The 51st Hallimond Lecture
Time's arrow, time's cycle: Granulite metamorphism and geodynamics
- Michael Brown, Tim Johnson
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- Published online by Cambridge University Press:
- 12 April 2019, pp. 323-338
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Although the thermal evolution of the mantle before c. 3.0 Ga remains unclear, since c. 3.0 Ga secular cooling has dominated over heat production—this is time's arrow. By contrast, the thermal history of the crust, which is preserved in the record of metamorphism, is more complex. Heat to drive metamorphism is generated by radioactive decay and viscous dissipation, and is augmented by the influx of heat from the mantle. Notwithstanding that reliable data are sparse before the Neoarchean, we use a dataset of temperature (T), pressure (P) and thermobaric ratio (T/P at the metamorphic ‘peak’), and age of metamorphism (t, the timing of the metamorphic ‘peak’) for rocks from 564 localities ranging in age from the Cenozoic to the Eoarchean eras to interrogate the crustal record of metamorphism as a proxy for the heat budget of the crust through time. On the basis of T/P, metamorphic rocks are classified into three natural groups: high T/P type (T/P >775°C/GPa, mean T/P ~1105°C/GPa), including common and ultrahigh-temperature granulites, intermediate T/P type (T/P between 775 and 375°C/GPa, mean T/P ~575°C/GPa), including high-pressure granulites and medium- and high-temperature eclogites, and low T/P type (T/P <375°C/GPa, mean T/P ~255°C/GPa), including blueschists, low-temperature eclogites and ultrahigh-pressure metamorphic rocks. A monotonic increase in the P of intermediate T/P metamorphism from the Neoarchean to the Neoproterozoic reflects strengthening of the lithosphere during secular cooling of the mantle—this is also time's arrow. However, temporal variation in the P of intermediate T/P metamorphism and in the moving means of T and T/P of high T/P metamorphism, combined with the clustered age distribution, demonstrate the cyclicity of collisional orogenesis and cyclic variations in the heat budget of the crust superimposed on secular cooling since c. 3.0 Ga—this is time's cycle. A first cycle began with the widespread appearance/survival of intermediate T/P and high T/P metamorphism in the Neoarchean rock record coeval with amalgamation of dispersed blocks of lithosphere to form protocontinents. This cycle was terminated by the fragmentation of the protocontinents into cratons in the early Paleoproterozoic, which signalled the start of a new cycle. The second cycle continued with the progressive amalgamation of the cratons into the supercontinent Columbia and extended until the breakup of the supercontinent Rodinia in the Neoproterozoic. This cycle represented a period of relative tectonic and environmental stability, and perhaps reduced subduction during at least part of the cycle. During most of the Proterozoic the moving means for both T and T/P of high T/P metamorphism exceeded the arithmetic means, reflecting insulation of the mantle beneath the quasi-integrated lithosphere of Columbia and, after a limited reorganisation, Rodinia. The third cycle began with the steep decline in thermobaric ratios of high T/P metamorphism to their lowest value, synchronous with the breakup of Rodinia and the formation of Pannotia, and the widespread appearance/preservation of low T/P metamorphism in the rock record. The thermobaric ratios for high T/P metamorphism rise to another peak associated with the Pan-African event, again reflecting insulation of the mantle. The subsequent steep decline in thermobaric ratios of high T/P metamorphism associated with the breakup of Pangea at c. 0.175 Ga may indicate the start of a fourth cycle. The limited occurrence of high and intermediate T/P metamorphism before the Neoarchean suggests either that suitable tectonic environments to generate these types of metamorphism were not widely available before then or that the rate of survival was low. We interpret the first cycle to record stabilisation of subduction and the emergence of a network of plate boundaries in a plate tectonics regime once the balance between heat production and heat loss changed in favour of secular cooling, possibly as early as c. 3.0 Ga in some areas. This is inferred to have been a globally linked system by the early Paleoproterozoic, but whether it remained continuous to the present is unclear. The second cycle was characterised by stability from the formation of Columbia to the breakup of Rodinia, generating higher than average T and T/P of high T/P metamorphism. The third cycle reflects colder collisional orogenesis and deep subduction of the continental crust, features that are characteristic of modern plate tectonics, which became possible once the average temperature of the asthenospheric mantle had declined to <100°C warmer than the present day after c. 1.0 Ga.
Article
Constraints on the Equations of State of stiff anisotropic minerals: rutile, and the implications for rutile elastic barometry
- Gabriele Zaffiro, Ross J. Angel, Matteo Alvaro
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- 22 April 2019, pp. 339-347
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We present an assessment of the thermo-elastic behaviour of rutile based on X-ray diffraction data and direct elastic measurements available in the literature. The data confirms that the quasi-harmonic approximation is not valid for rutile because rutile exhibits substantial anisotropic thermal pressure, meaning that the unit-cell parameters change significantly along isochors. Simultaneous fitting of both the diffraction and elasticity data yields parameters of KTR0= 205.14(15) GPa, KSR0= 207.30(14) GPa, $K_{TR0}^{\prime} $= 6.9(4) in a 3rd-order Birch-Murnaghan Equation of State for compression, αV0= 2.526(16) × 10–5 K–1, Einstein temperature θE = 328(12) K, Anderson-Grüneisen parameter δT = 7.6(6), with a fixed thermal Grüneisen parameter γ = 1.4 to describe the thermal expansion and variation of bulk modulus with temperature at room pressure. This Equation of State fits all of the available data up to 7.3 GPa at room temperature, and up to 1100 K at room pressure within its uncertainties. We also present a series of formulations and a simple protocol to obtain thermodynamically consistent Equations of State for the volume and the unit-cell parameters for stiff materials, such as rutile. In combination with published data for garnets, the Equation of State for rutile indicates that rutile inclusions trapped inside garnets in metamorphic rocks should exhibit negative residual pressures when measured at room conditions.
Magnesioleydetite and straβmannite, two new uranyl sulfate minerals with sheet structures from Red Canyon, Utah
- Anthony R. Kampf, Jakub Plášil, Anatoly V. Kasatkin, Barbara P. Nash, Joe Marty
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- 28 May 2018, pp. 349-360
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Magnesioleydetite (IMA2017-063), Mg(UO2)(SO4)2·11H2O, and straβmannite (IMA2017-086), Al(UO2)(SO4)2F·16H2O, are two new minerals from mines in Red Canyon, San Juan County, Utah, USA. Magnesioleydetite occurs in the Markey mine and straβmannite occurs in both the Markey and Green Lizard mines. Both minerals are secondary phases found in efflorescent crusts on the surfaces of mine walls. Magnesioleydetite occurs in irregular aggregates (to ~0.5 mm) of blades (to ~0.2 mm) exhibiting the following properties: transparent to translucent; pale green–yellow colour; vitreous lustre; white streak; non-fluorescent; brittle; Mohs hardness ≈ 2; irregular fracture; one perfect cleavage on {001}; and calculated density = 2.463 g/cm3. Straβmannite occurs in irregular aggregates (to ~0.5 mm) of equant crystals (to ~0.2 mm) exhibiting the following properties: transparent; light yellow–green colour; vitreous to greasy lustre; nearly white streak; bright greenish-blue fluorescence; somewhat brittle, Mohs hardness ≈ 1½; irregular fracture; one good cleavage on {001}; measured and calculated densities of 2.20(2) and 2.173 g/cm3, respectively; optically biaxial (–); α = 1.477(2), β = 1.485(2) and γ = 1.489(2) (white light); 2Vmeas. = 72(2)°; dispersion r > v (slight); orientation Y = b, X ∧ c = 20° (in obtuse β); pleochroism with X = nearly colourless, Y = pale green–yellow and Z = light green–yellow (X < Y < Z). The empirical formulas for magnesioleydetite and straβmannite are (Mg0.56Fe0.26Zn0.11Mn0.01)Σ0.94(U0.99O2)(S1.015O4)2·11H2O and Al1.00Na0.16(U0.99O2)(S1.00O4)2[F0.58(OH)0.42]·16H2O, respectively. Magnesioleydetite is monoclinic, C2/c, a = 11.3513(3), b = 7.7310(2), c = 21.7957(15) Å, β = 102.387(7)°, V = 1868.19(16) Å3 and Z = 4. Straβmannite is monoclinic, C2/c, a = 11.0187(5), b = 8.3284(3), c = 26.6727(19) Å, β = 97.426(7)°, V = 2427.2(2) and Z = 4. The structures of magnesioleydetite (R1 = 0.016 for 2040 I > 2σI reflections) and straβmannite (R1 = 0.0343 for 2220 I > 2σI reflections) each contain uranyl-sulfate sheets based on the protasite-anion topology.
Gem amphiboles from Mogok, Myanmar: crystal-structure refinement, infrared spectroscopy and short-range order–disorder in gem pargasite and fluoro-pargasite
- Maxwell C. Day, Frank C. Hawthorne, Umberto Susta, Giancarlo Della Ventura, George E. Harlow
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- 14 September 2018, pp. 361-371
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The crystal structures of six gem-quality pargasites and fluoro-pargasites from Mogok, Myanmar, space group C2/m, Z = 2, have been refined to R1 indices of 2.20–2.90% using MoKα X-radiation. The unit formulae were calculated from the results of electron-microprobe analysis, and were used with the refined site-scattering values and the observed mean bond lengths to assign site populations. TAl occurs at both the T(1) and T(2) sites but is strongly ordered at T(1). [6]Al is partly disordered over the M(2) and M(3) sites but does not occur at the M(1) site. ANa is split between the A(2) and A(m) sites and K occurs at the A(m) site. The infrared spectra in the principal OH-stretching region were measured and the fine structure was fit to component bands. The component bands were assigned to short-range ion arrangements over the configuration symbol M(1)M(1)M(3)–O(3)–A–O(3):T(1)T(1) using the refined site-populations and the expected frequencies from previously assigned spectra in more simple amphibole compositions, and correspond to the local arrangements: (1) MgMgMg–OH–Na–OH:SiAl; (2) MgMgMg–OH–Na–F:SiAl; (3) MgMgAl–OH–Na–OH:SiAl and (4) MgMgAl–OH–Na–F:SiAl.
Rinkite-(Y), Na2Ca4YTi(Si2O7)2OF3, a seidozerite-supergroup TS-block mineral from the Darai-Pioz alkaline massif, Tien-Shan mountains, Tajikistan: Description and crystal structure
- Leonid A. Pautov, Atali A. Agakhanov, Vladimir Yu. Karpenko, Yulia A. Uvarova, Elena Sokolova, Frank C. Hawthorne
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- 29 June 2018, pp. 373-380
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Rinkite-(Y), ideally Na2Ca4YTi(Si2O7)2OF3, is a new rinkite-group (seidozerite-supergroup) TS-block mineral from the Darai-Pioz alkaline massif, Tian-Shan mountains, Tajikistan. The mineral is of hydrothermal origin. It occurs as aggregates (up to 1.5 cm long) of acicular crystals 0.1–1.0 mm thick, and as separate elongated columnar, flattened-prismatic crystals up to 1 cm long with rectangular or rhombic sections up to 0.5 mm across. Associated minerals are quartz, aegirine, microcline, neptunite, pectolite, calcite, eudialyte-group minerals, fluorite, titanite, turkestanite, kupletskite, galena, albite and pyrochlore-group minerals. Crystals are transparent and colourless to occasionally white, with a vitreous lustre. Rinkite-(Y) has a white streak, uneven, conchoidal fracture and does not fluoresce under a cathode or ultraviolet light. Cleavage is very good on {100}, no parting was observed, Mohs hardness is ~5, and it is brittle, Dmeas. = 3.44(2) g/cm3, Dcalc. = 3.475 g/cm3. It is biaxial (+) with refractive indices (λ = 590 nm) α = 1.662(2), β = 1.666(2), γ = 1.685(5); 2Vmeas. = 50(3) and 2Vcalc. = 49.7°. It is nonpleochroic. Rinkite-(Y) is monoclinic, space group P21/c, a = 7.3934(5), b = 5.6347(4), c = 18.713(1) Å, β = 101.415(2)° and V = 764.2(2) Å3. The six strongest reflections in the X-ray powder diffraction data [d(Å), I, (hkl)] are: 3.057, 100, (006, $\bar{2}$12, 210); 2.688, 28, (016); 9.18, 24, (002); 2.929, 17, ($\bar{2}$13, 211); 3.559, 15, (104, 014) and 2.783, 14, (021). The empirical formula calculated on 18 (O + F) is Na2.11(Ca3.74Sr0.03Mn0.03)Σ3.80(Y0.50Nd0.16Ce0.16Gd0.07Dy0.06Sm0.05Pr0.03La0.03${\rm U}_{0.01}^{{\rm 4 + }} {\rm )}_{\Sigma 1.07}{\rm (T}{\rm i}_{0.85}{\rm N}{\rm b}_{0.17}{\rm W}^{6+}_{0.01}{\rm T}{\rm a}_{0.01}{\rm )}_{\Sigma 1.04}\left( {{\rm S}{\rm i}_{4.03}{\rm O}_{14}} \right){\rm O}_{1.40}{\rm F}_{2.60}$ with Z = 2. The ideal formula is Na2Ca4YTi(Si2O7)2OF3. The crystal structure was refined on a twinned crystal to R1 = 4.59% on the basis of 1489 unique reflections (F > 4σF) and is a framework of TS (Titanium-Silicate) blocks. The TS block consists of HOH sheets (H – heteropolyhedral, O – octahedral) parallel to (100). In the O sheet, the Ti-dominant [6]MO1 site ideally gives 1 Ti apfu. The [8]MO2 and [6]MO3 sites are ideally occupied by Na and (NaCa) apfu. In the H sheet, the [7]MH site is occupied by Ca1.13Y0.50REE0.37, (REE = rare-earth element), ideally (CaY), <MH–φ> = 2.415 Å and the [7]AP site is occupied by Ca1.81REE0.19, ideally Ca2, <AP–φ> = 2.458 Å. The MH + AP sites ideally give (Ca3Y) apfu. The MH and AP polyhedra and Si2O7 groups constitute the H sheet. Linkage of H and O sheets via common vertices of MH and AP polyhedra and Si2O7 groups with MO1–3 polyhedra results in a TS block. The TS block in rinkite-(Y) exhibits linkage 1 and stereochemistry typical for the rinkite group (Ti = 1 apfu) of the seidozerite supergroup. For rinkite-(Y), the ideal structural formula of the form AP2MH2MO4(Si2O7)2$ \left( {{\rm X}_{\rm M}^{\rm O} } \right)_2\left( {{\rm X}_{\rm A}^{\rm O} } \right)_2{\rm is }\;\left( {{\rm C}{\rm a}_3{\rm Y}} \right){\rm Na}\left( {{\rm NaCa}} \right){\rm Ti}\left( {{\rm S}{\rm i}_2{\rm O}_7} \right)_2\left( {{\rm OF}} \right){\rm F}_2 $ with Z = 2. The mineral is named rinkite-(Y) as it is structurally identical to rinkite-(Ce) and Y is the dominant rare-earth element.
Subaerial sulfate mineral formation related to acid aerosols at the Zhenzhu Spring, Tengchong, China
- Lianchao Luo, Huaguo Wen, Rongcai Zheng, Ran Liu, Yi Li, Xiaotong Luo, Yaxian You
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- 14 January 2019, pp. 381-392
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The Zhenzhu Spring, located in the Tengchong volcanic field, Yunnan, China, is an acid hot spring with high SO42− concentrations and intense acid aerosol generation. In order to understand the formation mechanism of sulfate minerals at the Zhenzhu Spring and provide a better insight into the sulfur isotope geochemistry of the associated Rehai hydrothermal system, we investigated the spring water hydrochemistry, mineralogy and major-element geochemistry of sulfate minerals at the Zhenzhu Spring together with the sulfur-oxygen isotope geochemistry of sulfur-containing materials at the Rehai geothermal field and compared the isotope results with those in other steam-heated environments. Subaerial minerals include a wide variety of sulfate minerals (gypsum, alunogen, pickeringite, tamarugite, magnesiovoltaite and a minor Mg–S–O phase) and amorphous SiO2. The δ34S values of the subaerial sulfate minerals at the Zhenzhu Spring varied subtly from –0.33 to 1.88‰ and were almost consistent with the δ34S values of local H2S (–2.6 to 0.6‰) and dissolved SO42− (–0.2 to 5.8‰), while the δ18O values (–8.94 to 20.1‰) were between that of the spring waters (–10.19 to –6.7‰) and atmospheric O2 (~23.88‰). The results suggest that most of the sulfate minerals are derived from the oxidation of H2S, similar to many sulfate minerals from modern steam-heated environments. However, the rapid environmental change (different ratio of atmospheric and water oxygen) at the Zhenzhu Spring accounts for the large variation of δ18O. The formation of subaerial sulfate minerals around the Zhenzhu Spring is related to acid aerosols (vapour and acid water droplets). The intense activity of spring water around vents supply the aerosol with H2SO4 (H2S oxidation and acid water droplets formed by bubble bursting) and few cations. Deposition of the acid sulfate aerosol forms the acid condensate, which attacks the underlying rocks and releases many cations and anions to form subaerial sulfate minerals at the Zhenzhu Spring.
Pampaloite, AuSbTe, a new mineral from Pampalo gold mine, Finland
- Anna Vymazalová, Kari Kojonen, František Laufek, Bo Johanson, Chris J. Stanley, Jakub Plášil, Patricie Halodová
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- 04 July 2018, pp. 393-400
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Pampaloite, AuSbTe, is a new mineral discovered in the Pampalo gold mine, 65 km east of Joensuu, Finland. It forms anhedral grains (up to ~20 μm) intergrown with gold, frohbergite and altaite. Pampaloite is brittle and has a metallic lustre. Values of VHN25 lie between 245 and 295 kg/mm2, with a mean value of 276 kg/mm2, corresponding to a Mohs hardness of ~4–5 (measured on synthetic material). In plane-polarised light, pampaloite is white with medium to strong bireflectance, weak reflectance pleochroism from slightly pinkish brown to slightly bluish white (only visible in grains of synthetic material containing multiple orientations), and strong anisotropy, with blue to light brown rotation tints; it exhibits no internal reflections. Reflectance values of pampaloite in air (R1,R2 in %) are: 60.0, 62.5 at 470 nm, 62.5, 64.8 at 546 nm, 63.2, 65.6 at 589 nm and 63.7, 66.0 at 650 nm. Ten electron-microprobe analyses of natural pampaloite give an average composition: Au 44.13, Sb 27.44 and Te 28.74, total 100.31 wt.%, corresponding to the empirical formula Au1.00Sb1.00Te1.00 based on 3 atoms; the average of eleven analyses on synthetic pampaloite is: Au 44.03, Sb 27.26, and Te 29.08, total 100.38 wt.%, corresponding to Au0.99Sb1.00Te1.01. The density, calculated on the basis of the empirical formula, is 9.33 g/cm3.The mineral is monoclinic, space group C2/c, with a = 11.947(3), b = 4.481(1) Å, c = 12.335(3) Å, β = 105.83(2)°, V = 635.3(3) Å3 and Z = 8. The crystal structure was solved and refined from the single-crystal X-ray-diffraction data of synthetic AuSbTe. The pampaloite crystal structure can be considered as a monoclinic derivative of the CdI2 structure composed of [AuTe3Sb3] octahedra. The strongest lines in the powder X-ray diffraction pattern of synthetic pampaloite [d in Å (I) (hkl)] are: 4.846(24)($\bar{2}$02), 3.825(18)(111), 2.978(100)($\bar{3}$11), 2.968(50)(004), 2.242(25)(020), 2.144(55)(313), 2.063(33)($\bar{3}$15) and 1.789(18)(024).
Mineralogy of the baotite-bearing Gundrapalli lamproite, Nalgonda district, Telangana, India
- Gurmeet Kaur, Roger H. Mitchell
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- 31 January 2019, pp. 401-411
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We describe the mineralogy of a lamproite dyke from Gundrapalli village (Nalgonda district), Telangana, India. The dyke consists of a mineral assemblage characteristic of lamproites in terms of the presence of amphiboles (mainly potassic-richterite together with potassic-arfvedsonite, magnesio-riebeckite, Ti-rich potassic-magnesio-arfvedsonite, potassic-magnesio-arfvedsonite, katophorite and potassic-ferri-katophorite), Al-poor pyroxene, phlogopite (Ti-rich, Al-poor), pseudomorphed leucite, spinel (chromite-magnesiochromite), fluorapatite, baryte, titanite, rutile, barytocalcite, calcite, ilmenite, hydro-zircon, baotite, strontianite, allanite, quartz and pyrite. The absence of wadeite and priderite have been compensated for by the presence of baotite, rutile, titanite, baryte and hydro-zircons. The presence of the secondary phases: allanite, hydro-zircon, chlorite, quartz and cryptocrystalline silica, implies that the dyke has undergone deuteric alteration. On the basis of its typomorphic mineralogy the Gundrapalli dyke has been classified as a pseudoleucite-phlogopite-amphibole-lamproite. We report the presence of the rare mineral baotite from this lamproite, the first recognition of baotite from a lamproite in India. The mineralogy of the baotite-bearing Gundrapalli lamproite is analogous to the baotite-bearing Kvaløya lamproite from Troms, Norway.
Ferri-fluoro-katophorite from Bear Lake diggings, Bancroft area, Ontario, Canada: a new species of amphibole, ideally Na(NaCa)(Mg4Fe3+)(Si7Al)O22F2
- Roberta Oberti, Massimo Boiocchi, Frank C. Hawthorne, Neil A. Ball, Robert F. Martin
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- 02 July 2018, pp. 413-417
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Ferri-fluoro-katophorite is the second species characterised involving the rootname katophorite in the sodium–calcium subgroup of the amphibole supergroup. The mineral and its name were approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification, IMA2015-096. It was found in the Bear Lake diggings, Bancroft area, Ontario, Canada, where coarse euhedral crystals of amphibole, phlogopite, sanidine solid-solution (now coarsely exsolved to microcline perthite), titanite, augite, zircon and fluorapatite crystallised from a low-viscosity silicocarbonatitic magma of crustal origin. Greenish grey prismatic crystals of ferri-fluoro-katophorite generally protrude from the walls into a body of coarsely crystalline calcite, but they also occur away from the walls, completely enclosed by calcite. The empirical formula derived from electron microprobe analysis and single-crystal structure refinement is: A(Na0.55K0.32)Σ0.87B(Na0.79Ca1.18Mn2+0.03)Σ2.00C(Mg3.29Mn2+0.02Fe2+1.19Fe3+0.31Al0.09Ti4+0.08Li0.02)Σ5.00T(Si7.39Al0.61)Σ8.00O22W[F1.23 (OH)0.77]Σ2.00. Ferri-fluoro-katophorite is biaxial (–), with α = 1.640(2), β = 1.652(2), γ = 1.658(2), 2Vmeas. = 68.9(2)° and 2Vcalc.. = 70.1°. The unit-cell parameters are a = 9.887(3), b = 18.023(9), c = 5.292(2) Å, β = 104.66(3)°, V = 912.3(6) Å3, Z = 2 and space group C2/m. The strongest ten lines in the powder X-ray pattern [d values (in Å) I (hkl)] are: 2.708, 100, (151); 2.388, 74, (131); 3.139, 72, (310); 8.449, 69, (110); 2.540, 65, ($\bar{2}$02); 2.591, 53, (061); 2.739, 47, ($\bar{3}$31); 2.165, 45, (261); 3.279, 44, ($\bar{2}$40); 2.341, 43, ($\bar{3}$51).
Discovery of Se-rich canfieldite, Ag8Sn(S,Se)6, from the Shuangjianzishan Ag–Pb–Zn deposit, NE China: A multimethodic chemical and structural study
- Degao Zhai, Luca Bindi, Panagiotis C. Voudouris, Jiajun Liu, Stylianos F. Tombros, Kuan Li
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- 08 October 2018, pp. 419-426
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During a study of the ore minerals belonging to the recently discovered Shuangjianzishan Ag–Pb–Zn deposit in NE China, we have discovered exceptional selenium enrichment in canfieldite (up to 11.6 wt.% of Se). Incorporation of Se into canfieldite has been investigated by an integrated approach using field emission scanning electron microscopy, electron microprobe and single-crystal X-ray diffraction. Canfieldite has been identified as one of the dominant Ag-bearing ore minerals in the studied deposit, which occurs mostly in slate-hosted vein type Ag–Pb–Zn ore bodies. Selenium is either homogeneously or, remarkably, heterogeneously distributed in the different canfieldite fragments studied. Chemical variations of Se are mostly attributable to a series of retrograde reactions resulting in diverse decomposition and exsolution of primary phases during cooling, or alternatively, related to influxes of Se-rich fluids during the formation of canfieldite. To evaluate the effects of the Se-for-S substitution in the structure, a crystal of Se-rich canfieldite [Ag7.98Sn1.02(S4.19Se1.81)Σ6.00] was investigated. The unit-cell parameters are: a = 10.8145(8) Å and V = 1264.8(3) Å3. The structure was refined in the space group F$\bar{4}$3m to R1 = 0.0315 for 194 independent reflections, with 20 parameters. The crystal structure of Se-rich canfieldite was found to be topologically identical to that of pure canfieldite. If the short Ag–Ag contacts are ignored (due to the disorder), the two Ag atoms in the structure can be considered as three-fold (Ag1) and four-fold (Ag2) coordinated. Tin adopts a regular tetrahedral coordination. As in the case of Te-rich canfieldite, the refinement of the site-occupancy factor indicates that Se is disordered over the three anion positions.
Middlebackite, a new Cu oxalate mineral from Iron Monarch, South Australia: Description and crystal structure
- Peter Elliott
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- 02 July 2018, pp. 427-433
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Middlebackite is a new supergene mineral formed in the upper levels of the Iron Monarch quarry, South Australia. It occurs as aggregates of blue, prismatic crystals up to 0.3 mm across comprising individual crystals up to 0.05 mm in length associated with atacamite and mottramite. Crystals are translucent with a vitreous lustre and have a pale blue streak. Middlebackite is brittle with one perfect cleavage and uneven fracture. Mohs hardness is ~2. The calculated density is 3.64 g cm–3. Crystals are biaxial (+) with α = 1.663(4), β = 1.748(4) and γ = 1.861(4) (measured in white light). The calculated 2V is 86.7°. Pleochroism is X = colourless, Y = very pale blue and Z = dark sky blue; Z > Y > X. The empirical formula unit, based on six oxygen atoms per formula unit is Cu2.00(C2O4)Cl0.02(OH)1.98. Middlebackite is monoclinic, space group P21/c with a = 7.2597(15), b = 5.7145(11), c = 5.6624(11) Å, β = 104.20(3)°, V = 227.73(8) Å3 and Z = 2. The five strongest lines in the powder X-ray diffraction pattern are [d(Å), (I), (hkl)]: 7.070 (16) (100), 3.739 (100) (11$\bar{1}$), 2.860 (18) (020), 2.481 (12) (12$\bar{1}$) and 2.350 (9) (300). The crystal structure was refined from synchrotron single-crystal X-ray diffraction data to R1 = 0.0341 for 596 observed reflections with F0 > 4σ(F0). The structure is based on sheets of edge- and corner-sharing octahedra parallel to the bc plane. Sheets link in the a direction via oxalate anions.
Substitution mechanisms in In-, Au-, and Cu-bearing sphalerites studied by X-ray absorption spectroscopy of synthetic compounds and natural minerals
- Olga N. Filimonova, Alexander L. Trigub, Dmitriy E. Tonkacheev, Max S. Nickolsky, Kristina O. Kvashnina, Dmitriy A. Chareev, Ilya V. Chaplygin, Elena V. Kovalchuk, Sara Lafuerza, Boris R. Tagirov
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- Published online by Cambridge University Press:
- 04 March 2019, pp. 435-451
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Sphalerite is the main source of In – a ‘critical’ metal widely used in high-tech electronics. In this mineral the concentration of In is commonly correlated directly with Cu content. Here we use X-ray absorption spectroscopy of synthetic compounds and natural crystals in order to investigate the substitution mechanisms in sphalerites where In is present, together with the group 11 metals. All the admixtures (Au, Cu, In) are distributed homogeneously within the sphalerite matrix, but their structural and chemical states are different. In all the samples investigated In3+ replaces Zn in the structure of sphalerite. The In ligand distance increases by 0.12 Å and 0.09–0.10 Å for the 1st and 2nd coordination shells, respectively, in comparison with pure sphalerite. The In–S distance in the 3rd coordination shell is close to the one of pure sphalerite. Gold in synthetic sphalerites is coordinated with sulfur (NS = 2.4–2.5, RAu–S = 2.35 ± 0.01 Å). Our data suggest that at high Au concentrations (0.03–0.5 wt.%) the Au2S clusters predominate, with a small admixture of the Au+ solid solution with an Au–S distance of 2.5 Å. Therefore, the homogeneous character of a trace-element distribution, which is commonly observed in natural sulfides, does not confirm formation of a solid solution. In contrast to Au, the presence of Cu+ with In exists only in the solid-solution state, where it is tetrahedrally coordinated with S atoms at a distance of 2.30 ± 0.03 Å. The distant coordination shells of Cu are disordered. These results demonstrate that the group 11 metals (Cu, Ag and Au) can exist in sphalerite in the metastable solid-solution state. The solid solution forms at high temperature via the charge compensation scheme 2Zn2+↔Me++Me3+. The final state of the trace elements at ambient temperature is governed by the difference in ionic radii with the main component (Zn), and concentration of admixtures.
New arsenate minerals from the Arsenatnaya fumarole, Tolbachik volcano, Kamchatka, Russia. IX. Arsenatrotitanite, NaTiO(AsO4)
- Igor V. Pekov, Natalia V. Zubkova, Atali A. Agakhanov, Dmitry I. Belakovskiy, Marina F. Vigasina, Vasiliy O. Yapaskurt, Evgeny G. Sidorov, Sergey N. Britvin, Dmitry Y. Pushcharovsky
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- 04 July 2018, pp. 453-458
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The new durangite-group mineral arsenatrotitanite, ideally NaTiO(AsO4), was found in the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with orthoclase, tenorite, hematite, johillerite, bradaczekite, badalovite, calciojohillerite, arsmirandite, tilasite, svabite, cassiterite, pseudobrookite, rutile, sylvite, halite, aphthitalite, langbeinite and anhydrite. Arsenatrotitanite occurs as prismatic, tabular, lamellar or acicular crystals up to 0.3 mm × 0.8 mm × 2 mm. They are separated or combined in open-work aggregates up to 2 mm across or interrupted crusts up to 2 mm × 5 mm in area and up to 0.3 mm thick. Arsenatrotitanite is transparent, brownish red to pale pinkish-reddish or almost colourless, with vitreous lustre. It is brittle and the Mohs’ hardness is ~5½. Cleavage is perfect on {110} and the fracture is stepped. Dcalc is 3.950 g cm–3. Arsenatrotitanite is optically biaxial (+), α = 1.825(5), β = 1.847(6), γ = 1.896(6) (589 nm) and 2Vmeas. = 70(5)°. Chemical composition (wt.%, electron-microprobe) is: Na2O 12.26, CaO 3.10, Al2O3 4.39, Fe2O3 9.57, TiO2 17.11, SnO2 1.03, As2O5 50.17, F 3.29, O = F –2.39, total 99.53. The empirical formula based on 5 (O + F) apfu is (Na0.91Ca0.13)Σ1.04(Ti0.49Fe3+0.27Al0.20Sn0.02)Σ0.98(As1.00O4.00)(O0.60F0.40). Arsenatrotitanite is monoclinic, C2/c, a = 6.6979(3), b = 8.7630(3), c = 7.1976(3) Å, β = 114.805(5)°, V = 383.48(3) Å3 and Z = 4. The strongest reflections of the powder X-ray diffraction (XRD) pattern [d,Å(I)(hkl)] are: 4.845(89)($\bar{1} {11}}$), 3.631(36)(021), 3.431(48)(111), 3.300(100)($\bar{1} {12}}$), 3.036(100)(200), 2.627(91)(130) and 2.615(57)(022). The crystal structure was solved from single-crystal XRD data with R = 1.76%. Arsenatrotitanite belongs to the titanite/durangite structure type. It is named as an arsenate of sodium (natrium in Latin) and titanium isostructural with titanite.
The crystal structure of Ni-rich gordaite–thérèsemagnanite from Cap Garonne, France
- Stuart J. Mills, Owen P. Missen, Georges Favreau
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- 14 March 2019, pp. 459-463
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The crystal structure of Ni-rich gordaite–thérèsemagnanite has been determined from a sample collected at pillar 80 in the North mine, Cap Garonne, Var, France. The structure was refined to R1 = 0.0693 for 935 reflections with I > 2σ(I). The mineral is isostructural with gordaite, forming a layered structure with an extensive hydrogen-bonding network. The possible polytypic relationship between gordaite, thérèsemagnanite and guarinoite is also discussed. The guarinoite formula (Zn,Co,Ni)6(SO4)(OH,Cl)10·5H2O is also likely to be incorrect and is more likely to be Na(Zn,Co)4(SO4)(OH)6Cl·5–6H2O, meaning that guarinoite is equivalent to Co-rich gordaite-2H and would not be a distinct mineral species.
Potassic-magnesio-arfvedsonite, KNa2(MgFe2+Fe3+)5Si8O22(OH)2: mineral description and crystal chemistry
- Momchil Dyulgerov, Roberta Oberti, Bernard Platevoet, Milen Kadiyski, Ventzislav Rusanov
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- 02 July 2018, pp. 465-472
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The complete mineral description of potassic-magnesio-arfvedsonite, a recently approved (IMA2016-083) new species of the amphibole supergroup is provided using electron microprobe analysis (EMPA), laser ablation inductively coupled plasma mass spectrometry, single-crystal structure refinement, Mössbauer and Raman spectroscopy, as well as measurement of optical and physical properties. The holotype material was found in syenitic and granitic dyke rocks in association with quartz, potassium feldspar and aegirine–augite from the Buhovo–Seslavtsi pluton, Bulgaria. Potassic-magnesio-arfvedsonite is monoclinic C2/m, with unit-cell parameters: a = 9.9804(11), b = 18.0127(19), c = 5.2971(6) Å, β = 104.341(2)° and V = 922.61 Å3. In transmitted plane-polarised light (λ = 590 cm–1), potassic-magnesio-arfvedsonite is pleochroic: X = yellow pale-green, Y = green and Z = dark-violet brown. It is biaxial (–), α = 1.645(2), β = 1.655(2), γ = 1.660(2) and 2Vmeas. = 60° and 2Vcalc. = 70°. The empirical unit formula obtained from EMPA and structure refinement is A(K0.86Na0.0.08)0.94B(Na1.74Ca0.25 Mn2+0.01)2.00C(Mg2.67Fe2+1.42Fe3+0.76Ti0.12Mn2+0.03)5.00TSi8O22W(OH1.58F0.22O0.20)2.00. The Fe3+/Fetot ratio (0.35) is consistent with both the Mössbauer spectra and the single-crystal structure refinement. The 10 strongest X-ray powder reflections [d values (in A°), I, (hkl)] are: 8.519, 80.5, (110); 3.402, 67.3, (131); 3.295, 41.0, (240); 3.173, 65.0, (310); 2.752, 35.6, ($\bar{3}$31); 2.715, 100.0 (151); 2.591, 44.1, (061); 2.542, 73.2, ($\bar{2}$02); 2.348, 38.5, ($\bar{3}$51); 2.174, 42.0, (261). Potassic-magnesio-arfvedsonite is the product of strongly peralkaline and potassic (perpotassic) magma compositions. Trace-element analysis shows that this amphibole did not exert significant control on trace-element distribution in the crystallising peralkaline magma.
Discreditation of the pyroxenoid mineral name ‘marshallsussmanite’ with a reinstatement of the name schizolite, NaCaMnSi3O8(OH)
- Joel D. Grice, Aaron J. Lussier, Henrik Friis, Ralph Rowe, Glenn G. Poirier, Zina Fihl
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- 22 April 2019, pp. 473-478
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Schizolite, originating from the type locality, Tutop Agtakôrfia, in the Ilímaussaq alkaline complex, Julianehåb district, South Greenland, was described initially by Winther (1901) with additional data being supplied by Bøggild (1903). Recently, a proposal for the new mineral ‘marshallsussmanite’ was submitted to, and approved by, the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA2013-067) by Origlieri et al. (2013). Results from the detailed examination of two schizolite cotype samples presented here, using single-crystal and powder X-ray diffraction, and optical properties, confirms it to be equivalent to ‘marshallsussmanite’. Historical precedence sets a priority for discrediting the name ‘marshallsussmanite’ in favour of the original, more-than-a century-old name, schizolite. The two schizolite samples investigated vary slightly in physical and chemical properties but are consistent overall. The prismatic crystals are pale red or pink to brownish. Schizolite is brittle with a splintery aspect. It is biaxial (+), with average optical parameters: α = 1.626 ± 0.003, β = 1.630 ± 0.002, γ = 1.661 ± 0.002, 2Vmeas = 71(4)° and 2Vcalc = 40°; there is no pleochroism. Electron microprobe analysis shows both samples have nearly identical compositions (differences <0.4 wt.% oxide), with the mean values of: SiO2 52.6(4); Al2O3 0.005(1); FeO 2.54(2); MnO 13.86(9); CaO 17.9(4); Na2O 8.9(1); and H2O 2.59(2) wt.% oxide; this corresponds to a mean formula of: Na1.00(2)Ca1.11(7)Mn0.68(1)Fe0.12(0)Si3.041(1)O8(OH). Final least-squares structure refinements for both samples converged at R1 values ≤2.0%; H atoms were located in all refinements.
NEWSLETTER 49
IMA Commission on New Minerals, Nomenclature and Classification (CNMNC)
New minerals and nomenclature modifications approved in 2019
- Ritsuro Miyawaki, Frédéric Hatert, Marco Pasero, Stuart J. Mills
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- 24 May 2019, pp. 479-483
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Front Cover (OFC, IFC) and matter
MGM volume 83 issue 3 Cover and Front matter
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- 09 July 2019, pp. f1-f2
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Back Cover (IBC, OBC) and matter
MGM volume 83 issue 3 Cover and Back matter
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- 09 July 2019, pp. b1-b2
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