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Caryopilite and Greenalite from the Manganese Deposits

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Caryopilite and Greenalite from the Manganese Deposits The ClayScienceSocietyClay Science Society of Japan Clby Science IS, 79-86 (2014) -PapeF CARYOPILITE AND GREENALITE FROM THE MANGANESE DEPOSITS IN SHIKOKU, SOUTHWEST JAPAN MAsAHARu NAKAGmafi'', MAsAro FuKuoKAb, KENTA4o KAKEHi", Go KAKiucHia, YuuKi TAMAKJa and TAKAAKi TANIGucHI" al 1iculty ofSbience, Kbchi Uhiversiol Kbchi 780-8520, J4pan tFkeculty ofintegratedArts and SZriences, H}roshima Uhiversipt Higashi-Hiroshima 739-8521, Jopan (Received November 1, 2014. Accepted Nevember 20,2014) ABSTRACT serpentine mineral, a major constituent of manganese ores Caryopilite,Mn2'-rich group is the intheNorth Chichibu belt in the Shikoku region, SW Japan, The Nomh Chichibu belt is thc Jurassic accretionary complex containing abundant chert beds of Permian-1[tiassic age and has been subjected to low-grade metamorphism of the prehnite-pumpellyite to pumpellyite-actinolite facies. Caryopilite close to Mn end-member in compo- sition and having IMpolytype commonly occur in the chert-hosted manganese deposits. Greenalite, the Fe2' analogue of caryopilite, has 1T polytype and rarely occurs in some chert-hosted deposits. Fe-rich caryopilite having intermediate composition between caryopilite and greenalite and having IMpolytype occurs in an iron-manganese deposit and a manganese deposit associated with basalt. Manganoan chlorites also eccur in these deposits, Key words: Caryopilite, Greenalite, Manganese deposit, Accretionary complex, Shikoku INTRODUCTION GEOLOGY AND DEPOSIT Caryopilite is an Al-poor and Mn2"-rich serpentine group The locations of the manganese and iron-manganese ore de- mineral, and greenalite is its Fe2' analogue. They are now posits are shown together with the geotectonic subdivision of known to have modulated structures containing islands of Shikoku in Fig. 1 . The Shikoku Island is composed of several tetrahedral rings (Guggenheim and Eggleton, 1988, 1998). accretionary belts which display various grades of regional Caryopilite occurs as a major constituent of manganese ores metarnorphism, The Sanbagawa metamerphic belt, on the in Japan and was described as bementite in older literature,south ofMTL, is a high-P/T type regional metamorphic belt, It Greenalite is rare and is known to oecur in seme banded iron is composed ofbasic, quartz, pelitic and psarnmitic schists of formatiens, In the Shikoku region of SW Japan, a manganoan the greenschistfblueschist to eclegite facies. The southernmost greenalite was found in the manganese ore from the Matsuo part of the Sanbagawa belt was once called the Mikabu belt, mine, Kochi Prefecture, and was named tosalite for lbsa, the The Nomh Chichibu belt comprises the Early-Middle Jurassic old distriet name of Koehi (Ybshimura, 1967), accretienary complexes and has been subjected to low-grade In the Shikoku region, several accretionary belts are distrib-metamorphism of the prehnite-pumpellyite to pumpellyite- uted and characterized by different grades of regional meta- actinolite facies. The South Chichibu belt comprises the morphism. Bedded manganese ore deposits occur in many Middle Jurassic to Early Cretaceous accretionary complexes. localities within the accretionary belts, Caryopilite is a major These complexes ofNonh and South Chichibu belts are com- constituent of the manganese ores. ln this paper, we report the posed of tenigenous clastic rocks containing older oceanic paragenesis and ehemical characteristics of caryopilite and blocks of chert, limestone and greenstone. The southemmost greenalite in the manganese ores, together with some genetic regien of the Shikoku is occupied by the Cretaceous North considerations. Shimanto and Tertiary South Shimanto belts which comprise the clastics-dominated accretionary complexes. [[he manganese and iron-manganese deposits are disuib- uted in the Sanbagawa, Mikabu, North Chichibu and South . Corresponding author: Masaharu Nakagawa, Faculty ofScience, Kochi Chichibubelts.The depositsare abundant especially in the University, Kochi 780-8520, Japan. e-mail: [email protected] Chichibubeltswhich contain abundant chert beds.Some NII-ElectronicNII-Electionic Library Service TheTheClayScience Clay Science Society of Japan 80 M. NakagaM,a et at, FIG, 1, Distribution ofmanganese and iron-manganese deposits shown within the generalized geological framewerk of Shikoku, SW Japan (modi- fied from Nakagawa 2012). e: rnanganese -: 1-1O: the mine number mentioned in Table 1.MTL: et al,, 2009, deposit, iren-manganese deposit. Median Tectonic Line. BTL: Butsuzo Tlectonic Line. Ryoke: Ryoke metamorphic belt. Sanbagawa: Sanbagawa metamorphic belt. Mk/ Mikabu greenstone, N. Chichibu: North Chichibu belt, Kr: Kuresegawa belt. S, Chichibu: South Chichibu belt. N. Shimanto: Nerth Shjmanto belt, S. Shimanto: South Shirnanto belt, The geological subdivisjon is based en Suyari et al. (1991), Matsuoka ct al. (1998) and GSJ (201O). manganiferous iron deposits of small scale occur in the North old mines in the Shikoku region (Fig. 1). The geolgy and his- Shimanto belt. tory ofthe rnines are reviewed in the comprehensive treatises In the Shikoku region, the manganese deposits can be clas- by Ybshimura (1952, 1969) and Miyahisa and Sawamura sified into two types based on the geological setting, mineral- (1973). We have re-examined the ore deposits based on our ogy and genetic characteristics (Nakagawa et al., 2009, 2011; new field and laboratory investigations. The wall rock charac- Nakagawa, 2012), The manganese deposits occur mostly teristics and available fossil age data fbr the ore deposits are in bedded chert or its rnetamorphosed equivalent. In these summarized in Table 1. In the Chiehibu belts, the microfossil deposits classified as Type I, the ores consist mainly of rho- ages of the chert are Permian to Triassic around the deposits, dochrosite, caryopilite, rhodonite and braunite. These chert- whereas the ages of the clastic matrix of olistostrome are hosted manganese ores are considered to have been manga- Jurassic. nese nodulefcrust-bearing siliceous sediments on deep-sea The ore samples were examined by X-ray powder diffi/ac- floor and have been converted to manganese ores by low- tion (XRD) method to characterize the constituent minerals grade metamorphism through subduction-accretion process. ofthe samples, employing a Rigaku MultiFlex diffractometer The mineral assemblages ofthe ores refleet the rnetarnorphic housed at the Kochi University. The representative ore sam- grade ofthe accretionary complexes. Some manganese depos- ples were polished well with diamond paste and analyzed its were metamorphosed at the deeper levels. using an electron probe microanalyzer (EPMA) housed at the Iron-manganese deposits and some manganese deposits,Hiroshima Uniyersity. To obtain quantitative estimates on classified as Type II, are associated with greenstone and red mineral chemistry, EPMA analyses were performed with a chert. The mineralogy and texture of these ores are differentJEOL JXA-8200 Superprobe at an aecelerating voltage of 15 from those of the chert-hosted manganese ores. Geoehemi- kV; a bearn current of 10 nA and a beam diameter of3 pm. cal similarities of these ores to those of modern submarine The quantitative calculation of all elements was done by ZAF hydrothermal deposits were noted by Kato et al. (2005) and correctlon, Fojinaga et al. (2006). These deposits occur directly over basalt and are considered to have been the hydrothermal RESUIJIrSANDDISCUSSION precipitates assoeiated with the mid-oceanic ridge or oceanic islandvolcanism. Ml'neralogy ofmanganese ores The mineral constituents of the ore samples have been ANALYTICALPROCEDURE examined by XRD and EPMA analyses. The results are summarized in Table 2. Back-scattered electron images of the For the present study of caryopilites, manganese and iron- representative samples are shown in Fig, 2. manganese ore samples were collected frorn the representative Manganese deposit ofthe Minamiyama mine (No. 1, Fig, 1) NII-ElectronicNII-Electronic Library Service The ClayScienceClay Science Society of Japan Cti,),qpiliteandGreenalitefivmShikoku 81 TABLE 1,Wall roek eharacteristics and fossil age data efmanganese and iren-manganese deposits in Shikoku. No. Mine Tbrrane TYpe Wall rock Ageofchert 12345678910Minamiyama MikabuNorthChichibuIIIIIIIIIIIIQuartzschist FukuharaDesuNiroMatsuoAnanai-Fukinaro ChertChertChertGreenstone,Early-MiddleTriassic NomhChichibu Permian Nonh Chichibu Nonh Chichibu chert Nonh Chichibu Greenstone, red chert Middle Permian Arianai-Honomori NorthChichibu Greenstone, red chert PerrnianEarlyPerrnian Kunimiyarna NorthChiehibu (FeMn) Greenstone, red chert Tbkoroyama Nomh Chichibu II ChertChert Ttiassic Hitogawa South Chichibu The mine numbers are the same as those in Fig. 1. The age data for chert are based on the biostratigraphic studies by Suyari et al. (1982, 1983), Momoi et al. (1992), Fojinaga and Kato (2005), and others. TABLE 2.Mineral constiments of manganese and iron-manganese ore sarnples examined by EPMA, AnalysisNo. Mine Constituentminerals 1,21 Minamiyama Rhedonite,pyroxmangite,spessartine,rhodochresite,caryopilite, manganoan chlorite, quartz, ganophyllite, tephroite le17, FukuharaFukuharaDesuNiroNiroNiroMatsuoAnanai-FukinaroQuartz,caryopilite,rhodonite,barianbannisterite 182,3415, Quartz, greenalite, stilpnemelane Quartz, caryopilite, rhodochresite, rhedonite Quartz,caryopilite,rhodonite,ganophyllite 1622, Quartz, greemalite, rhodoehrosite 2311,125,6 Quartz, rhodochrosite, manganoan chlerite, barite Iron-richcaryopilite,rhodochrosite,magrietite Caryopilite, barian ganophyllite,
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