J. Japan, Assoc. Min.P etr. Econ. Geol. 74, 406-412, 1979

MALLARDITE FROM THE JOKOKU MINE, HOKKAIDO, JAPAN

MATSUO NAMBU, KATSUTOSHI TANIDA and TsUYOSHI KITAMURA

Research Institute of Mineral Dressing and Metallurgy, Tohoku University, Katahira, Sendai 980, Japan

and

EIhHI KATO

J6koku Mine, Chugai Co. Ltd., Kaminokuni, Hiyama, Hokkaido 049-06, Japan

Mallardite, MnSO4.7H2O, reported only from its original locality, the Lucky Boy mine, Utah (Carnot, 1879), was found from the Jokoku mine, Hokkaido, Japan. The mineral occurs as efflorescences which are composed of aggregates of minute fibers or

prismatic crystals on the walls of mine passages. X-ray powder diffraction pattern shows that it is monoclinic with a0=14.15, b0=6.50, c0=11.06A, ƒÀ=105•‹36', Z=4 and space group P21/c seems probable from the analogy with melanterite and bieberite. Wet chemical analysis leads to an emperical formula of

(Mn0.90, Mg0.11)1.01S1.00O4,00•E6.8H2O, showing the material to be very close to the ideall formula MnSO4•E7H2O. The mineral is colorless with vitreous luster, and transparent to translucent. Powdered material is white in color. It is readily soluble in cold water. Specific gravity is 1.838 (calc.). Optically biaxial possitive with large optic axial angle. Extinction angle is Z•Èc=44•‹. Refractive indices measured by the immersion method are ƒ¿=1.462, ƒÀ=1.465, ƒÁ =1.474, and ƒÁ-ƒ¿=0.012, all •}0.003.

Studies on the stability relation among synthetic manganese sulfate hydrates (Cottrell, 1900) and the field evidence in adits where the material was collected indicate that mallardite is formed at temperatures below about 10•Ž and under high relative humidity.

•@ Berman and Frondel, 1951), but•@ no INTRODUCTION reliable data of these minerals are known. Mallardite was originally described by This very rare mineral was found by one Carnot (1879) from the Lucky Boy mine, of the authors (E. K.) in adits of 80 meter. Utah which is the only one definite locality level of the J6koku mine in February, 1977. of the mineral. Its identification is based In this paper, the mode of occurrence and only on chemical analysis and optical mineralogical properties of mallardite from properties which are lacking in refractive the mine are presented together with brief indices, so that mineralogical data of this discussion on its stability and genesis. mineral are very scanty. Moreover, a cuprian and zincian variety is said to occur OCCURRENCE in the Bayard area of the Central District, The J6koku mine, the largest producer

Grand County, New Mexico (Palache, of manganese in Japan, is located at

(Manuscript received July 3, 1979) Mallardite from the JSkoku mine, Hokkaido, Japan 407

lead deposits have been proved to occur in the paleozoic limy rocks, being developed around the lower part of veins (Ohta, Honda and Nishiyama, 1971). The ore minerals are composed mainly of rhodochrosite associated with subordinate amounts of sphalerite, galena and pyrite, and with many kinds of minor minerals. Gangue minerals include quartz, dolomite, ankerite, kutnahorite, manganoan calcite and a small quantity of clay minerals such as chlorite, sericite and kaolin minerals (Nambu and Kitamura, 1974). These are altered in the zones of oxidation to limonite consisting of goethite and lepidochrosite, and to various manganese dioxide minerals such as nsutite, cryptomelane, pyrolusite,

Fig. 1 Map showing the location of JSkoku lithiophorite, manganite and wad. In mine, Hokkaido, Japan. adition, plumbogummite occurs rarely in the aggregates of goethite and quartz. Kaminokuni-machi, Hiyama District about Mallardite was found in adits of the 80 60km southwest of Hakodate, Hokkaido meter level of the Jokoku mine. Localities are shown in Fig. 2. The mineral occurs (Fig. 1.). The ore deposits are composed of about ten epithermal fissure-filling mainly as delicate fibrous efflorescences and manganese-zinc-lead veins cutting Paleozoic occasionally crusts on the adit wall. It slate and Miocene volcanic rocks (Miura appears directly on the surface of rhodo and Omura, 1961; Nishio, 1966). But, chrosite and other manganese-bearing recently pyrometasomatic manganese-zinc minerals such as manganoan calcite and

Fig. 2 Locality map of mallardite at the 80m level of JSkoku mine. Sample from No. 1 was used for the present study. Uwaban and Shitaban mean a hanging wall and a foot wall, respectively. O:Locality 408 M. Nambu, K. Tanida, T. Kitamura and E. Kato

Table I Optical properties of mallardite, melanterite and bieberite.

1: Mallardite, Jokoku mine, Hokkaido, Japan. Present study. 2: Melanterite (Synthetic, Larsen and Glenn, 1920). 3: Bieberite (Synthetic, Larsen and Glenn, 1920).

the hardness and the specific gravity. The

calculated specific gravity is 1.838, which is

slightly lower than the measured value 1.846 for artificial MnSO4.7H,O (Giinther,

1912).

A distinct cleavage is observed on (001)

under the petrographic microscope. It is

biaxial positive with a large optic angle,

extinction angle is z•Èc=44•‹, and refractive Fig. 3 Photographs of fresh mallardite (upper) and jokokuite pseudomorph (lower) indices measured by the immersion method derived from the dehydration of mallar using Na light at 12•Ž are ƒ¿=1.462, ƒÀ= dite on exposure to dry air at ordinary 1.465, ƒÁ=1.474, (all •}0.003) and ƒÁ-ƒ¿= room temperature. 0.012. These values are somewhat lower kutnahorite, and occasionally as pore or than those of other members of the melan fracture-filling in mother rocks. terite group. Optical properties of mal

Under the microscope, they consist of lardite are compared with those of melan aggregate of hair-like, needle-like and long terite and bieberite in Table 1. columnar crystals, generally between about

0.5 and 12mm in length, and between 0.2 CHEMICAL COMPOSITION and 1mm across (Fig. 3). Chemical analysis was made by the Mallardite is ordinarily not associated normal wet method on the handpicked pure with other sulfate minerals, but rarely materials after the confirmation of their admixed with j6kokuite (MnSO4•E5H2O) purity through the x-ray powder method. and/or ilesite (MnSO4• 4H2O). The results are compared with those The material from the location No. 1 of mallardite from Lucky Boy mine, Utah in Fig. 2 was used for the present study. (Carnot, 1879) and theoretical value of MnSO4.7H20 in Table 2. The material

PHYSICAL AND OPTICAL PROPERTIES from J6koku mine contains 1.59% of MgO

The needles of mallardite are colorless which substitutes for MnO. with vitreous luster and transparent to The empirical formula for the J6koku translucent. The powdered material is material calculated on the basis of O=4 in white in color. It is too fine to measure the anhydrous part is NLIallardite from the JBkoku mine, Hokkaido, Japan 409

Table 2 Chemical analysis of mallardites Table 3 X-ray powder data of mallardite from J6koku mine, Hokkaido from the J6koku mine. and Lucky Boy mine, Utah.

1: Jokoku 'mine, Hokkaido. Japan. Present study. 2: Lucky Boy mine, Utah (Carnot, 1879). 3: Theoretical MnSO4•E7H2O.

* Calculated on the basis of a0=14.15, b0=6.50, c0= 11.06A, ƒÀ=105•‹36'. (Mn0.90OMg0.11)1.01S1.00O4.00•E6.8H2O, ** Pattern at lB•Ž. Fe/Ma radiation. showing the material to be very close to the theoretical MnSO4.7H2O. Table 4 Unit cell parameters of mallardite, melanterite and bieberite.

X-RAY POWDER STUDY

X-ray powder data on a part of purified material used for chemical analysis was obtained by the diffractometer method employing Mn-filtered Fe-radiation. The comparison of d-spacings and intensity ratios between mallardite and melanterite 1: Mallardite, Jakoku min,, Hokkaido, Japan. Present study. 2: Melanterite (JCPDS Card, No.22-633). (FeSO4•E7H2O; JCPDS Card No. 22-633) 3: Bieberite (JCPDS Card, No.16-487). or bieberite (CoSO4•E7H2O; JCPDS Card No.

16-487) shows a close agreement. There together with those of melanterite and fore, it is considered that these three miner bieberite are summarized in Table 4. als are isostructural.

The x-ray powder diffraction pattern THERMAL ANALYSIS is successfully indexed on a monoclinic cell with a0=14.15, b0=6.50, c0=11.06A, ƒÀ= DTA and TG of mallardite were carried

105•‹36', Z=4 in terms of the analogy with out simultaneously in air by means of a melanterite and bieberite. Possible space Thermoflex unit made by Rigaku-Denki Co., Japan, using about 350mg of pure group is P21/c by the same reason as the material. Heating rate was 10•Ž per above. The indexed x-ray powder pattern is presented in Table 3, and unit cell minute. dimensions and calculated specific gravity The DTA and TG curves are shown in 410 M. Nambu, K. Tanida, T. Kitamura and E. Kato

Fig. 4 DTA and TG curves of mallardite from Jokoku mine.

Fig. 4. It is characterized by the three distinctive endothermic peaks at 163•Ž,

325•Ž and 1,005•Ž, accompanying with the three faint but sharp endothermic peaks at

25•Ž, 90•Ž and 895•Ž.

The TG curve shows three steps of weight loss, namely between room tem perature and 200•Ž, between 260•Ž and 360•Ž, and between 725•Ž and 1,025•Ž.

The first and second steps of weight Fig. 5 The solubility of manganous sulfate in water (Cottrell, 1900, rewritten loss are due to the formation of manganese by Mellor (1932)). sulfate monohydrate (MnSO4.H2O) and anhydrous sulfate (MnSO4) by the dehydra ponents from manganese carbonate con tion of crystalline water, respectively. The sisting mainly of rhodochrosite and man third step is derived from expelled SO3, and ganoan calcite, and from sulfide minerals the final product after heated to 1,080•Ž such as pyrite, sphalerite and galena. consists mainly of hausmannite. These The occurrence of this mineral in the phenomena were examined by the x-ray adit of 80m level of J6koku mine is limited powder method and chemical analysis. to the cold season from November to June From the comparison between TG curve in which the adit temperature is below and DTA, it may be concluded that three about 15•Ž and relative humidity is over peaks at 25•Ž, 90•Ž and 163•Ž are due to about 98 per cent. In other seasons, as the the dehydration of about 85% water which adit temperature will rise to over about corresponds to about 6 molecules of water, 15•Ž, mallardite dehydrates gradually to and the peak at 325•Ž may be caused by jokokuite or to ilesite. However, the mor the loss of the remained 1 molecule of water. phological aspects of j6kokuite and ilesite Lastly, the two peaks at 895•Ž and 1,005•Ž show that a part of them are precipitated are due to vaporization of SO,. immediately from relatively warm solution

above about 15•Ž. GENESIS AND STABILITY OF MALLA On exposure to air for several days at RDITE 20•Ž and 60 per cent relative humidity,

The efflorescences of mallardite on the mallardite dehydrated to form a white adit wall apparently precipitated secondarily powdery material, which on x-ray examina from surface and mine waters carrying com tion proved to be tetrahydrate without Mallardite from the Jdkoku mine , Hokkaido, Japan 411

forming an intervening pentahydrate phase . Dana's System of Mineralogy, 7th Ed., Part On the other hand, the stabilities of the II, 507-508, John Wiley and Sons, New York. Cottrell, F. G. (1900), On the stability of manganous hydrates of manganous sulfate with 1, 4 , sulfate. Jour. phys. Chem., 4, 637-656. 5 and 7 molecules of water of crystallization Giinther, E. (1912), Untersuchungen fiber die were determined by Cottrell (1900) for tem Beziehungen zwischen eutropsichen and isomorphen Substanzen (Inaug.-Dissert., Jena peratures between -10•Ž and +100•Ž. 1908, 33 SS). Zs. Krist., 50, 1912, 91-92 The ranges of their stability in the presence (Ausziige). of aqueous solution are illustrated in Fig. Larsen, E. S. and Glenn, M. L. (1920), Some min 5. This figure indicates that the transition erals of the melanterite and chalcanthite

temperatures of MnSO4•E7H2O ?? MnSO4•E groups with optical data on the hydrous sulphates of manganese and cobalt. Amer. 5H20+2H2O and MnSO4. 5H2O ?? MnSO4•E Jour. Sci. ser. IV, 50, 225-233. H2O+4H2O are nearly 9•Ž and 27•Ž Mellor, J. W. (1932), A Comprehensive Treatise on Inorganic and Theorictial Chemistry, 12, 401- respectively, and that tetrahydrate having 427. the transition temperature of nearly 14•Ž Miura, H. and Omura, H. (1961), Geology and ore from pentahydrate is an unstable phase. deposits of the Jdkoku mine, southwestern Hokkaido. Mining Geol., 11, 53-57 (In Experimental studies on the phase Japanese with English summary). equilibrium in the systems of manganous Nambu, M. and Kitamura, T. (1974), Mineral com sulfate and water made by Cottrell (1900), position of Pb-Zn-Mn ores for Jdkoku mine, and the natural conditions of temperature Hokkaido, with special reference to the new occurrence of plumbogummite in Japan. and humidity in adits where mallardite was Chigaku-Kenkyu, 25, 102-110 (in Japanese).•\ formed will suggest that the mineral , Tanida, K., Kitamura, T. and Kato, E.

crystallized from mine water at tem (1978), Jdkokuite, MnSO4.5H.O, a new mineral from the Jdkoku mine, Hokkaido, Japan. peratures below about 10•Ž and under Miner. Jour., 9, 28-38. suturated humidity. Nishio, J. (1966), On the deposits and prospecting

of the Jdkoku mine. Mining Geol., 16, 132- 142 (in Japanese with English summary). ACKNOWLEDGEMENTS Ohta, S., Honda, T. and Nishiyama, Y. (1971), The authors are indebted to Drs. Metasomatic lead, zinc and manganese deposits of Jdkoku mine. Data on a subcommittee for Shimpei Kano and Yoichi Muramatsu of the autum research meeting of the Mining and Tohoku University for their critical reading Met. Inst. of Japan, F-1, 1-3 (in Japanese).

of this manuscript. Palache, C., Berman, H. and Frondel, C. (1951), Dana's System of Mineralogy, Part II, 487- 493, John Wiley and Sons, New York. REFERENCES Taylor, D. (1952), The system MnSO4 H2SO4

Carnot, A (1879), Bull. soc. min., 2, 117. cited in H2O. Jour. Chem. Soc., London, 2370-2375. 412 M. Nambu, K. Tanida, T. Kitamura and E. Kato

北海道上国鉱山産マラー ド鉱について

南部松夫 ・谷田勝俊 ・北村 強 ・加藤栄一

上 国 鉱 山 の80mレ ベ ル の 諸 坑 道 か ら,本 邦 新 産(世 界 で 二 番 目)の マ ラ ー ド鉱 が 発 見 さ れ た 。 長 さ0.5～12 mm,径0.2～1mmの 毛 状 な い し柱 状 の 多 数 の 微 細 結 晶 が 霜 柱 状 に 集 合 し て,坑 道 壁 面 に 付 者 し て い る の が 普

通 で あ る 。 絹 糸 状 光 沢 を 有 し,無 色 透 明 な い し 半 透 明,比 重(計 算 値)1.838, (001)面 に劈 開 が 明 瞭 で あ る 。 二 軸 性 正 で あ っ て 光 軸 角 は 大,消 光 角(Z∧c)44°,屈 折 率 は α=1.462,β=1,465,γ=1.414(±0.003)で あ

る 。O=4と し て 計 算 し た 組 成 式 は(Mn0.90Mg0.11)1.01S1.00O4.00・6.8H2Oで あ る 。 単 斜 晶 系, P21/c, Z=4, a0

=14.15, b0=6.50 , c0=11.06A, β=105°36'。 こ の 鉱 物 は,産 状 お よ びMnSO4-H2O系 の 平 衡 実 験 か ら 約 10℃ 以 下 の 温 度,飽 和 に 近 い 湿 度 条 件 下 で 晶 出 し た こ と が 推 定 さ れ る 。