Indium in cassiterite and ores of tin deposits

Ore Geology Reviews 66 (2015) 99–113

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Indium in cassiterite and ores of tin deposits

G.G. Pavlova a, S.V. Palessky a, A.S. Borisenko a,b, A.G. Vladimirov a,c, Th. Seifert d, Luu Anh Phan e

a Institute of Geology and Mineralogy, Russian Academy of Sciences, Siberian Branch, Koptyuga pr. 3, 630090 Novosibirsk, Russiab Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk, Russiac Tomsk State University, Lenina str., 36, 634050 Tomsk, Russiad TU Bergakademie Freiberg, Brennhausgasse 14, D-09596 Freiberg, Germanye Institute of Geological Sciences, Academy of Science and Technology, Chua Lang str. 84, Hanoi, Vietnam

http://dx.doi.org/10.1016/j.oregeorev.2014.10.0090169-1368/© 2014 Elsevier B.V. All rights reserved.

a b s t r a c t
a r t i c l e i n f o
Article history:Received 20 July 2014Received in revised form 6 October 2014Accepted 8 October 2014Available online 29 October 2014

Keywords:IndiumSn–sulfide mineralizationSn–In polymetallic oreRussia Far EastIndium content detectionHigh grade indium ore

The results obtained with LA-ICP-MS by less abundant lighter 113In isotope and EPMA show that in cassiterite ofcassiterite–quartz veins the indium contents do not exceed 160 ppm, while cassiterite from Sn–sulfide veins ischaracterized by higher indium contents from 40 to 485 ppm; sulfides of Sn–sulfide veins unlike sulfides ofcassiterite–quartz veins also have the highest indium contents: Fe-sphalerite (100–25,000 ppm), chalcopyrite(up to 1000 ppm), and stannite (up to 60,000 ppm). Indium contents in the Sn–sulfide ore of the Tigrinoe andPravourmiiskoe deposits obtained using SR-XRF, ICP-MS and atomic absorption methods range from 10 to433 ppm with average values of 56–65 ppm. Indium-rich Sn–sulfide mineralization in five large Sn–Ag ore dis-tricts of the Far East Russia (Khingansky, Badzhalsky, Komsomolsky, Arminsky, Kavalerovsky) provides the impe-tus for further exploration of deposits with Sn–sulfide mineralization as themost promising indium resources inRussia. Empirical observations from geology and geochronology of cassiterite–quartz and Sn–sulfidemineraliza-tion show that the combined contribution from granite and alkaline–subalkaline mafic sources and multistageore-forming processes doubled indium resources of deposits being the main factors in the formation of highgrade indium mineralization.

© 2014 Elsevier B.V. All rights reserved.

1. Introduction

Indium is a rare element and trace component in the composition ofthe Earth's crust. World production of indium has steadily increasedduring the last 10 years, because of increased demand for applicationin electronics, ultra-high vacuum technique, solar power plants, semi-conductor and other industries. In Russia, commercial grade indium iscurrently recovered as a by-product from Sn–massive sulfide deposits(Gaiskoe and Sibaiskoe deposits, Urals), which have indium contentsof 10–25 g/t. The growing demand for indium requires the evaluationof In contents in other types of deposits in an effort to identify alter-native resources. Known indium resources and contents in ore havebeen evaluated in many deposits around the world (Schwarz-Schampera and Herzig, 2002), but until now there are only fewpublished data for deposits in Russia. Many Russian researchershave studied the composition of ores and indium-bearing minerals,as well as indium contents in the ores and magmatic rocks (Butovaet al., 1998; Flerov, 1976; Flerov et al., 1971; Gamyanin and Kokin,1991; Gavrilenko and Pogrebs, 1992; Genkin and Muravjova, 1963;Indolev and Nevoisa, 1974; Ivanov and Rozbianskaya, 1961; Ivanovet al., 1963; Kiselev, 1948; Komarova and Novorossova, 1959;Nekrasov, 1966; Nikulin, 1967; Orlova, 1956; Pavlovskiy et al.,1977; Prokin and Buslaev, 1999; Semenyak et al., 1994; Zabarinaet al., 1961).

There are indium minerals (indite FeIn2S4, roquesite CuInS2 andlaforetite AgInS2) and In-containing mineral-carriers in the oreveins of tin deposits. Indite replaced by dzhalindite In(OH)3 wasfound in fissures in cassiterite of cassiterite–quartz veins and inquartz veinlets intersecting quartz-cassiterite aggregate (Dzhalindadeposit, Khingansky ore district, Sikhote-Alin) (Genkin and Muravjova,1963). In addition, there are micro-inclusions of stannite in cassiteritecrystals (Fig. 1A) and veinletswith quartz, hydromica, In-bearing stanniteand Fe-sphalerite in cassiterite aggregate (Fig. 1B, C), so reported highindium contents in cassiterite according to quantitative spectral analysismust be taken with a large degree of caution. Roquesite occurs usuallyin associationwith chalcopyrite in Sn–sulfide andVMSdeposits, laforetiteis usually deposited in the composition of Sn-sulfide ore with galena andsphalerite, and in Sn–Ag carbonate veins at the periphery of Sn–Ag oredistricts. In the oxidation zone indium enters the composition ofsupergene mineral yonomamite. However, whole indium, which hasbeen recovered during processing of the ores of hydrothermal tin andSn-bearing VMS deposits, occurs as impurity in the In-bearing sulfidesand sulfosalts. In recent years new data on the In contents in themineral-carriers has been obtained (Cook et al., 2009, 2011a,2011b,2011c; Gavrilenko and Pogrebs, 1992; Jovic et al., 2011; Jung andSeifert, 1996; Kieft and Damman, 1990; Kissin and Owens, 1989; Mouraet al., 2007; Murakami and Ishihara, 2013; Murao et al., 2008; Ohta,1989; Seifert, 1994; Seifert and Sandmann, 2006; Semenyak et al.,

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Fig. 1. Stannite in cassiterite crystal and aggregate: A — photomicrograph of stannitemicro-inclusions (≤0.03 wt.% In, Table 2) in cassiterite crystal, quartz–cassiterite vein,Khrustalnoe deposit, Far East Russia. B — SEM image of cassiterite cut by veinlet with 1and 3 — stannite (0.14 and 0.24 wt.% In, Table 3), 2 and 4 — cassiterite, 5 — hydromica.C — SEM image of veinlet in cassiterite with 1 — stannite (0.22 wt.% In, Table 3), 2 — Fe-sphalerite, 3 — cassiterite, 4 — tantalite–columbite, 5 — hydromica.

100 G.G. Pavlova et al. / Ore Geology Reviews 66 (2015) 99–113

1994; Shimizu et al., 1986; Sinclair et al., 2006; Ye et al., 2011): Fe-sphalerite (0.1–7, rarely up to 13.5 wt.%), chalcopyrite (up to 0.1 wt.%),bornite (up to 0.4 wt.%), stannite and kësterite (≤3 wt.%), stannoidite(~0.1 wt.%), petrukite (0.7–6 wt.%), and sakuraiite (up to 17–23 wt.%).

It has been known that sulfide and sulphosalt minerals in some tinand VMS deposits contain modest amounts of indium, but the question

of whether indium can also be hosted in cassiterite remains poorlyconstrained. Common methods for determining the indium content incassiterite include electron probe microanalysis (EPMA), wet chemicalor spectral analysis but these methods do not provide satisfactoryanswers to the question. The disadvantage of EPMA is that the mini-mum detection limit of analysis (±0.06 wt.%) may exceed the actualIn content in the mineral. In addition, analytical precision may be lowbecause of superposition of the Sn and In analytical lines. The disadvan-tages of wet chemical and spectral analysis include the fact that, firstly,cassiterite often contains mineral micro-inclusions (indite, stannite)which contain indium as main components (up to a few wt %). It istherefore possible to overestimate the results obtained from samplescontaining such micro-inclusions. Second, wet chemical and spectralanalyses also have minimum detection limits that do not permit detec-tion of In contents below 10 ppm (0.001 wt.%).

2. Samples and deposits

Sample material was selected from tin deposits of the Far East Russiaand Northern Vietnam, Yakutia, Kyrgyzstan (Tian-Shan), Tadjikistan(Pamir), Germany (Erzgebirge), and the only Sn deposit in Tuva(Russia) (Appendix A). Cassiterite samples are selected from cassiterite–quartz veins of the Deputatskoe large tin deposit in Yakutia, Trudovoe(Tian-Shan), Trezubetz and Kobrigen (Pamir) Sn deposits, from cassiter-ite–quartz and cassiterite–sulfide veins of tin deposits in Vietnam andTuva by authors during field works.

Cassiterite from cassiterite–quartz and cassiterite–sulfide veins ofseveral tin deposits of the Far East Russia including Silinskoe, Khrustalnoe(Kavalerovsky ore district, Sikhote-Alin), Valkumey, Pervonachalnoe(Chukotka), Pridorozhnoe and Solnechnoe (Komsomolsky ore district,Sikhote-Alin) are selected from the vein samples in mineral collectionsof the Institute of Geology and Mineralogy SB RAS. Sulfides are takenfrom cassiterite–sulfide veins of the Tigrinoe, Khrustalnoe, Pridorozhnoe(Far East Russia), and Tashkoro (Kyrgyzstan) deposits. Samples from theTigrinoe deposit are taken from themine and represented by cassiterite–quartz veins with muscovite, cassiterite–quartz greisen and sphaleriteore veins fromquartz–topaz–cassiterite–sulfideveins in different propor-tions. Ore samples of the Pravourmiiskoe deposit are taken from the aditand consist of predominating sulfides: chalcopyrite, sphalerite and arse-nopyrite (from 15 to 50%) with cassiterite (5%), quartz and topaz (from15 to 50%), tourmaline (up to 10%), and bornite (up to 25% in 118–87sample), ± rare fluorite, wolframite.

Tailings of cassiterite taken from the Novosibirsk tin plant consist ofuniform mixture of fine mineral particles which range from sand-typegrain size to a few micrometers, in some samples ore minerals arecompletely oxidized (samples Sn-z 1–3), whereas others are weaklyoxidized sulfides. Average chemical composition of tailings (wt.%):SiO2 28.9, Al2O3 7.3, CaO 5.6, Sn 1.8, WO3 0.13, Zn 0.5, Cu 0.6, Pb 0.7,Fe 16.1, As 2.6, S 3.3, Sb 0.01. Tailings were analyzed for purposes ofcomparison.

2.1. Deposits

Cretaceous tin mineralization in Pamir is represented by simplecassiterite–quartz veins and greisen at the Trezubetz and Kobrigen de-posits (97.5 ± 1.0 − 98.2 ± 1.0 Ma, 40Ar/39Ar, muscovite) localized inCarboniferous, Permian and Triassic terrigenous-carbonate rocks andlinked with adamellite, granite, leucogranite and ongonite dikes100.5 ± 1.8 Ma (40Ar/39Ar, zinnwaldite) of the Bazardara complex(Pavlova et al., 2010).

The Deputatskoe is highest grade tin deposit in Yakutia. The Sn–AgDeputatsky ore district is located in Jurassic flysch sediments intrudedby hidden granitic pluton with accompanying greisen (112 Ma). Multi-stage mineralization consists of: 1) greisen-1 and cassiterite–quartzveins, 2) cassiterite–tourmaline–sulfide, and 3) low-temperature car-bonate veins with siderite, galena, sphalerite and Ag–Pb–Sb sulfosalts.

101G.G. Pavlova et al. / Ore Geology Reviews 66 (2015) 99–113

Zonation patterns of different types of mineralization consist ofcassiterite–quartz veins in the center of the ore district close to thehidden granite pluton, cassiterite–sulfide ore (quartz veins withsphalerite, chalcopyrite, arsenopyrite, pyrite, stannite and minorcassiterite) localized around central part, and Ag-bearing carbonateveins at the periphery. Numerous dikes occur in the ore field of theDeputatsky ore cluster: pre-granitic diorite porphyry and lamprophyre,and post-granite lamprophyre, rhyolite, granite porphyre dikes andgreisen-2 (106.1 ± 1.2 Ma, 40Ar/39Ar) simultaneous with indium-bearing quartz–tourmaline–cassiterite–sulfide veins (106.3 ± 1.2 Ma)(Pavlova et al., 2009, 2014a). The time gap between granite intrusion,greisen-1, cassiterite–quartzmineralization, and lamprophyre, rhyolite,granite-porphyre dikes, greisen-2, and cassiterite–sulfide veins is about6 Ma. The geochemical feature of Sn–sulfide mineralization reveals asignificant enrichment in indium, which often occurs as an impurityin sulfides, rarely forms own minerals. Indium contents in the Fe-sphalerite from Sn–sulfide veins of the Deputatskoe, Ege-Khaya, andIlintass deposits according to EPMA data are up to 0.5 wt.%, and from100 to 10,000 ppm by the results of the chemical analysis (Indolevand Nevoisa, 1974; Ivanov and Rozbianskaya, 1961; Nekrasov, 1966).

The known In resources in the Erzgebirge-Krušné hory area are con-nected with late-Variscan (320–290 Ma) Sn–F(Li) sulfide polymetallicgreisen- and skarn-type mineralization (Ehrenfriedersdorf and Poehladeposits), and Sn–Ag(Au)-base metal vein-type mineralization(e.g., Freiberg, Marienberg, Annaberg, and Hora Svaté Kateriny de-posits) (Seifert, 2014). The indium-bearing quartz veins of the Freibergdeposit with predominating Fe-sphalerite, chalcopyrite, pyrite, galena,arsenopyrite, pyrrhotite, minor cassiterite and stannite are hosted byPaleozoic metamorphic rocks (gneisses, schists and meta-black shales).Magmatic rocks are represented only by Carboniferous–Permian gran-ite/rhyolite small intrusions and lamprophyre dikes, and crosscuttedby In-bearing polymetallic sulfide veins (Seifert, 1994, Seifert, 2008).

The Tigrinoe deposit (Arminsky ore district, Sikhote-Alin, Russia) islocalized in Early Cretaceous dark flysch host rocks of the Zhuravlevskyterrane intruded by Late Cretaceous granodiorite–adamellite-granites,protolithionite and zinnwaldite granites (90–70 Ma) and monzonite(89 Ma) according to K–Ar, Rb–Sr and Ar–Ar data (Belyatsky et al.,1998; Gonevchuk et al., 2005, 2010; Lebedev et al., 1999; Rub et al.,1991, 1998; Tomson et al., 1996). Two stages of mineralization of theTigrinoe deposit include: 1) greisen and cassiterite–quartz veins, and2) Sn–sulfide veins (Gonevchuk et al., 2010; Rodionov et al., 2006).Zinnwaldite granite-porphyry (≤85Ma) formed just after the intrusionof monzonite (Burelomny stock, 89 ± 4 Ma), is K-rich, and differs fromgranite by lower silica and high alkali contents (up to 10 wt.%) (Rubet al., 1986, 1991). Monzonite and zinnwaldite granite are pre-ore forSn–sulfide mineralization (Rub et al., 1991). In addition, lamprophyredikes and small stocks of gabbro, syenite, kersantite, diorite anddiorite-porphyre are found at the Tigrinoe deposit and around in theArminsky ore district (Baskina, 1988, Baskina et al., 2004, 2005;Ivanova and Dudnik, 1991). Age of formation of the cassiterite–quartzmineralization is in the range from 90 to 80Ma, and for Sn–sulfidemin-eralization common interval is estimated as 80–70 Ma at the Tigrinoedeposit (Gonevchuk et al., 2010).

The Pravourmiiskoe deposit is situated in the Badzhalsky ore districtof the Khabarovsk region. Basement of the Badzhalsky terrane is com-posed of rocks of the Jurassic accretion prism (Gonevchuk et al.,2010). Early–Late Cretaceous igneous rocks include post-accretionEarly Cretaceous alkaline gabbro-pyroxenite, monzonite and syenite(~125 Ma), granodiorite, quartz diorite and andesite (~115 Ma), gran-ites and rhyolites of the Badzhalsky complex (105–90 Ma), monzoniteof the Silinsky gabbro–syenite–monzonite complex (89 Ma) andongonite dikes (89.6 ± 1.5 Ma, U–Pb SHRIMP-II) (Alekseev et al.,2013; Gonevchuk, 2002; Gonevchuk et al., 2010; Lebedev et al., 1999).Most researchers considered a genetic link between indium-bearingSnmineralization and granite of the Verhneurmiisky pluton (Badzhalskycomplex)with a 40Ar/39Ar age in the range of 100.2± 0.5–97.6±0.6Ma

(Semenyak et al., 2006). Formation of greisens and most productivetin mineralization (cassiterite–quartz stage) occurred in the range of92–88 Ma (Lebedev et al., 1999), 91.8 ± 2.3 Ma (Sm–Nd; Ishihara et al.,1997). Superimposed upon greisen, the next stage of Sn–sulfidemineral-ization with pyrrhotite, sphalerite, chalcopyrite, stannite, roquesite andassociated tourmaline metasomatite (83–78 Ma) (Krivovichev et al.,1996; Lebedev et al., 1999) is closer to the age of the Silinsky monzonitecomplex (89 Ma).

The Pridorozhnoe deposit of the Komsomolsky ore district occurs inthe northern contact of the Silinskymonzonitemassif hosted byMiddleJurassic sedimentswhich are partially overlain by Neogene basalts. Bothcassiterite–quartz and cassiterite–sulfide veins are known at the depos-it. The Pridorozhnoe deposit represents the lowest part of the ore-forming system of the Komsomolsky ore district. At the deep levels ofthe deposit, tourmaline metasomatite turns into vein-like bodies oftourmaline greisen (Finashin, 1986). Sn–sulfidemineralization is repre-sented by quartz veins with pyrite, pyrrhotite, Fe-sphalerite, stannite,chalcopyrite and marcasite, and minor cassiterite. Sn–sulfide minerali-zation superimposed on cassiterite–quartz veins is accompanying bytourmaline metasomatite and formed simultaneously with monzoniteof the Silinsky volcano-plutonic complex (Gonevchuk et al., 2010).The Solnechnoe deposit of the Komsomolsky district is hosted in theoverlying Upper Jurassic rocks. Quartz-tourmaline-sulfide mineraliza-tion is characterized by abundant sulfides (pyrrhotite, arsenopyrite,sphalerite) at the deep level and widespread galena and sulfosalts atthe middle level. The upper level of the deposit is composed byquartz-carbonate-sulfide and quartz-calcite veins with poor sulfides(Finashin, 1986).

The Khrustalnoe, Arsenyevskoe and Silinskoe deposits (situated in15–20 km from each other) are in the Kavalerovsky Sn–Ag ore district.The oldest intrusions in the ore district are subalkaline monzonite togranosyenite of the Berezovka-Ararat complex (110–92 Ma)(Gonevchuk et al., 2010, 2011). Besides granite of Cretaceous age, mon-zonite–granosyenite − K-rhyolite of the Uglovsky volcano-plutoniccomplex (90–78 Ma) intruded the Upper Jurassic–Lower Cretaceousterrigenous rocks (Gonevchuk et al., 2011; Orekhov et al., 2006).Miner-alization of the Sn–sulfide and cassiterite–quartz stages formed in theArsenyevskoe deposit during this time (90–80 Ma). Younger Li–F gran-ite, andesite-basalt, leucogranite and K-rhyolite dikes represent a suiteof magmatic rocks of the Paleogene age. The cassiterite–quartz andSn–sulfide mineralization of the Paleogene age (about 60 Ma)overprinted the Cretaceous mineralization of the Arsenyevskoe deposit(Gonevchuk et al., 2010; Kokorin et al., 2008; Tomson et al., 1996). Dou-bled indium resources of the high grade Arsenyevskoe deposit had beenformed in the interval of 90–60 Ma as a result of multistage Cretaceousand Paleogene ore-forming processes. Cretaceous mineralization of theKhrustalnoe and Silinskoe deposit was formed in two stages: quartz–chlorite–cassiterite and quartz–tourmaline–cassiterite–sulfide withsphalerite, chalcopyrite, pyrrhotite and pyrite restricted to differentfault systems (Finashin, 1986).

Tin deposits of Chukotka (Pervonachalnoe and Valkumey) are locat-ed in theMesozoic host rocks of the Chaunsky tin-ore district.Magmaticrocks of the district are adamellite-granite-leucogranite (89.4± 0.7Ma,U–Pb SHRIMP-II), gabbro, diorite- and monzodiorite porphyre,lamprophyre, zinnwaldite granite (88.0 ± 0.7 Ma, U\Pb SHRIMP-II)and ongonite dikes (84.1 ± 1.1 Ma, U\Pb SHRIMP-II) (Alekseev et al.,2013). Ore deposits were formed in three stages: 1) cassiterite–quartzvein with topaz, arsenopyrite and wolframite, 2) cassiterite–tourmaline–sulfideveinswhich cutmafic dikes and3) carbonate-sulfide veinswith ga-lena and sphalerite (Onihimovskyet al., 1979). The Pervonachalnoedepos-it is characterized by domination of the cassiterite–quartz mineralization.

Tin deposits in Northern Vietnam (Pio Oak, Tuyen Quang and NgheAn) are located in Permian–Carboniferous terrigenous-carbonate rocksintruded by Cretaceous Pio Oak granite (40Ar/39Ar age 89–84 Ma,Vladimirov et al., 2012), Upper Paleozoic–Cretaceous Nui Dienggranite- and granodiorite-porphyre, and Cretaceous–Paleogene Ban


Chieng granosyenite (Tran, 2000) respectively. Sample material wastaken from greisen and cassiterite–quartz vein in exocontact of the PioOak granite massif, and from cassiterite–sulfide quartz veins in greisenat the other deposits.

The Trudovoe, Tashkoro, Uch-Koshkon and other tin deposits arehosted in the Silurian, Devonian and Carboniferous volcanic and terrige-nous–carbonate rocks of the Sary-Dzhaz ore district in Kyrgyzstan, and inintruding Early Permian granites. Mineralization had been formed dur-ing 3 stages: cassiterite–quartz and later quartz–tourmaline–cassiterite–sulfide veins separated from each other by granite–porphyre intrusion,and calcite–siderite veins with galena, sphalerite, other sulfides,sulfosalts and native bismuth. Mineralization is considered to belinked with Early Permian A-granite intrusions of the Kokshaal com-plex (Jenchuraeva et al., 2007; Konopelko et al., 2007). In addition todiorite, granodiorite, adamellite and granite–leucogranite of colli-sional stage (299–295 Ma) there are post-collisional intraplatelamprophyre dikes, monzonite, syenite, alkali rapakivi granite ofthe Early Permian Djangart complex (296 ± 4 Ma) in the Sary-Dzhaz ore district, ongonite and elvan hybrid rocks (Konopelkoet al., 2007). Ore deposits in the Sary-Dzhaz district are consideredto be related to Early Permian post-collisional event of Late Paleozoic col-lision of Karakum–Tarim continent and the Paleo-Kyrgyz-Kazakhstancontinent.

The single Bylyktyhemskoe tin deposit in Tuva (Southern Siberia) isassociated with a granite massif intruding Paleozoic (Middle Devonian)carbonate-terrigenous host rocks. Mineralization is represented bycassiterite–quartz veinlets and Sn–sulfide veins with minor cassiteriteand Cu-sulfides preliminary dated at about 360Ma by 40Ar/39Armethod(A.S. Borisenko, unpublished data).

3. Analytical method for the determination of indium in cassiterite

Indium occurs in nature as two isotopes: 115In and 113In, 95.7%and 4.3%, respectively. Analysis of indium content in cassiteriteusing the most common isotope is complicated by the fact that themain 115In analytical line superimposes 115Sn line of tin, which isthemajor component (79%). To determine indium impurity contentsin cassiterite the LA–ICP–MS analysis of cassiterite monocrystals wasconducted with the determination of indium concentration by theless abundant lighter 113In isotope (Pavlova et al., 2012). For investi-gation we chose single cassiterite crystals, selected using a scanningelectron microscope, which do not contain micro-inclusions of otherIn-bearing minerals.

The method involves measuring the signal intensity from the113In, 113Cd, 110Cd and 111Cd analytical lines with subsequentmathematical processing to eliminate interference from the cadmi-um analytical lines and the calculation of indium concentration incassiterite using external standard and taking into considerationthe internal standard, which is used as the iron and/or titaniumcontents, indicated by EPMA.

Determination of 113In content is also prevented by the presenceof the 113Cd analytical line. Since the signal from 113-atomic massline is the superposition of signals from lines 113In and 113Cd, thevalue of signal from the 113In analytical line is determined by sub-traction of the signal contribution from the 113Cd line. The cadmiumcontents in cassiterite are less than 0.001% by independent EPMAand LA–ICP–MS data or indium content of more than an order ofmagnitude higher than cadmium, so the contribution from cadmiumanalytical line is negligible. We can take into account only two ana-lytical lines: 110Cd and 111Cd, because signals from the other cadmi-um isotopes have strong interference from tin, which is the maincomponent (79%).

In general, the calculation of the concentration of indium isperformed using an external standard by formula (1). As an externalstandard was used NIST-612 glass (National Institute of Standards andTechnology/USA). Intensity of 113Cd analytical line was calculated by

formulas (2) and (3) as well for sample and standard and thenaveraged.

Cx ¼ CStd:I113Smp−ICd113SmpI113Std−ICd113Std

ð1Þ

ICd113 ¼ ICd110 �A

Cd113

ACd110

ð2Þ

ICd113 ¼ ICd111 �A

Cd113

ACd111

ð3Þ

where

Сх, СStd indium concentration in the sample and external standardcorrespondently;

I113 Smp, Std signal intensity from 113 analytical lines in the sampleand standard;

ICd113 Smp, Std signal intensity of cadmium 113 analytical lines insample and standard correspondingly.

ICd110, 111 signal intensity from analytical lines of Cd 110 and 111correspondently;

АCd110,Cd111,Cd113 natural abundance of cadmium isotopes 110, 111 и113 correspondingly.

Correction of systematic error and indium concentration in cassiter-ite was performed using internal standard such as the iron and/ortitanium according to formula (4).

CIn ¼ Cx �CIntStdEPMA

CIntStdLAICPMSð4Þ

where

CIn real indium concentration;Cx concentration determined by LA-ICP-MS;CIntStdLAICPMS concentration of internal standard determined by

LA-ICP-MS;CIntStdEPMA concentration of internal standard determined by EPMA.

We used NIST 612 as an external standard. The systematic error wascorrected byusing an internal standard (Fe, Ti). The concentration of theinternal standard was determined by EPMA. It is a simple method toanalyze low indium traces in difficult matrix of cassiterite.

4. Methods

LA-ICP-MS analysis was performed on cassiterite crystals with a193 nm Excimer laser coupled to an ELEMENT-2 FINNIGAN MATmass-spectrometer (Germany) with New Wave UP213 laser ablationsystem. We used a 60-s analysis with laser-on at 80 μm diameter spotsize for all analyses. The following isotopes were monitored: 47Ti, 49Ti,55Mn, 56Fe, 57Fe, 66Zn, 67Zn, 68Zn, 93Nb, 107Ag, 109Ag, 110Cd, 111Cd,113Cd, 112Sn, 114Sn, 115Sn, 113In, 115In, 121Sb, 123Sb, 181Ta, 182W, 183W,184W, 206Pb, 207Pb, 208Pb, 232Th, 238U in both low andmiddle resolutions.Analytical accuracy is about 10%. EPMA and LA-ICP-MS analyses werecarried out on well characterized cassiterite and sulfide samples fromcassiterite–quartz veins and cassiterite–sulfide veins. Results obtainedusing these methods by comparable elements (Fe, Ti) coincide on 95%in limits of the 96%-confidence probability (confidence interval ±2σ).

Determination of indium in sulfide minerals was performed byEPMA using Camebax-micro instrument (counting time of 10 s perelement) and energy dispersive X-ray microanalysis (sphalerite of the

Table 1Indium and other element contents (ppm) in cassiterite by LA–ICP–MS.

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23

Ti 300 140 3700 1000 3.3 3.5 95 40 2300 5.7 200 5000 1900 2.0 4000 400 800 600 90 190 2700 59 4870Mn 0.10 24 4.3 1.3 5.7 12 116 0.80 2.2 0.5 0.93 1.6 0.24 0.28 1.4 0.70 0.44 0.15 5.2 18 8.5 b0.10Fe 2400 3000 8700 10,000 7400 5400 5200 12,00 6600 10,000 4300 2300 2200 6600 1100 2000 3000 2600 2700 2800 2800 1800 300Zn b0.10 2.8 1.5 0.48 2.4 4.4 3.8 2 0.54 0.75 0.25 0.51 0.84 0.13 0.82 0.09 0.38 0.30 0.11 7.3 0.92 0.49 b0.10Nb 0.08 0.65 180 2.6 b0.10 0.10 0.23 3.1 0.21 2.1 31 32 b0.10 0.77 500 1300 721 4.8 1500 1000 2000 25In 5.8 39 22 83 46 49 79 30 144 41 75 33 12 21 5.8 6.5 20 8.6 4.3 2.5 21 79 3.8Sb 120 25 140 150 200 160 100 8 69 200 18 14 26 300 2.2 52 185 31 8.8 2.7 2.6 2.7 2.4Ta b0.01 0.03 0.61 0.02 b0.10 0.01 0.01 b0.10 0.05 b0.10 0.04 1.5 1.2 b0.01 0.03 1.4 49 31 0.01 560 260 1500 2.3W 500 4500 63 76 200 700 140 20 240 700 1500 1200 300 64 40 2600 68 5.4 15 42 24 41 2.0Pb 0.02 0.25 0.28 0.43 1.7 1.3 0.70 5 0.12 0.08 0.04 0.09 0.14 0.04 0.03 0.14 0.20 0.08 0.03 0.27 0.10 0.09 0.03Th 0.01 0.07 0.01 0.19 0.17 0.10 0.03 b0.10 0.09 0.01 0.01 0.03 0.03 0.03 0.01 0.01 0.01 0.03 0.01 0.13 0.04 0.01 b0.10U 1.4 1.0 8.8 1.8 0.13 0.18 0.04 3 1.2 1.0 0.55 2.1 1.1 0.29 0.90 7.0 5.7 2.1 1.3 2.5 1.4 2.7 0.15

Abbreviations:Khrustalnoe deposit, Kavalerovsky ore district (1–11): 1, 2— crystals of d k cassiterite from the central part of cassiterite–quartz veinwith rare arsenopyrite, 3, 4— light cassiterite from the same vein, 5, 6— usual brown cassiterite fromthe selvage of cassiterite–quartz vein; 7— “woody tin”; 8, 9— dark brown cassiterite f m the Sn–sulfide vein, 10— light brown and 11— dark brown cassiterite from Sn–sulfide veinlet.Silinskoe deposit, Kavalerovsky ore district: 12, 13— cassiteritecrystals fromcassiterite–quartz vein.Valkumey deposit, Chukotka: 14— cassiterite crystal m cassiterite–quartz vein.Pervonachalnoe deposit, Chukotka: 15— cassiterite from cassiterite–quartz vein.Pridorozhnoe deposit, Komsomolsky ore district: 16—darkbrown cassiterite and 17, 18— light brown cassiterite from cassiterite–quartz veins.Solne noe deposit, Komsomolsky ore district: 19— cassiterite crystal from cassiterite–quartz vein.Kobrigen deposit, Pamir: 20— dark zone of cassiterite crystal, 21— trans-parent zone of the same crystal; 22— dark cassiterite from cassiterite–quartz vein.Trezub s deposit, Pamir: 23— light zone of cassiterite crystal from cassiterite–quartz vein, 24— dark zone of the same crystal.Trudovoe deposit, Sary-Dzhaz ore district, Tien-Shan: 25— light zone of cassiterite crystal from cassiterite–quartz vein, 26— dark zone the same crystal, 27, 28— cassiterite crystals from the same vein.Deputatskoe deposit, Yakutia: 29, 30— large crystals from cassiterite–quartz vein.Bulyktyhemskoedeposit, Tuva: 31, 32—fine-grained cassiterite dissemination in sericite aggregate.NgheAn eposit, Vietnam:33–37— cassiterite fromquartz veins.PioOak deposit, northernVietnam:38–42— cassiterite fromcassiterite–quartz veins andgreisen.TuyenQuangdeposit, Vietnam: 43–45 — cassiterite from cassiterite–quartz veins.

Table 1 (continued)

24 25 26 27 28 29 30 32 33 34 35 36 37 38 39 40 41 42 43 44 45

Ti 6200 120 430 60 440 11 8500 6.1 15 3500 150 7900 1200 530 7500 6600 3800 8000 410 6100 3800 6700Mn b0.10 b0.10 0.53 0.72 1.3 1.5 1.7 3.3 7.8 0.49 2.4 0.62 2.2 7.2 2.6 7.8 0.45 46 1.2 1.3 0.41 2500Fe 500 900 800 2400 2100 12,000 10,000 00 5300 9700 10,000 1500 180 3100 350 490 660 2400 10,000 1000 330 1700Zn 0.66 b0.10 0.34 0.84 2.7 0.31 1.2 2.3 2.5 b3.0 b3.0 b3.0 b3.0 6.4 b3.0 b3.0 b3.0 b3.0 8.7 3.0 b3 33Nb 6.9 b0.1 6.7 1.6 10 0.15 194 0.31 15 6.5 0.17 88 9.6 0.48 990 2400 19 1270 34 1460 580 1700In 20 3.6 4.5 8.2 7.9 24 86 77 485 34 257 0.36 0.40 5.6 0.37 0.52 3.5 1.1 160 2.5 0.40 1.4Sb 1.4 3.1 66 9.1 23 56 102 50 66 50 1400 35 41 15 2.0 2.7 1.2 2.3 3.6 3.8 3.8 3.0Ta 0.22 b0.01 0.88 0.05 2.5 b0.01 0.02 0.03 1.0 0.14 b0.01 3.3 0.46 b0.01 150 170 4.3 1200 6.2 620 320 360W 7.9 81 1000 19 16 700 1900 00 1400 1600 160 3000 4000 1100 800 1200 25 2600 600 200 470 200Pb 0.04 0.07 42 0.26 3.8 0.15 0.27 0.58 1.3 0.20 0.29 0.17 0.28 1.2 0.40 0.13 0.05 0.38 4.7 0.34 0.55 1.6Th b0.01 b0.001 0.31 b0.01 b0.01 b0.01 0.01 1.8 1.4 b0.04 0.11 b0.04 0.03 0.58 0.01 b0.04 0.04 0.05 0.29 b0.04 b0.04 6.4U 1.2 0.94 17 0.65 4.0 6.1 11 1.5 2.6 8.7 21 9.9 23 14 25 3.5 0.93 18 15 3.0 28 48

103G.G.Pavlova

etal./Ore

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Tigrinoe deposit) on a scanning electronmicroscope TESCANMIRA 3LM(accelerating voltage 20 kV, current 1 nA, counting time of 60 s) at theAnalytical Center IGM SB RAS. Calibration of the instruments wasmade by high quality synthetic standards.

The indium content in the ore samples from the Tigrinoe andPravourmiiskoe deposits are determined by SR-XRF, ICP-MS and atomicabsorption spectroscopy (AAS) methods, indium in sulfideminerals aredetermined by EPMA, SEM methods and in cassiterite using EPMA andLA-ICP-MS. Synchrotron radiation X-ray fluorescent analysis (SR-XRF)is a powerful method for determination of indium and germaniumcontents in the ore samples and tailings of tin plant. SR-XRF analysiswas performed at the Synchrotron Radiation Center of the Institute ofNuclear Physics, Novosibirsk (http://ssrc.inp.nsk.su/CKP/eng/stations/passport/3/), Yu.P. Kolmogorov. SR-XRF in comparison with traditionalXRF method is characterized by following advantages: 1) small angulardivergence and continuous spectrum of synchrotron radiation (SR)allow effective implement of monochromatic excitation tunable overwide energy range with X-ray focusing optics, thereby making possibleselective excitation of elements in the samples of complex chemicalcomposition; 2) SR natural polarization reduces the background in-duced by radiation scattered on the sample and improve the detection

Table 2The composition of sulfide minerals from cassiterite–quartz veins of the Khrustalnoe (Russian

Sample Fe Cu Zn S Ag

SphaleritePia Oak 1.51 1.01 61.95 33.33 b0

1.05 0.71 62.42 33.19 b01.31 2.93 58.69 33.97 b02.08 b0.04 62.98 34.11 b01.58 0.10 63.09 33.46 b03.26 0.04 61.45 33.40 b0

Tuyen Quang 7.82 b0.04 58.32 33.78 b07.73 b0.04 57.34 33.95 b0

Khrustalnoe 12.60 b0.04 52.33 33.60 b011.62 b0.04 53.10 33.53 b011.34 0.12 53.47 33.57 b0

ChalcopyritePia Oak 29.30 34.51 0.03 34.96 0

29.05 34.80 0.04 35.34 b029.04 34.53 0.10 35.18 029.40 34.54 0.07 35.20 b029.30 34.68 0.03 35.36 b029.51 35.00 0.05 34.66 b0

Tuyen Quang 29.43 34.77 0.04 35.54 b029.42 34.66 0.05 35.11 b029.57 34.56 0.05 35.13 b029.34 34.62 0.07 35.10 029.47 34.84 0.09 35.52 b029.16 34.67 0.05 35.11 b0

Khrustalnoe 30.80 32.10 1.64 34.75 b030.23 34.15 0.06 34.62 b029.60 33.83 0.06 33.83 b0

PyritePia Oak 46.71 b0.04 b0.04 53.62 b0

46.80 b0.04 b0.04 53.49 b046.14 0.29 0.06 53.10 b0

Khrustalnoe 47.35 b0.04 b0.04 53.79 b047.45 b0.04 b0.04 53.05 b047.23 b0.04 b0.04 53.64 b0

KësteritePia Oak 2.75 28.41 10.95 28.68 0

2.90 28.55 10.79 28.71 02.84 28.47 10.89 28.88 0

Grains of Fe–Cu–Zn–(Sn)–S composition in intergrowth with stannitePia Oak 2.08 17.42 33.67 30.37 0Khrustalnoe** 17.16 15.66 32.62 32.98 b0

Stannite micro-inclusions in cassiteriteKhrustalnoe ** 16.98 24.37 1.37 28.90 0** 12.37 28.52 0.87 29.87 0

limit; and 3) high intensity of SR beams allow local analysis with highspatial resolution,wide range of SR allows to choose the energy of quan-ta excitation for the most optimal analysis of elements in the sample.Standard samples (RUS-1 ST SEV 2028–79, RUS-2 2029–79, RUS-3793–76, RUS-4 794–76) are provided by the Analytical Center of the In-stitute of Geology and Mineralogy, Novosibirsk. Evaluation of indiumcontents in the ores and minerals was performed on 8 technologicalsamples of standard ore (60–80 kg) from the Tigrinoe deposit and 10ore samples from the Pravourmiiskoe deposit. Samples of tails fromthe Novosibirsk tin plant were selected and studied for comparison.

Atomic absorption spectroscopy (AAS) was carried out at the Insti-tute of Geology andMineralogy (Novosibirsk) by L.N. Bukreeva. Atomicabsorption analysis using flame and electrothermal atomization tech-niques performed by SOLAAR M6 instrument (Thermo Electron, USA),which is equipped with Zeeman and deuterium background corrector.The analysis was performed according to the certified method, and ac-curacy of the analysis is confirmed by the correct determination of theState standards. Indium determination in the ore is complicated by thefact that indium chloride compounds are highly volatile and someportion of indium may be lost at boiling in open air. Therefore, samplepreparation was carried out by two methods: ordinary dissolution in

Far East), Tuyen Quang and Pia Oak (Vietnam) deposits (wt.%).

Cd In Sn Sb Total

.05 2.20 0.04 0.07 b0.03 100.11

.05 2.25 b0.03 0.08 b0.03 99.70

.05 0.95 0.04 0.93 b0.03 98.82

.05 1.39 0.03 b0.03 b0.03 100.60

.05 1.52 0.03 0.03 b0.03 99.81

.05 1.21 0.03 b0.03 b0.03 99.40

.05 0.29 0.04 b0.03 b0.03 100.25

.05 0.30 0.05 b0.03 b0.03 99.38

.05 0.20 b0.03 b0.03 b0.03 98.74

.05 0.19 b0.03 b0.03 b0.03 98.45

.05 0.15 b0.03 b0.03 b0.03 98.66

.13 b0.05 0.06 0.06 b0.03 99.05

.05 b0.05 0.05 0.05 b0.03 99.33

.09 b0.05 b0.03 0.06 b0.03 99.00

.05 b0.05 0.04 0.06 b0.03 99.32

.05 b0.05 b0.03 b0.03 b0.03 99.40

.05 b0.05 b0.03 b0.03 b0.03 99.25

.05 b0.05 b0.03 0.12 b0.03 99.90

.05 b0.05 0.05 0.12 0.04 99.45

.05 b0.05 b0.03 0.10 b0.03 99.43

.05 b0.05 b0.03 0.08 b0.03 99.26

.05 b0.05 0.09 0.05 b0.03 100.06

.05 b0.05 0.10 0.08 b0.03 99.17

.05 b0.05 b0.03 b0.03 b0.03 99.29

.05 b0.05 b0.03 b0.03 b0.03 99.06

.05 b0.05 b0.03 0.45 b0.03 97.80

.05 b0.05 b0.03 b0.03 b0.03 100.33

.05 b0.05 b0.03 b0.03 b0.03 100.29

.05 b0.05 b0.03 0.27 b0.03 99.86

.05 b0.05 b0.03 b0.03 b0.03 101.14

.05 b0.05 b0.03 0.12 b0.03 100.62

.05 b0.05 b0.03 0.03 b0.03 100.90

.05 0.34 0.12 27.31 b0.03 98.63

.07 0.32 0.11 27.24 b0.03 98.72

.05 0.37 0.12 27.30 0.04 98.96

.064 0.588 0.11 16.78 b0.03 101.09

.05 0.08 b0.03 b0.03 b0.03 98.50

.08 b0.05 b0.03 25.80 n.d. 97.55

.12 b0.05 b0.03 26.71 n.d. 98.50

http://ssrc.inp.nsk.su/CKP/eng/stations/passport/3/

http://ssrc.inp.nsk.su/CKP/eng/stations/passport/3/

Table 3The composition of sulfide minerals from Sn–sulfide ores from Russian Far East deposits, Tashkoro deposit in Kyrgyzstan, Nghe An deposit in Vietnam, Freiberg in Germany and Toyohadeposit in Japan (wt%).

Sample Fe Cu Zn S Ag Cd In Sn Mn Total

SphaleriteTigrinoe 7.43 0.42 57.35 32.77 b0.05 0.29 0.75 n.d. 0.25 99.26

7.11 0.48 57.48 32.75 b0.05 0.27 0.70 n.d 0.17 98.967.99 0.39 57.15 32.88 b0.05 0.38 0.69 n.d. 0.27 99.758.01 0.33 56.83 32.95 b0.05 0.33 0.65 n.d. 0.30 99.407.36 0.27 57.77 33.30 b0.05 0.35 0.52 n.d. 0.23 99.80

11.38 0.24 53.06 33.12 b0.05 0.32 0.49 n.d. 0.71 99.326.56 0.23 59.02 33.30 b0.05 0.35 0.48 n.d. 0.25 100.226.25 0.25 59.25 33.50 b0.05 0.27 0.45 n.d. 0.22 100.197.44 0.25 57.62 33.30 b0.05 0.33 0.43 n.d. 0.78 100.166.57 0.22 58.65 33.76 b0.05 0.29 0.38 n.d. 0.29 100.176.68 0.21 59.06 33.59 b0.05 0.15 0.31 n.d. 0.65 100.65

13.99 b0.04 50.86 33.17 b0.05 0.31 0.30 n.d. 0.56 99.1913.40 0.10 50.99 33.07 b0.05 0.31 0.18 n.d. 0.91 98.87

Pravourmiiskoe 0.96 0.24 62.84 31.29 n.d. 1.05 0.03 n.d. n.d 96.41(Semenyak et al., 1994) 2.28 0.48 63.23 31.45 n.d. 0.47 0.19 n.d. n.d. 98.10

0.76 0.83 61.31 31.44 n.d. 0.87 1.01 n.d. n.d. 96.221.48 1.83 61.39 31.89 n.d. 0.91 2.38 n.d. n.d 99.88

Khrustalnoe 9.27 0.56 55.10 33.11 b0.05 0.29 0.22 0.04 n.d 98.6010.54 0.18 54.95 33.29 b0.05 0.27 0.15 b0.03 n.d. 99.4010.33 0.15 54.91 32.93 b0.05 0.24 0.14 b0.03 n.d. 98.7010.33 0.19 55.00 32.94 b0.05 0.26 0.14 b0.03 n.d 98.869.67 0.50 54.57 33.19 b0.05 0.27 0.13 0.07 n.d. 98.40

11.17 0.20 53.00 33.23 b0.05 0.27 0.12 b0.03 n.d. 98.00Pridorozhnoe 5.32 1.42 59.22 32.92 b0.05 0.16 0.12 b0.03 n.d. 99.16

ChalcopyriteKhrustalnoe 29.59 34.56 0.06 34.36 0.13 b0.05 0.10 0.04 n.d 98.84

29.77 34.53 0.04 34.53 0.12 b0.05 0.06 0.05 n.d. 99.1029.52 34.50 0.06 34.35 0.11 b0.05 0.06 0.06 n.d. 98.6629.50 34.24 0.08 34.29 0.10 b0.05 0.05 0.04 n.d 98.3029.27 33.91 0.16 34.49 0.14 b0.05 0.03 0.08 n.d. 98.08

Pridorozhnoe 29.89 34.05 0.05 34.67 0.20 0.08 0.07 0.08 n.d. 99.09Nghe An (Vietnam) 28.49 34.70 0.06 35.38 b0.05 b0.05 0.09 0.08 n.d 98.80

28.61 34.81 0.05 35.28 b0.05 b0.05 0.10 0.08 n.d. 98.9327.70 34.18 0.84 35.21 b0.05 b0.05 0.18 0.11 n.d. 98.22

Pyrite (Sb)Pridorozhnoe 44.43 0.61 0.01 51.36 0.24 b0.05 b0.03 b0.03 (3.55) 100.20

43.41 0.53 0.06 51.54 0.31 b0.05 b0.03 b0.03 (2.95) 98.80

StanniteKhrustalnoe ** 13.40 28.75 1.40 29.98 0.08 b0.05 0.05 24.85 n.d. 98.53** 13.68 28.73 1.45 29.17 0.05 b0.05 0.15 25.72 n.d. 98.95

16.98 25.37 3.37 29.77 0.09 b0.05 0.20 24.09 n.d. 99.87Tigrinoe 12.16 28.26 3.38 29.69 0.14 b0.05 0.08 25.85 0.04 99.60

11.54 26.19 6.97 30.28 0.06 b0.05 0.11 24.49 0.08 99.72** 11.72 28.25 2.79 30.07 0.08 b0.05 0.14 26.77 0.03 99.85** 11.29 26.84 5.32 29.71 b0.05 b0.05 0.15 25.09 0.03 98.46

7.71 29.01 6.80 29.33 b0.05 b0.05 0.15 26.57 0.07 99.65** 11.46 26.65 6.40 29.79 b0.05 b0.05 0.22 24.33 0.04 98.89

11.22 28.63 4.10 29.85 b0.05 b0.05 0.24 26.92 0.04 101.00** 11.47 26.88 6.13 29.92 b0.05 b0.05 0.24 24.69 0.04 99.37

11.08 28.57 3.77 30.06 0.37 b0.05 0.25 26.60 0.06 100.7611.28 28.62 3.98 29.45 0.16 b0.05 0.26 26.65 0.04 100.4411.06 28.66 4.00 29.78 0.14 b0.05 0.27 26.42 0.08 100.4110.84 28.73 3.80 29.27 0.18 b0.05 0.31 26.52 0.09 99.74

Pridorozhnoe 11.75 29.32 1.82 29.35 0.15 b0.05 1.81 25.25 n.d. 99.4511.71 29.27 1.57 29.38 0.05 b0.05 1.56 26.00 n.d 99.5411.39 29.48 1.74 29.12 0.03 b0.05 1.18 26.04 n.d. 99.98

Pravourmiiskoe(Semenyak et al., 1994)

13.38 22.62 7.75 28.45 n.d. 0.16 5.92 20.41 n.d. 98.6912.37 26.26 5.77 29.83 n.d 0.07 2.75 24.39 n.d. 101.4412.33 25.99 6.09 29.26 n.d. 0.07 1.88 24.35 n.d. 99.9711.87 29.07 1.81 29.46 n.d. 0.07 0.37 28.43 n.d. 101.08

Tashkoro/Kyrgyzstan 12.55 28.58 1.47 29.35 b0.05 b0.05 1.20 25.79 n.d. 98.9412.63 28.46 1.28 29.01 0.05 b0.05 1.06 25.78 n.d. 98.2712.61 28.78 1.37 29.39 0.07 b0.05 1.05 25.59 n.d. 98.8612.32 28.65 1.50 29.77 0.07 b0.05 0.83 26.83 n.d. 99.9712.19 29.11 1.19 29.15 b0.05 b0.05 0.35 26.95 n.d. 98.9412.34 29.44 1.12 29.44 b0.05 b0.05 0.15 26.75 n.d. 99.24

KësteriteToyoha/Japan 4.84 25.66 12.12 28.13 1.57 n.d. 1.86 25.98 n.d. 100.16(Ohta, 1989) 3.65 25.48 17.05 29.33 0.26 n.d. 1.83 21.91 n.d. 99.51

(continued on next page)


Table 3 (continued)

Sample Fe Cu Zn S Ag Cd In Sn Mn Total

Grains of Fe–Cu–Zn–Sn–S composition in intergrowth with stannite*Tashkoro/Kyrgyzstan 14.82 9.27 44.04 33.64 b0.05 0.11 0.05 0.04 n.d. 101.97

14.85 14.11 35.90 33.49 b0.05 0.09 0.06 0.07 n.d. 98.57Pravourmiiskoe (Semenyak et al., 1994) 1.41 11.91 35.22 28.44 n.d. 1.06 20.17 0.47 n.d. 98.68

1.81 12.09 35.29 28.90 n.d. 1.35 19.71 0.29 n.d. 99.442.10 11.20 36.80 29.70 n.d. 1.20 17.10 0.20 n.d. 98.30

Freiberg/Germany microscopic grains in pyrite(Seifert and Sandmann, 2006)

4.63 14.35 39.29 31.17 0.46 0.28 1.27 2.54 7.15* 101.145.39 14.18 37.85 30.28 0.28 0.24 1.72 5.80 2.33* 98.076.42 4.08 52.84 34.31 n.d. 0.37 1.29 0.30 0.29* 99.90

19.19 19.61 5.62 34.48 0.21 0.07 2.85 17.21 n.d. 99.2416.80 10.47 25.87 37.97 n.d. 0.17 1.51 6.59 0.80* 101.189.20 6.10 46.31 35.08 n.d 0.27 1.44 2.08 0.23* 100.71

26.64 9.63 12.46 41.74 n.d. 0.05 1.75 7.12 n.d. 99.3917.85 11.16 24.25 37.37 n.d. 0.11 1.58 6.83 n.d. 99.15

Notes: values* — Pb contents in mineral grains, **— stannite microinclusions in cassiterite; n.d.— not detected.


hydrochloric and nitric acids, and alternate dissolution in sulfuric acid.Upon dissolution of the ore samples in sulfuric acid, In concentra-tions in solutions appeared 30 ppm higher, but this method canmea-sure only the ore samples with high In contents (N20–30 ppm),because after dilution of the solution for measurement device, valueswere below detection limit of the method. Correction of the resultsusing ICP–MS carried out at the Agilent 7500 s mass spectrometerdevice at the Analytical Center of the Institute of Geology and Miner-alogy (Novosibirsk) by V.S. Palessky and I.V. Nikolaeva.

5. Results

Indium contents in cassiterite from cassiterite–quartz and Sn–sulfide vein of tin deposits of Russian Far East, Southern Siberia,Pamir and Tien-Shan, as determined using LA-ICP-MS method com-bined with EPMA are very different and values range from 0.1 to485 ppm (Table 1). First results show that the indium contents arehigher in cassiterite and sulfides of Sn–sulfide veins.

Indium contents range from2.5 to 80 ppm in the cassiterite of cassit-erite–quartz veins from the Kobrigen deposit (Pamir). Cassiterite fromcassiterite–quartz veins of the Trudovoe deposit (Sary-Dzhaz ore dis-trict) is characterized by mostly W impurities and does not containmuch indium. Abundances of 5.7 to 21 ppm In have been determinedin the cassiterite from cassiterite–quartz veins of Chukotka (Valkumey,Pervonachalnoe deposits). Cassiterite of cassiterite–quartz veins of tindeposits of Russian Far East also is not enriched in indium: 6.5 to20 ppm at the Pridorozhnoe deposit (Komsomolsky ore district), from5 to 83 ppm at the Khrustalnoe and Silinskoe deposits (Kavalerovskyore district). Woody tin contains indium ~80 ppm. Indium contents incassiterite from Pia Oak and Tuyen Quang deposits are in the rangefrom 0.5 to 160 ppm, and up to 257 ppm in the Nghe An deposit. Cassit-erite fromquartz veins of the upper level of the Solnechnoe deposit con-tains only 4 ppm In. Dark brown cassiterite of cassiterite–quartz veinsdiffers by higher contents of trace elements, typical impurities of W,Ta and Nb in cassiterite are specific for cassiterite–quartz granite-related mineralization.

Cassiterites from Sn–sulfide veins at the Khrustalnoe deposit containfrom 40 to 300 ppm indium. The highest contents of indium are detect-ed in cassiterite from sericite aggregate of the Bulyktyhemskoe deposit(from 177 to 485 ppm).

Sulfides of cassiterite–quartz veins do not contain high quantitiesof indium (Table 2), whereas sulfide of Sn–sulfide veins are the mainmineral-carriers of indium: Fe-sphalerite, chalcopyrite, stannite(Table 3), and ownminerals of indium roquesite and laforetite. Roquesiteobserved in Sb-sulfide ores of the Pravourmiiskoe (Semenyak et al.,1994) andother deposits of Primorye (Gonevchuk et al., 2010). Roquesiteand indium-bearing sulfides are found in the Prasolov deposit (KunashirIsland, Kuriles) and Kudryavy volcano (Iturup Island, Kuriles) (Chaplygin

et al., 2004; Kovalenker et al., 1993). Chalcopyrite of Sn–sulfide veinsfrom the Khrustalnoe deposit contains up to 0.1 wt.% In by EPMA dataand in the other deposits of the Far East from 250 to 560 ppm In(Gonevchuk et al., 2010). Stannite of the Khrustalnoe and Tigrinoedeposit contains up to 0.2 wt.% and 0.31 wt.% In, respectively; stanniteof the Tashkoro deposit contains up to 1.2 wt.%, and up to 1.8 wt.% inthe Sn–sulfide ore of the Pridorozhnoe deposit (Primorye). Kësteriteforming intergrowths with chalcopyrite, sphalerite and stannite is acharacteristic mineral of Sn–sulfide veins of the Kester deposit inYakutia, it contains up to 1500 ppm In (Kiselev, 1948; Nekrasov,1966). Kësterite from the Toyoha deposits contains 1.86 wt.% In (Ohta,1989), whereas kësterite from cassiterite–quartz veins of the Pia Oakdeposit (Vietnam) only 0.1 wt.% (Tables 2, 3).

The EPMA analytical data show that indium contents in Fe-sphaleriteof the Sn–sulfide veins from Khrustalnoe deposit range from 1000 to2200 ppm, in the Pridorozhnoe deposit from 1000 to 1200 ppm, from1800 to 7500 ppm in the Tigrinoe and 100–25,000 ppm in thePravourmiiskoe deposits. Indium abundances from 90 to 4700 ppmoccur in the sphalerite of Sn–sulfide veins from the Ege-Khaya depositand from 50 to 3400 ppm in the sphalerite of the Deputatskoe deposit(Yakutia) (Indolev and Nevoisa, 1974). Quite a regular distribution ofindium in sphalerite is the specific feature of hydrothermal mineraliza-tion, zonal distribution observed only in sphalerite of sub-surface min-eralization of the Toyoha deposit (Cook et al., 2009, 2011a,2011b).Sphalerite of Sn–sulfide mineralization has a dark brown to blackcolor and high concentration of Fe and In impurities, in contrast tosphalerite of honey and red color from later carbonate veins withAg-sulphosalt at the periphery of Sn–Ag ore district, which does notcontain indium.

By comparison, indium contents in sphalerite fromVMS deposits arelower: from 10 to 85 ppm (Balcooma and Broken Hill in Australia;Huston et al., 1995; Schwarz-Schampera and Herzig, 2002), from 19 to230 ppm at the Sibaiskoe deposit (Ural) (Prokin and Buslaev, 1999),from 100 up to 600 ppm in the Neves Corvo and up to 270 ppm inLagoa Salgala (Portugal) (Benzaazoua et al., 2002; Gaspar, 2002).

Average of 16 determinations of indium contents in the tailingsof Novosibirsk tin plant is about 30 ppm, which is similar to indiumcontent in VMS deposits (Gaiskoe, Sibaiskoe). In addition, results ofX-ray fluorescence analysis showed the presence of significant Agcontents in the tailings up to 200 ppm. Total indium reserves inthe tailings of the Far East concentrating factory is about 170 t(Semenyak et al., 2014).

Indium contents in bulk-ore of the Tigrinoe and Pravourmiiskoe tindeposits (Far East Russia)with cassiterite–quartz and cassiterite–sulfidemineralization using SR–XRF, atomic absorption and ICP–MS methodsrange from 2.5 up to 433 ppm with average values of 56 ppm and65 ppm respectively (Table 4, 5) (Pavlova et al., 2014c). Indium-bearing Sn–sulfide mineralization of the Far East Russia is known in

Table 4Indium and other element contents (ррm) in the Sn–sulfide ore of the Tigrinoe and Pravourmiiskoe deposits, in the ore from Vietnam deposits and in the tailings samples fromthe Novosibirsk tin plant by the results of SR-XRF (XF), atomic absorbtion (AA) and ICP-MS (ICP) methods.

Sample Сu (XF) Zn (XF) As, wt.% (XF) Ag (XF) Ga (XF) Ge (XF) Nb (XF) Y (XF) Zr (XF) In (XF) In (AA) In (ICP)

Sn–sulfide Tigrinoe deposit1 1337 2783 (0.50) 19.5 19.8 9.5 21.3 133 71 3.0 b52 343 14,377 (2.5) 22.4 21.4 52.9 37.7 33.6 8.7 40.5 283 1941 25,259 (8.3) 24.4 15.6 29.7 40.3 26.2 8.4 56 374 474 1265 (1.12) 4.0 15.4 11.0 33.8 17.8 23.3 3.0 b55 738 1946 (0.05) 2.2 15.9 5.6 66 14.8 15.6 8.1 b56 7253 20,607 (7.0) 22.2 16.8 12.4 30.8 29.6 14.9 6.5 8.57 756 4281 (0.2) 5.6 12.6 23.9 33.6 17.1 12.9 6.1 b58 1482 105,735 (19.9) 13.9 37 37.0 20.1 28.2 16.1 400 400–433

Sn–sulfide Pravourmiiskoe deposit1-86 15,684 259 (15.6) 11.8 7.6 43.8 7.5 9.0 35.5 36.8 22 39118-87 1201 165 (28.8) 27.4 19.0 85.0 18.8 6.0 13.9 120 109138-87 1023 77 (3.1) 3.3 5.4 47.6 2.5 27.5 43.4 8.3 b5 1.2153-83 108,993 859 (21.4) 129.0 11.7 19.7 8.8 6.0 46.5 30.3 2918-87 41,768 711 (5.5) 15.0 11.8 58.0 9.9 12.6 72 35.2 37 3226-87 13,120 332 (5.3) 7.6 1.5 6.6 3.9 27.1 112 38.2 3640-86 40,285 390 (11.2) 45.3 9.5 31.1 10.9 5.0 5.0 130 11557-86 3775 284 (4.1) 2.8 6.7 10.2 3.8 10.7 98 9.1 157-86 15,477 447 (0.1) 5.8 4.4 7.2 5.0 24.7 130 47 2672-86 302,935 598 (2.4) 35.2 3.6 16.8 4.9 16.8 64 111 110

Cassiterite–quartz Pia Oak deposit (ICP)T22-35-3c 1277 932 667,342 2.71 1.61 343 2.8T22-35-4 1749 1060 705,833 1.39 0.78 194 2.9T22-141 198 36.6 78.4 0.82 9.25 135 5.0

Cassiterite–quartz Tuyen Quang deposit (ICP)Т22-8-4 6272 1245 6074 1.92 1.76 0.0 1.1Т22-8-5 60,385 1578 16,267 88 44.7

Sn–sulfide Nghe An deposit (ICP)T22-46-4 6805 1295 95,814 53.7 114T22-46-3 34,430 411 667,342 268 12.3T22-46-2-1 10,356 321 705,833 302 6.0 19T22-46-2-4 34,688 430 669,588 429 11 37T22-46-2-4 13,800 112 306,900 250 0.6 0.3 270 37T22-46-2-1 3900 48 303,000 3.5 0.4 0.3 270 19T22-131 25 1280 1970 6.1 0.4 0.6 41 16Т22-1-1 2300 1220 145 0.08 2.5 3.2 0.06 b2 1.5Т22-43-1-1 3200 570 36,300 41 0.3 14 28 3.6 5.6Т22-43-2-1b 195 120 10,800 14 0.07 0.9 11 3.0 3.9

Tailings of the Novosibirsk tin plantSn-z 1 3884 3888 (7.5) 61 31.5 29Sn-z 2 3403 3777 (7.7) 38.8 19.3 16Sn-z 3 3868 3171 (6.1) 84 20.7 23Sn-z 4 13,301 4416 (2.6) 197 38.3 32Sn-z 5 9527 3383 (3.4) 111 24.5 16 18Sn-z 5 9789 3556 (3.8) 154 32.8Sn-z 5 5738 2168 (2.3) 78.0 12.6 14.0 5.3 79 180 20.5Sn-z 6 6428 6125 (8.9) 61 40.0 54 44


five large Sn ore district (Khingansky, Badzhalsky, Komsomolsky,Arminsky, Kavalerovsky). Indium contents and reserves of indium inthese deposits can be assigned to the high grade category (Pavlovaet al., 2014c, Semenyak et al., 2014), this allows the suggestion thathigh grade indium-bearing Sn–sulfide mineralization was formed as aresult of bimodal magmatism in an active continental margin settingas the most promising indium resources in Russia (Pavlova et al.,2014b, 2015).

6. Discussion

Two controversies are under considerationwith arguments focusingon whether the Sn–sulfide mineralization is granitic intrusion-relatedor linked with contribution from melts derived from upper mantle.Indium as a trace element is traditionally associated with Sn miner-alization. Three types of mineralization are usually recognized in large

tin deposits of Sn–Ag ore districts: 1) cassiterite–quartz with minorarsenopyrite, rare chalcopyrite and stannite; 2) cassiterite–sulfide (orSn–sulfide) with predominating sulfides and indium-bearing minerals(chalcopyrite, sphalerite, pyrite, stannite, roquesite, etc.); and 3) Sn–Ag-basemetal (or Sn–Ag) represented by siderite–calcite veinswith ga-lena, sphalerite, chalcopyrite, gudmundite and Ag–Pb–Sb sulfosalts,often with native bismuth. These types of mineralization are formedduring three corresponding stages in large Sn–Ag ore districts. Empiricalobservation of mineralization and magmatism in the different tindeposits and Sn–Ag ore districts shows that cassiterite–quartz, cassiter-ite–sulfide and Sn–Ag mineralization as products of three correspond-ing stages occur only in largest deposits of the district (for example,Deputatskoe deposit). In the other deposits of the same district wecan observe products of separate stage (such as cassiterite–quartz, Sn–Ag) or overprinted stages in different proportions (first and second, sec-ond and third). At that, deposits of the Sn–Ag ore district bear different

Table 5Element contents (ppm) in the ores of tin deposits and in the tailings of theNovosibirsk Snplant (numerator: element contents range, denominator: average values).

Tigrinoe Pravourmiiskoe Tails of tin plant

In 3−43365:6

8:3−13056:6

16−5428:7

Сu 343−72531790

1201−30295355426

3403−133016992

Zn 1265−10573522031

77−859412

2168−44163811

Ag 2:2−24:414:3

2:8−12928:3

38:8−19798

Ga 12:6−3718

1:5−198

12.6

Ge 5:6−5322:8

6:6−8528:8

14

Nb 20−6635:5

2:5−18:87:6

5.3

Y 15−13337:5

5−27:515:5

79

Zr 8:4−7121:4

5−13062

130


Sn, indium and Ag contents. Cassiterite and quartz were deposited atthe beginning of both cassiterite–quartz and cassiterite–sulfide stagesat highest temperature, and then sulfides at the temperature lowering.

Usually Sn mineralization is associated with tin-bearing granites.Russian researchers usually considered Snmineralization (including in-dium bearing) of Yakutia, Far East Russia and Vietnam as linked withgranodiorite and granite-leucogranite magmatism (Flerov, 1976,Rodionov, 2005), S-and A-granites (Moura et al., 2007; Rodionov et al.,2006, Li et al., 2007; Ivanov, 2010; Vladimirov et al., 2012) or I-typegranitoids (Gonevchuk et al., 2010). Formation of Sn–In sulfidemineral-ization of the Dachang district in China is genetically related to Creta-ceous subvolcanic granite porphyry (Ishihara et al., 2011).

1) Sn mineralization of the cassiterite–quartz stageTin mineralization in the ore districts of Russian Far East with the

highest grade of cassiterite is represented by high-temperature(450–300 °C) (Sushchevskaya et al., 1995, 2002) cassiterite–quartzveins. Cassiterite as major mineral was deposited earlier, whileminor arsenopyrite, rare pyrite, chalcopyrite and stannite crystallizedas later minerals of this stage. According to published fluid inclusiondata, ore deposition occurred from the NaCl-dominating solutionswith concentrations from 1 to≤10wt.%. Indium contents in mineralsof this stage are not high. The typical deposits are Polyarnoe andOdinokoe in northern Yakutia, Pio Oak in northern Vietnam.

2) Sn–sulfide (Sn–In polymetallic) mineralization of the cassiterite–sulfide stage

Mineral composition of the Sn–sulfide ore considerably differs fromthe composition of cassiterite–quartz ore by predomination of sulfides,small quantity of cassiterite and presence of own indium minerals, asobserved in the Sn deposits of Russian Far East as well as in the otherSn deposits of the world. The main minerals of Sn–sulfide ores aresphalerite, chalcopyrite, pyrrhotite and stannite, minor and rare are cas-siterite, stannoidite, roquesite, mawsonite, and laforetite. Cassiterite inSn–sulfide ores is fine-grained in intergrowths with sphalerite, pyrrho-tite, and stannite. A distinctive feature of the Sn–sulfide ores is thepresence of indium sulfide minerals (indite, roquesite), and In-bearingFe-sphalerite, chalcopyrite, stannite, sometimes sakuraiite, petrukite,cylindrite and frankeite and intermediate mineral phases of the stan-nite–kësterite–sakuraiite series (Gavrylenko et al., 1992; Genkin andMuravjova, 1963; Irving et al., 1957; Seifert and Sandmann, 2006;Semenyak et al., 1994). Sometimes it is difficult to distinguish mineralsof the first and second stages in the deposits where Sn–sulfide mineral-ization overprints cassiterite–quartz veins and greisen in the same orefield. Cassiterite–sulfide veins are superimposed on the cassiterite–quartz veins and greisen at the Tigrinoe and Khrustalnoe deposits, orpartially separated in space from cassiterite–quartz mineralization andgreisen at the Pravourmiiskoe and Deputatskoe deposits (Pavlovaet al., 2009, 2014a, 2015).

Published data of fluid inclusion study in quartz of Sn–sulfide veinssuggest that In-bearing sulfide mineral paragenesis crystallized attemperatures of 400–350 °C (Borisenko et al., 1997) and In-containing

Fe-sphalerite at 305 °C (Zhang et al., 1988, 2007). Established favorabletemperature for indium-bearing minerals crystallization is used in themodern technologies such as indium deposition from volatile In-chlorides at 350 °C. Sn–sulfide mineralization, unlike the cassiterite–quartz one, is characterized by high salt concentrations of the ore-forming fluids (57–32 wt.%) and a specific set of ore elements such asPb, Zn, Sn, Cu, In, Ag, Mn, As, and Sb in the hydrothermal solutions(Borisenko et al., 1997; Pavlova and Borovikov, 2010).

Sn–Ag mineralization of the last low-temperature (≤250 °C) stagerepresented by quartz–siderite–calcite veins with galena, sphalerite,chalcopyrite, ±gudmundite and Ag–Pb–Sb sulfosalts, occasionallywith native bismuth is localized in the upper level of the ore-formingsystem and at the periphery (Pavlova and Borisenko, 2009). Mineralparagenesis of this stage contains only trace indium, which mostly hadbeen deposited during the Sn–In cassiterite–sulfide stage at the highertemperature (350–300 °C), therefore there are no In-minerals, andsphalerite of this stage does not contain indium.

6.1. Arguments focusing on distinct origin of cassiterite–quartz andSn–sulfide mineralization

1) Minerals of cassiterite–quartz and Sn–sulfide veins have differentgeochemical features. From the undertaken study we can see thatsulfides and cassiterite from Sn–sulfide ores have higher indiumcontents than minerals of cassiterite–quartz veins.Sn–sulfide mineralization is accompanied by the formation ofquartz-tourmaline metasomatic rocks, and the composition oftourmaline is a hallmark indicator of Sn–sulfide mineralization.Tourmaline is present in Sn–sulfide ores in association with biotitein the deep levels in contrast to the association of tourmaline withlepidolite, albite and Li–Fe mica (protolithionite, zinnwaldite) inLi-rich granitic pegmatites and aplite. In the ore field of Sn–sulfidedeposits with green colored acicular tourmaline, unlike the tourma-line of pegmatites which usually forms large well-shaped crystals.The composition of tourmalines from Sn–sulfide deposits is repre-sented by schorl-dravite series and characterized by high contentsof Pb (10–280 ppm), Zn (5–190 ppm), Fe (up to 100 ppm) and Ni(up to 112 ppm), Co (3–10 ppm), Cr (100 ppm), Ti (300–850), V(up to 200 ppm), Sr (up to 100 ppm), Mn (up to 850 ppm), Cuand Ag (0.1–1.5 ppm), in contrast to the composition of tourmalineof elbaite–olenite composition from granitic pegmatites, which con-tains Li, Sn, Nb, Sc, Be (according to Gorelikova, 1988; Gonevchuk,2002; Taylor and Slack, 1984; Henry and Guidotti, 1985; Ertl et al.,2010). Composition of tourmaline from metasomatic ore systemsaccompanying Sn–sulfide mineralization clearly reflects the rela-tionship between mineralization and magmatic rocks of maficcomposition unlike the tourmaline of granite pegmatites.High concentrations of typical for Sn–sulfide mineralization oreelements have been determined in the biotites from K-monzoniteof the Silinsky complex: Zn (60–580 ppm), Cu (11–45 ppm), Pb(5–123 ppm), Ni (20–112 ppm), Co (18–65 ppm), Cr (24–378 ppm),Ag (0.1–2.1 ppm),V and Mn (Gonevchuk, 2002).

2) Tin productive cassiterite–quartz mineralization and later tin-poorSn–sulfide mineralization are separated in time and often in space.Cassiterite–quartz mineralization with accompanying greisen occursas distinct manifestation at the Odinokoe and Polyarnoe deposits inYakutia (Flerov, 1976). Sn–sulfide mineralization is superimposedon cassiterite–quartz mineralization at the Tigrinoe deposit,superimposed and partly separated in space (Deputatskoe,Pravourmiiskoe deposits) or occur as distinct occurrence (Freibergdistrict). The Sn–sulfide mineralization is separated in time from theprevious one by crushing and brecciation of quartz–cassiterite veinsand greisen, the time gap between cassiterite–quartz and Sn–sulfidestage in different ore districts is in the range from5 to 10Ma. Cassiter-ite–tourmaline–sulfide veins sometimes are restricted to the fault sys-tem of other structural orientation than cassiterite–quartz


(Khrustalnoe/Sikhote-Alin, Chukotka) (Onihimovsky et al., 1979;Rodionov, 2005). The main productive tin mineralization representedby cassiterite–quartz veins is formed simultaneouslywithgranite. For-mation of Sn–sulfide mineralization coincides in time with graniteporphyry and rhyolite dikes and subalkaline to alkaline mafic rocks.A large region with In-bearing tin mineralization is situated in theVerkhoyansk province of Yakutia where most of known tin depositsoccur (from the north to the south): Churpunya, Chokurdakh,Odinokoe, Polyarnoe, Deputatskoe, Ege-Khaya, Kester, Honorskoe,Ilintass, Anomalnoe, and Vysokogornoe. These deposits are hosted inthe Carboniferous–Permian and Triassic–Jurassic carbonaceous terrig-enous strata of the Verkhoyansk fold-thrust belt. Among them onlyDeputatskoe is a high grade tin deposit. The Odinokoe and Polyarnoetin deposits in northern Yakutia with greisen and cassiterite–quartzmineralization are linked with Cretaceous granite–leucogranite(112 Ma) which intruded Jurassic terrigenous host rocks. The samemineralization represented by cassiterite–quartz veins is known atthe Deputatskoe deposit. Overprinting of main indium-bearing Sn–sulfide mineralization of the second stage on previous cassiterite–quartz mineralization at the Deputatskoe deposit coincides in timewith the intrusion of lamprophyre, rhyolite- and granite-porphyredikes (106 Ma) (Pavlova and Borisenko, 2009; Pavlova et al., 2009,Pavlova et al., 2014a, 2014b). The time gap between formation of cas-siterite–quartz and Sn–sulfidemineralization is about 6Ma. Other de-posits in Yakutia are characterized by poor Sn mineralization ingreisen and cassiterite–quartz veins, dominant Sn–sulfidemineraliza-tion and diverse granite, mafic and alkaline mafic magmatism.Indium-bearing Sn–sulfide quartz veins of the Freiberg, Marienbergand Annaberg deposits with dominating pyrite, sphalerite, chalcopy-rite, galena, arsenopyrite, pyrrhotite, stannite, and cassiterite are relat-ed to bimodal lamprophyre and granite/rhyolite magmatism (Seifert2008) and partly separated in space from the high grade tin depositslinked with granite magmatism.Genetic relation of Sn–sulfide mineralization to alkaline–subalkaline mafic magmatism is confirmed by similar age ofmineralization (83–78 Ma) and igneous rocks of K-monzonite–syenite–granosyenite volcano-plutonic complexes of the FarEast Russia: Silinsky volcano-plutonic complex (89 Ma) in theBadzhalsky and Komsomolsky ore districts (Gonevchuk et al.,2010), gabbro-monzonite–monzodiorite and monzonite–syenite(89 Ma) in the Arminsky ore district (Finashin, 1986; Ivanov et al.,

Table 6Contents of tin, silver and indium in the rocks (ppm).

Sn In Ag Publi

Clark 1.5–2.5 0.07–0.11 0.07–0.08 ShawSedimentary rocks 5 0.05 0.1 VinoArgillite 5–10 0.055 0.3–6 EskeBlack shale 5 1.0 1.1 YudoCoals 0.002–0.17 0.056–0.2 YudoSulfides of black shales 25–70 10–20 Shaw

PandAndesite 0.2 0.035–0.052 0.08 ShawGranite 1.5–3 0.02–0.07 0.004–0.13 VinoRhyolite 4–9 0.07–0.036 0.05–0.4 IvanoGranodiorite 4–6 0.021–0.12 0.053 IvanoGranite-porphyry 10–13 0.14 0.06–0.1 IvanoMonzonite 3 0.13 0.02–0.06 IvanoSyenite 1–3 0.08–0.38 0.1–0.6 IvanoBasalt 1–1.5 0.05–0.43 0.11 SchwSulfides of basalts 0.1–592 70–100 PiercDiabase 0.055 0.12 IvanoGabbro 1–1.5 0.05–0.15 0.11 IvanoAlk basite and basalt 0.05–0.3 0.02–0.26 IvanoUltrabasite 0.5 0.02–0.05 0.01–0.06 WedPrimitive mantle 0.1–0.17 0.014 0.008 LaulMORB 0.4–1.35 0.03–0.1 Yi etOIB (Atlantic) 0.3–2.7 0.05–0.14 Yi et

1980), Uglovsky K-monzosyenite–granosyenite, K-rhyolite, trachyte(90 Ma) and Paleogene andesite-basalt, leucogranite and K-rhyolite(60 Ma) in the Kavalerovsky district (Finashin, 1986; Finashin andWeide, 1976; Gonevchuk, 2002). The presence of a mantle chamberin the Badzhalsky and Komsomoslsky districts at the time of granitebatholith formation is suggested by geophysical data (Lishnevskiyand Gershanik, 1992).

3) Cassiterite–quartz and Sn–sulfide mineralization veins are charac-terized by relatively high temperatures of formation, but differentcomposition and concentrations of the ore-forming fluids.

4) Comparing the Sn, In and Ag contents in various igneous and sedi-mentary rocks, it can be noted that the higher Sn contents are ob-served in sedimentary rocks (shales) and granites, whereas indiumand silver contents are higher in mafic rocks (Table 6). Indium con-tent in mafic magma was estimated as 0.058 ppm (Wager et al.,1958). High indium contents of 0.1–0.4wt.% had been found inmon-zonite and syenite rocks (Table 6). High indium abundances in oce-anic island basalts (0.05–0.14 ppm) and especially in sulfides inbasalts from 0.1 to 23 ppm (Axial Seamount, Pacific Ocean),24–90 ppm (Manus basin) and 0.02–592 ppm (Lau Basin)(Schwarz-Schampera and Herzig, 2002) are indicating effective re-moval of indium from themelts of mafic composition. Some authorsexplained the low indium contents in the deposits of spreadingzones by its high volatility (Yi et al., 1995).Both crustal and mantle melts are characterized by some quantitiesof Sn, In and Ag, which could be derived, transported and depositedby hydrothermal fluids with appropriate PTX-parameters, but con-tribution from multiple sources increases ore potential of deposits.

5) Isotope geochemical data from Sn–sulfide deposits of Russian FarEast (Gonevchuk et al., 2010) and 3He/4He ratios in between 1.2and 2.9 Ra of inclusion fluids in the ore veins of the Tongkeng-Changpo largest deposit in the Dachang ore district (Minghai et al.,2007) and Furong deposit (Li et al., 2007) in China indicate influenceof mantle source. Isotope and geochemical study of the Ag–Sb min-eralization of the Gorny Altai, NW Mongolia and Pamir related tointraplate alkaline mafic magmatism (Pavlova and Borisenko,2009; Pavlova and Borovikov, 2010; Pavlova et al., 2008, 2010;Vasyukova et al., 2011) and Ag–Hg–Sb mineralization linked withsubalkaline–alkaline mafic magmatism (Borisenko et al., 2014)have shown similar age of mineralization with dikes of alkali maficrocks (lamprophyres) and syenite intrusions.

cation

(1952), Vinogradov (1962), Voitkevich et al. (1977)gradov (1962), Grigoriev (2011)nazy (1980)vich and Ketris (1994), Marakushev (2009)vich et al. (1985), Yudovich and Ketris (1994)(1952), Hamaguchi and Kuroda (1959), Kuroda et al. (1990), Ivanov (1963),alai et al. (1983)(1952), Pierce and Peck (1961) Ivanov (1963), Yi et al. (1995), Kuroda et al. (1990)

gradov (1962), Ivanov (1963), Kuroda et al. (1990), Grigoriev (2011)v (1963), Finashin (1986), Kuroda et al. (1990)v (1963), Finashin (1986)v (1963), Finashin (1986)v (1963), Finashin (1986), Grinev (1990)v (1963), Kuroda et al. (1990),arz-Schampera and Herzig (2002), Tao et al. (2011), Yi et al. (2000)e and Peck (1961), Schwarz-Schampera and Herzig (2002), Tao et al. (2011)v (1963), Pierce and Peck (1961)v (1963), Wager et al. (1958)v (1963), Medvedev and Almukhamedov (2012), Vasyukova et al. (2011)epohl (1978), Vinogradov (1962)et al. (1972), Sun and McDonough (1989), Yi et al. (2000)al. 1995 (2000)al. (2000), Sun and McDonough (1989)


The Sn–sulfide In-rich mineralization has formed along convergentplate margins and linked with

i) bimodal magmatism (granite and alkaline mafic) in volcano-plutonic belts (Sikhote-Alin/Russia) of active continental marginsand in a back-arc setting (Cenozoic mineralization of Bolivia),basalt-rhyolite magmatism in ensialic arcs (Prasolov, Kudryavy vol-cano, Kuriles);

ii) bimodal postorogenic magmatism (granitoid and alkaline mafic) inthe continental collision zones (Hercynian Sn ore districts inEurope and Tian-Shan, Cretaceous Sn–ore districts in Yakutia).

Episodic compression and tension settings on the continental marginsand convergent plate boundaries determinebimodalmagmatismandmul-tistageprocesses ofmagmatismandmineralization. The specific set and se-quence of magmatic rocks including adamellite, biotite and two mica-granite, small intrusions of monzonite and syenite, trachyte, lamprophyredikes, Li–F granite, ongonite dikes, granite porphyre and rhyolite dikesand diatrems indicate existence of chambers of granite and alkaline–subalkaline mafic melts in the same space and time. The combined contri-bution fromgranite andmaficmagmatismproducedfluids leads to the for-mationof highgrade indiummineralization in the large Sn–Agoredistricts.Hybrid rocks couldbe a result of injection of high-temperaturemantlemeltinto lower temperature granite melt of final stage of differentiation alongstrike-slip fault in structurally weak zone of lithosphere with mantleheterogeneity (Scarrow et al., 2011) or under specific geodynamic regime.According to (Maughan et al., 2002; Sparks and Marshall, 1986), meltmixing causes effective convection which could provoke an explosion insubvolcanic system. But evidence of such events which affected the Sn-ore systems is a question to be tackled by further investigations.

7. Conclusions

1. Our study has shown that indium concentration in cassiteritefrom cassiterite–quartz veins does not exceed 160 ppm, and cas-siterite from Sn–sulfide ores is characterized by higher indiumcontents from 40 to 485 ppm. Sulfides of Sn–sulfide ores in con-trast to cassiterite–quartz mineralization have highest indium

contents: Fe-sphalerite (100–25,000 ppm), chalcopyrite (up to1000 ppm), stannite up to 60,000 ppm. Fe-sphalerite prevailsin the Sn–sulfide ore of the Tigrinoe deposit, and there are no In-minerals in the ore, but significant quantities of indium occur as impu-rity in Fe-sphalerite. Chalcopyrite predominates in the Sn–sulfideore ofthe Pravourmiiskoe deposit, and indium contents in chalcopyrite aresignificantly lower, providing a good reason why indium forms itsown minerals (roquesite, etc.) in the ore and enters the compositionof sulfosalts.

2. Indium contents in the Sn–sulfide ores f the Tigrinoe andPravourmiiskoe deposits range from 10 to 433 ppm with averagevalues 56–65 ppm. Indium-bearing Sn–sulfide mineralization in fiveSn ore districts of the Far East Russia (Khingansky, Badzhalsky,Komsomolsky, Arminsky, Kavalerovsky)with high grade category re-serves allows to consider the Sn–sulfide ores as the most promisingindium resources in Russia.

3. Specific feature of In-bearing tin deposits is the spatial and temporalassociation with adamellite, biotite and two mica-granite, small in-trusions of monzonite and syenite, trachyte, lamprophyre dikes, Li–F granite, ongonite dikes, granite porphyre and rhyolite dikes anddiatrems. The combined contribution from granite and alkaline–subalkaline mafic sources and produced fluids led to the formationof indium-rich Sn–sulfide mineralization. Diverse magmatism withcrustal andmantle sources of ore elements resulting in superpositionof Sn–sulfide and cassiterite–quartz mineralization, and multistageore-forming process doubling resources (for example, Cretaceousand Paleogenic events at the Arsenyevskoe deposit) are themain fac-tors of high grade Sn–In–sulfide mineralization formation.

Acknowledgments

The authors are very grateful to reviewers, Nigel Cook and FrancoPirajno for efficient editorial handling that improved considerably theearly version of the manuscript. The research is supported by theRussian RFBR (grant No. 14-05-00191) and grant from the SiberianBranch RAS No 123.

Appendix A. Samples and tin deposits

Deposit, sample
Ore sample Mineral paragenesis
Trezubetz (Pamir), 1-238
Cassiterite–quartz vein Cas, Q Kobrigen (Pamir), KN-7b " Q, Cas Valkumey (Chukotka), VII-15/7 " Cas, Q, Musc Pervonachalnoe (Chukotka), 15/23 " Q, Cas, Ap, Cp, Po Khrustalnoe (Sikhote-Alin), 15/10, " Q, Cas 15/12-1 " Q, Cas, minor Ap, Cp, St as inclusion in Cas 15/12b " Cas, Q, “woody tin” in a rim of the vein Silinskoe (Sikhote-Alin), 15/14 " Q, Cas Pridorozhnoe (Sikhote-Alin),VII-15/30 " Q, Cas, minor Py, Cp Solnechnoe (Sikhote-Alin), III-15/20 " Q, Cas Pia Oak, T22-31-2-2, V-08-6/4 " Q, Cas Pia Oak, V-08-12/3 " Q, Cas, Sp, Cp, Kë Nghe An, T22-41-1 " Q, Cas, Cp, Py, Ap, Po Tuyen Quang, T22-8-1, T22-92-1, 2 Q, Cas Trudovoe (Tian-Shan), P 2537 " Q, Cas Deputatskoe, 3540 " Q, Cas massive aggregate Khrustalnoe (Sikhote-Alin), 15/12-2 Cassiterite–sulfide vein Q, Cas, Fe-Sp, Ap, Cp, hydromica 15/13 " Q, Cp, Ca, Fe-Sp, Ga, sericite Pridorozhnoe, 15/31 " Q, Cas, Fe-Sp, Cp, St, Py, Po Tashkoro (Tian-Shan), 5389 " Q, Sp, Cp, Cas, St, Py, Kë Tigrinoe, KP-3260, adit 7, level 770 m " Q, Sp, Cas, Ap, St, Top Tigrinoe, KP-1671, adit 5, level 850 m Greisen with mainly Sp Q, Fe-Sp, Top, Cas aggregate cemented by hydromica with Fe-Sp, Cp, St Tigrinoe, KP-1908, adit 5, level 850 m Greisen with mainly Sp Q, Fe-Sp, Musc, hydromica KP-2403, bore hole 506, level 870 m Greisen with Sp Q, Fe-Sp, Cp Nghe An, T22-41-2 (Table 1, # 34) Cassiterite–sulfide vein Q, Cp, Ap, Py, Cas, Bulyktyhemskoe, 235 Q-hydromica-Sct vein Cas crystals in hydromica-sericite aggregate
Abbreviations: Q— quartz, Cas— cassiterite,Musc—muscovite, Ap— arsenopyrite, Py—pyrite, Po—pyrrhotite, Cp— chacopyrite, St— stannite, Kë— kësterite, Top— topaz, Fe-Sp— Fe-sphalerite,Sct— sericite.


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Indium in cassiterite and ores of tin deposits

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