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The new mineral feynmanite (IMA2017-035), Na(UO2)(SO4)(OH)·3.5H2O, was found in both the Blue Lizard and Markey mines, San Juan County, Utah, USA, where it occurs as a secondary phase on pyrite-rich asphaltum in association with chinleite-(Y), gypsum, goethite, natrojarosite, natrozippeite, plášilite, shumwayite (Blue Lizard) and wetherillite (Markey). The mineral is pale greenish yellow with white streak and fluoresces bright greenish white under a 405 nm laser. Crystals are transparent with vitreous luster. It is brittle, with Mohs hardness of ~2, irregular fracture and one perfect cleavage on {010}. The calculated density is 3.324 g cm-3. Crystals are thin needles or blades, flattened on {010} and elongate on [100], exhibiting the forms {010}, {001}, {101} and {10-1}, up to about 0.1 mm in length. Feynmanite is optically biaxial (–), α = 1.534(2), β = 1.561(2), γ = 1.571(2) (white light); 2Vmeas. = 62(2)°; no dispersion; optical orientation: X = b, Y ≈ a, Z ≈ c; and pleochroism: X colourless, Y very pale green yellow, Z pale green yellow (X < Y < Z). Electron microprobe analyses (WDS mode) provided (Na0.84Fe0.01)(U1.01O2)(S1.01O4)(OH)·3.5H2O. The five strongest X-ray powder diffraction lines are [dobs Å(I)(hkl)]: 8.37(100)(010), 6.37(33)(-101,101), 5.07(27)(-111,111), 4.053(46)(004,021) and 3.578(34)(120). Feynmanite is monoclinic, P2/n, a = 6.927(3), b = 8.355(4), c = 16.210(7) Å, β = 90.543(4)°, V = 938.1(7) Å3 and Z = 4. The structure of feynmanite (R1 = 0.0371 for 1879 Io > 2I) contains edge-sharing pairs of pentagonal bipyramids that are linked by sharing corners with SO4 groups, yielding a [(UO2)2(SO4)2(OH)2]2– sheet based on the phosphuranylite anion topology. The sheet is topologically identical to those in deliensite, johannite and plášilite. The dehydration of feynmanite to plášilite results in interlayer collapse involving geometric reconfiguration of the sheets and the ordering of Na.
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... It occurs on gypsum-coated asphaltum in association with andersonite, calcite, gypsum and natromarkeyite (Kampf et al., 2020a). Other new minerals recently described from the Markey mine are feynmanite (Kampf et al., 2019a), leószilárdite (Olds et al., 2017), magnesioleydetite (Kampf et al., 2019b), markeyite (Kampf et al., 2018), meyrowitzite (Kampf et al., 2019c), pseudomarkeyite (Kampf et al., 2020a), straβmannite (Kampf et al., 2019b) and uroxite (Kampf et al., 2020b). ...
Article
The new mineral paramarkeyite (IMA2020–024), Ca2(UO2)(CO3)3·5H2O, was found in the Markey mine, San Juan County, Utah, USA, where it occurs as a secondary phase on gypsum-coated asphaltum in association with andersonite, calcite, gypsum and natromarkeyite. Paramarkeyite crystals are transparent, pale green-yellow, striated tablets, up to 0.11 mm across. The mineral has white streak and vitreous lustre. It exhibits moderate bluish white fluorescence (405 nm laser). It is very brittle with irregular, curved fracture and a Mohs hardness of 2½. It has an excellent {100} cleavage and probably two good cleavages on {010} and {001}. The measured density is 2.91(2) g cm–3. Optically, the mineral is biaxial (–) with α = 1.550(2), β = 1.556(2), γ = 1.558(2) (white light); 2V = 60(2)°; strong r > v dispersion; orientation: Y = b; nonpleochroic. The Raman spectrum exhibits bands consistent with UO22+, CO32– and O–H. Electron microprobe analysis provided the empirical formula (Ca1.83Na0.20Sr0.03)∑2.05(UO2)(CO3)3·5H2O (+0.07 H). Paramarkeyite is monoclinic, P21/n, a = 17.9507(7), b = 18.1030(8), c = 18.3688(13) Å, β = 108.029(8)°, V = 5676.1(6) Å3 and Z = 16. The structure of paramarkeyite (R1 = 0.0647 for 6657 I > 2I) contains uranyl tricarbonate clusters that are linked by Ca–O polyhedra to form heteropolyhedral layers. The structure of paramarkeyite is very similar to those of markeyite, natromarkeyite and pseudomarkeyite.
... The Green Lizard mine is also a type locality for greenlizardite (Kampf et al., 2018b), shumwayite (Kampf et al., 2017b) and meitnerite (Kampf et al., 2018c). The Markey mine is also a type locality for feynmanite (Kampf et al., 2019), leószilárdite (Olds et al., 2017) and markeyite (Kampf et al., 2018a). ...
Article
Magnesioleydetite and straßmannite, two new uranyl sulfates minerals with sheet structures from Red Canyon, Utah - Anthony R. Kampf, Jakub Plášil, Anatoly V. Kasatkin, Barbara P. Nash, Joe Marty
Article
The new minerals natromarkeyite, Na 2 Ca 8 (UO 2) 4 (CO 3) 13 (H 2 O) 24 ⋅3H 2 O (IMA2018-152) and pseudomarkeyite, Ca 8 (UO 2) 4 (CO 3) 12 (H 2 O) 18 ⋅3H 2 O (IMA2018-114) were found in the Markey mine, San Juan County, Utah, USA, where they occur as secondary phases on asphaltum. Natromarkeyite properties are: untwinned blades and tablets to 0.2 mm, pale yellow green colour; transparent; white streak; bright bluish white fluorescence (405 nm laser); vitreous to pearly lustre; brittle; Mohs hardness 1½ to 2; irregular fracture; three cleavages ({001} perfect, {100} and {010} good); density = 2.70(2) g cm-3 ; biaxial (-) with α = 1.528(2), β = 1.532(2) and γ = 1.533(2); and pleochroism is X = pale green yellow, Y ≈ Z = light green yellow. Pseudomarkeyite properties are: twinned tapering blades and tablets to 1 mm; pale green yellow colour; transparent; white streak; bright bluish white fluorescence (405 nm laser); vitreous to pearly lustre; brittle; Mohs hardness ≈ 1; stepped fracture; three cleavages ({10 1} very easy, {010} good, {100} fair); density = 2.88(2) g cm-3 ; biaxial (-) with α = 1.549(2), β = 1.553(2) and γ = 1.557(2); and it is nonpleochroic. The Raman spectra of markeyite, natromar-keyite and pseudomarkeyite are very similar and exhibit bands consistent with UO 2 2+ , CO 3 2-and O-H. Electron microprobe analyses provided the empirical formula Na 2.01 Ca 7.97 Mg 0.03 Cu 2+ 0.05 (UO 2) 4 (CO 3) 13 (H 2 O) 24 ⋅3H 2 O (-0.11 H) for natromarkeyite and Ca 7.95 (UO 2) 4 (CO 3) 12 (H 2 O) 18 ⋅3H 2 O (+0.10 H) for pseudomarkeyite. Natromarkeyite is orthorhombic, Pmmn, a = 17.8820(13), b = 18.3030(4), c = 10.2249(3) Å, V = 3336.6(3) Å 3 and Z = 2. Pseudomarkeyite is monoclinic, P2 1 /m, a = 17.531(3), b = 18.555(3), c = 9.130(3) Å, β = 103.95(3)°, V = 2882.3(13) Å 3 and Z = 2. The structures of natromarkeyite (R 1 = 0.0202 for 2898 I > 2σI) and pseudomarkeyite (R 1 = 0.0787 for 2106 I > 2σI) contain uranyl tricarbonate clusters that are linked by (Ca/Na)-O polyhedra forming thick corrugated heteropolyhedral layers. Natromarkeyite is isostructural with markeyite; pseudomarkeyite has a very similar structure.
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The new minerals natromarkeyite (IMA2018-152), Na 2 Ca 8 (UO 2) 4 (CO 3) 13 (H 2 O) 24 ·3H 2 O, and pseudomarkeyite (IMA2018-114), Ca 8 (UO 2) 4 (CO 3) 12 (H 2 O) 18 ·3H 2 O, were found in the Markey mine, San Juan County, Utah, USA, where they occur as secondary phases on asphaltum. Natromarkeyite properties: untwinned blades and tablets to 0.2 mm, pale yellow-green colour; transparent; white streak; 2 bright bluish white fluorescence (405 nm laser); vitreous to pearly lustre; brittle; Mohs hardness 1½ to 2; irregular fracture; three cleavages ({001} perfect, {100} and {010} good); 2.70(2) g cm-3 density; biaxial (-) with α = 1.528(2), β = 1.532(2), γ = 1.533(2); pleochroism: X pale green yellow, Y ≈ Z light green yellow. Pseudomarkeyite properties: twinned tapering blades and tablets to 1 mm; pale green-yellow colour; transparent; white streak; bright bluish white fluorescence (405 nm laser); vitreous to pearly lustre; brittle; Mohs hardness ~1; stepped fracture; three cleavages ({10-1} very easy, {010} good, {100} fair); 2.88(2) g cm-3 density; biaxial (-) with α = 1.549(2), β = 1.553(2), γ = 1.557(2); nonpleochroic. The Raman spectra of markeyite, natromarkeyite and pseudomarkeyite are very similar and exhibit bands consistent with UO 2 2+ , CO 3 2-and O-H. Electron microprobe analyses provided the empirical formula Na 2.01 Ca 7.97 Mg 0.03 Cu 2+ 0.05 (UO 2) 4 (CO 3) 13 (H 2 O) 24 ·3H 2 O (-0.11 H) for natromarkeyite and Ca 7.95 (UO 2) 4 (CO 3) 12 (H 2 O) 18 ·3H 2 O (+0.10 H) for pseudomarkeyite. Natromarkeyite is orthorhombic, Pmmn, a = 17.8820(13), b = 18.3030(4), c = 10.2249(3) Å, V = 3336.6(3) Å^3 and Z = 2. Pseudomarkeyite is monoclinic, P2 1 /m, a = 17.531(3), b = 18.555(3), c = 9.130(3) Å, β = 103.95(3)°, V = 2882.3(13) Å^3 and Z = 2. The structures of natromarkeyite (R1 = 0.0202 for 2898 I > 2sigmaI) and pseudomarkeyite (R1 = 0.0787 for 2106 I > 2sigmaI) contain uranyl tricarbonate clusters that are linked by (Ca/Na)-O polyhedra forming thick corrugated heteropolyhedral layers. Natromarkeyite is isostructural with markeyite; pseudomarkeyite has a very similar structure.
Article
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Uranyl sulfates, including those occurring in Nature (∼40 known members), possess particularly interesting structures. They exhibit a great dimensional and topological diversity of structures: from those based upon clusters of polyhedra to layered structures. There is also a great variability in the type of linkages between U and S polyhedra. From the point of view of complexity of those structures (measured as the amount of Shannon information per unit cell), most of the natural uranyl sulfates are intermediate (300–500 bits per cell) to complex (500–1000 bits per cell) with some exceptions, which can be considered as very complex structures (>1000 bits per cell). These exceptions are minerals alwilkinsite-(Y) (1685.95 bits per cell), sejkoraite-(Y) (1859.72 bits per cell), and natrozippeite (2528.63 bits per cell). The complexity of these structures is due to an extensive hydrogen bonding network which is crucial for the stability of these mineral structures. The hydrogen bonds help to propagate the charge from the highly charged interlayer cations (such as Y ³⁺ ) or to link a high number of interlayer sites ( i.e. five independent Na sites in the monoclinic natrozippeite) occupied by monovalent cations (Na ⁺ ). The concept of informational ladder diagrams was applied to the structures of uranyl sulfates in order to quantify the particular contributions to the overall informational complexity and identifying the most contributing sources (topology, real symmetry, interlayer bonding).
Article
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The new mineral markeyite (IMA2016-090), Ca9(UO2)4(CO3)13·28H2O, was found in the Markey mine, San Juan County, Utah, USA, where it occurs as a secondary phase on asphaltum in association with calcite, gypsum and natrozippeite. The mineral is pale yellowish-green with white streak and fluoresces bright bluish white under a 405 nm laser. Crystals are transparent and have vitreous to pearly lustre. It is brittle, with Mohs hardness 1 1/2 to 2, irregular fracture and three cleavages: perfect on {001}; good on {100} and {010}. The measured density is 2.68 g cm⁻³. Crystals are blades, flattened on {001} and elongate on [010], exhibiting the forms {100}, {010}, {001}, {110}, {101}, {011} and {111}. Markeyite is optically biaxial (-) with α = 1.538(2), β = 1.542(2) and γ = 1.545(2) (white light); the measured 2V is 81(2)°; the dispersion is r < v (weak); the optical orientation is X = c, Y = b, Z = a; and pleochroism is X = light greenish yellow, Y and Z = light yellow (X > Y ≈ Z). Electron microprobe analyses (energy-dispersive spectroscopy mode) yielded CaO 18.60, UO3 42.90, CO2 21.30 (calc.) and H2O 18.78 (calc.), total 101.58 wt.% and the empirical formula Ca8.91(U1.01O2)4(CO3)13·28H2O. The six strongest powder X-ray diffraction lines are [dobs A(I)(hkl)]: 10.12(69)(001), 6.41(91)(220,121), 5.43(100)(221), 5.07(33)(301,002,131), 4.104(37)(401,141) and 3.984(34)(222). Markeyite is orthorhombic, Pmmn, a = 17.9688(13), b = 18.4705(6), c = 10.1136(4) A, V = 3356.6(3) A³ and Z = 2. The structure of markeyite (R1 = 0.0435 for 3427 Fo > 4σF) contains uranyl tricarbonate clusters (UTC) that are linked by Ca-O polyhedra forming thick corrugated heteropolyhedral layers. Included within the layers is an additional disordered CO3 group linking the Ca-O polyhedra. The layers are linked to one another and to interlayer H2O groups only via hydrogen bonds. The structure bears some similarities to that of liebigite.
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Published two-body bond-valence parameters for cation–oxygen bonds have been evaluated via the root mean-square deviation (RMSD) from the valence-sum rule for 128 cations, using 180 194 filtered bond lengths from 31 489 coordination polyhedra. Values of the RMSD range from 0.033–2.451 v.u. (1.1–40.9% per unit of charge) with a weighted mean of 0.174 v.u. (7.34% per unit of charge). The set of best published parameters has been determined for 128 ions and used as a benchmark for the determination of new bond-valence parameters in this paper. Two common methods for the derivation of bond-valence parameters have been evaluated: (1) fixing B and solving for R o ; (2) the graphical method. On a subset of 90 ions observed in more than one coordination, fixing B at 0.37 Å leads to a mean weighted-RMSD of 0.139 v.u. (6.7% per unit of charge), while graphical derivation gives 0.161 v.u. (8.0% per unit of charge). The advantages and disadvantages of these (and other) methods of derivation have been considered, leading to the conclusion that current methods of derivation of bond-valence parameters are not satisfactory. A new method of derivation is introduced, the GRG (generalized reduced gradient) method, which leads to a mean weighted-RMSD of 0.128 v.u. (6.1% per unit of charge) over the same sample of 90 multiple-coordination ions. The evaluation of 19 two-parameter equations and 7 three-parameter equations to model the bond-valence–bond-length relation indicates that: (1) many equations can adequately describe the relation; (2) a plateau has been reached in the fit for two-parameter equations; (3) the equation of Brown & Altermatt (1985) is sufficiently good that use of any of the other equations tested is not warranted. Improved bond-valence parameters have been derived for 135 ions for the equation of Brown & Altermatt (1985) in terms of both the cation and anion bond-valence sums using the GRG method and our complete data set.
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The new computer program SHELXT employs a novel dual-space algorithm to solve the phase problem for single-crystal reflection data expanded to the space group P 1. Missing data are taken into account and the resolution extended if necessary. All space groups in the specified Laue group are tested to find which are consistent with the P 1 phases. After applying the resulting origin shifts and space-group symmetry, the solutions are subject to further dual-space recycling followed by a peak search and summation of the electron density around each peak. Elements are assigned to give the best fit to the integrated peak densities and if necessary additional elements are considered. An isotropic refinement is followed for non-centrosymmetric space groups by the calculation of a Flack parameter and, if appropriate, inversion of the structure. The structure is assembled to maximize its connectivity and centred optimally in the unit cell. SHELXT has already solved many thousand structures with a high success rate, and is optimized for multiprocessor computers. It is, however, unsuitable for severely disordered and twinned structures because it is based on the assumption that the structure consists of atoms.
Article
The new minerals klaprothite (IMA2015-087), Na6(UO2)(SO4)4(H2O)4, péligotite (IMA2015-088), Na6(UO2)(SO4)4(H2O)4, and ottohahnite (IMA2015-098), Na6(UO2)2(SO4)5(H2O)7·1.5H2O, were found in the Blue Lizard mine, San Juan County, Utah, USA, where they occur together as secondary phases. All three minerals occur as yellowish green to greenish-yellow crystals, are brittle with irregular fracture, have Mohs hardness of about 2½ and exhibit bright bluish-green fluorescence, and all are easily soluble in RT H2O. Only klaprothite exhibits cleavage; perfect on {100} and {001}. Quantitative EDS analyses yielded the empirical formulas Na6.01(U 26 1.03O2)(S0.993O4)4(H2O)4, Na5.82(U1.02O2)(S1.003O4)4(H2O)4 and Na5.88(U0.99O2)2(S1.008O4)5(H2O)8.5 for klaprothite, péligotite and ottohahnite, respectively. Their Raman spectra exhibit similar features. Klaprothite is monoclinic, P21/c, a = 9.8271(4), b = 9.7452(3), c = 20.8725(15) Å, β =98.743(7)°, V = 1975.66(17) Å3 and Z = 4. Péligotite is triclinic, P-1, a = 9.81511(18), b =9.9575(2), c = 10.6289(8) Å, α = 88.680(6)°, β = 73.990(5)°, γ = 89.205(6)°, V = 998.22(8) Å3 and Z = 2. Ottohahnite is triclinic, P-1, a = 9.97562(19), b = 11.6741(2), c = 14.2903(10) Å, α = 113.518(8)°, β = 104.282(7)°, γ = 91.400(6)°, V = 1464.59(14) Å3 and Z = 2. The structures of klaprothite (R1 = 2.22%) and péligotite (R1 = 2.28%) both contain [(UO2)(SO4)4]6– clusters in which one SO4 group has a bidentate linkage with the UO7 polyhedron; Na–O polyhedra link clusters into thick heteropolyhedral layers and link layers into frameworks; the structures differ in the configuration of Na-O polyhedra that link the layers. The structure of ottohahnite (R1 = 2.65%) contains [(UO2)4(SO4)10]12– clusters in which each UO7 polyhedron has a bidentate linkage with one SO4 group; Na–O polyhedra link clusters into a thin heteropolyhedral slice and also link the slices into a framework. The minerals are named for Martin Heinrich Klaproth (1743–1817), Eugène-Melchior Péligot (1811–1890) and Otto Hahn (1879–1968).
Article
The new minerals fermiite (IMA2014-068), Na4(UO2)(SO4)3·3H2O and oppenheimerite (IMA2014-073), Na2(UO2)(SO4)2·3H2O, were found in the Blue Lizard mine, San Juan County, Utah, USA, where they occur together as secondary alteration phases in association with blödite, bluelizardite, chalcanthite, epsomite, gypsum, hexahydrite, kröhnkite, manganoblödite, sideronatrite, tamarugite and wetherillite. Fermiite descriptive details: pale greenish-yellow prisms; transparent; vitreous lustre; bright greenishwhite fluorescence; white streak; hardness (Mohs) 2½; brittle; conchoidal fracture; no cleavage; slightly deliquescent; easily soluble in RT H2O; densitymeas = 3.23(2) g cm–3; densitycalc = 3.313 g cm–3. Optically, biaxial (+), α = 1.527(1), β = 1.534(1), γ = 1.567(1) (white light); 2Vmeas. = 51(1)°, 2Vcalc. = 50°; dispersion r < v, distinct. Pleochroism: X, Y = colourless, Z = pale greenish yellow; X = Y < Z. Energy dispersive spectroscopic (EDS) analyses yielded the empirical formula Na3.88(U1.05O2)(S0.99O4)3(H2O)3. Fermiite is orthorhombic, Pmn21, a = 11.8407(12), b = 7.8695(5), c = 15.3255(19) Å, V = 1428.0(2) Å3 and Z = 4. The structure (R1 = 2.21% for 1951 Io > 3σI ) contains [(UO2)(SO4)3] chains that are linked by bonds involving five different Na–O polyhedra to form a framework. The mineral is named for Italian-American theoretical and experimental physicist Dr. Enrico Fermi (1901–1954). Oppenheimerite descriptive details: pale greenish-yellow prisms; transparent; vitreous lustre; bright greenish-white fluorescence; white streak; hardness (Mohs) 2½; slightly sectile; three good cleavages, {1-10}, {011} and {101}; irregular fracture; slightly deliquescent; easily soluble in RT H2O; density(calc) = 3.360 g cm–3. Optically, biaxial (+), α = 1.537(1), β = 1.555(1), γ = 1.594(1) (white light); 2Vmeas. = 72(2)°, 2Vcalc. = 70°; dispersion is r > v, moderate, inclined; optical orientation: X ≈ ⊥ {101}, Z ≈ [11-1]; pleochroism: X very pale greenish yellow, Y pale greenish yellow, Z greenish yellow; X < Y < Z. EDS analyses yielded the empirical formula Na1.94(U0.97O2)(S1.02O4)2(H2O)3. Oppenheimerite is triclinic, P-1, a = 7.9576(6), b = 8.1952(6), c = 9.8051(7) Å, α = 65.967(5), β = 70.281(5), γ = 84.516(6)°, V = 549.10(8) Å3 and Z = 2. The structure (R1 = 3.07% for 2337 Io > 3σI ) contains [(UO2)(SO4)2(H2O)] chains that are linked by bonds involving two different Na–O polyhedra to form a framework. The mineral is named for American theoretical physicist Dr. J. Robert Oppenheimer (1904–1967).
Chapter
This chapter demonstrates a wide structural diversity of actinyl compounds containing hexavalent cations of S, Cr, Se, Mo, and W. Several factors control such diversity: (i) coordination of cations: both actinide and hexavalent cations may have different coordinations; (ii) mode of linkage of coordination polyhedra: all combinations of corner and edge sharing among polyhedra are allowed; of special interest is the high frequency of edge sharing between UO7 pentagonal bipyramids and SO4 tetrahedra; actinyl polyhedra polymerize by sharing either equatorial anions or even apical anions; (iii)high flexibility of structural units consisting of actinyl polyhedral and TO4 tetrahedra that are analysed by means of statistical investigations of U-Obr-T bond angles; among different units, uranyl molybdates show the widest variation of the angular characteristics, in agreement with their strong tendency to formation framework structures.