Ore Geology Reviews, 7 (1992) 225-248

Elsevier Science Publishers B.V., Amsterdam - - Printed in The Netherlands

225

Tin-bearing skarns of South China: Geological setting and mineralogy

J. C h e n a, C. H a l l s b a n d C.J. S t a n l e y c

aDepartment of Earth Sciences, University ofNanjing, Nanjing, China bDepartment of Geology, Imperial Colloge, London, UK CDepartment of Mineralogy, British Museum (Natural History), London. UK
(Received July 26, 199 l; revised version accepted January 1, 1992 )

ABSTRACT Chen, J., Halls, C. and Stanley, C.J., 1992. Tin-bearing skarns of South China: Geological setting and mineralogy. Ore Geol. Rev., 7: 225-248. Tin in skarns forms a significant part of the total Sn resource of South China, and erosion of these primary deposits has produced rich alluvial concentrations, creating the basis for a historically important tin-mining industry. The skarns are genetically related to S-type (Transformation Series) granites of Yanshanian age, emplaced in carbonate sequences, mainly of Devonian and Triassic age. These occupy the Hercynian-Indosinianstructural depressions within the Caledonian Foldbelt, constituting the Nanling Ranges of South China. Most of the Sn skarns in this broadly-defined province contain calcic mineral assemblages, which include andradite-grossular, hedenbergite-diopside, actinolite-tremolite, idocrase, wollastonite, epidote, chlorite and magnetite, with or without various sulphides. In certain cases, Sn is located in minerals such as cassiterite, malayaite and nordenskioldine. In many other deposits, Sn substitutes in the structure of calc-silicates and oxides, in particular in andradite, titanite, actinolite, epidote, axinite and rutile. At Gejiu in Yunnan Province, andradite can carry up to 5.14 wt% SnO2. In this case, it is believed that Sn4+ together with Mg2+ substitutes for Fe3 in the octahedral sites, a coupled substitution which can be represented by the equation: Sn4 + Mg2+ = 2 Fe3+. The behavior of Sn during skarn formation is governed by the P-T-x conditions of the skarn-forming solutions. Eh and pH variations and changes in the chemical potentials of major and trace elements (e.g., fS2 ), play a crucial role in determining the prevailing equilibria. During the high-temperature and alkaline stage of prograde metasomatism, an association of andradite + diopside formed under oxidizing conditions when Sn entered the lattice of andradite; or, in environments deficient in Fe, Mg and A1, but rich in Sn, malayaite formed. The association hedenbergite + grossular was formed under reducing conditions, and in this case Sn was retained in the hydrothermal solutions, becoming available for reactions at lower temperature. The rare Sn mineral nordenskioldine was formed at a late stage, during prograde alteration where conditions were uncommonly B rich and depleted in F, CO2 and, especially, Si. Sn was not deposited as cassiterite until the system evolved to retrograde low-temperature and acid conditions. During this stage, cassiterite formed with magnetite, actinolite and fluorite at the expense of tin-bearing andradite (e.g., Shizhuyuan, Hunan Province), or precipitated from the ore-forming solution together with chlorite and sulphides (e.g., Debao, Guangxi Province) or with quartz and sulphides (e.g., Dachang, Guangxi Province ). Cassiterite, together with calcite, even formed at the expense of nordenskioldine in place (e.g., Gejiu). Malayaite was also formed with quartz and calcite at this stage (e.g., Zhengiialong, Jiangxi Province).

Introduction
Five main types of primary Sn deposits are found within the extensive districts of W- and

Correspondence to: J. Chen, Department of Earth Sciences, University of Nanjing, Nanjing, P.R.China.

Sn-bearing polymetallic mineralization spread across the Caledonian terrane of the South C h i n a F o l d b e l t . T h e s e are: ( 1 ) Cassiterite-wolframite-quartz lodes; (2) Cassiterite-sulphide lodes; ( 3 ) Greisen bodies; (4) Porphyry-type deposits; and

0169-1368/92/$05.00 1992 Elsevier Science Publishers B.V. All rights reserved.

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( 5 ) Tin-bearing skarns. Deposits of the first four categories, with large ore reserves, have contributed significantly to the Sn production of the People's Republic of China (PRC), and a number of detailed studies have been made during the last forty years ( e.g., Hsu, 1943; Chen, 1964; Tu, 1988; Peng and Cheng, 1988). Less attention has been given to geological and geochemical research on skarn deposits, although there have been some recent reviews (e.g., Ren, 1982; Zhao et al., 1990). In South China, important tin-bearing skarns occur in widely-separated areas. The best known are Gejiu (Yunnan Province), Dachang (Guangxi Province) and Shizhuyuan

( Hunan Province ), the locations are shown m Fig. 1. Although they are generally characterized by low grades, they have high tonnages so that the reserves of Sn metal contained in them are large. For example, the Shizhuyuan skarn contained 0.1-0.2 wt% SnO2 but its reserve of Sn metal is in the order of 100,000 tonnes. The tin-bearing skarns are only one of a variety of metalliferous skarn formations associated with granitic intrusions. W-rich, Be-rich and MoBi skarns are also regionally important and may contain Sn in complex parageneses. Ren (1982) reviewed the occurrence and geochemistry of tin-bearing magnetite skarns in South China, and the distribution of Sn in garnets from the Shizhuyuan deposit has been

Dr. Chen(1954) received his Ph.D. from Nanjing University, Nanjing, P.R. China in 1985, and taught at the university for five years before becoming an associate professor. His research interests are in tin, tungsten and gold deposits and especially in skarns.

C. Halls is Senior Lecturer in the Mining Geology Research Group in the Department of Geology, Royal School of Mines, Imperial College of Science, Technology and Medicine, London. Hc graduated from University College London in 1964 and received his Ph.D. in 1969 at University CoUcgc London, on the silver-bearingarscnide veins of Cobalt, Ontario. Hc was employed as a consultant mineralogistfor the N e w Brunswick Research and ProductivityCouncil,returningto universityteachingand researchat the Royal School of Mines in 197 I. He has worked on the interpretationof paragcncticproblems in S n - W mineralization associatedwith granitesin Bolivia, S W England and South China and is activelyinvestingthe relationshipbetween mechanism, para~nesis and zoning in these systems. He has a particularinterestin the descriptionand classification pncumatolyof ticalterationand brccciasoriginatingfrom granites.
C. Stanley (1954) was educated at Southwell. He received his Ph.D. from the University of Aston in Birminglaam in 1980 and joined the Department of Mineralogy at the British Museum (Natural History) in the same year. As a specialist ore mineralogist hehas published books and Iml~rS both on the pure and applied aspects of the science in collaboration with numerous scientists worldwide. At the Natural History Museum in London he iscurrently head of"the programmes on Mineralogy and Origin of Ore Deposits and Environmental Mineralogy.

TIN-BEARING SKARNS OF S. CHINA: GEOLOGICAL SETTING AND MINERALOGY

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20

LOCATION OF SOME MAJOR TINBEARING SKARN DEPOSITS IN SOUTH CHINA

LAOS
:!i!i]::::i:::~.::..:::: : :.ii.i ~:ii :.:!4:1! .:.:....: 105 110 115

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skarn 300 400

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deposits 500km
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Fig. 1. L o c a t i o n o f s o m e m a j o r t i n - b e a r i n g skarn d e p o s i t s in S o u t h China

studied by Liu et al. ( 1983 ) and Chen ( 1987 ). Experimental synthesis of skarn assemblages has also been investigated by Chen and Wu ( 1988 ). Much uncertainty remains, however, concerning the geochemical behavior of Sn during skarn formation, although valuable reviews have been given by Nekrasov ( 1971 ), Smirnov ( 1976 ), Taylor ( 1979 ) Einaudi et al. ( 1981 ),Aleksandrov and Vernadsky ( 1985 ), and Kwak (1987). The aim of the present paper is to review the geological setting and particular aspects of the mineral assemblages occurring in some tinbearing skarn deposits from South China, paying particular attention to the mineralogical location of Sn in the skarns, and the geochem-

ical behavior of Sn during the different stages of skarn formation.

Geological setting of tin-bearing skarns in South China Nature of skarns

The Caledonian Foldbelt of South China has been divided by Xu et al. (1982) into four broadly NEE-trending morpho-tectonic subunits bordering the Yangtze-SW China Platform. Taken from NW to SE these are: ( 1 ) the Proterozoic geanticlinal belt; (2) the post-Caledonian zones of uplift;

228

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(3) the Hercynian-Indosinian depressions; and (4) the coastal Mesozoic volcanic belt. Tin-bearing skarns have formed mainly within littoral to neritic sedimentary sequences located in the Hercynian-Indosinian depressions. The skarn bodies are located mostly in Devonian and Triassic carbonate sequences at the contacts of Yanshanian granite intrusions. The Shizhuyuan skarn, for example, is located in the contact-metamorphic zone of the Qianlishan two-mica granite which intrudes the carbonate sequence of the Upper Devonian Shetianqiao Formation (Fig. 2 ), and contains five styles of mineralization (see Fig. 3). In the Gejiu Sn field, there are four main deposits, that is the Malage, the Songshujiao, the Laochang and the Kafang as shown in Fig. 4. These deposits were formed in carbonate se-

Fig. 2. Geological setting of the Shizhuyuan W-, Sn-, Moand Bi- bearing skarn deposit.( Modified from Chen, 1981 ). 1. Outcrop of skarn; 2. Qianlishan Yanshanian granite; 3. Yanshanian granite porphyry, 4. Yanshanian quartz porphyry; 5. Quaternary sediments; 6. Shetianqiao Formation, Upper Devonian limestone and shale; 7. Qiziqiao Formation, Middle Devonian limestone; 8. Tiaomajian Formation, Middle Devonian sandstone. STS: Shizhuyuan-Taipingli syncline; SYA: Shizhuyuan-Yejiwei anticline.

quences of the Triassic Gejiu Formation at the contacts of porphyritic to equigranutar biotite granites. (The term granite used in this study is s e n s u s t r i c t o based on the classification of Streckeisen, 1976). The ages of these granites have been determined as 84-115 Ma using the K / A r method on biotite (Wang, 1983 ). In the Gejiu field, the only extensive outcrop of skarn is the Damoshan Sn-Bi skarn, which forms part of the Malage deposit. It extends along the contact of the Baishachong biotite granite, forming a zone 260 m long and about 20 m wide (see Fig. 5). In certain cases, the skarn bodies are not formed in limestones but within metabasic volcanic or intrusive rocks in the close vicinity of the granites as in the Chahe Sn deposit in Sichuan Province. Here, the skarn bodies are found in the contact zone between Proterozoic metasandstone and diabase, the main ore body extending for 400 m along strike and for 750 m down dip in the metadiabase (Liu, 1983). The morphology of the skarns is chiefly determined by the geometry of the contact between the granite and the host lithology,which is often complex. Lensoid shapes are most typical, extending from the granite contacts into the envelope of metasomatically altered carbonate wall rocks. Such bodies can have lengths in the order of 800-1000 m, widths of 600-800 m and thicknesses of 200-300 m (Wang et al., 1982 ). In general, the skarn bodies are stratabound and have low aspect ratios, but some of them display more rigorous stratiform geometry. For example, at Dulong on the border between Yunnan Province and Vietnam, the skarn ore bodies are formed within a defined carbonate unit of the Tianpen Formation of Middle Cambrian age, which was intruded by a granite of Late Yanshanian age. The main ore body is located within this stratum, having a thickness of only about 10 m, but extending for more than 1000 m along strike (Chen, 1985 ). The tin-bearing skarns are commonly associated with other tin-bearing lode structures, the most important of which are those contain-

TIN-BEARING SKARNS OF S. CHINA: GEOLOGICAL SETTING AND MINERALOGY

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Fig. 3. Geological section through the Shizhuyuan skarn deposit, showing the location of the five ore types. (Modified from Wang et al., 1982.) 1. Greisen with W-Sn-Mo-Bi; 2. Skarn with W-Sn-Mo-Bi; 3. Skarn with W-Bi; 4. Skarn with Bi; 5. Marble with cassiterite-sulphide-tourmaline stockwork veining; 6. Marble; 7. Qianlishan granite; 8. Granite porphyry (A-B is shown in Fig. 2).

IAISHACON6~ 6itANIT[ ~

IIALAGE ~ ORE O00Y

OAPlOSHAN SKARfl

Fig. 5. Geology of the Damoshan skarn from the Gejiu tin field. Fig. 4. Regional geology of the Gejiu tin field, showing the distribution of intrusions and tin deposits. (Modified from Peng and Cheng, 1988. ) 1. Quaternary regolith; 2. Ailaoshan pre-Cambrian metamorphic terrane; 3. Baishachong Yanshanian granite; 4. Longchahe Yanshanian granite; 5. Late Yanshanian syenite; 6. Indosinian gabbro; 7. Basalt; 8. Blind ore body; 9. Position of Gejiu city. Tf. Falang Formation, Middle Triassic siltstone and shale; Tg:.Gejiu Formation, Middle Triassic limestone; Mlg: Malage deposit; Ssj: Songshujiao deposit. The box delineates the area of Fig. 5. ing c o m p l e x cassiterite-sulphide parageneses. T y p i c a l l y , the skarn ores are s i t u a t e d in the imm e d i a t e z o n e o f the e x o c o n t a c t , w h e r e a s the cassiterite-sulphide veins are l o c a t e d b e y o n d the z o n e o f skarn f o r m a t i o n in the s u r r o u n d i n g marbles. T h i s is the case in the o r e f i e l d o f D a c h a n g , w h e r e S n - C u - Z n s k a r n o c c u r s imm e d i a t e l y o n the c o n t a c t b e t w e e n the Longxiangai biotite granite o f L a t e Y a n s h a n i a n

age and carbonate units of Middle to Upper Devonian age. Stratiform, veinlet and stockwork ores, containing cassiterite and sulphides, are located further from the granite contact in siliceous shales, black shales, marls and limestones of Upper Devonian age (Fig. 6). In some instances, cassiterite-sulphide deposits have formed by the superimposition of tin-bearing hydrothermal assemblages on the skarns at a late stage, thus leading to the formation of economically valuable ore bodies, such as those at Dulong and Chahe.

Associated granites

SW

NE

Fig. 6. Diagrammaticsection across the western mineralization zone of the Dachang tin field, illustrating spatial relationshipsof various stylesof tin mineralization. 1. TongchejiangFormation, Upper Devonian marl and shale; 2. Liujiang Formation, Upper Devonian limestone; 3. Liujiang Formation, Upper Devonian siliceous shale; 4. Majiao Formation, MiddleDevonian limestoneand shale; 5. LongxianggaiYanshaniangranite; 6. Yanshaniandiorite-porphyrite; 7. Cassiterite-sulphideveins; 8. Cassiterite-sulphide stoekwork; 9. Stratiform Zn-Sn mineralization; 10. Stratiform Cu-Zn mineralization; 11. Skarn CuSn-Zn mineralization.

The productive Sn skarns in South China have formed mainly at the contacts o | medium- to fine-grained biotite or biotite-muscovite granites formed as late differentiates from a larger composite Yanshanian pluton. They are characterized by strong deuteric alteration, originating at the transitional stages of their evolution. K-feldspathization, albitization and greisenization typically form a sequence in the alteration of the apical zones of these granites which, with associated lode structures, provide the basis for the five tier model of hydrothermal development reviewed by Gu ( 1982 ). Sn mineralization, whatever the style of emplacement, is invariably related to those hydrothermally specialized granites, within which strong albitization or greisenization has taken place. The petrological characteristics of the tinproductive Yanshanian granites, formed during the interval from 80 to 190 Ma (Xu and Zhu, 1988), are compatible with the formation by crustal anatexis and they are thus classified within the S-type of Chappell and White (1974), also designated the Transformation type by Xu et a1.(1984). They have oxygen isotope compositions with ~]80 in the range 9.3-14.0%o corresponding mainly to the HH field of Taylor (1968), and they have initial isotope ratios for strontium in the range 0.7100.735; both features pointing to an anatectic origin for these Yanshanian granites (Xu and Zhu, 1988). The chief mineral component is K-feldspar which is often present as large phenocrysts (megacrysts) set in a phaneritic matrix, or else as subhedral to anhedral, sometimes microperthitic grains, making up an average of 27-42% by volume of the rock (see Table 1 ). Plagioclase is euhedral to subhedral, twinned on some combination of the Cadsbad, albite or pericline laws, and is normally zoned within the compositional range from Anlo..3o to about Ans. The average ptagioclase content is 17-33% by volume. Quartz is usu-

TIN-BEARINGSKARNSOF S. CHINA:GEOLOGICALSETTING AND MINERALOGY TABLE 1 Petrographic characteristics of some representative tin-bearing granites from South China K-feldspar 1 2 3 4 5 6 Microperth. (38%) Microperth. ( 27% ) Microperth. (37%) Microperth. ( 42% ) Microperth. (33%) Microperth. (30%) Plagioclase An~ 2-An30 (28%) Ans-An ~ 5 ( 33% ) An2o-An38 (23%) An~5-An3o ( 17% ) An~o-An25 (28%) Ans-An2o (25%) Quartz Irregular (28%) Irregular ( 32% ) Irregular (34%) Irregular ( 35% ) Irregular (30%) Irregular (35%) Micas Bio. ( 4% ), Musc.(1%) Bio. ( 3% ), Musc. ( 4% ) Bio. (3%), Musc.(2%) Bio. (1%), Musc. ( 3% ) Bio. (5%), Musc. (3%) Bio. (5%), Musc. (4%) Other minerals

231

Top.,Flu.,Zir.,
Mon.,Gad.,Wolf. Top. ,Gad. ,Flu. ,Mon., Wolf.,Cass.,Py. Ilm.,Py.,Top.,Flu., Tour.,Zir.,Ap. Ilm.,Py.,Top.,Flu., Tour.,Zi r.,Ap. Ilm.,Py.,Flu., Zir.,Ap. Ilm.,Zir., Cass.,Ap.

Note: 1: Coarse- to medium-grained biotite granite from Shizhuyuan; 2: Medium- to fine-grained two mica granite from Shizhuyuan; 3: Porphyritic biotite granite from Dachang; 4: Medium- to fine-grained two mica granite from Dachang; 5: Coase- to medium-grained granite from Dulong; 6: Medium- to fine-grained two mica granite from Dulong.

ally anhedral, occupying the interstices between the feldspars, making up some 30% of the rock. Biotite is the principal ferromagnesian mineral, although in many parts of the hydrothermally productive granites it is retrogressively altered to chlorite. It makes up about 1-5% of the rock and is typically enriched in lithium up to 2000-5000 ppm, coinciding with the field of compositions described by Hall ( 1971 ) as protolithionite. Muscovite is characteristically a product of deuteric alteration within the mineralized granites, forming at the expense of biotite. For this reason the amount of muscovite increases in the later, more hydrothermally specialized, facies of these granites. The chemical composition of the muscovite corresponds with phengite or Li-phengite. Tourmaline and topaz, separately, may be present up to 1% by volume in these granites. Other accessory minerals, which contribute a total of up to about 1%, include ilmenite, pyrite, apatite, zircon, fluorite, monazite and cassiterite. The chemical compositions of typical tinbearing intrusions are shown in Table 2. The

content of S i O 2 is commonly between 73-75%, and the total alkali content ( K 2 0 -k- N a 2 0 ) is always greater than 7.5%. All the granites which have associated Sn mineralization also show significantly high contents of Sn in their unmineralized facies. A study of Sn contents within eight selected tin-bearing intrusions from South China shows that the typical average content for these granites lies in the range between 15 and 40 ppm (Chen, 1985 ), whereas tin-barren granites contain an average of about 3 ppm Sn. These differences are similar to those reported for granites in the USSR by Barsukov (1957), by Hesp and Rigby ( 1975 ) from Australian granites, and by Tischendorf et al. (1978) from the Erzgebirge ( former GDR: see also Lehmann, 1988). Sn in the unmineralized parts of the Yanshanian plutons is mainly located in biotite and muscovite. The two micas make up less than 10 wt% of the granite, but they contain more than 50% by weight of the Sn (Table 3). A comparison of biotites from tin-bearing and tin-barren granites shows that the former have Sn contents of greater than 100 ppm, whereas

TABLE 2 Average compositions of some representative tin-bearing granites from South China Oxides ( wt% ) Shizhuyuan A (3) 75.51 0.06 12.26 0.60 0.98 0.00 0.02 0.74 3.50 4.79 0.00 0.71 99.20 B (3) 74.32 0.04 13.43 0.52 0,60 0.00 0.05 0.74 4.38 4.68 0.0 l 0.61 99.37 (' (3) 72.06 0.27 13.84 0.45 1.34 0.41 0.06 1.49 2.98 4.81 0.26 Dachang D (6) 73.65 0.09 14.18 0.42 0.74 0.24 0.07 0,91 3,29 4.82 0.30 1.33 98.71 E (4) 73.20 0.17 14.25 0.36 1.23 0.27 0.10 0.93 3.44 4.15 0.19 Dulong t= (3) 73.27 0.11 i 3.91 0.82 1.34 0. t 6 0.03 0.36 3.44 5.37 0.04 {;ejit~ (i (3) 74.65 0.04 13.04 0,38 1,02 0,24 0.03 1.15 4.00 4.23 0.0 I

SiO: TiO2 A1203 Fe203 FeO MgO MnO CaO Na20 K20 P2Os L.I. Total

97,95

99.84

98,84

99.28

Note: A: Coarse- to medium-grained biotite granite; B: medium- to fine-grained two mica granite: C: porphyritic biotite granite; D: two mica granite; E: medium-grained two mica granite; F: medium-grained granite; G: fine-grained biotite granite. Number in brackets is the number of samples from each pluton analyzed. Analyses made in the Chemical Laboratory of the Department of Earth Sciences, Nanjing University.

the latter contain less than 20 ppm Sn (Chen and Zhou, 1988).

Prograde minerals
Garnet is the most abundant component of the skarn bodies and usually makes up 30-50% by volume of the rock. It forms characteristically euhedral or subhedral grains in massive aggregates and often displays optical zonation related to chemical composition, For instance, garnets from the exoskarn at Damoshan in Gejiu have dark green cores with more than 95 mol% andradite, whereas in the yellow marginal zones the andradite content falls to about 85 mol%. Garnet compositions faU mainly inthe grandite field with less than 10 tool% s ~ i n e + almandine + pyrope (Sp + AI + Pr), except in the case of the W-dominant skarn at Yaogang,xian (see Table 4), Within this grandite field, the Sp + AI + Pr content increases as

Miaeralo~ of the tin-bearing skarns

Most of the tin-bearing skarns from South China fall within the field of calcic skarns as defined in the classification of Nekrasov (1971) and as used by Einaudi and Burt (1982). The major gangue minerals are garnet, pyroxene, amphibole, idocrase, wollastonite, epidote, chlorite, fluorite and quartz. The main opaque minerals are magnetite, pyrrhotite, pyrite, chalcopyrite, sphalerite, galena, bismuthinite, molybdenite, scheelite and cassiterite. The scheelite, as at Shizhuyuan, may show systematic variations in Mo content.

TIN-BEARING SKARNSOF S. CHINA: GEOLOGICALSETTING AND MINERALOGY TABLE3 Distribution of tin among the main rock-forming minerals in some samples of tin-bearing granites from South China Minerals Shizhuyuan 1 Qua~z A B C A B C A B C A B C A B C 28 1.2 1.9 35 2.6 5.3 28 3.5 5.7 7 143 57.8 2 32 1.2 1.9 28 1.2 1.7 30 2.2 3.3 8 172 68.7 3 32 1.5 1.8 27 4.9 4.8 33 4.5 5.4 7 213 54.2 Dachang
1

233

Dulong
1 2

K-~ldspar

Plagioclase

Biotite

Muscovite

33 2.3 3.0 37 15.0 22.0 23 4.0 3.7 5 140 27.8 2 154 12.2

30 7.6 10.9 33 3.5 5.5 28 9.3 12.4 5 130 31.0 3 188 26.9

35 0.5 1.0 30 4.5 7.5 25 6.8 9.4 5 118 32.6 4 141 31.2

Note: A: Wt% of the mineral in granite sample; B: Tin content of the mineral, in ppm; C: Percentage distribution of tin in the mineral. 1: Central facies of the granite; 2: Marginal facies of the granite; 3: Supplementary intrusive facies of the granite. Tin analyses carried out in the Central Laboratory of the Geological Bureau, Jiangsu Province.

the proportion of W in the skarn increases relative to Sn. For example, garnet from the tinrich skarns of Xinlu, Gejiu and Dachang contains less than 3 mol% (Sp + A1 + Pr), whereas the Sn-W skarns at Yaogangxian and Shizhuyuan contain garnet with 10-25 mol% (Sp + A1 + Pr). It seems that garnet from Sn skarns is dominantly andradite whereas, garnet from W skarns contains more of the grossular and (Sp + A1 + Pr) molecules (Fig. 7 ). Pyroxene is mainly diopsidic to hedenbergitic in composition, and displays a regular decrease in Mn content with increase in Mg/Fe ratio, generally containing less than 10 mol% johannsenite. The composition of the pyroxene is obviously controlled by the ambient Eh conditions in the skarn environment during crystallization. Under relatively oxidizing conditions, the skarn-forming fluid is rich in ferric iron, and so the association andradite-diop-

side is stable. The skarn at Gejiu, for example, contains garnet with more than 85 mol% andradite in association with pyroxene containing less than 15 mol% hedenbergite. In a reduced skarn environment, however, the characteristic association is of ferrous- and manganese-rich (hedenbergitic) pyroxene with grossular-rich garnet. This assemblage is present in samples from the Yaogangxian skarn which contains about 50 mol% hedenbergite (Table 5) and less than 15 mol% andradite (Table 4). Pyroxene and garnet together make up the main anhydrous assemblage in the inner zones of the skarn close to the intrusive contacts. Idocrase occurs typically with wollastonite in the external zones of the skarn bodies, forming either an idocrase-wollastonite assemblage, or an idocrase-wollastonite-grossularite assemblage as at Shizhuyuan, and in the tin-bearing

234 TABLE 4

i ; i ,% ~ .~ ,

Microprobe analyses of garnets from tin-bearing skarn assemblages, South China

Oxides (wt%) ( 1) mean n'=9 37.48 0.19 19.49 nd 4.41 1.99 7.84 0.08 27.92 99.41 std. dev. 0.10 0.03 0.23 0.26 0.55 0.76 0.02 0.97 (2) mean n=8 35.83 0.08 3.84 1.33 24.81 0.24 0.45 0.25 33.78 100.59 std. dev. 0.35 0.05 2.13 0.30 2.53 I),20 0.03 0.03 0.14 (3) mean n=5 37.23 0.17 11.73 0.22 15.38 std. de~. 0.14 0.05 0.67 0.07 0.75 (4) mean n = 15 36.67 0.16 9.39 0.33 18.76 0.95 2.60 0.12 31.44 100.41 std. dev. 0.16 0.07 0.8I 0.04 1.17 0.27 0.28 0.01 0.54 ~5 mean n = 21 34.96 0.0l J.29 2.54 27.54 std. dev. 0.09 0.01 0.25 0.34 0.32

SiO2 TiO2 AlzO3 SnO2 Fe203 FeO MnO MgO CaO

Total

0.61 0.04 35.72 101.09

0.08 0.02 0.20

0.52 0.35 33.30 100.50

0.03 0.05 0.11

Cations per 24 oxygens

Si AI(IV) AI(VI) Ti(VI) Sn ( VI ) Fe s+ Fe 2+ Mn 2+ Mg Ca Am Sp Pr Gr Ad 5.88 0.12 3.48 0.02 0.52 0.26 1.04 0.02 4.69 0.04 0.17 0.00 0.65 0.13 5.94 0.06 0.66 0.01 0.09 3.t2 0.03 0.06 0.06 6.00 0.0 t 0.01 0.01 0.14 0.83 5.88 0.12 2.07 0.02 0.01 1.83 0.08 0.01 6.05 0.00 0.01 0.00 0.51 0.47 5.92 0.08 1.71 0.02 0.02 2.29 0.13 0.36 0.03 5.44 0.02 0.06 0.00 0.34 0.57 5.92 0.08 0.18 0.00 0.17 3.51 0.07 0.09 6.03 0.00 0.01 0.01 0.03 0.9

Note: "n is number of analyses; a: Wavelength dispersive analyses at 20kV; b: Garnet analyses presented as cations per 24 O, and F%O3 and FeO calculated assuming stoichiometry of 16 cations; c: nd means below detecting limit;
d: Sample locations: (1) Yaogangxian; (2) Xinlu; (3) Dachang; (4) Shizhuyuan; and (5) Gejiu.

skarn deposit at Dachang. It is common for both minerals to form at the expense of calcite and silicates in impure marbles at the early stage of contact metamorphism. Idocrase-wollastonite bands are a distinctive feature of the marbles produced by alteration from the banded impure limestones of the Upper Devonian Shetianqiao Formation at Shizhuyuan, and the idocrase-rich a ~ m b l a t ~ of the exoskarn at Gejiu has also formed by alteration of

argillaceous limestone. Idocrase from these skarns often contains some F and Be; for example in the Shizhuyuan skarn, the idoerase contains about 175 ppm Be.

Retrograde minerals
The amphiboles from the tin-bearinB.skarns at Gejiu and Dachang are ~-'een or grey in color, with compositions ranging from tremolite to

TIN-BEARING SKARNSOF S. CHINA: GEOLOGICAL SETTING AND MINERALOGY

Am+Sp+Pr Yaogangxian

235

,~ /"
/

~
~

v Dachang .Shizhuyan . D?moshan

Gr

Ad

Fig. 7. Composition of garnets in Sn- and W-bearing skarns from South China, expressed as molecular proportions of grossular (Gr), andradite (Ad) and almandine + spessartine + pyrope ( A m + S p + P r ) .

ferroactinolite, and show strong pleochroism in thin section. At Shizhuyuan, however, both actinolite and pargasite occur. Pargasite, in this case, is black in hand specimen and in thin section displays strong pleochroism. Compositionally it is rich in Na, Fe and A1. The actinolite skarn at Debao is composed of actinolite, chlorite, epidote, idocrase, andradite and mica, and contains the main Sn and Cu ores. It occurs together with garnet skarn and magnetite skarn. Cassiterite, pyrite, chalcopyrite, sphalerite and bismuthinite are either disseminated in the skarn, or located in the late-stage quartz veinlets which cut the skarn. Mineral textures show that actinolite in the skarn formed at the expense of andradite and that the cassiteritesulphide paragenesis was deposited in the late retrograde stage of the skarn evolution. Epidote and chlorite, the typical minerals of the late retrograde stage of skarn development, always replace earlier skarn minerals. Epidote typically replaces pyroxene or garnet, in places forming pseudomorphs, whereas chlorite tends to form replacements after amphibole and garnet. Epidote and chlorite commonly occur closely associated with quartz, amphibole, cassiterite, fluorite and some sulphides, forming

economically valuable ores, as in the case of the Debao, and the Dulong. Deposition of sulphides at a late stage is accompanied by the retrogression of earlier silicates to hydrous phases, such as epidote, chlorite and fluorite. Because of the partly pseudomorphous and chronologically late relationship of the sulphides and the hydrous alteration minerals formed during this stage of evolution, Zharikov (1970) and Smirnov (1976) use the term superimposed mineralization. A number of economically exploitable Sn ore bodies have formed in this way by the process ofparagenetic superimposition; e.g., at Dulong and at Debao. In places, the sulphides extend beyond the skarn into the surrounding marble or hornfels, forming sulphide-cassiterite veins within the carbonate country rocks. Such is the case at Dachang where there are valuable Sn-Zn lodes (Chen, 1965), and at Gejiu where massive quartz sulphide cassiterite replacement bodies have formed in the Triassic limestones beyond the main skarn zone (Wang, 1972).

Zonation of mineral assemblages

The tin-bearing skarns generally show a zonal arrangement of mineral assemblages within the metasomatic column, which can be related to different sub-stages in the process of skarn formation. The corresponding zones display variable thicknesses, ranging from several centimeters to tens of meters depending on location. A typical example of this zoned structure is in the Shizhuyuan skarn and is as follows: (1) medium-grained biotite-muscovite granite; (2) K-feldspathized two-mica granite; (3) albitized two-mica granite; (4) greisenized granite; (5) plagioclase-amphibole-chlorite-magnetite skarn; (6) amphibole-ferrodiopsidegarnet skarn; (7) ferrodiopside-garnet skarn; (8) idocrase-garnet skarn; (9) wollastoniteidocrase striped skarn; and (10) marbles.

236 T~BLE 5 Microprobe analyses of clinopyroxene from tin-bearing skarns, South China Oxides (wt%) t 1)
.

(2 )
. . . . . . . . . . . . . . . . . . . . . .

13) std. dev. 0.28 0.05 0.63 0.07 0.39 0.04 mean n= 3 52.88 0.54 7.37 0.47 13.17 25.40 99.82 std. dev. 0.82 0.25 3.32 0.04 2.18 0.41 mean n= 6 51.62 1.25 13.05 1.68 9.16 23.92 100.67 s td. de~. 0.65 (3.45 1.6 I 0.35 1.28 0.25

mean n *= 2 50.08 0.46 15.28 2.62 7.14 23.69 99.28

std. dev. 0.36 0.36 0.04 0.67 0.32 0.32

mean Jt = 4 52.64 I)A0 4.27 0.57 15.05 26.20 99.14

SiO: AI2O3 FeO MnO MgO CaO Total

Cations per 6 oxygens

Si AI ( IV ) AI (VI) Fe 2+ Mn 2+ Mg Ca Hd Jo Di Note: 1.98 0.02 0.00 0.50 0.09 0.42 1.00 0.50 0.09 0.41 1.97 0.02 0.00 0.13 0.02 0.84 1.05 0.13 0.02 0.85 1.98 0.02 0.01 0.23 0.02 0.73 1.02 0.24 0.02 0.74 1.97 0.03 0.03 0.42 0.05 0.52 0.98 0.41 0.05 0.51

*n is number of analyses; a. Wavelength dispersive analyses at 20kv; b. All Fe assumed to be present as F e ( 2 + L

c. Sample location: (1) Yaogangxian; (2) Gejiu; (3) Xinlu; (4) Shizhuyuan.

The mineralogical location of tin in the skarn assemblages

Cassiterite

The occurrence of Sn in stanniferous skarn assemblages, both as Sn minerals and as tinbearing calc-silicates, has been t h e subject of recent reviews by Taylor (1979), Eadington and Kinealy ( 1983 ) and Kwak ( 1987 ). Cassiterite is generally identified as the most common Sn mineral to form under skarn conditions (Burt, 1978 ). It may occur in magnetiterich skarns, such as the Lost River Mine, Alaska (Desborough and Sainsbury, 1970) and the Dadin Fe skarn in Guangdong province, South China (Chen and Hou, 1978), and it also occurs in sulphide-rich skarns as at Debao

(Liang and Wu, 1984). Cassiterite is the principal Sn mineral in sulphide replacement bodies formed in carbonate sequences, such as those of in South China (Chen, 1964; Wang, 1972), in Malaysia (Hosking, 1970), and in Tasmania, Australia (Groves et al., 1972; Newnham, 1975; Ransom and Hunt, 1975 ). Cassiterite is commonly present as minute inclusions within the magnetite of tin-bearing skarn assemblages. At Ma An Shan (Saddle Mountain) in Yunnan province, for example, micron-sized inclusions of cassiterite are locked in magnetite (Ren, 1982 ) which occurs in association with andradite, diopside, chondrodite, collbranite and phlogopite. The skarn of the Dadin deposit contains 0.014-0.50 wt% Sn. Here again the Sn is as cassiterite which occurs mainly as < 10/zm inclusions in magne-

TIN-BEARING SKARNS OF S. CHINA: GEOLOGICAL SETTING AND MINERALOGY

237

tite, a relationship which Desborough and Sainsbury (1970) ascribe to exsolution of Sn from the magnetite structure. The magnetite at Dadin is intergrown with fayalite, Mg spinel, garnet, humite, paigeite, collbranite, hematite and sulphides (Chen and Hou, 1978). In some cases, although cassiterite is closely intergrown with magnetite, it is not the product ofunmixing ofa cassiterite-magnetite solid solution. A typical example is the Shizhuyuan tin-bearing skarn in which minute cassiterite grains (2-20 /tm) commonly occur on the margins of, or in cracks within magnetite as well as in the interstices of fluorite and along cleavages in actinolite near the magnetite (Chen et al., 1992a). These textural relationships show that the cassiterite was deposited by hydrothermal solutions after the magnetite and actinolite had crystallized. Moreover, the cassiterite-magnetite-actinolite-fluorite assemblage always forms by replacement in situ of an andradite-rich garnet-ferrosalite skarn in the deposit. Hence, the cassiterite can be explained as a result of the release of Sn from the structure of andradite during alterations; in this case, the andradite contains about 0.4 wt% Sn. Another important tin-bearing paragenesis is cassiterite-bearing chlorite and actinolite skarn. Ores of this type generally contain of the order of 0.3-0.5 wt% SnO2. The cassiterite occurs in aggregates of small equant crystals, distributed irregularly in the interstices of the skarn minerals, and is significantly coarser than cassiterite present as inclusions in the magnetite-rich skarns. In the Debao Sn skarn, for example, the cassiterite in the magnetite skarn is usually 1-5/tm in diameter, whereas cassiterite in the chlorite-actinolite skarn has a grain size of about 20-50 pm, with some grains larger than 100 pm (Liang and Wu, 1984). The chlorite-actinolite-cassiterite ore is economically more important than the tin-bearing magnetite skarn; recovery from the chlorite-actinolite ores reaches 40% with a Sn grade of 40 wt% in the resulting concentrates (Lai and Li, 1987).

The cassiterite in chlorite-actinolite skarn has a close relationship with sulphides; the relative abundance of sulphides in the skarn can often be a useful guide to Sn mineralization. On the basis of their sulphide parageneses, the tin-bearing chloritic skarn rocks in South China have been grouped into five sub-types (Lai and Li, 1987). These are: ( 1 ) chlorite-magnetite-arsenopyrite-chalcopyrite skarn; (2) chlorite-amphibole-arsenopyrite-sphalerite skarn; (3) chlorite-amphibole-garnet-pyrrhotite skarn; (4) chlorite-amphibole-pyrite-chalcopyrite skarn; and (5) actinolite-arsenopyrite-magnetite skarn. Cassiterite-bearing polymetallic sulphide ores, which have formed by replacement of carbonate lithologies, constitute the main mineable Sn resource in the PRC at the present time. These ores can be either pyrite- or pyrrhotite-rich. For example, in the Dachang Sn deposit, the dominant Fe sulphide is pyrite, whereas the ores at Gejiu are predominantly pyrrhotite bearing. The sulphide ores are commonly formed beyond the skarn zone as a result of replacement by later low-temperature fluids which follow chemically reactive horizons, thus creating conformable stratabound bodies. At Gejiu, the ore consists chiefly of actinolite, tremolite, epidote, chondrodite, pyrrhotite, native bismuth or bismuthinite, arsenopyrite, chalcopyrite, cassiterite and pyrite. Pyrrhotite makes up 50 vol% of the ore. At Dachang, however, quartz and tourmaline are abundant, together with minerals pyrite, Ferich sphalerite, arsenopyrite, pyrrhotite and cassiterite. Malayaite Malayaite (CaSnSiOs), the Sn analogue of titanite, is another mineral occurring in a wide range of Sn-bearing skarns, as for example in Malaysia (Alexander and Flinter, 1965; Hosk-

ing, 1970), Thailand (John, 1967 ), Cornwall, England (El Sharkawi and Dearman, 1966), Japan (Shimazaki, 1968: Takenouchi and Shoji, 1969), the Soviet Union (Nekrasov. 1973) and Australia (Plimer, 1982). It was first recorded in China in 1979, as a result of a study to the Zhengjialong Sn skarn by geologists from the Laboratory of the Bureau of Geology and Mineral Resources of Jiangxi Province (1979). The skarn bodies in this deposit are located in the aureole of the Yanshanian Zhengjialong granite at the contact with carbonate units belonging to the Dengying Formation of Upper Sinian (Proterozoic) age. The skarn consists mainly of grandite garnet, diopside, amphibole, chlorite and magnetite, together with sulphides and cassiterite superimposed in later stages of the paragenetic evolution. Malayaite occurs with calcite forming veinlets which cut grandite and diopside skarn. This paragenetic relationship is in accord with the findings of Takenouchi and Shoji ( 1969 ) and Takenouchi ( 1978 ) who observed that malayaite commonly crystallizes with calcite, quartz or wollastonite after the garnet-pyroxene stage of the skarn evolution. Tin-bearing titanite is not an uncommon phase in Sn skarn bodies. Ramdohr (1934) reported the occurrence of tin-bearing titanite coexisting with ordinary titanite in aggregates of greenish garnet and wollastonite from Arandis, Namibia. Shimazaki (1968) described the occurrence of tin-bearing titanite in the wollastonite, diopside and green garnet zone formed between limestone and massive skarn at the Tsumo Mine, Shimane Prefecture, Japan. Titanite commonly occurs in the same deposit with its Sn analogue, malayaite (e.g., Plimer, 1982; Van Marcke de Lummen and Verkaeren, 1985). Tin-bearing titanite with 0.1-3.0 wt% SnO2 has been observed in several Sn skarn in South China (e.g., Shizhuyuan, Xinlu and Debao ). Electron probe studies showed that there might be two generations of titanite in the Xinlu Sn skarn. The early titanite, containing 0.17-0.26 wt% SnO2, occurs

as irregular grains associated typically with vesuvianite, andradite and diopside. The later generation, with 1.72-2.72 wt% SnO,~ has a euhedral prismatic form and occurs in aggregates of actinolite, chlorite and fluorite, which formed at the expense of vesuvianite and andradite. Nordenskioldine Nordenskioldine, the Ca-Sn borate (CaSnB206 ), is of relatively rare occurrence. It has been described both from calcic skarns, such as those of Chukotka, N.E.Yakutia, USSR (Alexsandrov, 1974; Nekrasov, 1971 ), and the Stiepelmann mine, Namibia (Ramdohr, 1934), and from magnesian skarns as at the Uchkoskon deposit, Central Asia, USSR (Marshukova et al. 1969; Materikov, 1977 ), and in the S.W. Brooks Mrs. area, Alaska, USA (Alexsandrov, 1975 ). In China, this rare mineral is only known from the Damoshan exoskarn at Gejiu (Wei, 1982) where it is part of an assemblage consisting mainly of andradite, vesuvianite, diopside, magnetite, fluorite and calcite. Nordenskioldine takes the form of whitish or pale-yellow, fiat rhombohedral crystals growing at the expense of andradite, or forming clusters in the interstices between andradite grains. The andradite at Damoshan contains from 1-5 wt% SnO> and the associated nordenskioldine gives near stoichiometric analyses of 55 wt% SnO> as shown in Table 6. At Damoshan, nordenskioldine was subject to replacement by cassiterite. Small grains of cassiterite, together with calcite, formed at the expense of nordenskioldine, following cleavages and forming larger pseudomorphous aggregates at the terminations of the larger prismatic crystals (Chen et al., 1992b). This cassiterite can be explained by the breakdown of nordenskioldine when the chemical potential of CO2 rose with falling temperature during the retrograde stage of the paragenetic evolution. Nordenskioldine at the Damoshan skarn was

TIN-BEARING SKARNS OF S. CHINA: GEOLOGICAL SETTING AND MINERALOGY

239

TABLE 6 Microprobe analyses of nordenskioldine, cassiterite and varlamoffite from the Damoshan tin-bearing skarn at Gejiu Oxides Nordenskioldine Cassiterite Varlamoffite

(wt%) SiOz A1203 SnO2 CaO FeO MnO MgO Bi203 Total

1 0.19 0.14 55.01 19.83 0.31 0.03 0.02 0.00 75.53

2 0.20 0.03 55.66 19.96 0.31 0.01 0.02 0.00 76.19

1 0.28 0.15 97.04 0.00 1.91 0.17 0.07 0.00 99.62

2 0.29 0.01 97.61 0.00 1.11 0.01 0.04 0.00 99.06

1 3.75 5.12 81.92 0.83 0.38 0.00 0.16 0.00 92.14

2 4.03 3.79 80.48 l. 14 2.76 0.06 0.10 0.09 92.46

3 3.72 5.61 80.94 0.95 0.25 0.07 0.02 0.13 91.68

also replaced by varlamoffite, an amorphous and semi-amorphous hydrated oxide of Sn (Sharko, 1971 ). This mineral formed coatings around nordenskioldine or occupied cleavages and fractures of it, in places cutting grains of cassiterite which had formed at an earlier stage at the expense of the original nordenskioldine. These relationships show that varlamoffite was formed later than the cassiterite-calcite association, probably during a stage of supergene oxidation. Varlamoffite from this deposit has higher contents of S n O 2 , S i O 2 and A1203 but less FeO (see Table 6) when compared to varlamoffites from Malaysia (Alexander and Flinter, 1965)and the USSR (Sharko, 1971 ). These differences are best explained by the differences in the compositions of the parent Sn minerals and the solutions responsible for their alteration. For example, varlamoffites formed by oxidation of stannite are characterized by higher contents of Fe and Cu (Sharko, 1971 ).

Tin-bearing silicates
Sn can be substituted in varying amounts into many skarn silicates, among which tin-rich garnets have been analyzed most often because of their unusually high Sn concentrations (0.45.8 wt%) (Mulligan and Jambor, 1968; McIver and Mihalik, 1975; Plimer, 1982). Table

7 shows the maximum values of S n O 2 in garnets from several Sn skarns in South China. Values are generally in the range of 0.02-2.0 wt%, with a maximum of 5.14% for the green andradites from Gejiu. The Sn substituted in the garnet structure can account for most of the Sn in some skarn mineralization. For example, the Damoshan Sn skarn at Gejiu is composed mainly of garnet, diopside and idocrase and has a Sn grade of about 1-7 wt%. Most of the Sn in the rock is located in garnet which has a range of S n O 2 concentration from 0.75-5.14, wt%. Another good example is the Shizhuyuan tin-bearing skarn, in which more than half of the total Sn is located in the structure of andradite and grossular, which, on average, have 0.15 wt% Sn (see Table 8 ). The Sn content in different growth zones of garnet is variable, reflecting the availability of Sn during mineral growth. According to studies on andradite from the Gejiu, it is clear that Sn substituted preferentially within the Fe-rich cores of garnet (Chen et al., 1992b). The incorporation of Sn in the lattice of garnet was believed to be due to the substitution of S n 4+ for Fe 3+ in the octahedral site (e.g., Mclver and Mihalik, 1975; Butler, 1978; Amthauer et al., 1979). This substitution model could also be supported by compositional data of tin-bear-

240 [ABLE 7 The SnO2 contents of some Sn-bearing calcsilicates and oxides in skarns from South China Location Mineral Max. content

}I. "; '," I . , !

Reference

(wt%)
Yaogangxian Xinlu Gejiu Dachang Shizhuyuan Debao Debao Shizhuyuan Gejiu Debao Shizhuyuan Shizhuyuan Gejiu Xinlu Gejiu Debao Grossular Andradite Andradite Grandite Grandile Andradite Diopside Ferrodiopside Vesuvianite Amphibole Pargasitc Epidote Axinite Titanite Magnetite Rutile 0.02 1.90 5.14 0.38 0.67 1.92 0.16 0.14 0.10 0.69 0.66 0.37 0.15 2.72 0.55 3.06 Present study Present study Present study Present study Prosent study Liang and Wu, 1984 Liang and Wu, 1984 Present study Present study Liang and Wu, t984 Liu el al., l'~83 Present study No.308 Team, 1981 Present study No.308 Team, 1981 Present study

TABLE 8 Distribution of tin between the constituent minerals of the tin-bearing skarns of Shizhuyuan Minerals Garnet Fluorite Idocrase Wollastonite Epidote Amphibole Pyroxene Magnetite Cassiterite The others Total A 1185.180 340.117 57.344 85,579 59.691 69.440 35.757 48.927 0.499 1117.856 3000.39 B 3%506 11.337 1.91 t 2.853 1.990 2.315 1.192 1.631 0.017 37.257 100.000 C 1525.0 0.4 318.5 13.3 305.0 6577.0 92.0 224.0 787839.0 D 1807.400 0.136 18.264 1.138 18.206 456.707 3.289 10.959 393.132 73.689 2782.920 E 64.781 0.005 0.655 0.041 0.653 16.369 0.118 0.365 14.091 2.677 100.000

Note: A: Weights of constituent minerals in the sample (g); B: Percentage weight of constituent minerals in sample; C: Tin contents of constituent minerals (ppm); D: Distribution by weight of tin in constituent minerals(mg); E: Percentage distribution of tin between constituent minerals. Analyses carried out in the Central Laboratory of the Geological Bureau, Jiangsu Province, using quantitative spectrographic methods.

ing garnets from South China. The garnet from Shizhuyuan, for example, contains 0.09-0.67 wt/0 SnO2 and has a composition in the range from 21-74 mol% andradite; whereas the garnet from Gejiu with 0.75-5.14 wt% SnO2, con-

tains from 83-98 mol% andradite. In the case of the garnet from Yaogangxian, which has a low Sn content, the composition is only 10-18 mol% andradite. The same trend can also be recognized within individual skarn bodies. For

TIN-BEARING SKARNSOF S. CHINA: GEOLOGICAL SETTING AND MINERALOGY

241

instance, the andradite-rich ( > 60 mol%) garnet situated in the inner zone of the Shizhuyuan skarn has 0.37-0.67 wt% SnO2, whereas the grossular-rich garnet located in the outer zone has less than 0.2 wt% SnO2. Mclver and Mihalik ( 1975 ) also described some garnets of almost pure andradite composition from the skarn formed around the pegmatite at Davib Ost, Namibia, which contain up to 5.82 wt%
SnO2.

It has been known that tin-bearing garnets in skarns are always andradite-rich grandite, whereas the content of Sn detected in other garnets is never more than 0.01% (Dadak and Novak, 1965). This seems to show that there should be some correlation between Fe 3+ and Sn 4+. Moreover, studies by Dadak and Novak (1965), and by Mclver and Mihalik (1975) have shown that the unit-cell dimensions of tinrich garnets is related directly to the Sn content, reaching values even higher than the m a x i m u m given by Skinner (1956) for pure andradite (12.048/k). This p h e n o m e n o n has been observed in garnet from the Sn skarn of Shizhuyuan (see Table 9 ). The Sn content of this garnet is directly correlated with ferric iron, as well as with the unit cell dimension. The tinrich andradite containing 5.14 wt% SnO2, which was synthesized by Chen and Wu (1988), gave a unit cell value of 12.0715 A, obviously in excess of the cell value for pure Sn
TABLE 9

free andradite. The higher value of the unit-cell dimension is undoubtedly due to the incorporation of Sn in the andradite structure. The effective ionic radii of Sn 4+ and Fe 3+ in six-fold coordination were calculated by Whittaker and Muntus (1970) to be 0.77 ,~ and 0.63/k, respectively, and thus the substitution of the larger Sn ions for Fe in the octahedral sites is evidently responsible for the increase in the unit cell dimension of the garnet. Furthermore, Mossbauer spectral studies have demonstrated that Sn entering the garnet structure diadochically would be 4 valent and occupy the octahedral sites (Amthauer et al., 1979; Chen, 1987). The substitution of Sn 4+ for Fe 3+ in the octahedral sites of the garnet lattice requires a compensatory substitution to maintain the charge balance. Thus, a coupled substitution of the type S n 4+ 4- Fe 2+ = 2 Fe3+has been suggested by Mulligan and Jambor (1968), McIver and Mihalik ( 1975 ) and Amthauer et al. (1979). In some cases, however, although all the iron is allocated to the octahedral position, a deficiency of cations in the octahedral sites remains, and there is an excess of bivalent cations for the dioctahedral sites (see Table 4). This deficiency could be explained either by a substitution of the type 3 Sna+(oct) = 4 Fe 3 (oct) (Nekrasov, 1971 ), or by allowing

Unit-cell dimensions and concentrations of tin and iron oxides in natural and synthetic garnets Sample number SnO2 (wt%) Fe203 (wt%) Andradite (mol%) Unit-cell dimension (A) Reference

M007 M010 M009 112-1"

0.394 0.265 0.100 5.14 5.82 1.07

20.44 14.26 7.63 22.11 24.50 28.25

0.69 0.46 0.22 0.84 1.00

12.0026 11.9600 11.8597 12.0715 12.0860 12.0790

Chen and Wu, 1988 Chen and Wu, 1988 Chen and Wu, 1988 Chen and Wu, 1988 McIver and Mihalik, 1975 Dadak and Novak, 1966

*Synthetic andradite, the others are natural.

242

, -,-:

some other bivalent cation, such as Mg :+ to enter the octahedral site, e.g.:
S n 4 + ( o c t ) 4- Mg 2+ (oct)

= 2 Fe 3+ ( oct )

teration of garnet. The minerals of the later generation are usually accompanied or followed by cassiterite. Geochemical behavior of tin during skarn formation Rose and Burt (1979), and Einaudi et al. ( 1981 ) described an ideal sequence of skarnforming events as follows: (1) isochemical contact metamorphism accompanying emplacement of a magma; (2) metasomatism accompanying crystallization of the magma and evolution of an ore fluid; and (3) retrograde alteration accompanying final cooling of the system. This continuous evolutionary sequence has been recognized in many skarn deposits (e.g., Eadington and Kinealy, 1983; Mathieson and Clark, 1984; Kwak, 1987; Newberry et al., 1991 ), in which a progressive decrease in both temperature and salinity has been observed during the successive stages which follow primary skarn formation (Kwak, 1987). But, recently, discontinuous evolution in skarn genesis has also been reported from some skarn deposits, such as in the Sangdong, Korea (Moon, 1981 ), the Lost River, Alaska (Dobson, 1982 ), and the JC, Southern Yukon ( Layne and Spooner, 1991 ). In these deposits, an increase in temperature and/or salinity at a late stage of skarn formation occurs. This could be explained by a new invasion of fluids into the system. The geochemical behavior of Sn during skarn formation has been discussed by several authors. For example, Nekrasov (1971), Aleksandrov and Vernadsky (1985) assessed the influence of pH on the behavior of Sn during the different stages of skarn formation. Burt ( 1978 ) defined the physico-chemical conditions which favour the stability of major Sn minerals such as cassiterite, malayaite and nordenskioldine in the skarn environment. Eadington and Kinealy ( 1983 ) reviewed some aspects of the hydrothermal reactions involving Sn during the three main stages of skarn

Based on the results of electron probe microanalysis of garnets from some skarns of South China(see Table 4), a definite positive correlation between Mg and Sn in the garnet structure has been established (see Fig. 8). In the Damoshan skarn, the coefficient of correlation between the contents of SnO2 and MgO in the garnet is 0.9174 (Chen et al., 1992b). Moreover, similarity between the ionic radii of S n 4+, Mg 2+ and Fe 3, as calculated by Whittaker and Muntus (1970), suggests that the coupled substitution in which S n 4+ and Mg 2+ replace Fe 3 in the octahedral sites in andradite provides the best explanation for the observed correlation between Mg and Sn contents in the andradite structure. Appreciable amounts of Sn can enter the structure of other silicates and oxides in skarn assemblages. These minerals include amphibole, epidote, axinite and rutile (Table 7 ), and in skarn assemblages they are often formed at the expense of tin-bearing garnet during the retrograde stage of evolution. Thus, the Sn in these minerals is probably partly derived by al0.40 r 0.3,~
S n v*

"q

Yaogangxlan ' Dachang . Shiznuyan

* ]

0.2~

Damoshan

"' X~nlu ooo

0.16

c~ eoeo
0.08

eo

0.00 0.00

o.o,

Los' o[,~
MgVl

0.16

0.20

Fig. 8. Positive correlation between Sn and Mg in the garnet structure expressed as cations per formula unit bassed on 24 oxygen atoms.

TIN-BEARING SKARNS OF S. CHINA: GEOLOGICAL SETTING AND MINERALOGY

243

evolution. It is evident that changes of ambient conditions during the metasomatic and the retrograde stages should be responsible for precipitation of Sn from skarn-forming fluids. Metasomatic stage The metasomatic stage of skarn growth begins when the magma approaches solidus conditions and the hydrothermal fluids separate from the silicate melt (Burnham, ! 979 ). These fluids rise along the contacts of the pluton, penetrating and reacting with the carbonates and early metamorphic silicates in the aureole. Infiltration of these fluids also introduces Sn and associated elements such as F and B into the skarn at this stage. Sn mineralization can occur, but the process is very sensitive to physico-chemical changes in the environment. The ambient redox conditions, for example, are regarded as one of the main factors constraining the behavior of Sn at this stage. Under conditions of high oxygen fugacity, between the magnetite-haematite and nickel-nickel-oxide oxygen buffers (Eadington and Kinealy, 1983 ), ferric-rich andradite will be dominant and most of the Sn will be lattice-bound within it. However, at low oxygen fugacities below the quartz-magnetite-fayalite oxygen buffer (Eadington and Kinealy, 1983), ferrous-rich calcsilicate minerals such as hedenbergite, which are unable to take much Sn into their crystal lattice, will be abundant. Sn is then retained in the hydrothermal solutions and contributes to cassiterite mineralization at a later stage of skarn evolution. In the case of Gejiu, the economically significant Sn ores, such as the Shongshujiao cassiterite-sulphide skarn deposit, are always related to reduced skarns composed mainly of hedenbergite, actinolite, tremolite, chlorite and sulphides. In contrast, the oxidized skarns, such as the Damoshan skarn with an assemblage ofandradite + diopside, lacks cassiterite mineralization. Temperature is another important variable governing the geochemical behavior of Sn dur-

ing skarn formation. At temperatures above 400C, in the field of stability of the typical skarn minerals andradite, magnetite and hedenbergite, Sn should be bound in silicates, mainly in the lattice of andradite. Eadington and Kinealy ( 1983 ) suggest that cassiterite will only form at temperatures less than 400C, in agreement with experimental syntheses made by Chen and Wu ( 1988 ), which were designed to test the conditions under which tin-bearing skarns could be formed. Andradite, hedenbergite, magnetite, malayaite and cassiterite were synthesized in these experiments (Table 10), in which andradite, hedenbergite and malayaite were the phases typically formed above 400 C, whereas cassiterite was only detected in below 350C. The synthetic andradite contained up to 5.14 wt% SnO2, depending on the Sn concentration in the solution (see Table 11 ), and SnO2 in hedenbergite reached 1.99 wt%. The malayaite produced experimentally were colorless, allotriomorphic grains with a diameter of 0.01-0.03 mm, and an X-ray diffraction pattern matching natural malayaite. The experiments show that, above 400 C and 0.5 kb, SiO2, as an active component, tends to combine with Ca and Fe to form andradite, and if Sn concentrations are high, malayaite. The reaction during synthesis being of the type: 11 CaCO3 +4 H2SiO3 +5 FeC12 + SnCI4 +02 = Ca3 Fez ( SiO4 ) 3 ( a n d r a d i t e ) + CaSnSiO5 (malayaite) + Fe304 (magnetite) + 7 CaCI2 + 11 CO2 + 4 U20 At lower temperatures, however, SiO2 will become an inert component, garnet and malayaite will not be formed, and conditions favour the appearance of the cassiterite-quartz assemblage according to the following reaction: SnC14 + H2 SiO3 -t-2 CaCO3 = SnO2 +SiO2 + 2 CaCI2 + 2 C O 2 + H 2 0 The behaviour of Sn during skarn formation is also influenced by the relative abundance of

244 TABLE 10

~ : ~',:~ ',.

Results of hydrothermal syntheses of tin-bearing skarn assemblages using Shizhuyuan limestone (reaction in chloride sol utio~ with total concentration (NaC1 + KCI ) at 6.6 wt% and NaCI:KCI = 1:t ) No. Starting material A H007 112-1 12-2 14-2 12-3 H004 H009 112-2 540 700 78 518 528 105 536 525 B 164 463 463 463 463 200 154 198 C 39 156 156 156 156 58 39 234 D 450 1967 2717 2853 3039 163 450 2408 E Temp. (~C) 500 500 500 450 400 400 450 350 Pres. (bar) 500 500 500 400 300 350 500 400 Time (h) 120 87 87 158 216 168 200 280 An+Mt+Hd Malay + Mt + An An + Mt + Malay H d + Mt + Malay + An Hd + Mt + Cat Hd+Mt+Cal Hd+An+Mt Q+Cal+Cas Product

Component reagents: A: SnC14.5H20; B: FeCI2.4H20; C: H2SiO3; D: CaCO3; E: Limestone (weight in mg). Products: An-andradite; Hd-hedenbergite; Mt-magnetite; Malay-matayaite; Q-quartz; Cal-calcite; Cas-cassiterite.

TABLE 11 Electron microprobe analyses of synthetic minerals (wt%) Sample Number 112-1 112-1 112-1 12-2a 12-2b Minerals SiO2 A1203 FeO CaO MgO SnO2 TiO2

Malayaite Andradite Hedenbergite Andradite Andradite

23.87 35.60 47.78 35.60 35.53

4.34 1.59

0.26 22.11 23.80 31.59 31.82

22.05 31.78 20.50 33.07 33.30

1.00 3.48

50.72 5.14 1.99 0.39 0.33

2.69

Note: Analyses carried out in the Research Institute of Geology for Mineral Resources, CNNC, Guilin.

components such as Fe and Mg in the solutions and the surrounding environment. For example, malayaite tends to occur in assemblages with wollastonite, quartz and calcite in nature, as in the Dartmoor, England (El Sharkawi and Dearman, 1966), and the Zhengjialong, South China. Preliminary experiments by Takenouchi ( 1971 ) showed that when Fe and Mg are major components of the system, garnet or clinopyroxene with woUastonite and cassiterite are formed in preference to assemblages with malayaite (Eadington and Kinealy, 1983 ). Under conditions in which B is enriched, and concentrations of F, CO2 and especially SiO2 are very low, Sn will be incorporated in the rare borate, nordenskioldine (Burr, 1978). In the Damoshan, nordenskioldine is usually formed

at the expense of andradite, or occurs in interstices within it. However, the nordenskioldine is overprinted by an assemblage with calcite, fluorite and cassiterite. This indicates that the skarn-forming solution was deficient i n Si, F and CO2 when nordenskioldine was precipitated,but became enriched in these components later.

Retrograde stage
The retrograde alteration stage of skarn formation occurs most probably below 400C, and is marked by crystallization of biotite, hornblende, magnetite, eaaidote, chlorite, sulphides and cassiterite. During initial retrograde alteration, cassiterite is associated with hornblende, magnetite and fluorite, forming at

TIN-BEARING SKARNS OF S. CHINA: GEOLOGICAL SETTING AND MINERALOGY

245

the expense of tin-bearing andradite (e.g., Shizhuyuan). Such cassiterite is very fine grained and often closely intergrown with magnetite. In boron-rich and low-silica environments, cassiterite, together with calcite, replaces nordenskioldine during this stage: e.g., at Brooks Mountain, Seward Peninsula (Aleksandrov, 1974, 1975 ), in some deposits in Central Asia (Sokolov and Komarov, 1968; Lisitsyn and Malinko, 1971), and at Gejiu. When alteration takes place below 350 C, cassiterite often occurs with chlorite and quartz, forming Sn ores of the economically important chloritecassiterite skarn type, currently exploited in some mineralized districts in South China. Mainly, however, cassiterite is associated with sulphides in the latest stage of retrograde alteration, in which structural control is important. The cassiterite can be deposited with sulphides and quartz in lode structures beyond the limit of the main skarn mineralization, as at Dachang, or in parageneses with chalcopyrite and pyrrhotite superimposed on the earlier skarn association thus forming massive sulphidecassiterite ores as at Gejiu. Where the sulphide paragenesis is not well developed, the skarn has less economic importance, as is the case at Shizhuyuan. Ultimately, under supergene conditions, varlamoffite may form at the expense of cassiterite (e.g., Malaysia: Alexander and Flinter, 1965), stannite (e.g., USSR: Sharko, 1971; S.W.England: Russell and Vincent, 1952) and nordenskioldine ( e.g., Gej iu, China ).

sheng and the staff of RIGMR (Guilin) provided valuable scientific advice and logistical help. J. Chen acknowledges the help from Profs. Xu Keqin, Wang Dezi, Liu Yingjun, Hu Shouxi, Zhu Jinchu, Ji Shouyuan, Zhou Xinmin, Li Zhaolin and Associates Wang Henian, Zhang Jingrong and Ye Jun for their valuable advice and assistance received during M.Sc and Ph.D studies at Nanjing University. Reviews by D.I. Groves and M. Stemprok have improved the manuscript. The award of a British Council Fellowship to J. Chen is gratefully acknowledged.

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Acknowledgements
This review has been possible through the generosity of many geologists from exploration teams, mining companies and research institutions in China, who provided samples and unpublished data. Particular thanks are due to Mrs Wang Zhifeng and members of 308 Geological Team in Gejiu, Mr Chen Shimo and members of 408 Geological Team in Shizhuyuan, and Mr Ye Xushen and members of 215 Geological Team in Dachang. Mr Liu Dong-

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