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A NEW COPPER SULFATE-CARBONATE HYDROXIDE HYDRATE MINERAL, (Mn, Ni, Cu)8(SO4)4(CO3)(OH)6¥48H2O, from NAKAURI, AICHI PREFECTURE , JAPAN

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A NEW COPPER SULFATE-CARBONATE HYDROXIDE HYDRATE MINERAL, (Mn, Ni, Cu)8(SO4)4(CO3)(OH)6¥48H2O, from NAKAURI, AICHI PREFECTURE , JAPAN J. Japan. Assoc. Min. Petr. Econ. Geol., 71, 183-192, 1976 A NEW COPPER SULFATE-CARBONATE HYDROXIDE HYDRATE MINERAL, (Mn, Ni, Cu)8(SO4)4(CO3)(OH)6¥48H2O, FROM NAKAURI, AICHI PREFECTURE , JAPAN JUJIN SUZUKI Department of Earth Sciences, Aichi University of Education, Kariya MASAHIRO ITO Laboratory of Earth Sciences, Department of General Education , Nagoya University, Nagoya TSUTOMU SUGIURA Department of Chemistry, Aichi University of Education , Kariya Nakauriite is a new mineral found as fissure-fillings in serpentinite . There are two types appearing in different modes of occurrences, and showing a few faint differences in X-ray diffraction and DTA patterns. Both show very fine needle-like and prismatic forms with characteristic sky-blue color. It is effervescent in HC1, H,S04 and HNO3. Chemical analysis gave Mn0 .01, N10.231 Cu7.770 (SO4)3.904(CO2) (OH)6.232 48.4H2O or (Mn, Ni, Cu)8 (SO4)4 (CO3) (OH)6.48H2O as C=1 for empirical cell contents. The most intense X-ray diffraction lines (in A) are 7.31 (100), 4.840 (14), 3.936 (14), 3.652 (20), 3.552 (13), 2.397 (14), 2.367 (16), 2.332 (14) and 1.9148 (16). The 7.823A-line appears with variable intensities. Nakauriite is pleochroic, X-colorless, Y=very light greenish blue, Z=pale sky-blue to very light blue. The mineral is biaxial negative with ƒ¿=1.585, ƒÀ=1.604, ƒÁ=1.612 (all•}0.001), 2V(-)=65.3 (calc.), showing positive elongation. Extinction is parallel to the outline. Five endothermic reactions are found at 78, 150, 186, 330 and 396•Ž of peak maxima, respectively, the last two being characteristically strong. Infrared absorption gives two characteristic bands at 3000 and 1360cm-1. The name is for the locality. INTRODUCTION on New Minerals and Mineral Names, IMA. At first, this very clear sky-blue mineral Many species of ore minerals have been was found on some serpentinite fragments known in the serpentinite mass, that is, removed from an abandoned mine in Sam magnetite, native copper, chalcocite, cup bagawa metamorphic belt at Nakauri, about rite, digenite, djurleite, cobalt pentlandite, 6km southeast of Shinshiro, Aichi Pre heazlewoodite, and as secondary minerals, fecture, Japan. Soon after, this mineral was tenorite, malachite, brochantite and azurite. noted to occur as fracture-fillings in the Only two sulfate-carbonate hydroxide brucite-bearing serpentinite mass and was hydrate minerals have been reported so far: named nakauriite for the locality. The carbonate-cyanotrichite (Ankinovich et al., mineral and the name were approved in 1963) and jouravskite (Graudefroy and advance of publication by the Commission Permingeat, 1965). Nakauriite is the third (Manuscript recieved, April, 2, 1976) 184 J. Suzuki, M. Ito and T. Sugiura one of this kind. In this paper, detailed description of this mineral will be reported in comparison with that of carbonate cyanotrichite which is somewhat similar to nakauriite in appearance. MODE OF OCCURRENCE Nakauriite which is conspicuously sky blue in color by the naked-eye is found as fissure-fillings in the fractured serpentinite body containing hard and massive Fig. 1. A mode of occurrence of nakauriite. serpentinite blocks. The serpentinite is composed mainly of serpentine minerals, in X-ray diffraction and DTA patterns, opaque minerals, brucite, pyroaurite, which will be discussed in each section artinite, hydromagnesite, "yoshikawaite"1) mentioned below. (Suzuki and Ito, 1973), coalingite and aragonite. Coalingite occurs as veins as OPTICAL AND OTHER PHYSICAL PRO sociated with pyroaurite. PERTIES Nakauriite shows two modes of occur Nakauriite occurs commonly as bundled rences: Type 1 and Type 2. aggregates of very small slender to fibrous Type 1 occurs as veins cutting the crystals, whose sizes are less than about 0.2 massive serpentinite and the fractured mm in length, 0.006mm in width. It is serpentinite. The mineral is commonly clear sky-blue in color and pleochroic with associated with chrysotile and a small X=colorless, Y=very light greenish blue, amount of magnetite, and rarely with broch Z=pale sky-blue to very light blue. The antite and malachite in massive serpentinite. refractive indices for sodium light are ƒ¿= Type 2 occurs along fractures in sheared 1.585•}0.001, ƒÀ=1.604•}0.001, ƒÁ=1.612 serpentinite. It is commonly associated •} 0.001 by the immersion method. Birefring with chrysotile, magnetite, artinite and ence is moderate; ƒÁ-ƒ¿=0.027, ƒÀ-ƒ¿=0.019, pyroaurite. Free growth of very fineƒÁ-ƒÀ =0.009. The minera is biaxial nega grained slender crystal aggregates of the tive with 2V(-) 65.3•K(calculated). Extinc mineral is commonly found in the small tion is parallel to the outline of the crystal openings of fractured serpentinite (Fig. 1.). with positive elongation. Cleavage and Crystals of Type 2 are relatively smaller twinning are not observed. than those of Type 1, commonly associated The density was determined by flota with fair amounts of extremely fibrous ones. tion of clear crystals in Clerici solution, Any distinguishable differences in which gave a value of 2.39•}0.02g/cm3. chemical composition and optical properties The denity calculated by Gradstone and are not observed between the two types. Dale's equation is 2.30g/cm3, in well agree However, some slight differences are noticed ment with the observed value. 1) Application to the IMA Commission on New Minerals and Mineral Names for an approval of the name is pending. A new copper sulfate-carbonate hydroxide . hydrate mineral 185 Carbonate-cyanotrichite shows similar ponent in nakauriite. Although the sample pleochroism, but has higher refractive was prepared by careful hand-picking under indices and double refraction, showing the binocular microscope, even the most optically positive sign and negative elonga purified concentrate was still found to be tion. contaminated by chrysotile, judged from the data of DTA. CHEMICALCOMPOSITION Quantitative chemical analysis for the The sample which was thoroughly purified sample was made by atomic absorp tion analysis for CaO, MgO, total iron, MnO purified was used for qualitative analysis by X-ray fluorescence method. Electron and CuO, flame spectrochemical analysis for Na2O and K2O, titration method for Fe2O3, probe microanalysiswas also made in order to check the validity of the data obtained by the X-ray fluorescenceanalysis. As the Table 2. X-ray powder diffraction data for na kauriite from Nakauri, AichiPrefecture, specimen is too brittle to prepare evenly Japan. polished section for EPMA, hand-picked specimen mounted on extremely pure bery llium plate was carbon-coated as it was. Effervescency in HCl, H2SO4 and HNO3 positively shows the presence of CO,-com Table 1. Chemical compositions of nakauriite and associated chrysotile from Nakauri, Achi Prefecture, Japan. A. Nakauriite and the admixed chrysotile. * Plus serpentine mineral . B. Chrysotile associated with nakauriite. ** For not-pulverized slender crystals. C. Nakauriite, corrected for the admixed 1) Calculated by A. Kato. Orthorhombic, a 14.585, chrysotile and normalized. b 11.47, c 16.22A, Z=2, density (calc) 2.35g/cm3. 186 J. Suzuki, M. Ito and T. Sugiura gravimetric analysis for A12O3, SiO2 and and 1:1, respectively. H2O, spectrophotometric analysis for TiO2 and SO42-,and volumetric analysis for CO2. X-RAY DATA The chemical composition of the purified sample and the chrysotile associated with X-ray powder data for the new mineral nakauriite are listed in Table 1, together were obtained, using Ni-filtered CuKa radia with the rationalized mole percentages. tion. The whole X-ray diffraction data at Contamination effect by the admixed chry room temperature are shown in Table 2 and sotile was eliminated based on the SiO2 Figure 2. Nakauriite gives clearly different content of the purified sample. pattern from that for carbonate-cyanotri The formula of nakauriite is Mn0.019 chite. Ni0.231Cu7.770(SO4) 3.904 (CO3) (OH)6.232 ¥48.4H2O, Some differencesare noted in the X-ray and is idealized as (Mn, Ni, Cu)8 (SO4)4(CO3) diffraction patterns of Type 1 and Type 2 (OH)6¥48H2O as C =1 for empirical cell of nakauriite as follows: (1) The reflection contents. Although a very small amount line of 7.82A appears characteristicallyin of ZnO and Fe2O3are found in the chemical Type 2, and shows change of peak height analysis, these may be neglected for the depending on the orientations; if the chemical formula of the mineral. The mole powder specimen is rubbed strongly on ratio of SO4 to CO3 of nakauriite, carbonate the holder, the peak height increases. Type cyanotrichite and jouravskite is 4:1, 1:2 1 shows fairly faint reflectionline of 7.82A, Fig. 2. X-ray diffraction patterns for nakauriite, A, Type 1; B , Type 2. CuK. radiation was used for 2ƒÆ. A new copper sulfate-carbonate hydroxide hydrate mineral 187 even undetectable in some cases. But it not changed by orientation effect mentioned appears distinguishable when the sample is above. rubbed strongly on the holder (3) The whole reflection lines for Type 2 .(2) The patterns for the reflection lines of are generally weaker than those for Type 1. medium peak heights are characteristically The reflection lines of 7.31 and 3.65A different between the two types especially in may be assigned to those of the admixed the range of d-spacing of 5.54 to 3.43A and chrysotile. But these lines are concluded to 2.43 to 2.31A. Apparent peak heights of be essential ones for nakauriite, based on lines of 3.55 and 1.914A are also distinctly their thermal behaviours. The thermal different on the patterns between the two effects on the whole X-ray diffraction pat types. These relations in peak heights are terns of the mineral were investigated by Fig.
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