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(La), a New Mineral of the Epidote Group from Andros Island, Greece

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(La), a New Mineral of the Epidote Group from Andros Island, Greece American Mineralogist, Volume 81, pages 735-742.1996 Solid solution between piemontite and androsite-(La), a new mineral of the epidote group from Andros Island, Greece PAOLA BONAZZI,l SILVIO MENCHETTI,l AND THOMAS REINECKE2 lDipartimento di Scienze delia Terra, Universita di Firenze, via La Pira 4, 1-50121 Florence, Italy 21nstitut fUr Minera1ogie, Ruhr-Universitat Bochum, Universitatsstrasse 150, D-44801 Bochum 1, Germany ABSTRACT A new member of the epidote group, androsite-(La), was found at Andros Island, Cyclades, Greece, as an accessory constituent of metamorphic Mn-rich rocks. Associated minerals are rhodochrosite, braunite, rhodonite, spessartine, and quartz. The mineral is brown-red in color, transparent with vitreous luster and very strong pleochroism. Lattice parameters are a = 8.896(1), b = 5.706(1), c = 10.083(1) A, (3= 113.88(1)°, V = 468.0(1) A3, Z = 2, space group P2/m. Crystal-structure refinement and chemical analyses yielded the ideal formula (Mn,Ca)REEAIMnHMnH(SiO.)(Si207)0(OH). Another Mn-rich sample of the epidote group was found at Varenche Mn-mine, Valle di Saint Barthelemy, Western Alps, Italy; because of its chemical composition and crystallographic features, it can be consid- ered an intermediate member of the piemontite-androsite-(La) series. INTRODUCTION urn of the University of Florence (sample no. 2074/RI). Until 1988, the only known REE-bearing mineral of The second mineral, collected at the Varenche mine (Valle the epidote group was allanite, which can be described by di Saint Barthelemy, Western Alps, Italy) is piemontite the ideal formula CaREEA12FeH(Si3011)0(OH). In re- with REE content greater than that found in any REE- cent years other epidote minerals containing lanthanide bearing piemontite previously described (Williams 1893; elements as dominant cations in the A2 site have been Kramm 1979; Schreyer et al. 1986; Bonazzi et al. 1992; described. In the structure of dissakisite-(Ce), Ca- Bermanec et al. 1994). This mineral also has the MnH Ca substitution but to a lesser extent than androsite- REEA12Mg(Si30II)0(OH) (Grew et al. 1991), the excess "" positive charge due to REEH replacing Ca is balanced by (La). The chemical composition of these piemontite sam- the substitution of Mg. This mineral is therefore consid- ples suggests the existence of a continuous solid solution ered to be the Mg analog of allanite. Dollaseite-(Ce), between piemontite and androsite-(La). CaREEAIMg2(Si30Il)F(OH) (Peacor and Dunn 1988), is characterized by a more complex substitution. The pres- OCCURRENCE, PARAGENESIS, AND PHYSICAL ence of two divalent cations in the octahedral sites is PROPERTIES coupled with the substitution of F- for 02- on the 04 The sample (79/517) containing androsite-(La) was site. A new member of the epidote group with the for- collected on the heap of a former test pit for Mn ores, mula (Ca,REE)REE(Mg,Fe)MnAl(Si3011)OH(F,0) was situated at an altitude of 950 ill on the peak plateau of found by Sokolova et al. (1991) at Inyl'chek Massif, Kir- Petalon Mountain, Andros Island, Cyclades, Greece. The giziya (former USSR). In this mineral, subsequently Mn-rich metamorphic rocks at this site are made up of named khristovite-(Ce) by Pautov et al. (1993), two oc- highly oxidized quartzitic schists, quartzites, and Mn-rich tahedral sites are mostly occupied by divalent cations (Mg pyroxenoid and carbonate rocks (Reinecke 1983; Re- in M1 and Mn in M3). Electrostatic balance is achieved inecke and Hatzipanagiotou 1987), among which the more by REP+ substituting for Ca and by the substitution of Ca-poor assemblages (e.g., spessartine quartzite, rhodo- F for 0 at the 04 site. nite + rhodochrosite + braunite felse) occasionally have The present paper reports the results of a crystal-chem- androsite-(La) as a minor or accessory constituent. The ical study of two REE minerals of the epidote group that ferromanganoan metasediments in central Andros form have chemical compositions and cation populations not part of a volcano-sedimentary sequence that experienced previously recognized in any member of this group. The low-grade, high-pressure metamorphism (P > 11 kbar, T first one, named androsite-(La) after its original locality = 360-420 °C; Reinecke, unpublished data) followed along (Andros Island, Greece), is a new mineral with the ideal the uplift path by a greenschist facies overprint. formula (Mn,Ca)REEMnHMnH Al(Si3011)0(OH) (ap- In Mn-rich silicate-carbonate rock 79/517, minute proved by the International Mineralogical Association grains of androsite-(La) (commonly with a maximum di- Commission on New Minerals and Mineral Names). Type ameter of 20-60 ~m, rarely up to 200 ~m) are randomly material has been deposited at the Mineralogical Muse- interspersed in a fine- to medium-grained matrix of rho- 0003-004X/96/0506-0735$05.00 735 --------- 736 BONAZZI ET AL.: CRYSTAL CHEMISTRY OF ANDROSITE-(La) hematite quartzites and braunite- and spessartine-bearing rocks, with variable proportions of rhodochrosite, cros- site-magnesioriebeckite, phlogopite, phengite, clinoch- lore, talc, Na-bearing pyroxene, rutile and barite, and un- common minerals such as ardennite, Mn-rich berzeliite, kutnahorite, and tirodite (Baldelli et al. 1983; Reinecke, unpublished data). The VA90/1 gneiss contains the relic high-pressure assemblage aegirine (Jd35-37Ac61Aug2-4'partly replaced by very fine-grained intergrowths of albite and dochrosite, patchy rhodonite, fine-grained subhedral hematite), spessartine, hematite, colorless crossite, quartz, braunite, and rare fishnet-type garnet (85 mol% spes- phengite, with minor rutile and REE-rich piemontite. sartine, 9 mol% grossular, 6 mol% andradite). Andro- Abundant albite poikiloblasts in the matrix, manganoan site-(La) crystals are subhedral to euhedral, untwinned, phlogopite replacing phengite and crossite, and magne- brown-red in color, transparent, with vitreous luster. sioriebeckite rims around crossite are interpreted as Pleochroism in plane-polarized light is very strong: X = members of a lower pressure assemblage. The REE-rich pale orange-brown and Z = deep brown-red (Y not de- piemontite described here occurs as a few scattered grains, termined). The mean refractive index, calculated from 20-180 ,urn in diameter, in the gneiss. It forms euhedral, the Gladstone-Dale relationship using the constants giv- prismatic crystals, brownish-red in color, commonly en by Mandarino (1976), is 1.877. The observed density twinned after {100}, and displays vivid absorption colors' is >4.03 g/cm3 (it sinks in Clerici solution); the calculated (X = pale orange-brown, Y = orange-brown, and Z = value is 4.21 glcm3. bright orange-red). The second mineral was found in a fine-grained, red- dish-brown gneiss (VA90/1) sampled on the dump of the abandoned Mn mine at Varenche, Valle di Saint Barthe- EXPERIMENTALMETHODS lemy, a few kilometers northeast of Nus, Valle d'Aosta, An X-ray powder pattern of androsite-(La) (Table I) Italy. The metasedimentary rocks at Varenche probably was obtained from a few minute grains by means of a form part of the Tsate nappe (= Combin Unit s.s., Dal Gandolfi camera (diameter = 114.6 mm, Ni-filtered CuKa Piaz 1988; Marthaler and Stampfli 1989), a composite radiation). For the crystal-structure study, two optically nappe made up of calcschists, MORB-type metabasalts homogeneous crystals, AND-517 and VA-I a, were se- and metagabbros, serpentinites, and pelagic (partly man- lected from rock samples 79/517 (Andros) and VA90-1 ganiferous) metasediments, which were metamorphosed (Varenche), respectively. Unit-cell parameters and inten- at greenschist-facies conditions. They locally retain relics sity data were measured on an Enraf Nonius CAD4 dif- of a low-grade, high-pressure metamorphism (Sperlich fractometer with graphite-monochromatized MoKa ra- 1988; Reinecke, unpublished data). The highly oxidized, diation. Crystal data and experimental details are reported Mn-rich rocks consist mainly of varicolored spessartine- in Table 2. Intensities were corrected for Lorentz and BONAZZI ET AL.: CRYSTAL CHEMISTRY OF ANDROSITE-(La) 737 TABLE 3. Atomic positional and displacement parameters for TABLE 4. Atomic positional and displacement parameters for androsite-(La) the REE-rich piemontite from Varenche xl a ylb zlc U..,(A') xla ylb zlc u..,(A') A1 0.7587(1 ) 0.7500 0.1525(1) 0.0117(3) A1 0.7590(1) 0.7500 0.1523(1) 0.0128(3) A2 0.5922(1) 0.7500 0.4275(1) 0.0110(1) A2 0.5942(1) 0.7500 0.4256(1 ) 0.0123(1 ) Si1 0.3504(2) 0.7500 0.0368(2) 0.0086(4) Si1 0.3440(1) 0.7500 0.0399(1 ) 0.0082(4) Si2 0.6937(2) 0.2500 0.2809(2) 0.0080(5) Si2 0.6893(1) 0.2500 0.2787(1) 0.0081(4) Si3 0.1915(2) 0.7500 0.3251(2) 0.0066(5) Si3 0.1864(1) 0.7500 0.3213(1) 0.0072(4) M1 0.0000 0.0000 0.0000 0.0070(3) M1 0.0000 0.0000 0.0000 0.0086(3) M2 0.0000 0.0000 0.5000 0.0085(6) M2 0.0000 0.0000 0.5000 0.0072(5) M3 0.3130(1) 0.2500 0.2099(1) 0.0129(3) M3 0.3020(1) 0.2500 0.2151(1) 0.0126(3) 01 0.2470(3) 0.9925(5) 0.0266(3) 0.0143(10) 01 0.2401(3) 0.9921(4) 0.0327(3) 0.0154(8) 02 0.3140(3) 0.9746(5) 0.3601 (3) 0.0104(10) 02 0.3087(3) 0.9763(4) 0.3578(2) 0.0114(8) 03 0.8052(3) 0.0133(5) 0.3306(3) 0.0116(9) 03 0.7998(3) 0.0135(4) 0.3357(3) 0.0139(7) 04 0.0576(5) 0.2500 0.1317(4) 0.0082(13) 04 0.0558(4) 0.2500 0.1313(3) 0.0095(11 ) 05 0.0481(4) 0.7500 0.1584(4) 0.0103(14) 05 0.0450(4) 0.7500 0.1524(3) 0.0116(11) 06 0.0796(5) 0.7500 0.4211 (4) 0.0097(13) 06 0.0740(4) 0.7500 0.4153(4) 0.0101(11) 07 0.5189(5) 0.7500 0.1773(5) 0.0139(15) 07 0.5154(4) 0.7500 0.1768(4) 0.0162(12) 08 0.5545(5) 0.2500 0.3430(5) 0.0211 (17) 08 0.5410(4) 0.2500 0.3286(4) 0.0208(14) 09 0.6036(5) 0.2500 0.1042(5) 0.0174(16) 09 0.6153(4) 0.2500 0.1027(4) 0.0203(14) 010 0.0913(5) 0.2500 0.4338(5) 0.0079(13) 010 0.0865(4) 0.2500 0.4311(4) 0.0093(11 ) H 0.100(7) 0.2500 0.350(7) 0.07(1) H 0.062(6) 0.2500 0.341(6) 0.05(1) polarization effects and for absorption (North et al.
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