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User:Jsoto3/Bergenite

Bergenite
General
CategoryUranylPhosphate
Formula
(repeating unit)		Ca2Ba4[(UO2)3O2(PO4)2]3(H2O)16
Identification
Colorwhite to colorless
Crystal habitacicular
Mohs scale hardness2-3
Streakyellow white
Diaphaneitysemitransparent
Density4.1
Other characteristicsradioactive

Bergenite is a rare uranyl phosphate of the more specific phosphuranylite group. The phosphuranylite-type sheet in bergenite is a new isomer of the group, with the uranyl phosphate tetrahedra varying in an up-up-down, same-same-opposite (uuduudSSOSSO) orientation. All bergenite samples have been found in old mine dump sites. Uranyl minerals are a large constituent of uranium deposits [1].

The phosphuranylites are one of the two major groups of the uranyl series, and are the most extensive of the uranium minerals. Uranyl phosphates include 45 different minerals, at least 16 of which belong to the phosphuranylite type topology, including dumontite, vanmeersscheite, upalite, and the most characteristic, phosphuranylite. As explained by Frost et al., the uranyl phosphates display diverse chemical and structural features, which often exhibit the geochemical conditions present during formation [2]. Bergenite is the barium-phosphuranylite member space group P2/c [3].


Structure and Composition

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The chemical composition given by Locock and Burns was determined by qualitative electron microprobe examination on a JEOL JXA-8600 Superprobe at a voltage of 15kV and current of 0.9 nA. The ideal composition of Bergenite is Ca2Ba4[(UO2)3O2(PO4)2]3(H2O)16 [4]. Calcium and barium substitute for each other, with the precise filling of the Ba(1) site 96.8% Ba and 3.2% Ca, and the Ba (2) site containing 87.9% Ba and 12.2% Ca, with Frost (2007) assuming no vacancies and only Ca and Ba substitution. These results give the idealized formula of Ba4/3Ca2/3. A microprobe analysis gave oxide percentages of P2O5 10.96%. UO3 62.54%, BaO13.96%, Cao 2.44%, and HrO 10.06% [5].

Uranyl minerals in general are very complicated, with two thirds of the 173 species’ structure unknown. Bergenite, like other phosphuranylite minerals, consists of uranyl phosphate sheets. Bergenite’s uranyl phosphate sheet is a new geometrical isomer of the group which differs in the orientation of the phosphate tetrahedra, and contains H2O along with calcium and barium cations in the interlayer. The structure was determined by direct methods. As proposed by Frost et al., Uranyl pentagonal dipyramids share edges with each other, and are then connected to uranyl hexagonal dipyramids on both sides. The hexagonal dipyramids then link with phosphate tetrahedra to form sheets that connect to adjacent pentagonal chains. The phosphate tetrahedra holding the uranyl chains together display an up-up-down-up-up-down, same-same-opposite orientation (uuduudSSO) [6].

Two formula units of the unit cell contain three UO2O5 pentagonal dipyramids, two UO2O5 hexagonal dipyramids, and three PO4 tetrahedra. The Ba(1) site is in 11-fold coordination with oxygen atoms from UO2 polyhedra, and Ba(2) site is in ten-fold coordination with UO2 ions and H2O [7]. Also included in the structure of bergenite are hydrogen-bonded water molecules, with the network displaying very weak to strong H-bonds. The inconsistency of the bonds originally caused confusion as to whether it was H2O or OH within the mineral, but further observations of Raman spectra proved it to be water. It is the placement of the water molecules that determines the stability of the structure [8]. The positions of the hydrogens in the unit cell remain undiscovered.

Physical properties

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Bergenite forms as a dark yellow crust with well-developed, small thin needle-like crystals [9]. An original description of bergenite is the orthorhombic symmetry and a density greater than 4.1 g/cubic cm [10]. There is not much information available in the articles on its appearance or physical properties.

Geologic occurrence and Location

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Phosphuranylites usually precipitate from solution containing uranium, phosphorus, potassium, and calcium. Most phosphuranylite, and all bergenite specimens, are generated from the waste of various mines. This is a low temperature and often low pressure process. Bergenite occurs in fractures of quartz, muscovite, and plagioclase, especially along cleavage [11].

Bergenite was first discovered at a now deserted mine dump of the SDAG Wismut 254 Shaft in Mechelgrun, Vogtland Mining Disrict, Saxon, Germany near the city of Bergen in Lower Saxony. Bergen has a population of around 17,000 people, and is the home to a large NATO base. It is also where the Bergen-Belson concentration camp was located, and site of the Sieben Steinhäuser dolmens that date back to the Stone Age. Other samples have also been found in uranium deposits in Black Forrest, Federal Republic of Germany, and in graphitic uranium ore in South Korea.

Special Characteristics

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Uranyl phosphates are looked at for environmental concerns, for they are related to hydration-oxidation of used nuclear fuel [12]. As Burns suggests, uranyl minerals affect the concentration of uranium in groundwater and systems all around [13] . All of the samples discovered so far have been at old uranium containing mine dumps.

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References

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  1. ^ Burns, P. and Locock, A. (2003) The crystal structure of bergenite, a new geometrical isomer of the phosphuranylite group. Canadian Mineralogist, 41, 91-101.
  2. ^ Frost, R., Cejka, J., Ayoko, G., Weier, M. (2007) A Raman spectroscopic study of the uranyl phosphate mineral bergenite. Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy, 66, 979-984.
  3. ^ Burns, P. and Locock, A. (2003) The crystal structure of bergenite, a new geometrical isomer of the phosphuranylite group. Canadian Mineralogist, 41, 91-101.
  4. ^ Burns, P. and Locock, A. (2003) The crystal structure of bergenite, a new geometrical isomer of the phosphuranylite group. Canadian Mineralogist, 41, 91-101.
  5. ^ Cabri, J., Fleischer, M., and Pabst, A. (1981) New Mineral Names. American Mineralogist, 66, 1099-1103.
  6. ^ Frost, R., Cejka, J., Ayoko, G., Weier, M. (2007) A Raman spectroscopic study of the uranyl phosphate mineral bergenite. Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy, 66, 979-984.
  7. ^ Burns, P. and Locock, A. (2003) The crystal structure of bergenite, a new geometrical isomer of the phosphuranylite group. Canadian Mineralogist, 41, 91-101.
  8. ^ Frost, R., Cejka, J., Ayoko, G., Weier, M. (2007) A Raman spectroscopic study of the uranyl phosphate mineral bergenite. Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy, 66, 979-984.
  9. ^ Korzeb, S., Foord, E., and Lichte F. (1997) The chemical evolution and paragenesis of uranium minerals from the Ruggles and Palermo granitic pegmatites, New Hampshire. Canadian Mineralogist, 35, 135-144.
  10. ^ Burns, P. and Locock, A. (2003) The crystal structure of bergenite, a new geometrical isomer of the phosphuranylite group. Canadian Mineralogist, 41, 91-101.
  11. ^ Korzeb, S., Foord, E., and Lichte F. (1997) The chemical evolution and paragenesis of uranium minerals from the Ruggles and Palermo granitic pegmatites, New Hampshire. Canadian Mineralogist, 35, 135-144.
  12. ^ Frost, R., Cejka, J., Ayoko, G., Weier, M. (2007) A Raman spectroscopic study of the uranyl phosphate mineral bergenite. Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy, 66, 979-984.
  13. ^ Burns, P. (2000) A new uranyl phosphate chain in the structure of parsonsite. American Mineralogist, 85, 801-805.
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