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Thermodynamic Properties of Uranyl Minerals: Constraints from Calorimetry and Solubility Measurements Tatiana Y

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REVIEW pubs.acs.org/IECR Thermodynamic Properties of Uranyl Minerals: Constraints from Calorimetry and Solubility Measurements Tatiana Y. Shvareva,† Jeremy B. Fein,‡ and Alexandra Navrotsky*,† †University of California, Davis, Peter A. Rock Thermochemistry Laboratory, One Shields Avenue, Davis, California 95616, United States ‡University of Notre Dame, Department of Civil Engineering and Geological Sciences, 156 Fitzpatrick Hall, Notre Dame, Indiana 46556, United States 6+ 2+ ABSTRACT: More than 50 uranyl minerals, phases containing U as the uranyl UO2 cation, and hydroxide, carbonate, phosphate, and silicate anions, H2O, and alkali and alkaline earth cations, occur in nature and as corrosion products of spent nuclear fuel. Despite their importance and the need to understand their thermodynamics to predict uranium solubility, fate, and transport in the environment, reliable thermodynamic data have only been available recently. This paper summarizes recent studies of enthalpies of formation using high temperature oxide melt solution calorimetry and Gibbs free energies from solubility experiments. Standard state thermochemical parameters (at 25 °C and 1 bar) are tabulated and the stability and transformation sequences of these phases are discussed. The enthalpies of formation from oxides are discussed in terms of crystal structure and Lewis acid base interactions. À ’ INTRODUCTION For example, Santalova et al.16 reported enthalpy of formation As nuclear power becomes an increasing source of world of dihydrated (meta)schoepite UO3 3 2H2O from solution calo- rimetry in dilute HF as 1840.6 kJ/mol. Later, Tasker et al.17 energy, the environmental fate of actinides must be unambigu- À ously predicted. Because, in the long term, spent nuclear fuel is not determined the enthalpy of formation of UO3 3 2H2Oas 1825.4 ( 2.1 kJ/mol by calorimetry in more concentrated HF. ThereÀ were stable under moist oxidizing conditions, oxidative dissolution of ff radionuclides in groundwater with consequent formation of uranyl extensive solubility measurements with di erent techniques on 1 3 meta-schoepite that resulted in solubility products varying from minerals is a likely alteration pathway. À With uraninite (UO2) 18 21 being the major component of nuclear fuel, the most crucial 4.68 to 6.23. À Other uranyl oxide hydrates, becquerelite studies are focused on uranyl-based phases in which uranium is Ca[(UO2)3O2(OH)3]2 3 8H2O, clarkeite Na(UO2)O(OH), and 2+ compregnacite Na2[(UO2)3O2(OH)3]2 7H2O, have not been oxidized to the +6 state and is present as the UO2 cation. 3 1,4 6 studied directly by solution calorimetric methods. The solubility Numerous tests of natural analogs À and synthesized samples data strongly depend on the crystallinity of samples and had not (for example 2,7,8) on alteration of UO2 reveal uranyl oxide 22 hydrate minerals and uranyl silicates as major products. Also, been accurately determined. uranyl phosphates and carbonates can be formed under some Thermodynamic properties of uranyl carbonates are also poorly 5 constrained. There are several reliable solubility measurements for groundwater compositions. Mineral stabilities and solubilities 19,20,23 25 determine which solid phases form, and the distribution of rutherfordine UO2CO3 reported, À but the enthalpy of formation, 1689.6 ( 1.8 kJ/mol, accepted by Guillaumont et al.,14 uranium between solid and aqueous phases. Recently, it was also À shown that some uranyl minerals can incorporate Pu and Np into has been calculated from averaged solubility data and an experi- mentally determined standard entropy S° value,25 and not measured their structures, serving as host phases and thereby reducing heavy 26 9 12 directly. Alwan and Williams reported enthalpy and Gibbs free actinide mobility. À Thus, the knowledge of thermodynamic parameters for environmental actinide phases is critical for control, energy of formation for andersonite Na2Ca[(UO2)(CO3)3] 3 5H2O prevention, and remediation of radioactive contamination. but did not report experimental conditions or details of measure- Despite such obvious need for reliable thermodynamic data ments. Data on other uranyl carbonates are very limited and are restricted only to solubility estimates.13,14 for uranyl minerals, previously reported data are incomplete 27 and somewhat contradictory. Grenthe et al.,13 followed by Cordfunke et al. measured the enthalpy of formation of Guillaumont et al.,14 compiled and reviewed the chemical (UO2)3(PO4)2 by solution calorimetry in concentrated H2SO4 as 5491.3 ( 3.5 kJ/mol. With entropy values measured by thermodynamics of actinide materials and only very few values À 28 have been accepted as reliable for hydrated crystalline uranyl Barten, the Gibbs free energy of formation of (UO2)3(PO4)2, oxides, carbonates, phosphates, and silicates. These uranyl minerals are complex, structurally and chemically, with more Special Issue: Alternative Energy Systems: Nuclear Energy than 50 phases known,15 and the synthesis of pure materials and their detailed characterization are not straightforward. Received: February 4, 2011 Due to nonstoichiometry, their hydrous nature and complex Accepted: November 12, 2011 oxidation reduction behavior, the best choice of thermody- Revised: October 11, 2011 À namic measurement methods is a challenge. Published: November 12, 2011 r 2011 American Chemical Society 607 dx.doi.org/10.1021/ie2002582 | Ind. Eng. Chem. Res. 2012, 51, 607–613 Industrial & Engineering Chemistry Research REVIEW Table 1. Thermodynamic Functions for Formation from Oxides and Elements of Uranyl Minerals, under Standard Temperature and Pressure formula per one ΔHf, el, ΔGf, el, ΔSf, el, S°, phase, formula uranyl cation ΔHf, ox, kJ/mol kJ/mol kJ/mol J/mol 3 K J/mol 3 K uranyl oxides hydrates and peroxides metaschoepite UO 2H OUO(H O) 4.4 ( 3.1 1791.0 ( 3.2 1632.2 ( 7.4 532.5 ( 8.1 1356.6 ( 8.1 3 3 2 3 2 2 À À À À β-UO (OH) β-UO (OH) 26.6 ( 2.8 1536.2 ( 2.8 2 2 2 2 À À bequerelite Ca[(UO ) O (OH) ] 8H O Ca (UO )O (OH) (H O) 44.6 ( 2.2 1898.2 ( 2.3 1717.6 ( 4.4 605.8 ( 5.0 1407.8 ( 5.0 2 3 2 3 2 3 2 0.17 2 0.67 2 1.3 À À À À À clarkeite Na(UO )O(OH) Na(UO )O(OH) 150.6 ( 4.9 1724.7 ( 5.1 1635.1 ( 23.4 300.5 ( 23.9 891.0 ( 23.9 2 2 À À À À À Na-compreignacite Na (UO )O (OH)(H O) 53.5 ( 2.4 1822.7 ( 2.4 1674.3 ( 4.1 497.9 ( 5.0 1286.9 ( 5.0 0..34 2 0.67 2 1.2 À À À À À Na2[(UO2)3O2(OH)3]2 3 7H2O curite Pb (UO ) O (OH) •2H O Pb (UO ) O (OH) (H O) 161.5 ( 4.3 1645.4 ( 4.3 3 2 8 8 6 3 2 0.38 2 0.76 2 0.3 À À studtite (UO )O 4H O, oxide + H O (UO )O (H O) 22.3 ( 3.9 2344.7 ( 4.0 2 2 3 2 2 2 2 2 4 À studtite (UO )O 4H O, oxide + H O 75.7 ( 4.1 2 2 3 2 2 2 À uranyl carbonates rutherfordine UO CO UO CO 99.1 ( 4.2 1716.4 ( 4.2 2 3 2 3 À À andersonite Na Ca[(UO )(CO ) ] 5H O Na Ca[(UO )(CO ) ](H O) 710.4 ( 9.1 5593.6 ( 9.1 2 2 3 3 3 2 2 2 3 3 2 5 À À grimselite K NaUO (CO ) H OKNaUO (CO ) (H O) 989.3 ( 14.0 4431.6 ( 15.3 3 2 3 3 3 2 3 2 3 3 2 À À uranyl phosphates UO HPO 3H OUOHPO (H O) 241.0 ( 3.9 3223.2 ( 4.0 3072.3 ( 4.8 1302.3 ( 21.2 2774.1 ( 21.2 2 4 3 2 2 4 2 3 À À À À À (UO ) (PO ) 4H OUO(PO ) (H O) 227.2 ( 2.3 2333.7 ( 4.6 2046.3 ( 12.2 964.3 ( 6.2 1831.6 ( 20.6 2 3 4 2 3 2 2 4 2/3 2 4/3 À À À À À uranyl silicates soddyite (UO ) (SiO ) 2H O (UO )(SiO ) (H O) 117.8 ( 4.3 2022.7 ( 2.5 1826.1 ( 2.1 635.4 ( 10.9 1338.4 ( 10.9 2 2 4 3 2 2 4 1/2 2 À À À À À K-boltwoodite K(UO )(SiO OH) 1.3H O K(UO )(SiO OH)(H O) 238.5 ( 6.0 2768.1 ( 6.5 2758.6 ( 3.5 27.5 ( 7.3 1075.0 ( 7.3 2 3 3 2 2 3 2 À À À À À Na-boltwoodite Na(UO )(SiO OH) H O Na(UO )(SiO OH)(H O) 215.9 ( 6.5 2947.2 ( 4.0 2725.2 ( 2.6 352.5 ( 7.2 1386.6 ( 7.2 2 3 3 2 2 3 2 À À À À À uranophane Ca(UO ) (SiO OH) 5H O Ca (UO ) (SiO OH )(H O) 150.0 ( 4.3 3399.7 ( 4.0 3099.3 ( 5.6 1007.6 ( 12.0 2321.0 ( 12.2 2 2 3 3 2 0.5 2 3 0.5 2 2.5 À À À À À 5116.0 ( 5.5 kJ/mol, was established. However for hydrated data (Table 1) leads to systematics and comparison with predicted À forms that crystallize environmentally, (UO2)3(PO4)2 4H2O values for uranyl oxide hydrates, carbonates, phosphates, and 3 13,14 and (UO2)3(PO4)2 3 6H2O, only solubility was evaluated.
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    Page 1 of 9 1 2 3 4 5 6 7 Actinide separation inspired by self-assembled metal-polyphenolic 8 9 nanocages 10 †, §, †, ‡, § † # † † ⊥ 11 Lei Mei, * Peng Ren, Qun-yan Wu, Yu-bin Ke, Jun-shan Geng, Kang Liu, Xue-qing Xing, 12 Zhi-wei Huang, † Kong-qiu Hu, † Ya-lan Liu, † Li-yong Yuan, † Guang Mo, ⊥ Zhong-hua Wu, ⊥ John K 13 Gibson, ＆ Zhi-fang Chai, †, ¶ Wei-qun Shi †, * 14 15 † Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China 16 ‡ State key Laboratory of Nuclear Resources and Environment, School of Chemistry, School of Nuclear Science and Engineering, 17 East China University of Technology, Nanchang 330013, China. 18 ⊥Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China 19 # Spallation Neutron Source Science Center, Dongguan 523803, China 20 ¶ Engineering Laboratory of Advanced Energy Materials, Ningbo Institute of Industrial Technology, Chinese Academy of Sciences, 21 Ningbo 315201, China 22 ＆ Chemical Sciences Division, Lawrence Berkeley National Laboratory (LBNL), Berkeley, California 94720, USA 23 KEYWORDS: actinides; nano-extraction; uranyl-organic nanocage; self-assembly; pyrogallol[4]arene 24 25 26 ABSTRACT: The separation of actinides has a vital place in nuclear fuel reprocessing, recovery of radionuclides and 27 remediation of environmental contamination. Here we propose a new paradigm of nanocluster-based actinide separation, 28 namely nano-extraction, that can achieve efficient sequestration of uranium in an unprecedented form of giant coordination 29 nanocages using a cone-shaped macrocyclic pyrogallol[4]arene as the extractant. The U24-based hexameric 30 pyrogallol[4]arene nanocages with distinctive [U2PG2] binuclear units (PG = pyrogallol), that rapidly assembled in situ in 31 monophasic solvent, were identified by single-crystal XRD, MALDI-TOF-MS, NMR, and SAXS/SANS.
  • Icp-Oes and Xas Investigation of the Phytoextraction of Lanthanides and Actinides from Aqueous Environmental Solutions 1J.G

    Icp-Oes and Xas Investigation of the Phytoextraction of Lanthanides and Actinides from Aqueous Environmental Solutions 1J.G

    ICP-OES AND XAS INVESTIGATION OF THE PHYTOEXTRACTION OF LANTHANIDES AND ACTINIDES FROM AQUEOUS ENVIRONMENTAL SOLUTIONS 1J.G. Parsons, 2J.L. Gardea-Torresdey, 1K.J. Tiemann, 1J.R. Peratta-Videa, 1E. Gomez, and 1J.H. Gonzalez 1Department of Environmental Science and Engineering, 500 W. University Ave., University of Texas at El Paso, El Paso TX. 79968; Phone: (915)747-5359; Fax: (915)747- 5748. 2Department of Chemistry, 500 W. University Ave, University of Texas at El Paso, El Paso, TX 79968; Phone: (915)747-5359; Fax: (915)747-5748. Abstract Use of nuclear power raises questions about nuclear waste, especially how it can be minimized and stored safely. One alternative is extraction and reprocessing of the uranium from the spent fuel. But the reprocessing of spent fuel is very expensive and requires use of ion exchange resins that cannot be reused. Some biomaterials have been studied for their ability to extract lanthanides and actinides, such as uranyl cation from solution. In this study, the extraction of uranyl nitrate, uranyl acetate, and europium nitrate from aqueous solution using an alfalfa biomaterial was investigated. Major factors affecting the sorption of cations from solution are pH, time, and interfering cations. Studies were performed to investigate each of the above parameters. In addition, capacity studies were performed for comparison purposes with common methods to extract these cations from solutions. To investigate the chemical environment where uranyl and europium cations were bound to the alfalfa biomass, X-ray absorption spectroscopy studies were performed. The X-Ray absorption near-edge structure showed that europium(III) and uranyl cations remained in the same oxidation state when bound to the biomass, with characteristic LIII-edge energies for uranyl and europium(III) of 17.172 keV and 6.981 keV, respectively.