Canadian Mineralogist Vol. 16, pp.

539-545 (1978)

IN SKARNEOUITIBRIA THESYSTEM SUBSOLIDUS Ga$iOa-GaMgSi:Oa-GaFeSi:Os-GaMnSigOo

HIDEHIKO SHIMAZAKI

Universitvof Tokyo, Hongo, Tokyo 113"tapan GeolosicalInstitute,Faculty of Science, MICHIAKI BUNNO

UniversityMuseum,Universitvol Tokyo, Hongo, Tokyo l13, Japatt

ABsrRAcr Based on chemical compositions of minerals of series from three tho bustamite-ferrobustamits new localities in Japan, a complete solid solution is suggested from bustamite, ideally of composition CaMnSizOo. through CaSiOa-rich bustamite, to at ferrobustamite of composition Ca"FeSiuOra, relatively low temperatures. Bustamite-ferrobustamite solid solutions and wollastonite from skams or similar environments are essentially free of MgSiOt and belong to the system CaSiO3{aFeSi2O6CaMnSizOe, whereas clinopyroxenes associatedwith these pyroxenoids belong strictly to the system The field of CaMgSizOr{aFeSi:Oe{aMnSi2Ou. such clinopyroxenes can be divided into three dlstinct compositional regions depending on the associated pyroxenoids.

Sorvrrvrernr
Nous proposons une s6rie compldte de solutions solides, i temp6rature relativement basse, allant de i la ferrobustamite la bustamite (CaMnSiOJ (CarFeSieOrJ, en passant par les bustamites riches en CaSiOr. Les solutions solides bustamite-ferrobustamite et la wollastonite des skarns ou de milieux analogues contiennent trbs peu de MgSiOg; ces pyrox6noides font partie du systCme CaSiOrCaFeSigoe{aMnSizOa, tandis que les clinopyroxdnes qui leur sont associ6sfigurent dans le systdme CaMsSizOe{aFeSizOnCaMnSirOo. Ir domaine de composition de tels clinopyroxdnes peut se subdiviser en trois r6gions distinctes selon les pyrox6noides associ6s. Cfraduit par la R6daction) INTRoDUcrroN Tilley (1937, 1947, 1948) first described natural "iron-wollastonite" from basic igneous rocks and a contact skarn; the mineral has not been reported again until recently, except for one occurrence in andesite lava (Isshiki 1954). Our understanding of this mineral has recently made rapid progress: Rutstein (1971) redetermined the position of the solvus along the join CaSiOa{aFeSLOs first described in the classic

work of Bowen et al. (1933); Rutstein suggested that relatively iron-rich o'iron-wollastonite"would have a bustamite-typerather than a wollastonitetvpe structure. ln 1973, several important papers were published. Rapoport & Bnrnham (1973) found that ooiron-wollastonite" from ,a contact skarn in Skye (Tilley 1948), as well as at CaFeSi:Oesynthesized 1108"C dnd 2 kbar, has the bustamite-type structure. Matsueda (L973a) described the occurrence of 'oiron-wollastonite" from the Sampo mine, Japan, and drew attention to the distinct physical properties of the mineral in comparison to those of wollastonite. Shimazaki & Yamanaka (1973) also reported new occurrencesof a mineral with the bdstamite-typestructure from three localities in Japan, the Kagata, Ofuku and Ohta mines, and demonstratedthat the mineral is a discretephase, ideally CarFeSiuOra,in the system CaSiOgCaFeSi:Oo.Indeed, close associationsof wolin lastoniteand 'oiron-wollastonite" natural specimenswere interpretedby Matsueda(t974a,b) as clear evidenceof a miscibility gap between these minerals. The fact that the composition of all analyzed from various skarn deposits "iron-wollastonites" led is very close to CasFeSiuOta Shimazaki & Yamanaka (1973) to postulate that iron is restricted to one site among the. six cation sites in the bustamite structure.This site preference of iron" due to its small ionic radius, was recentlv confirmed by Yamanaka et al. (1977). has been recogAt present, ooiron-wollastonite" nized from more than ten localities in Japan. Based on the works cited above, tentative phase are relations along the join CaSiOrCaFeSisOo given in Figure 1. Knowledge of low-temperaturephase relations involving bustamite has also been accumulating (e.9., Mason 1973, 1975; Hodgson paper, 1975,Nambu et a|.1977). In the present on new data are presented the compositionand phaserelationsof mineralsin the quaternarysys-

539

540

THE CANADIAN MINERALOGIST

replacing a limestone lens is observed in biotite schist of the Ryoke metamorphic belt. The Ryoke metamorphic rocks, including biotite schist and thin beds of chert and limestone, are intruded by granitic rocks of late Cretaceous age. The outcrop of the skarn mass was oose prospected for tungsten. Three specimens collected from the outcrop were studied with an electron microprobe analyzer. Main constituents of the skarn are grosstilar, having important spessartine and almandine components, ferrosalite to hedenbergite, vesuvianite, wollastonite, ferrobustamite, actinolite, epidote with L4-17 mol. Vo pistacite component, titanite n'ith AlzOg up to about 9 wt. Vo, scheelite, pyrrhotite, guartz and calcite. As clearly indicated by these minerals, the skarn is generally poor in ferric iron. This characteristic of some scheelite skarns in Japan (Shimazaki L974, L977) is thought to be genetically Fe-bust. related to the relatively reduced nature of associated granitic rocks (Shimazaki 1976). A specimen from Tsuchiarashi (UMMI 20337) was labeled wollastonite in the collection of the University Museum, University of Tokyo. The deposit is located about 15 km south-southeast of Iida City, Nagano Prefecture, and was prospected for zinc and lead several decades ago. The area consists of Ryoke metamorphic rocks, including biotite schist with small limegranitic rocks. stone lenseso and Ryoke gneissose CaSi% l0 30 40 CaFeSi2O5The specimen is a skarn consisting of fibrous 20 FeSiO3 mole o/. ferrobustamite partly replaced by calcite and quartzogrossular with minor andradite, spessarFrc, l. Tentativesubsolidus relationsin the system CaSiOs-CaFeSirO". Dashedand dottedlines show tine and almandine components (up to 10 mol. the solvus curvesdetermined Rutstein (1971) Vo each), and hedenbergitewith a considerable by and Bowen et al. (1933),respectively. Abbrevia- iohannsenite component. tions: Woll. wollastonite, Fe-bust. ferrobustaA specimen from Kurodake (UMMI 20632) mite. Hd. hedenbergite. was also labeled wollastonite in the University Museum collection, University of Tokyo. Kuroformation is available on the crystal strucfure dak6, a peak of about 3000 m in height, is of "iron-wollastonite" from igneous environ- located about 35 km southeastof Toyama City, ments (Tilley 1937, 1947; Isshiki 1954), these Toyama Prefecture. The mineral paragenesis occurrences could be ftue iron-bearing wollas- of theseskarnswas describedby Fukuchi (1907); tonites because they were probably formed at an old chemical analysis of garnet from this temperatures above 800"C. At these tempera- localitv indicates grossular with about 9 wt. 7o tures, wollastonite can contain considerable MnO (Wada 1904).Ohmori (1941)rcported that iron, as experimentally determined by Rutstein garnet from this locality is andradite. According (1e7r). to Fukuchi (1907), the skarns contain garneto clinopyroxene, epidote, magnetite and quartz, and formed in limestone beds as a result of the DsscnrptroN oF SpEcIMENs intrusion of diorite; we have not yet had a In the present study, specimens from three chanceto studv the detailed geology of the area. localities were investigated. Our specimen consists of fibrous bustamite, Specimenswere taken from the Kasugayama euhedral andradite showing distinct zoning with deposit, located about 10 km southwest of Iida anomalous anisotropism under the microscope, City, Nagano Prefecture. A small skarn mass clinopyroxene, quartz and calcite. As will be

tem CaSiOrCaMgSLOnCaFeSizOdaMnSi,Oe from three localities in Japan, with a summary of low-temperature phase relations in this system. In accordance with Rapoport's & Burnham's (1973) nomenclatureand Mason's (1975) definition, ferrobustamite refers here to a phase with the bustamite-type structure and with a ratio Fe,/(Fe*Mn) >' 0.5; this name has not yet been approved by the Commission on New Minerals and Mineral Names, I.M.A. In the present discussion, only the phases occurring in skarns or similar environments will be considered. Little has been reported as to temperature conditions for these skarn deposits. From the intimate association with granitic intrusions, however, the deposits are thought to be genetically related and to have formed at temperatures below 600'C. Although no in-

SUBSOLIDUS EQUILIBRIA

IN SKARNS

541

shown below, the compositions of bustamite and other hand, bustamites and clinopyroxenesfrom clinopyroxene are very variable in this specimen. Kurodak6 show remarkable and irregular compositional variations. In bustamites, manganese Auer,yrrcer. Pnocsruns ewo Rpsur,rs and calcium seem to substitute for each other, Three fenobustamite-bearing specimensfrom with iron relatively constant. Typical analyses Kasugayama, and two each from Tsuchiarashi of bustamites and associatedclinopyroxenesare and Kurodakd, were studied in detail with an given in Table 1 as Nos. 12-16 n order to show electron microprobe analyzer. Count ratios of the range of variation. sample to standard were measured for Si, Al" Fe, Mn, Mg and Ca. The ratios were converted Busrnvrrrn-FERRoBUsTAMTTESoLrD SorurroN into oxide weight percentagesusing the method As stated above, occurrences of ferrobustaof Bence & Albee (1968). Detailed descriptions mite have been recognued at more than ten of the analytical procedure and the correction localities in Japan, in addition to Skye, Scotland factors used in this study have been given by (Iilley 1948). These ferrobustamitesare variable Nakamura & Kushiro (1970). In the present in composition. and ferrobustamites from Tsustudy, the totals of the corrected weight per- chiarashi (e.9., tO in Table 1) are the richest in centagesof SiOz, AlaOr. FeO, MnO, MgO and manganese.All analysesof ferrobustamites obCaO generally fall in the range of 98.5 to tained in this study and reported in the literalOL.S%o. ture are plotted (Fig. 2), as well as some Selectedanalysesare given in Table 1. Com- analyses of CaO-rich bustamites from Broken positions of coexisting phasesare connected by Hill (Mason 1973), Hijikuzu (Nambu el a/. a line in the table. A part of a specimen from 1977), and Kurodak6 (this study). Kasugayama (No. HS76O4L8l5) includes a These pyroxenoids usually contain less than mixture of subhedral crystals of three phases, 1.0 mol. Vo MgSiOg. The maximum value ferrobustamite, chnopyroxene and wollastonite among analyses plotted in Figure 2 is about (Nos. 1-3 in Table 1). In this specimen, two 2.5 mol. % MgSiOs (data from wet chemical two-phase assemblages, such as ferrobustamite analysesof two bustamitesfrom metamorphosed f clinopyroxene and clinopyroxene * wollas- bedded manganeseore-depositsof the Hijikuzu tonite, are also observed (Nos. 4-5 and 6-7 in mine: Nambu et al. 1977). This fact would Table l). Clinopyroxene in contact with ferro- justify plotting the analyses on a CaSiOr bustamite is notably richer in hedenbergitethan CaFeSizO-CaMnSirOu (or CaSiOrFeSiOr clinopyroxene near wollastonite. Ferrobustamites MnSiOg) diagram. from Kasugayama and Tsuchiarashi have rather Based on the distribution of chemical comconstant compositions in each specimen.On the positions, Nambu et al. (1977) suggestedthat
TABLE I. lllneral & FBS CPI asssblagg+4--l E PI$ToI|ITES ELECTMilPROBE A}IAIYSES BUSTAIIIIE $LID $LUTIOIIS, CTII{OPVROIBIES OF m FBS CPt CPI m FS CPX IO FBS ll CPX

12 BS

I3

s
49.0 0.0 4.0 15.3 0.0 31.0 99.3
5.98 0.m 0.41 1.58 o.(xt 4.05 67.1 26.2 6.8 0.0

l4 BS 49.7 0.0 q.2 8.6 0.1 :f5.5 99.1 5.99 o.(xl o.qz 0.87 0.@ 4.71 78,2 14.5 7.0 0.3

I0 CPI
47.7 0.1 l3.l 14.2 I.3 4.5 $.9 5.9f 0.01 I.36 I.49 0,24 3.00 49.3 24.5 u2,.3 3.9

t6 CPI 49.5 0,0 n.2 ll;6 3.9 23.2

99.4 5.99 .0.00 l.l3 l.19 0.70 3.@ 49.8 19.8 I8.8 ll.6

Sl0r AllUe rd*Itro lbo Cao

Total llunbors of st Al Fe l,ln lt Ca

50.2 iA.9 5 l . 0 4 9 . 6 t t 8 . 5 4 9 . 1 5 l . l 5 0 . 9 4 9 . 2 5 0 . 1 47.8 47.8 0.3 0.0 0.2 0.5 o . 2 o . 2 0.4 0.4 0.2 0.2 0.3 0.0 3.8 7.0 19.9 0 . 8 6 . 9 2 2 . 9 1 9 . 9 0.7 7. 3 2 3 . 1 6 . 3 m.l 5.5 7.2 18.3 4.5 3.5 t . 5 5.2 2.6 3.1 1.2 4.7 3.5 0.8 0.0 O.2 3.5 0 . 1 0 . 1 1.8 4.1 0.1 0.1 1.7 0.1 37.9 Zl.9 4 5 . 3 37.6 22.9 2tr.3 4 6 . 6 : t 8 . 3 2 2 . 7 t I . 7 n.4 8.3 100.0 99.3 99.9 9 9 . 6 9 9 . 1 9 9 . 9 9 9 . 9 1 0 1 . 5 l ( m . 5 9 9 . 8 98.5 !8.2
catlons on the basls 5,97 5.94 5.96 0.02 0.07 0.03 0.7O 2.02 0.@ 0.45 0.:16 0.t5 0.(B 0.65 0.02 5.79 4.82 2.8 95.9 2.s I .3 0.3 of l8 orygens 5.95 5.97 5.93 0.03 0.06 0.06 0.69 2.35 2.01 0.53 0.27 0.n 0.02 0.33 0.74 4.82 3.02 3.01 79.5 8.7 ll.4 0.3 50.5 49.5 4.5 5.? 39.4 33.1 5.5 12.2 5.97 0.03 0.07 0.12 0.m 5.82 96.5 2.0 1,2 0.3 5.98 0.02 0.71 0.46 0.02 4.82 5.98 0.04 2.35 0.36 0.31 2.95 5.98 0.u0 0,62 0.56 0.(P 4.82 5.97 0.04 2.10 0.76 0.15 2.99 s.94 0.00 0.40 1.93 0.00 3.78 51.9 3l .6 6.5 0.0

llole t of end onbers casf02 6.2 49.6 hsro; 7..5 6.0 Fesl0i ll.6 33.6 o.7 10.8 ilsslo;

80.2 49.4 80.1 49.8 6.0 9 . 3 r2.7 7,7 1 1 . 8 3 9 . 4 1 0 . 3 35.0 0.1 2,5 0.3 5,2

. Total Fe as FeO. !los. l-7: Hs76041815 (asugaFna. Nos. 8-9: HS76041516 Kasugayana.l{os. l0-ll: ilo.2(F37 Tsuchlarashl. llos. 12-16: l{o.20632 krodak6. BS: bustrnlta, Cfl[: cllnopyrcxene. FBS: ferubusta[lte, m: pltt3to||ltg.

s42

THE CANADIAN

MINERALOGIST

gu"1a611s-=f 'n
I i. 1

\,k* \
,
r.-i

\r " t i. \

ifr-. '"ii-,i .'

i=-..
I t!"

i
I

i )s+rc Ferrobustamite-i ry* i r 'l

r, :Tt t
t rl-1

.!

CaFcSi2O5 40

30 20 FcSiO,mcf %

t0

CaSiO3

Frc. 2. Compositional distribution of. bustamite-ferrobustamite solid solutions. Solid circles: analyses from the literature, including Tilley (1948, Skye), Rapoport & Burnham (1973, Skye), Matsueda (I973a,b, L974ah; Sampo, Kasuga, Tojo, Ohmin6), Mason (1973, Broken Hill), Shimazaki & Yamanaka (1973, Kasata, Ofukr:, Ohta), Matsuoka (1976, Tsumo) and Nambu et al. (1977, Hijikuzu). Open circles: this study (KR from Kurodak6, TC Tsuchiarashi and KS Kasugayama).

CaO-rich bustamite solid solutions could be divided into three groups: bustamite near CaMnSLOu, CaO-rich bustamites such as those from Broken Hilt and Hijikuzu, and ferrobustamites (conventional "iron-wollastonite"). As clearly shown in Figure 2, however, ferrobustamites from Tsuchiarashiand Kasugayamahave compositions between CaO-rich bustamites and ferrobustamites close to CasFeSieOre comin position. The composition of bustamites from Kurodak6 extends over regions of CaO-rich bustamites and bustamites near CaMnSirOu. These relations could be taken as evidence of complete solid solution from ferrobustamite of CasFeSieOre composition to bustamite s.s. (CaMnSLOo) at relatively low temperatures. Further mineralogical and mineral synthesis studies will be necessaryto confirm the complete solid solution from bustamite to ferrobustamite. Assuming implicitly the presence of a continuum between bustamite and ferrobustamite, Mason (1975) eave the compositionalrange of these minerals. Taking the results of this study and those of the study on Broken Hill minerals

by Hodgson (197$ into account, the tentative compositional limit of the bustamite-ferrobustamite solid solution at relatively low temperatures is also given in Figure 2. Matsueda (1974a) described a CaSiOrrich phase with about 9 moL lo FeSiO' and 6 Vo MnSiOs from the Sampo mine. Although its crystal structure is uncertain, the mineral could be a member of bustamite-ferrobustamite solid solution. Mel'nitskaya (1967) describedan occurrence of oomanganoferrous wollastonite" with 9-10 mol' 7o of both FeSiOs and MnSiOg, from a Russian skarn deposit. The crystal structure of the mineral is again uncertain, but it is probablv a member of bustamite-ferrobustamite solid solution, having a composition similar to those reported here from Tsuchiarashi. Sussorrpus Pnlss RsrerroNs IN THE SysrEM CeSTO-CeMGSI2Os_CAFESI,O6-CAMNSI,Ou of Assemblages bustamile{errobustamite plus wollastonite or clinopyroxene (or both) could be described as representative of subsolidus phaserelations in the systemCaSiOrCaMgSizOr

SUBSOLIDUS

EQUILIBRIA

IN

SKARNS

543

The phase relations in CaFeSLOT--CaMnSLOo. 'terthis svstem were previously inferred from nary" systemssuch as CaSiOs-Ca(Mg,Fe)SirOoCaMnSLOe or CaSiOTCaMgSLO-Ca(Fe,Mn) SizOu(e.g., Mason 1973, Matsueda 1973b, Shimazaki & Yamanaka 1973, Hodgson 1975). As shown in the previoussection,bustamite-ferrobustamitesolid solutions.as well as wollastonite, essentiallybelong to the ternary system CaSiOgIt CaFeSLOe--CaMnSirOu. is evident, however, that clinopyroxenes associated with these pyroxenoids cannot be representedin that system; of compositions thesemineralsmust be discussed in the quaternary system CaSiOrCaMgSi:Or CaFeSirO-CaMnSizOo. An examination of the chemical compositions of clinopyroxenes associated with bustamiteferrobustamite solid solutions or wollastonite (or both) reveals that their CaSiOs contents are mostly in the range of 50 :t I mol. 7o, although there are a few exceptions: e.,g.,about 54 mol. % CaSiO" in two clinopyroxenesfrom the Sampo mine, determinedby wet chemical analysis (Matsueda 1973b), This fact indicates that the clinopyroxenes associatedwith the pyroxenoids can be represented on the ternary system

CaMgSLO-CaFeSirO-CaMnSizOr. In contrasto clinopyroxenes associatedwith relatively CaOpoor bustamitesare subcalcic in composition, and their CaSiOscontentsare less than 50 mol' 7o. These relations are clearly recognized in from Broken Hill, which are the assemblages diagiven in CaSiO'-MnSiOa-(Fe,Mg,Zn)SiOa grams by Mason (1973) and Hodgson (1975), although neither reports specific chemical analyses of coexisting minerals. In summary, the pyroxenoids of bustamiteferrobustamite solid solution and wollastonite appear not to contain appreciable MgSiOr, and with thesepyroxenoids clinopyroxenesassociated are satnratedwith CaSiOsat about 5O mol. 7o. Accordingly, two triangular diagrams, CaSiOCaFeSLO-CaMnSirOu and CaMgSizO-CaFeSirO-CaMnSizOe suffice to describe the compositions of coexisting phasesbelonging to this quaternary system.Figure 3 illustrates these two pl'anesof the tetrahedron. In order to investigatethe phase relations between pyroxenoid and clinopyroxene in the system, results of reliable chemical analyses of natural two- and three-phase assemblagesare plotted (Fie. 3), together with our re$ults from

caMsSio5
(Ctinopyrorene) CaMgSi2O6
cpr

-w
Mnslo3 mol% BGtamite Wollastonite

\-..--, \ 'i "---?.*

CaFeSirOa

20
FeSiO3 mol%

CaSiO3

Frc. 3 Subsolidus phase relations in the CaSiOr-rich portion of the system Open circles show the compositions MeSiOg-FeSiOrMnSiOg{aSiOr. of coexisting clinopyroxene and wollastonite, solid circles chnopyroxene and ferrobustamite, and solid triangles clinopyroxene and bustamite. Open circles with a cross represent the compositions of coexisting clinopyroxene, wollastonite and ferrobustamite from Kasugayama (fable 1, Nos. 1-3). The abbreviations cpx0ust.), cpx(Fe-bust.) and cpx(woll.) indicate fields of clinopyroxenes able to coexist with bustamite, ferrobustamite and wollastonite, respectively.

544

THE CANADIAN MINERALOGIST

Table 1. Unfortunately no analyses of threephase assemblages are found in the literature, except for one wolla$tonite-ferrobustamite-clinopvroxene assemblageobtained in the present study (analyses Nos. 1-3 in Table l). These analysesare plotted in Figure 3 as open circles with a cross. In Figure 3, solid trianglesindicate the compositions of bustamitesand associated clinopyroxenes.They include analysesof minerals from Kurodak6 (Table 1, Nos. 12-16) and Hijikuzu (Nambu et al, 197O, L977). They show wide variations, as stated previously in the case of Kurodak6, even in one thin section, and the number of analyses in the bustamite field of Figure 3 is not equal to the number of analyses in the field labeled clinopyroxene (bust.). With this exception, each open or solid circle in the pyroxenoid fields is connected by a tie-line with a corresponding circle in the clinopyroxene fields. Although some tieJines cross, most of them seem to be mutually consistent, considering the limit of analytical error and possible temperature variations at the time of formation. The composition of clinopyroxene described as being associated with "iron-wollastonite" from Skye was determined by wet analysis of a bulk composition with impurities (Tilley 1948). The result is exceptionally rich in the diopside component as compared with other clinopyroxenes associatedwith ferrobustamite. and is not plotted in the figure. With respect to the assemblage wollastonite-ferrobustamite, Matsueda (1974a,b)and Matsuoka (1976) have already given compositions of coexisting pairs from several Japaneseskarn deposits, and these data are not repeatedin the figure in the interest of clarity. As shown in Figure 3, the field of clinopyroxene could be divided into three compositional pyroxenoids. regions,dependingon the associated In the diopside-hedenbergiteseries. a composition of about 85-90 mol. Vo hedenbergite seems to divide the clinopyroxenes into those that can coexist with wollastonite and those that can coexist with ferrobustamite. The introduction of a johannsenite component expands the field of clinopyroxenes that can coexist tvith ferrobustamite. Finally, clinopyroxenes that are richer still in johannsenite are associatedwith bustamites. Near the CaMnSi:Oe corner in Fi-gure 3, johannsenite is unstable with respect to bustamite under the conditions being ponsidered,especially at temperatures above 400"C (Lamb et al. 1972). But at temperatures below 400"C, johannsenite could be the stable phase instead

of bustamite, and the field of bustamite may possibly disappear near the CaMnSirOs corner. The phase relations of minerals close to CaMnSirOe in composition remain a problem. If data were available on the compositionsof clinopyroxenes that are relatively rich in diopside and johannseniteand associated with wollastonite or bustamite or both, it would bc possible to extend the boundary between clinopyroxenescoexisting with wollastonite and those coexisting with bustamite in Figure 3. Unfortunately we could not find reliable compositional data on such clinopyroxenesin the literature.
AcKNowLEDGEMENTS

We are much indebted to Professor D. M. Burt, Arizona State Universiry, for his critical reading of the manus.cript.Thanks are also due to Professor K. Chinzei, University of Tokyo, and Dr. M. Enjoji, University of Tsukuba, for information on the geology around Tsuchiarashi and Kurodak6, respectively,and to Mr. K. Sato, Geological Survey of Japan, for his discussions during the field work. This study was partly supported by a Grant in Aid for Scientific Research No. L54287 from the Ministrv of Education of Japan. RBreRENces BnNcr, A. E. & Ar.are, A. L. (1968): Empirical correction factors for the electron microanalysis of silicatesand ondes. I. Geol. 76, 382-403. BowrN, . N. L., Scnernrn, J. F. & PosN.ler, E. (1933): The system CaO-FeO-SiOr, Amer. J. !ci.226. 193-284. FuKUcru, N. (1907): Mineral paragenesgs the in found in Japan contact-metamorphic ore-deposits, Irl Beitragezur Mineralogie von Japan (T. Wada, ed.), 3, 75-109. Hooosou,C. J. (1975): The geologyand gpological development of the Broken Hill Lode, in the New Broken Hill Consolidated mine. Australia. II. Mineralogy.l. Geol. Soc.Aust. 22, 33-50. IssInKl, N. (1954): On iron-wollastonite from KanpE Volcano, Japan. Proc. Iapan Acad, .30, 869-872. LeLrs, C. L., Lrroslev, D. H. & Gnovrn, J. E. 0972): Johannsenite-bustamite: inversion and stability range.Geol, Soc.Amer. ProgramAbstr, 4, 571-572. Masor, B. (1973): Manganesesilicate minerals from Broken Hill, New South Wales. l. Geol. Soc.Aust. 20.397-404. (1975): Compositionallimits of wollastoAmer, Mineral, 60, 209-212. nite and bustamite. Marsuroa, H. (1973a): Iron-wollastonite from the Sampo mine showing properties distinct from those of wollastonite. Mineral. l, gapan) 7, 180-201. (1973b): On the mode of occurrence and

SUBSOLIDUS EQUILIBRIA

IN SKARNS

545

mineral paragenesis of iron-wollastonite skarn in the Sampo mine, Okayama Prefecture. ,Sci. Rep. Dep. Geol. Kyushu Univ. !l' 265'273 (in Jap.). (1974a): Immiscibilitv gap in the system CaSiO"{aFeSisOe at low tempratures. Mineral. l. Qapan) 7, 327'343. (1974b): Natural occurrences of the asProgram semblage iron-wollastonite-wollastonite. loint Mdt. Soc. Mining GeoI. lapan, Mineral. Soc. lapan, and lapan. Assoc. Mineralogists, Petrologists & Econ. Geologists, Abstr. A22 (in Jap.). MATsuoKA, M. (1976): Iron-wollastonite from the Tsumo mine. Shimane Prefecture. Program toint Meet. Soc, Minins Geol. Japan, Mineral, Soc. Japan, and Japan. Assoc, Mineralogists, Petrolo' gists & Econ. Geologists, Abstr. A46 (in Jap.). Mir,rNrrsreye, E. F. (1967): Manganoferrous wollastonite and its alteration. Zap. Vses. Mineral, Obshchest. 96, 297-905 (in Russ.; see Mineral. Abstr. L9, 47). NAKAMURA,Y. & Kusnno, I. (1970): Compositional relations of coexisting orthopyroxene' pigeonite and augite in a tholeiitic andesite from Hakone Volcano. Contr. Mineral. Petrology 26, 265-275. NAMBU, M., Tnnmt K. & Krteuune, T. (1970): Mineralogical study of manganese silicate ores in northeastern Japan. (9). Manganiferous hedenbergite from Hijikuzu mine, Iwate Prefecture. Res. Inst, Mineral. Dress. Met. Tohoku Univ.' Bull. 26, 123-132 (in JaP.). (1977): Mineralogical _, & study of manganese silicate ores in northeastern mine, Japan. (21), Bustamite from Hiiikuzu Iwate Prefecture. Res. Inst. Mineral' Dress. Met. Tohoku tlniv,, Bull. 39, 3142 (in Jap.)'

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