses for the plate-type Zr deposit show that trace amount of Al is incorporated as Zr-Al alloys with different chemical compositions between the top and bottom surface of the deposit. Addition of $AlF_3$ is effective in lowering the residual salt content in the deposit and in improving the current efficiency for Zr recovery.

• Economic and Environmental Geology
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• v.38 no.1
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• pp.23-31
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• 2005

This study was performed to investigate the effect of humic acid on the adsorption of arsenic onto hematite and its binding mechanism through the chemical speciation modeling in the binary system and the adsorption modeling in the ternary system. The complexation modeling of arsenic and humic acid was suitable for the binding model with the basis of the electrostatic repulsion and the effect of bridging metal. In comparison with the experimental adsorption data in the ternary system, the competitive adsorption model from the binary intrinsic equilibrium constants was consistent with the amount of arsenic adsorption. However, the additive rule showed the deviation of model in the opposite way of cationic heavy metals, because the reduced organic complexation of arsenic and the enhanced oxyanionic competition diminished the adsorption of arsenic. In terms of the reaction mechanism, the organic complex of arsenic, neutral As(III) and oxyanionic As(V) species were transported and adsorbed competitively to the hematite surface forming the inner-sphere complex in the presence of humic acid.