Beusite-(Ca), ideally CaMn22+(PO4)2, a new graftonite-group mineral from the Yellowknife pegmatite field, Northwest Territories, Canada: Description and crystal structure
Abstract:Beusite-(Ca), ideally Ca${\rm Mn}_{\rm 2}^{2 +} $(PO4)2, is a new graftonite-group mineral from the Yellowknife pegmatite field, Northwest Territories, Canada. It occurs in a beryl–columbite–phosphate rare-element pegmatite where it is commonly intergrown with triphylite–lithiophilite or sarcopside, and may form by exsolution from a high-temperature (Li,Ca)-rich graftonite-like parent phase. It occurs as pale-brown lamellae 0.1–1.5 mm wide in triphylite, and is pale brown with a vitreous lustre and a very pale… Show more
“…The interstices are mainly filled with rock-forming cristobalite or locally with small dendritic plagioclase and K-Na feldspar in small zones of high-silica Krich peraluminous glass. Accessory phases include fluorapatite and Fe-Mn-Ca phosphate, presumably from the graftonite-group (Figure 3f), with ideal crystal chemical formula (Fe 2+ MnCa) 3 (PO 4 ) 2 [19,20]. Vugs in the matrix are filled with supergene secondary phases: goethite, jarosite, calcite, and unidentified Si-Fe-P-H 2 O-bearing phases.…”
Melted rocks (clinkers and paralavas) of the Mongolian combustion metamorphic (CM) complexes were formed during modern and ancient (since the Quaternary) wild-fires of brown coal layers in the sedimentary strata of the Early Cretaceous Dzunbain Formation. According to XRD, Raman spectroscopy, and SEM-EDS data, cordierite, sekaninaite, indialite, ferroindialite, silica polymorphs, mullite, Fe-mullite, anhydrous Al-Fe-Mg silicate spinel (presumably new mineral), and other phases were identified. It has been established that isomorphic impurity of potassium in the cordierite-group minerals does not correlate with their crystal structure (hexagonal or orthorhombic). Indialite and ferroindialite retained their hexagonal structure in some fragments of the CM rocks, possibly due to the very fast cooling of local zones of sedimentary strata and the quenching of high-temperature K-rich peraluminous melt. Clinkers, tridymite–sekaninaite, and cristobalite–fayalite ferroan paralavas were produced by partial melting of Fe-enriched pelitic rocks (mudstone, siltstone, and silty sandstone) in a wide temperature range. The formation of mullite, Fe-mullite, and Al-Fe-Mg silicate spinel in clinkers developed from dehydration–dehydroxylation and incongruent partial melting of Fe-enriched pelitic matter (Al-Mg-Fe-rich phyllosilicates, ‘meta-kaolinite’, and ‘meta-illite’). Large-scale crystallization of these minerals in the K-rich peraluminous melts occurred, presumably, in the range of T > 850–900 °C. The subsurface combustion of coal layers heated the overburden pelitic rocks from sedimentary strata to T > 1050 °C (judging by the formation of cordierite-group minerals) or locally till the melting point of detrital quartz grains at T > 1300 °C and, possibly, till the stability field of stable β-cristobalite at T > 1470 °C. Ferroan paralavas were formed during the rapid crystallization of Fe-rich silicate melts under various redox conditions. From the analysis of the liquidus surface in the Al2O3–FeO–Fe2O3–SiO2 major-oxide system, it follows that the least high-temperature (<1250 °C) and the most oxidizing conditions occurred during the crystallization of mineral assemblages in the most-enriched iron silicate melts parental for cristobalite–fayalite paralava.
“…The interstices are mainly filled with rock-forming cristobalite or locally with small dendritic plagioclase and K-Na feldspar in small zones of high-silica Krich peraluminous glass. Accessory phases include fluorapatite and Fe-Mn-Ca phosphate, presumably from the graftonite-group (Figure 3f), with ideal crystal chemical formula (Fe 2+ MnCa) 3 (PO 4 ) 2 [19,20]. Vugs in the matrix are filled with supergene secondary phases: goethite, jarosite, calcite, and unidentified Si-Fe-P-H 2 O-bearing phases.…”
Melted rocks (clinkers and paralavas) of the Mongolian combustion metamorphic (CM) complexes were formed during modern and ancient (since the Quaternary) wild-fires of brown coal layers in the sedimentary strata of the Early Cretaceous Dzunbain Formation. According to XRD, Raman spectroscopy, and SEM-EDS data, cordierite, sekaninaite, indialite, ferroindialite, silica polymorphs, mullite, Fe-mullite, anhydrous Al-Fe-Mg silicate spinel (presumably new mineral), and other phases were identified. It has been established that isomorphic impurity of potassium in the cordierite-group minerals does not correlate with their crystal structure (hexagonal or orthorhombic). Indialite and ferroindialite retained their hexagonal structure in some fragments of the CM rocks, possibly due to the very fast cooling of local zones of sedimentary strata and the quenching of high-temperature K-rich peraluminous melt. Clinkers, tridymite–sekaninaite, and cristobalite–fayalite ferroan paralavas were produced by partial melting of Fe-enriched pelitic rocks (mudstone, siltstone, and silty sandstone) in a wide temperature range. The formation of mullite, Fe-mullite, and Al-Fe-Mg silicate spinel in clinkers developed from dehydration–dehydroxylation and incongruent partial melting of Fe-enriched pelitic matter (Al-Mg-Fe-rich phyllosilicates, ‘meta-kaolinite’, and ‘meta-illite’). Large-scale crystallization of these minerals in the K-rich peraluminous melts occurred, presumably, in the range of T > 850–900 °C. The subsurface combustion of coal layers heated the overburden pelitic rocks from sedimentary strata to T > 1050 °C (judging by the formation of cordierite-group minerals) or locally till the melting point of detrital quartz grains at T > 1300 °C and, possibly, till the stability field of stable β-cristobalite at T > 1470 °C. Ferroan paralavas were formed during the rapid crystallization of Fe-rich silicate melts under various redox conditions. From the analysis of the liquidus surface in the Al2O3–FeO–Fe2O3–SiO2 major-oxide system, it follows that the least high-temperature (<1250 °C) and the most oxidizing conditions occurred during the crystallization of mineral assemblages in the most-enriched iron silicate melts parental for cristobalite–fayalite paralava.
2 Abstract A classification and nomenclature scheme has been approved by the IMA-CNMNC (memorandum 66-SM/17) for the minerals of the graftonite group. The crystal structures of these minerals have three distinct sites that are occupied by Fe 2+ , Mn 2+ and Ca 2+ . These sites have coordination numbers [8], [5] and [6], and these differences lead to very strong order of Fe 2+ , Mn 2+ and Ca 2+ over these sites. As a result of this strong order, the following compositions have been identified as distinct species: graftonite: FeFe 2 (PO 4 ) 2 ; graftonite-(Ca): CaFe 2 (PO 4 ) 2 ;graftonite-(Mn): MnFe 2 (PO 4 ) 2 ; beusite: MnMn 2 (PO 4 ) 2 ; beusite-(Ca): CaMn 2 (PO 4 ) 2 .
“…The holotype and co-type samples are deposited in the collection of the Mineralogical Museum of University of Wrocław (University of Wrocław, Faculty of Earth Science and Environmental Management, Institute of Geological Sciences, Mineralogical Museum, 50-205 Wrocław, Cybulskiego 30, Poland), with catalogue numbers MMWr IV7927 [graftonite-(Mn) holotype], MMWr IV7928 [graftonite-(Mn) co-type], and MMWr IV7674 [graftonite-(Ca) and maneckiite holotype] (Pieczka et al ., 2017 a ). The third new mineral species in the graftonite group, beusite-(Ca), with the holotype coming from Canada, is described in a companion paper (Hawthorne et al ., 2018). Neither of these minerals was a valid unnamed mineral (Smith and Nickel, 2007; ).…”
Two new minerals of the graftonite group, graftonite-(Mn), ideallyM(1)MnM(2),M(3)Fe2(PO4)2, and graftonite-(Ca), ideallyM(1)CaM(2),M(3)Fe2(PO4)2, were discovered in phosphate nodules of two beryl–columbite–phosphate pegmatites at Lutomia and Michałkowa, respectively, in the Góry Sowie Block, Lower Silesia, southwest Poland. Graftonite-(Mn) is pinkish brown, whereas graftonite-(Ca) shows more brownish colouration. Both minerals have a vitreous lustre, a good cleavage observed along (010) and irregular fracture; both are transparent and neither of them is fluorescent. They are brittle and have a Mohs hardness of ~5. The minerals are non-pleochroic, colourless in all orientations, biaxial (+), with mean refractive indices α = 1.710(2) and 1.690(2), β = 1.713(2) and 1.692(2), and γ = 1.725(2) and 1.710(5), respectively. With complete order of Ca at theM(1) site, the formulae of the holotype crystals areM(1)(Mn0.70Ca0.30)M(2),M(3)(Fe1.34Mn0.60Mg0.06Zn0.01)Σ3(PO4)2for graftonite-(Mn) andM(1)(Ca0.98Mn0.02)M(2),M(3)(Fe1.38Mn0.56Mg0.05)Σ3(PO4)2for graftonite-(Ca). Both crystal chemistry and crystal-structure refinement (R1= 2.34 and 1.63%, respectively) indicate that theM(1) site is occupied dominantly by Mn in graftonite-(Mn) and by Ca in graftonite-(Ca), and theM(2) andM(3) sites are occupied by Fe2+and Mn2+, with Fe2+dominant over Mn2+at the aggregateM(2) +M(3) sites. Graftonite-(Mn) and graftonite-(Ca) are isostructural with graftonite,M(1)FeM(2),M(3)Fe2(PO4)2(monoclinic system; space-group symmetryP21/c), with the unit-cell parametersa= 8.811(2) Å,b= 11.494(2) Å,c= 6.138(1) Å, β = 99.23(3)° and V = 613.5(4) Å3, anda= 8.792(2) Å,b= 11.743(2) Å,c= 6.169(1) Å, β = 99.35(3)° andV= 628.5(1) Å3, respectively. The densities calculated on the basis of molar weights and unit-cell volumes are 3.793 g/cm3for graftonite-(Mn) and 3.592 g/cm3for graftonite-(Ca). The eight strongest lines in powder X-ray diffraction patterns on the basis of single-crystal data are, respectively [d, Å,I(hkl)]: 2.874, 100, (230 + 040); 2.858, 79, (221); 3.506, 73, (130); 2.717, 79, ($\bar{3}$11); 2.952, 55, (131); 2.916, 53, ($\bar{1}$12); 2.899, 44, (300); 3.016, 35, ($\bar{1}$02); and 3.654, 100, (130); 2.979, 85, (221); 3.014, 77, (230); 3.042, 76, (040 +$\bar{1}$12); 2.834, 68, ($\bar{3}$11); 3.097, 57, (131); 3.133, 56, ($\bar{1}$02); 2.542, 30, (311). Both minerals are common primary phosphates in phosphate nodules, occurring as lamellar intergrowths with sarcopside ± triphylite/lithiophilite, products of exsolution from a (Li,Ca)-rich graftonite-like parent phase crystallized at high temperature from P-bearing hydrosaline melts.
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