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Origin of chromite in mafic–ultramafic-hosted hydrothermal massive sulfides from the Main Uralian Fault, South Urals, Russia
´ S.G. Tesalina a,b, P. Nimis b,*, T. Auge c, V.V. Zaykov a
b a Institute of Mineralogy, Uralian Division, Russian Academy of Sciences, Miass 456301, Russia ` Dipartimento di Mineralogia e Petrologia, Universita degli Studi di Padova, Corso Garibaldi 37, 35137 Padua, Italy c ´ BRGM, B.P. 6009, 45060 Orleans Cedex 2, France

Received 21 November 2002; accepted 7 July 2003

Abstract Mafic – ultramafic-hosted hydrothermal Fe – Cu – (Ni – Co) sulfide ores from the Main Uralian Fault Zone (MUFZ), South Urals (Ivanovka and Ishkinino ore fields), contain a relatively large (up to 3%) proportion of chromite. This association is common for magmatic Fe – Ni – Cu sulfides, but definitely unusual for hydrothermal sulfides. Textural, morphological and compositional data are used here to gain an insight into the origin and significance of this unusual chromite – sulfide association. The studied chromites occur both as broken fragments and as euhedral or subhedral crystals, which are included in the sulfides or scattered in their talc F chlorite F saponite F quartz F carbonate matrix. They are characterized by high Cr/(Cr + Al) ratios (0.58 – 0.85) and range in composition from magnesiochromite to chromite sensu stricto. Textural, morphological and compositional features, as well as the occurrence of relatively high-silica, low-Ti, low-K melt inclusions in some of the crystals, indicate that the oreassociated chromites (i) are a mixed population of grains derived from mafic – ultramafic mantle and crustal magmatic rocks and mantle peridotite melting residua, (ii) have no genetic relation with the host sulfides and (iii) represent relicts derived from the hydrothermally altered country rocks. The compositions of the chromites and of the melt inclusions denote a clear suprasubduction zone signature. The melts parent to the cumulitic chromites had an arc tholeiitic to, possibly, boninitic affinity. These data suggest that the host mafic – ultramafic complexes formed in an early arc or forearc setting and do not represent obducted portions of MORB oceanic lithosphere. Hence, contrary to previous interpretations, the associated massive sulfides could not originate on a mid-ocean ridge, but rather in an early arc or forearc environment. Given the relatively short life of the western Uralian arc system, the most probable time window for sulfide ore deposition is confined to Early to Middle Devonian time. D 2003 Published by Elsevier B.V.
Keywords: Chromite; South Urals; Main Uralian Fault; VHMS deposits; Ivanovka; Ishkinino

1. Introduction Chromite, including magnesiochromite and chromite sensu stricto, is a common accessory mineral in mafic and ultramafic rocks. By virtue of its composi* Corresponding author. Fax: +39-0498272010. E-mail address: paolon@dmp.unipd.it (P. Nimis). 0024-4937/$ - see front matter D 2003 Published by Elsevier B.V. doi:10.1016/S0024-4937(03)00090-2

tional variability and sensitivity to the conditions of formation, chromite can serve as a useful petrological and geodynamic indicator (Dick and Bullen, 1984; Barnes and Roeder, 2001). Elevated concentrations of chromite in igneous mafic – ultramafic complexes, also in the form of chromitites, are commonly associated with variable amounts of magmatic sulfides (e.g. Whitney and

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S.G. Tesalina et al. / Lithos 70 (2003) 39–59

Naldrett, 1989). Chromite deposits in mantle or mantle – crust transitional sections of supra-subduction zone (SSZ) ophiolites can be associated with hydrothermal, volcanic-hosted massive sulfide (hereafter VHMS) deposits occurring at upper volcanic levels (e.g. Yumul and Balce, 1994). Nonetheless, the occurrence of chromite within the VHMS ores is definitely rare. One such example is represented by the Cu –Co – Zn deposit of Outokumpu, Finland, where spinels characterized by strongly variable Cr, Al, Mg, Fe and Zn contents have been found both in the ores and in the hydrothermally altered, volcano-sedimentary country rocks (Treloar, 1987). Another example was reported by Candela et al. (1989), who described detrital chromite in the seafloor hydrothermal sulfide ores of the Sykesville District, Maryland Piedmont. More recently, Melekestseva et al. (2001) reported the occurrence of abundant chromite in the ultramafichosted hydrothermal sulfide mineralization of Ishkinino, Main Uralian Fault Zone (hereafter MUFZ), South Urals. Based on textural relations, Melekestseva et al. (2001) suggested a possible syngenetic relation between the chromites and the sulfides. If correct, this interpretation would imply a hydrothermal growth for the chromites. Although hydrothermal chromites are certainly unusual, mobilization of chrome by reducing, Cl-rich hydrothermal fluids has been proposed to explain the presence of volatile and sodium-rich fluid inclusions in some chromites from ophiolite complexes (Johan et al., 1983; Johan, 1986), the occurrence of chromite in some gold and sulfide deposits from the Urals and Soudan (Novgorod et al., 1984; Hottin and Aloub, 1990), and some of the compositional features of spinels from Outokumpu (Treloar, 1987). Here, we aim to test the hypothesis of a hydrothermal genesis in the light of an extensive set of new analytical and textural data on sulfide-associated chromites from two VHMS deposits of the southern MUFZ. These include the Ishkinino deposit studied by Melekestseva et al. (2001) and a somewhat analogous occurrence located 55 km to the NNE near the village of Ivanovka (Fig. 1). The textural and compositional features of the chromites contained in the sulfides and in their host mafic and ultramafic rocks will be compared with those of worldwide chromites from different petrogenetic environments. The results will be used to discuss the origin and significance of

Fig. 1. Geological sketch map of the southern Urals, with location of the Ivanovka and Ishkinino ore fields.

chromites in the studied deposits and to gain an insight into the geodynamic setting of the host mafic –ultramafic massifs at the time of sulfide formation.

2. Geological setting of the Ivanovka and Ishkinino deposits The Urals are a linear orogenic belt that resulted from the Late Palaeozoic collision of the East European Platform with a Siberian –Kazakhian plate assemblage and interposed oceanic and island arc terranes. The suture zone between the colliding plates is marked by the MUFZ, a 2 – 10 km wide (locally up to 25 km wide), east-dipping fault system, which can be traced continuously along the Uralide orogen (e.g. Puchkov, 1997) (Fig. 1). In the south Urals, the MUFZ separates an accretionary wedge to the west, which carries slices of high-pressure metamorphic units of continental provenance (Maksyutov Complex), from a Late Emsian to Early Frasnian forearc –island arc complex (Magnitogorsk arc) to the east (Brown and Spadea, 1999). The earliest stage of the

2. unpublished work).g. Prokin and Buslaev. Spadea et al. Tessalina et al. where several examples of Cyprus-. Spadea et al. These particular pyrrhotite-rich deposits are not typical for the Urals. a mid-ocean ridge and a forearc setting. have been proposed (Wipfler et al. (b) Geological section of the Ishkinino deposit (modified after Subbotin et al. which was followed by arc-tholeiitic and low. (a) Geological section of the Ivanovka deposit (simplified after Buchkovskiy. 2000a. Zakharov and Zakharova.. Seravkin et al. / Lithos 70 (2003) 39–59 41 Magnitogorsk arc development is marked by boninitebearing arc-tholeiitic volcanism in its westernmost area (Baimak– Buribai region. 1970). 2002).g. 2002). with blocks of Ordovician to Middle Devonian volcanic and sedimentary rocks (e. 2001. namely.. Nimis et al. 1999).. Vertical distances to scale.. 1997. ´ The MUFZ mainly consists of a melange of serpentinites. The MUFZ is interpreted as the main damage zone that developed along the arc backstop during Late Devonian collision of the Magnitogorsk arc with the East European continental margin (Brown and Spadea. Herrington et al. 2000a. Ivanovka The Ivanovka sulfide deposit is located near the east-dipping western margin of the MUFZ (Fig... 1999. 2a). Herrington et al.. 1).b. 2001. Savelieva et al. densely packed ore lenses and layers within a largely brecciated.G. 2.. Mafic– ultramafic complexes in the MUFZ are considered by a number of authors to be relicts of Silurian oceanic material (e.. 2002). 2000a. Besshi-.. Fig. their significance is still debated and two contrasting paleogeodynamic environments.. 1993. 1975) (Fig. 1999. . A few of these complexes from the southern part of the MUFZ are host to subeconomic Fe – Cu – (Co – Ni) massive sulfide deposits. 2002). Baimak(Kuroko-) and Urals-type deposits occur (cf.. It consists of several. derived from mantle harzburgites. Main hostrock lithologies consist of extensively to completely hydrothermally altered mafic and ultramafic rocks. Zaykov et al. less abundant dunites and minor lherzolites. in press). which include the Ivanovka and Ishkinino deposits studied in the present paper (Zaykov et al. which included olivine-rich melagabbroids. Tesalina et al. gabbros... 1998).to highK calcalkaline volcanism (Maslov et al. up to 100 –150 m thick mafic – ultramafic sequence (Buchkovskiy. 2001). Although the hydrothermal seafloor or subseafloor origin of the Ivanovka and Ishkinino deposits is supported by an increasing wealth of mineralogical and textural data. Zaykov et al. Tessalina et al. 1970.1.. A description of main host-rock lithologies and ore facies of the two deposits is given below.S.

The latter are covered by clastic materials which include abundant ultramafic –mafic detritus (Zakharov and Zakharova. (ii) a melange of serpentinites after harzburgites and dunites (200 – 300 m). Si)-rich saponite (stevensite) F quartz rocks (Nimis et al. hydrothermally altered rocks lies between a footwall serpentinite and overlying pillow basalts. The sulfide mineralization comprises massive. cobaltite. Co-pentlandite. 4f). These aggregates are noteworthy for their strict resemblance to textures found in modern seafloor hydrothermal mounds at Middle Valley. The three main tectonic slices are overlain by a fourth slice made of cherts and terrigenous sediments of Late Devonian –Early Carboniferous age. The mound-like level is capped by a decimetric breccia layer made of clasts totally replaced by (Mg. According to recent biostratigraphic dating of conglomeratic interlayers. (ii) chalcopyrite – pyrite – pyrrhotite with chalcopyrite veins and nests with arsenopyrite. where it can reach 60% of the ore. The carbonatized clasts show ghosts that resemble the mesh textures typical of serpentinites.. The absence of clasts of the underlying ores and of clear tectonic microstructures suggests the sedimentary nature of this breccia. 1993. quartz or dolomite (Nimis et al. in press). Juan de Fuca Ridge. stockwork and disseminated ores consisting of pyrrhotite F pyrite F chalcopyrite assemblages. possibly Early – Mid Devonian age (Seravkin et al. Gorda Ridge (cf. possibly. named Eastern and Western. 1).. 2b). 2001). Ni)-sulfides (Nimis et al. basalts and mantle peridotites (Fig.42 S. Tesalina et al. (iii) basalts and basaltic andesites with calcalkaline to boninitic affinity (Simonov et al. 2. further epithermal overprint (Wipfler et al.. Fe-rich talc. Goodfellow and Franklin. Accessory minerals are chromite. respectively. sphalerite.G.4%) in ultramafichosted ores. It is located within an antiform structure (Fig. chromian saponite.. sandstones and Middle Devonian olistostromes with olistolites of siltstones. locally with chalcopyrite – cubanite intergrowths.. whereas cobalt and copper are enriched (0. 2002) and basaltic breccias (>500 m). Zierenberg et al. In particular. of Upper Silurian to possibly Early Devonian age (Sakmara strata. magnetite and calcite. veins and cement of pyrite. Sometimes they include millimetric. respectively) in mafic-hosted ores (Zakharov and Zakharova. Seravkin et al. and Escanaba Trough. native bismuth and pilsenite (Bi-telluride). and clastic textures with clasts of lath-like pyrrhotite aggregates and dissemination. gradually passing upwards to cherts.. Zaykov et al. 1993. . Fe)carbonates and green saponite. 1975).04 – 0. low-T (Fe.. 1999). 1975. set in a matrix made of green. occur at the edges of the antiform and are accompanied by talc and talc-carbonate hydrothermal alteration of serpentinites. (iii) chalcopyrite – arsenopyrite with banded texture. 1999): (i) pyrite – pyrrhotite with massive. with rare pentlandite. Cobaltite mostly occurs at the peripheries of the bodies. Co-pyrite. cherts and basalts (>200 m) (Maslov et al. amoeboid chromite grains. while ultramafic rocks and polymictic mafic– ultramafic breccias were dominantly transformed into talc F Mg-rich chlorite F carbonate F (Mg. followed by metamorphic annealing and. in press) (Fig. 3).. the basaltic and clastic units are of post-Silurian. siltstones. Ishkinino The Ishkinino sulfide deposit is situated 20 km west of the town of Gay (Fig. A pyrrhotite –pyrite– cobaltite– chalcopyrite –arsenopyrite mineralization with accessory chromite ´ occurs within the serpentinite melange sheet and composes seven ore bodies up to 15 m thick and several tens of meters long. porphyry. chlorite... 2000a.2.2 – 0..1% and 1. which occasionally include centimetric pockets and lenses of chromitite. Two ore zones. violarite and Ni – Co – Fe sulfide. Ni-glaucodot as well as traces of native gold. in press). Three main ore types can be recognized based on material extracted from a prospecting shaft in the Eastern ore zone (Wipfler et al. pentlandite and violarite inclusions. / Lithos 70 (2003) 39–59 dolerites. 2001). The nature of the Ishkinino ores is interpreted to reflect an original deposition of VHMS sulfides. which involves three tectonic slices mainly composed of (upwards): (i) tholeiitic basalts and cherts. chromite fragments and disseminated.8%. 1993). mafic protoliths were mostly transformed into chloritites. Nickel is slightly enriched (0. with carbonaceous schists and lenses of limestones. 2002). The sequence of ore-bearing. The uppermost ore level is characterized by network-like aggregates of lamellar pyrrhotite with interstitial Mg-rich saponite. Hydrothermal alteration of these rocks produced various mineral assemblages depending on protolith composition and hydrothermal conditions. >300 ´ m in thickness).

G. Description of drillhole DDH2T. . Tesalina et al. 2a). Ivanovka (cf. Fig.S. / Lithos 70 (2003) 39–59 43 Fig. 3.

Cp) ore (#Iv155. transformed into carbonate (Cb. White.8. 4.2. The big clast to the right includes an amoeboid chromite crystal (Chr). from right to left: (i) a microbreccia of light gray fragments of chloritite in a Mgsaponite F dolomite matrix with abundant idiomorphic cobaltite crystals (black) and a few nearly opaque euhedral crystals and fragments of chromite (arrows) and (ii) later veinlet of comb-like dolomite (#Iv132. Po) + chalcopyrite (white. reflected light). disseminated crystals are of (Fe. plane-polarized transmitted light). (d) Irregular fragment of chromite crystal associated with quartz (Qz) as matrix of pyrrhotite ore (Po). (c) Fracture in massive pyrrhotite ore (black) filled by. (e) Euhedral and fragmented chromite crystals (dark gray. Nc) and chalcopyrite (medium gray. with partially resorbed nickeline (white. fine. reflected light). (f) Breccia made of serpentinite clasts.7. (b) Euhedral and fragmented chromite crystals in talc (dark gray) matrix and partly included in pyrrhotite (light gray. included in late cobaltite crystal (light gray). Black matrix is talc. capping the massive sulfide deposit.4.3. . BSE image). plane-polarized transmitted light). Ni)-sulfides (#Iv80. Chr).G. Spinels near the margin appear extensively transformed into porous ‘‘ferritchromit’’ (#Ish610-12. light gray). (a) Cluster of chromite broken crystals (medium gray) associated with talc (dark gray. Microphotographs of chromites from Ivanovka (#Iv) and Ishkinino (#Ish). Tesalina et al. / Lithos 70 (2003) 39–59 Fig. dark gray) + saponite (Sap. Cp).44 S. BSE image). The spinel carries an inclusion composed of Mg-chlorite + Mg-saponite (#Iv149. Tlc) interstitial to pyrrhotite (light gray. and chromite crystal fragments (medium gray) in a saponite matrix. Po) (#Iv140.

3). The host spinel shows a ‘‘ferritchromit’’ alteration rim and inclusions near the margins have been altered into Mg-chlorite (#Ish59816). Tesalina et al. . (a) Rounded and negative crystal melt inclusions with daughter pyroxenes in pyrrhotite + chalcopyrite matrix.8). in euhedral spinel crystal. (f) Euhedral spinel with glass (black) + pyroxenes (grey) + chalcopyrite (not visible) inclusions in serpentinite after harzburgite (#Ish1). Sample materials from the Ishkinino deposit were taken from the damp of a prospecting shaft that crosscut the shallowest portion of the deposit (Fig. / Lithos 70 (2003) 39–59 45 3. 5. The drillhole is representative of the shallowest portions of the ore body and crosscuts several mineralized and barren levels. (e) Multiphase inclusion with cpx – opx intergrowth (#Iv175.8).S. Fig. The host spinel shows a tiny ‘‘ferritchromit’’ alteration rim (#Ish598-15). (d) Multiphase inclusion with void in the upper part. Analytical methods and sample materials Sample materials from the Ivanovka deposit were taken from a drillhole (DDH2T) obtained during a 1998 drilling campaign (Fig. (b) Melt inclusion showing negative crystal shape. The large inclusion near the bottom has been almost completely emptied during polishing. (c) Subhedral chromite in chalcopyrite – pyrite ore with melt inclusions along growth zone (#IshX). The light band between the glass and the hole is an artifact of sample topography (#Iv175. BSE images of melt inclusions in chromites from Ivanovka (#Iv) and Ishkinino (#Ish).G. with faceted subcalcic-augite daughter crystal.

using a 1-Am beam.G. operating at an accelerating voltage of 15 kV. Tesalina et al. beam current of 15 nA. TiO2 relations in chromites from Ivanovka (a. Natural and synthetic minerals (wollastonite for Ca and Si. Solid and thick symbols are used for chromites of clear magmatic origin that occur as euhedral crystals or fragments carrying melt inclusions. sphalerite for Zn). vanadinite for V. / Lithos 70 (2003) 39–59 2b) and from surrounding outcrops. Approximate trends for peridotite partial melting.46 S. . orthoclase for K. Fe. Polished thin sections of representative rocks. MnTi and Ni) and elemental Co were used as standards. Chemical analyses of chromites and melt inclusions were carried out using a CAMECA ‘‘CAMEBAX’’ electron microprobe (CNR-IGG Padova) equipped with four vertical WDS spectrometers. pure oxides (for Al. were prepared for optical and scanning electron microscopy and for electron microprobe analysis. 6. albite for Na. Open and thin symbols are used for chromites that occur as non-euhedral amoeboid crystals or as fragments of uncertain origin. b) and Ishkinino (c. TiO2 and Mg/(Mg + Fe2 +) vs. Cr. The CAMECA-PAP program was used Fig. counting time of 10 s for peak and 10 s for background. Cr/(Cr + Al) vs. d). olivine F pyroxene F chromite fractionation and low-grade alteration are shown as arrows. including both mineralized and barren types.

Ore-associated chromites occur either as disrupted grains (up to millimetric). Fields for arc volcanic rocks. and in associated hydrothermally altered rocks. in ore-associated chloritites and hanging wall pillow basalts from Ivanovka. Chromite fragments and octahedra are found either as inclusions in the sulfides (mostly pyrrhotite) or.01 wt. equipped with a tungsten cathode and four quadrant solid-state BSE detectors. series. 4b). more common.% have been truncated. and MORB basalts and peridotites after Kamenetsky et al. TiO2 vs. Multiphase history at Ivanovka is demonstrated by the presence of clasts made of chromite crystal fragments cemented by pyrite. Analyses are believed to be precise to within F 1– 2% relative for major and F 2 – 5% relative for minor oxides. f 160 AA filament emission and 35 mm working distance. / Lithos 70 (2003) 39–59 47 to convert X-ray counts into weight percent oxides. or as euhedral and subhedral octahedral crystals (up to 300 Am in size) (Figs. more rarely. Qualitative chemical microanalysis were carried out using an EDAX system with a ‘‘Sapphire’’ detector (LEAP + Si(Li) crystal).p. (2001). series. which have been in turn cemented by later sulfides. ocean island basalts (OIB). Euhedral to subhedral chromite crystals similar to those associated with the sulfide ores occur in some serpentinized dunites –harzburgites from the Ishkinino ore field and in talc-rich rocks. The analytical conditions were: 20 or 25 kV accelerating voltage. They are often located near the altered chromite rims or along partially healed cracks and usually have the same composition and optical orientation as the host sulfide. The chromites included in the sulfides tend to be located near the sulfide crystal margins (Fig.p.S. 4e). scattered in their talc F chlorite F saponite F carbonate F quartz matrix and veins (Fig. where it can represent up to 3% of the total. In both deposits. A few data with TiO2 below 0. Tesalina et al. Chromite in Ivanovka and Ishkinino ore fields Chromite is a common accessory mineral in Ivanovka and Ishkinino sulfide ores.G. c. Symbols as in Fig. b. Chromite in these rocks usually forms small (usually 5 –10 4. in cumulate melagabb- Fig. In the Ishkinino deposit. 6. The Arc low-Ti field corresponds to boninitic and tholeiitic p. sulfide inclusions in chromite are rare. 4a. Concentrations of chromite together with monazite crystals in a mixed sulfide –silicate breccia from the Ishkinino deposit are noteworthy. d). roids and. the Arc high-Ti field comprehends calcalkaline and tholeiitic p. 7. . Al2O3 relations in chromites from Ivanovka (a) and Ishkinino (b). supra-subduction zone (SSZ) peridotites. 4 and 5). which often form clusters of broken fragments. euhedral chromite is often included in cobaltite and arsenopyrite crystals (Fig. Scanning electron microscope (SEM) analyses were carried out using a CamScan MX2500 microscope.

11 51.25 0.43 15. 0.6 55.539 0.000 1.69 1.05 0.584 0.047 0.34 0.001 0.357 0.08 0.322 0.408 0.5 54. 0.002 0. d Sample taken from shaft damp.29 5.71 n.a.008 0.233 0.40 15.29 11.38 0.008 0.98 0.006 0.46 0.064 10 Ivanovka Iv36. a Sedimentary breccia capping massive sulphide body.38 21.29 9.001 0.065 8 Ishkinino Ish10-1bb Subhedral 0.010 0.90 13.93 16.95 n.03 0.004 3.079 Unit formula and Fe3 + based on four oxygens and three cations.588 0.01 0.006 0.022 5 Ivanovka Iv10b Subhedral 0.0 0.03 18.493 0.505 0.67 0.646 0.58 0.24 13.6 41.1 0.03 0.08 0.13 0.000 65.12 0.623 0.634 0.000 73.a. 52.012 0.000 1.18 0.15 48.a. 49.000 0.91 0.31 100.134 0.28 13.005 1.a.007 3.000 0.023 Serpentinites 4 Ivanovka Iv3b Amoeboid 0.000 68.506 0.089 0.4 0.8 49.000 71.10 19.64 18.33 0. Table 1 Representative electron microprobe analyses of chromian spinels from mafic – ultramafic rocks from Ivanovka and Ishkinino (all core analyses except where noted) Rock Basalt 1 Deposit Sample Habit SiO2 TiO2 Al2O3 V2O3 Cr2O3 Fe2O3 FeO MnO MgO CoO NiO ZnO Total Si Ti Al V Cr Fe3 + Fe2 + Mn Mg Co Ni Zn Sum 100Cr/(Cr + Al) 100Mg/ (Mg + Fe2 +) Fe3 +/Fe2 + Fe3 +/(Fe3 + + Ti + Cr + Al) Ivanovka IvBzb Euhedral (core) 0.001 0. chromite forms bigger grains (up to a few millimeters) which exhibit irregular to clearly amoeboid habits.98 14.14 0.002 3.47 n.445 0.364 0.005 3.000 0.045 Clastica 3 Ivanovka Iv80. 50.63 0.96 6.43 9.09 0.00 99.06 0.42 18.004 1.5 62.394 0.263 0.32 0.010 0.0c Euhedral 0.008 0.002 0.6 0.18 0.004 3.a.39 17.068 Olivine melagabbroid 9 Ivanovka Iv44.32 n.00 0.a.009 0.05 0.000 71.19 99.24 0.06 0.4 47.24 14.010 0.23 n.07 0.006 3. 54.002 0.01 13.001 0.085 0.001 0.008 0.a.56 0.002 3.00 0.00 14.0c Euhedral 0.16 99.00 0. 58.36 14.23 0.001 0.000 0.13 0.003 1.24 0.16 0.000 66.000 68. high concentrations of detrital chromite (up to 3– 5 modal %) occur in the breccia made of carbonatized serpentinite fragments that caps the main massive ore body (Fig.55 13. Finally.000 1. 0.20 0.002 0.672 0.002 0.48 S.a.002 0. w/incl.05 0.11 n.24 5.0 0.462 0.000 0.05 0.22 13.469 0.467 0. / Lithos 70 (2003) 39–59 Am and up to 1 mm) crystals.3c Fragment 0.001 7 Ishkinino IS-0117d Subhedral 0.01 99. b Samples taken from outcrops.31 13.128 0.524 0.a.001 0.284 0.045 0. . c Samples taken from drillhole DDH2T (numbers indicate depth in meters).26 19.10 99.003 3.556 0.13 47.47 3.31 10.09 99.05 0.000 1.93 0.25 n.85 0.a.584 0.6 50.375 0.7 0.274 0.87 5.45 0.2 0.364 0.83 0. In some serpentinites from both localities and in some talc-rich rocks from Ivanovka.000 0.39 n.000 0.7 46. which are included in altered olivine and pyroxene crystals or scattered in interstitial position.493 0.5 0.12 16.09 0.001 0.G. 0.4 63.04 0.000 3.009 0.009 0.000 67.000 1.005 0.57 0.13 0.003 0.11 0.10 0.97 1.11 100.126 0.05 0. 54.538 0. 0.67 0.444 0.271 0.002 0.07 0.: with melt inclusions.97 n.000 0.004 1.24 98.29 0.544 0.01 0.525 0.92 3.003 0.047 0.39 11.000 0.525 0.27 n.371 0.57 0.35 13. 0.09 0.000 72.43 0.579 0.19 99.8 0.87 0.010 0.626 0.23 0. at Ivanovka.157 0.21 51.043 2 Ivanovka IvBzb Euhedral (rim) 0.009 0. 4f).000 0.36 8.007 0.531 0.20 0.003 0.5 63.000 0.42 n.06 0.26 10.526 0. Tesalina et al.002 0.000 1.002 0.a.a.70 n.31 0.002 0.000 0.000 71.40 1.002 0.000 3.8 0.024 6 Ishkinino Ish8b Amoeboid 0.

10 0.047 0.63 15.7 50.0c Fragment (w/incl.20 1.003 0.13 9.7 41.78 0.22 56.004 0.01 0.002 0.002 0.61 0.04 0.71 0.78 4.59 0.01 0.394 0.001 0.0 0.70 19.315 0.32 8.380 0.339 0.79 0.125 0.33 2.81 0.08 53.188 0. Representative analyses are reported in Tables 1 and 2.001 3.09 0.3 35.57 0.08 0.08 0.043 0.05 0.0c Fragment (w/incl.29 0.50 99.80 23. Tesalina et al.102 0.28 12.504 0.002 1.3 0.00 0.10 0.50 0.000 79.28 0.18 99.23 0.37 0.488 0.22 58.27 8.061 14 Ivanovka Iv14.000 79. Some crystals exhibit a highly reflectant.001 0.9c Euhedral 0.004 0.34 0.38 6.590 0.79 0.56 1.006 1.61 3.81 0.33 9.73 0.13 100.00 0.0 11.122 0.16 46.006 1.368 0.09 0.06 0.009 0.19 9.6 0.759 0.61 4.004 0.107 0. 6 and 7.29 0.20 62.18 0.0 59.005 0.005 0.0c Euhedral 0.00 0.001 0.002 0.398 0.32 10. The compositions range from magnesiochromite to chromite sensu stricto.1 0.496 0.82 0.005 0.057 15 Ivanovka Iv14.659 0.25 0.19 8. / Lithos 70 (2003) 39–59 49 5.001 0.11 0.17 0.099 0.011 0.004 3.70 0.038 0.4c Fragment 0.06 21.19 55.000 79.000 0.24 59.02 0.003 0.18 0.46 0.2 0.146 0.285 0.18 0.58 5. Chromite chemistry The compositions of the cores of chromites from sulfide ores and mafic – ultramafic host rocks are illustrated in Figs.002 0.7 60.020 Chloritites 19 Ivanovka Iv134.10 0.96 0.000 0.93 1.24 55.000 85.044 20 Ivanovka Iv135.43 0.4c Euhedral 0.04 0.001 0.03 0.08 0.13 54.12 0.27 98.4 0.002 0.000 0.498 0.635 0.497 0.4 0.07 18.088 0.07 7.004 1.41 0.007 0.62 0. iron-rich alteration rim having a composition corresponding to ‘‘ferritchromit’’ (cf.593 0.95 0.580 0.23 99.000 81.009 0.518 0.001 0.024 13 Ivanovka Iv14.03 15.75 0.0c Fragment (w/incl.17 0.1 0.005 0.001 0.67 1.71 0.000 58.009 0.21 9.00 0.88 0.006 1.88 0.002 0.10 0.17 12.008 0.000 0.78 0.063 18 Ivanovka Iv155.13 48.880 0.001 0.439 0.2 0.022 17 Ivanovka Iv14.31 29.02 0.005 1.530 0.86 0.15 101.013 3.0 44.000 0.18 0. Burkhard.05 0.867 0.006 3.13 0.494 0.12 99.114 0.051 16 Ivanovka Iv14.07 20.09 0.000 0.15 8.003 0.54 4.44 101.001 0.06 0.003 0.000 0.594 0.016 0.S.003 1.049 0.480 0.36 99.003 3.000 80.001 0.383 0.000 0.350 0.806 0. porous.552 0.00 0.024 .11 0.500 0.7 10.004 1.21 9.03 0.5c Euhedral 0.03 0.409 0.00 0.00 20.003 0.006 3.23 0.07 0.03 0.015 0.3 49.03 99.42 22.83 29.404 0.009 3.) 0.0c Fragment (w/incl.03 0.56 17.4c Fragment 0.040 0.6 32.55 1.000 61.005 1.55 6.406 0.05 0.000 0.000 82.9 0.15 9.) 0.001 0.) 0.G.016 0.) 0.005 0.000 78.660 0.006 1.002 0. 1993) Talc F carbonate F chlorite F quartz F saponite F serpentine rocks 11 Ivanovka Iv108.06 0.003 3.019 12 Ivanovka Iv108.011 3.351 0.70 0.50 2.005 3.002 0.04 0.50 0.

0 40.02 0.04 0.96 0.8 Matrix Iv126.004 1.31 0.71 14.18 99.001 0.007 0.03 0.00 14.001 0.000 69.000 75.157 0.365 0.126 0.54 0.013 0.00 0.00 0.457 0.10 0.012 0.26 99.487 0.010 0.22 6.2 0.29 0.21 13.41 16.008 0.005 0.588 0.04 0.95 0.) (w/incl.04 0.03 0.13 99.000 75.00 0.666 0.03 0.007 1.03 0.12 0.04 0.01 7.) 0.003 0.2 56.001 0.21 0.00 0.006 3.71 0.30 4.75 4.003 0.00 0.591 0.10 0.001 0.006 3.36 99.G.000 0.323 0.005 0.04 0.252 0.000 0.006 0.002 0.501 0.5 43.36 1.15 61.002 0.09 0.27 14.57 6.000 0.00 0.30 3.) (w/incl.7 0.007 3.00 0.00 0.038 0.369 0.534 0.008 0.001 0.17 99.000 80.38 0.22 100.605 0.004 1.003 0.004 3.32 2.00 0.16 51.06 0.205 0.003 3.147 0.000 0.06 0.29 12.000 74.807 0.000 0.02 8.555 0.001 0.382 0.5 0.36 7.74 21.000 0.027 0.737 0.001 0.007 0.80 0. .007 1.166 0.000 74.005 1.000 0.000 0.001 0.154 0.361 0.68 0.63 20.52 0.13 6.268 0.78 0.009 0.575 0.5 0.17 26.440 0.573 0.68 0.522 0.04 22.515 0.059 0.4 0. pyrite or arsenopyrite crystals.654 0.08 0.001 0.14 0.34 11.61 0.9 0.32 12.07 99.6 25.005 3.24 100.00 12.01 0.0 46.09 0.16 52.05 0.40 0.427 0.08 0.02 0.009 0.03 0.004 1.09 0.076 0.009 0.000 0.22 58.98 0.442 0.50 0.10 0.001 0.004 3.18 0.10 0.17 98.4 55.002 1.16 0.000 0.000 0.28 0.87 23.14 15.002 0.02 0.007 0.531 0.1 Py Iv121.024 0.003 3.032 0.012 0.00 0.495 0.9 Matrix Iv86.88 0.085 Euhedral Euhedral Euhedral (w/incl.003 0.540 0.23 47.17 0.02 0. w/ol: with olivine inclusion.2 40.16 99.26 0.25 13.31 8.83 0.21 0.563 0.001 0.03 0.50 Table 2 Representative electron microprobe analyses of ore-associated chromian spinels from the Ivanovka (drillhole DDH2T.06 0.44 27.92 0.429 0.011 0.00 0.009 0.67 0.388 0.000 0.3 53.93 19.059 0.000 0.86 0.644 0.25 52.13 0.25 13.23 47.555 0.7 41.05 0.01 0.000 0.00 0.84 2.19 100.15 100.43 8.07 0.08 14.00 0.14 58.004 3.33 0.002 0.004 3.001 0.30 9.530 0.62 0.698 0.262 0. matrix: part of matrix of sulphide ore.31 9.597 0.444 0.) 0.3 20.006 1.004 0.23 0.7 0.003 1.003 0.03 12.004 3.63 0.01 0.67 0.18 0.25 Matrix Iv86.078 0.060 0.006 1.22 52.01 19.: with melt inclusions.008 0.492 0.001 0.000 0.01 0.006 0.0 0.000 71.18 0.060 S.010 0.624 0.8 Po Iv149. w/incl.031 0.330 0.458 0.357 0.006 3.45 18.22 0.04 0.000 84. Po.002 0.14 0.084 0.24 98.001 0.4 47.001 0.2 Matrix Iv175.496 0.4 63.120 0.002 0.405 0.001 0.567 0. sample numbers indicate depth in meters) and Ishkinino (shaft damp) deposits (all core analyses except where noted) 1 Deposit Sample Host Habit SiO2 TiO2 Al2O3 V2O3 Cr2O3 Fe2O3 FeO MnO MgO CoO NiO ZnO Total Si Ti Al V Cr Fe3 + Fe2 + Mn Mg Co Ni Zn Sum 100Cr/ (Cr + Al) 100Mg/ (Mg + Fe2 +) Fe3 +/Fe2 + Fe3 +/(Fe3 + + Ti + Cr + Al) 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 Ivanovka Ivanovka Ivanovka Ivanovka Ivanovka Ivanovka Ivanovka Ivanovka Ivanovka Ivanovka Ishkinino Ishkinino Ishkinino Ishkinino Iv82.28 47.04 0.004 3. / Lithos 70 (2003) 39–59 Unit formula and Fe3 + based on four oxygens and three cations.6 46.550 0.45 0.00 0.14 19.460 0.09 0.35 0. Py.063 0.17 21.002 0.45 8.000 73.002 3.006 1.87 0.783 0.000 83.3 0.168 0.20 52.6 0.079 0.11 99.22 5.03 0.054 0.002 0.56 0.000 58.006 1.000 73.000 70.02 0.360 0.001 0.91 0.384 0.28 0.000 0.008 1.006 0.60 0.009 0.000 72.006 1.24 11.004 3.401 0.001 0.008 0.006 0.009 0.006 0. Apy: included in pyrrhotite.47 0.12 0.001 0.504 0.12 6.04 0.80 5.73 0.31 13.33 11.25 57.030 0.001 0.02 0.009 3.000 0.030 0.005 1.288 0.37 0.75 19.000 0.89 0.005 0. Tesalina et al.3 0.12 0.19 100.8 Matrix Ishkinino Ishkinino Ishkinino Ish610-11 Ish610-11 Ish610-11 Ish610-12A Ish598-15 Ish598-15 Ish598-15 Po Po Apy Po Po Po Po Fragment Fragment Fragment Fragment Fragment Fragment Subhedral Fragment Fragment Fragment Subhedral Euhedral Euhedral Euhedral (w/ol) (core) (rim) (w/incl.20 11.394 0.006 0.556 0.75 0.471 0.10 62.000 0.008 0.000 0.22 54.6 0.3 61.004 0.6 0.000 69.000 71.16 0.015 0.20 0.074 0.23 10.264 0.29 99.01 0.31 21.17 0.02 10.26 0.49 0.006 1.32 0.9 Matrix Iv100.016 0.291 0.12 0.016 0.0 0.117 0.002 0.000 0.529 0.00 0.17 0.59 6.6 39.30 4.37 14.34 2.88 17.001 0.6 55.08 46.86 0.25 0.10 0.01 0.31 12.518 0.17 16.26 0.97 0.00 0.24 49.03 0.0 33.01 0.9 0.4 Matrix Matrix Iv126.34 9.03 0.20 0.03 13.00 0.2 0.02 0.76 0.87 2.45 Iv122.390 0.17 98.40 7.000 64.54 0.1 0.001 0.03 0.007 3.73 0.469 0.002 0.36 0.08 0.19 53.482 0.305 0.004 1.03 0.005 0.42 0.

4 0. All these observations indicate that the composition of the cores of the chromite crystals were not significantly modified by low-grade alteration processes.07 0.030 0.50 0.001 0.38 0.010 3.3 1.000 89.17 0.03 0.082 0.000 3.55 43.326 2 Ivanovka Iv10b Serpentinite Fragment (rim) 0.4a Talc rock Fragment 0. Moreover.009 0.004 0.302 3 Ivanovka Iv14.14 0.027 0.006 3.%) and unrelated to the contents of other major oxides.001 0.003 0. where present.08 0.5 2. show abrupt contacts with the inner portions of the grains. a Sample taken from drillhole DDH2T (numbers indicate depth in meters).00 0.047 0.003 0. A chromian magnetite may also develop either as overgrowths or as further alteration products on the ‘‘ferritchromit’’ rim.00 0.22 100.34 0.13 17.207 0.01 21.279 0.002 0.002 0.03 0.270 0.016 0.10 0. Matrix Habit SiO2 TiO2 Al2O3 V2O3 Cr2O3 Fe2O3 FeO MnO MgO CoO NiO ZnO Total Si Ti Al V Cr Fe3 + Fe2 + Mn Mg Co Ni Zn Sum 100Cr/(Cr + Al) 100Mg/(Mg + Fe2 +) Fe3 +/Fe2 + Fe3 +/(Fe3 + + Ti + Cr + Al) Ivanovka Iv108.04 0.07 0.94 22.80 0.46 0.002 0. This is also supported by the fact that Table 3 Representative electron microprobe analyses of ‘‘ferritchromits’’ from the Ivanovka and Ishkinino ore fields 1 Deposit Sample no.297 6 Ishkinino Ish598-15c Po ore Euhedral (rim) 0.297 0.32 1.97 1.000 90.033 0.4 4.22 0. 2000).035 0.001 0.022 0.20 27.615 0.967 0. The ‘‘ferritchromit’’ rims. b.84 0.38 0.004 0. Table 3).25 0.09 1.93 0.28 1.029 0.07 0.52 0.06 0.640 4 Ishkinino Ish610-12Ac Po ore Euhedral (rim) 0.04 0. 5a.001 0.021 0.004 0.973 0.138 0.006 0.06 0.29 0.00 0.000 97.27 0.66 0.42 0.005 1. .65 30.142 5 Ishkinino Ish598-15c Po ore Euhedral (rim) 0.056 0.24 99. where small euhedral crystals can be totally transformed into ‘‘ferritchromit’’.6 0.020 0.43 0.7 13.065 0.06 0.57 30.003 0.79 49.008 0.94 2.61 0.26 0.855 0. The latter remain mostly unzoned.951 0.85 0.92 3.96 0. This type of alteration is overwhelmingly more developed in the Ishkinino ores.36 99.37 0.000 97.136 0.6 2.390 0.60 0.46 0. c.010 0.950 0.69 0. Tesalina et al. / Lithos 70 (2003) 39–59 51 (Fig.77 9.701 Unit formula and Fe3 + based on four oxygens and three cations.001 0.016 1.000 93.48 0.000 0.594 0.08 0.026 0.002 0.17 41. except a slight rimward decrease in Mg/(Mg + Fe2 +) ratios (see analyses 2 and 3 in Table 2).95 0.691 1.0c Talc rock Fragment 0.047 0.36 29.96 0.44 43.529 1.67 0.2 2.00 97.3 wt.14 22.000 0.68 0.G.1 1. except some degree of reequilibration of fast-diffusing divalent cations (cf.11 30.966 0.004 3. c Sample taken from shaft damp.23 97.92 20.209 0. b Sample taken from outcrops.72 1.03 0.16 98.007 3.35 0. their SiO2 contents are invariably low ( < 0.92 30.022 0.19 0.42 40.9 0.04 0.008 0. Barnes.578 0.017 1.18 0.637 0.012 1.57 54.29 0.002 0.006 3.000 97.011 0.000 0.017 0.S.7 6.8 0.

The decrease of Mg# at virtually constant Cr# and TiO2 is consistent with zoning patterns found in individual crystals. with maximum contents of 0. are strongly depleted in Al and Mg and have higher relative proportion of oxidized vs. However.5 wt. the altered ‘‘ferritchromit’’ rims are enriched in Fetot.00 – 0.01 – 0. Such features indicate that the inclusions are primary and contain partly crystallized liquids parental to the host chromites (cf.23 wt.26).% ZnO. 6a and b).%). 6c. Tesalina et al. and similar or slightly lower Cr# values (68 – 72). 1984). the host chromites appear homogenous and mostly free of fissures or cracks.19 – 0.% in some orehosted examples.6 wt. Therefore. while they may show alteration into hydrous hydrothermal silicates (talc. and much lower Fe3 +/Fe2 + ratios (0.%). 5a).4 wt. A group of Cr-rich (Cr# =80 – 85) euhedral – subhedral chromites from talc-altered rocks shows a slight but definite increase in TiO2 with decreasing Cr# and Mg# (Fig.3 wt. 6.23 wt. The contents of zinc and nickel in the other samples are variable. reduced iron.% NiO in other ore-hosted chromites.37).06 – 0. and 100Mg/(Mg + Fe2 +) atomic ratios (hereafter Mg#) ranging between 8 and 64 (Fig. high ZnO contents (up to 0. Melt and mineral inclusions in chromites Euhedral and subhedral chromites from both sulfide ores and associated rocks frequently carry multiphase inclusions of glass and/or anhydrous silicate minerals up to 40 Am in size (Fig.%). comparable Cr# (71 – 74). only moderately high TiO2 (0. nickel and vanadium are comparable with those in the ore-hosted chromites from Ivanovka.6 wt. variations in Cr# and Mg# ratios do not appear to be associated with a systematic change in TiO2 contents. the measured contents of divalent cations are not necessarily representative of the original chromite compositions. more rarely.04). They are usually randomly scattered within the host mineral (Fig. only analyses of chromite cores that showed negligible or minor Mg ! Fe zoning have been selected for the present work.%). Chromites from Ishkinino ores form a coherent group characterized by decreasing Mg# (from 55 to 20) and little varied Cr# ratios and TiO2 contents (Cr# = 68 –76. euhedral and subhedral chromites from Ishkinino serpentinites have similar Mg# (36 – 49) and Fe3 +/Fe2 + ratios (0. Mg-saponite. Amoeboid chromites from Ishkinino serpentinites have lower Mg# (55 –60).%) (Figs. In all other samples from Ivanovka. Fig.5 wt.05 wt. They are characterized by highly variable Fe3 +/Fe2 + atomic ratios (0. c) and slight rimward decrease in Mg# values (see Section 5). 6a and b).%). The inclusions generally contain an aggregate of daughter minerals. Compared with the compositions of the chromite cores. Vanadium contents are mostly between 0.G.52 S. and reach 0. 5a and b). Chromites from chloritites form a distinct group characterized by Mg# values about 10.4 wt. reaching ca. d and 7b).8 wt. 5c).16 – 0. The contents of zinc.3 wt. serpentine) when occurring near the chromite margins (Fig. Amoeboid chromites from serpentinites and detrital chromites in the breccia capping the main massive sulfide orebody show the lowest TiO2 contents ( < 0. Chromites included in cobaltite and arsenopyrite are slightly enriched in CoO (up to 0. Apart from tiny ‘‘ferritchromit’’ alterations (Fig.1 and 0. Roedder.%) TiO2 contents (Tables 1 and 2. although overlap of different populations of data may have obscured any existing correlation.% V2O3. the absence of significant zoning may at least in part be the result of intracrystalline diffusion and rehomogenization.% ZnO in a few chromites in sulfides and talc-rich rocks and 0.2 –0. 5). 0.% V2O3. b. Mn and Ti.5 wt. Compared with the ore-hosted chromites. and Fe3 +/Fe2 + ratios close to 0. a small-volume residual glass and. Some are also enriched in V2O3 (up to 0. 7a). To minimize the effect of subsolidus reequilibration and hydrothermal alteration.%) and ZnO (up to 0. .6 wt.35) and. by relatively low ( V 0. Chromites from Ivanovka have 100Cr/(Cr + Al) atomic ratios (hereafter Cr#) ranging between 56 and 88. corresponding to higher contents of magnetite and chromite components (Table 3). Fe3 +/Fe2 + atomic ratios are relatively high and vary within a restricted range (0. they are aligned along crystal growth zones (Fig. given the small size of most chromite crystals.4 wt. Mg-chlorite.% NiO and 0. 5a.1. The inclusions show either round or negative crystal forms. TiO2 = 0.. except a few euhedral chromites from melagabbroids and serpentinites. 0. / Lithos 70 (2003) 39–59 melt inclusions (see next section) are usually well preserved when occurring within the inner portion of the chromite host.

the low residual melt/daughter Table 4 Representative electron microprobe analyses of glass and daughter minerals (analyses 1 – 4) and of isolated mineral inclusions (analyses 5 – 7) in ore-associated chromian spinels from Ivanovka (drillhole DDH2T.018b 0.2 – 2.000 – 4.S.01 1.a. FeO and.02 1.93 7.18 wt. 101.000 1.004 1. analyses 1.53 0.a.013 3 opx 57.01 0. Ca-rich clinopyroxene.10 0.990 0.65 0..31 1.23 4.67 wt.06 wt.13 34.53 1.74 1.01 n.00 0.%).8 1 Phase SiO2 TiO2 Al2O3 Cr2O3 FeO MnO MgO CaO Na2O K2O NiO Total Si Ti Al Cr Fe Mn Mg Ca Na K Ni Sum Glass 62. 1971).13 51.06 n.%.956 0.738 0.01 0.%) contents. 101. with one exception at 0. 100. sample numbers indicate depth in meters) and Ishkinino (shaft damp) deposits (cf.779 0.67 n. Na2O contents higher than in the other pyroxenes. a Inclusion contained daughter orthopyroxene.01 n.02 n.79 0.00 Iv82.95 0.082 0. .001 – 4.00 1. 99.952 0.148 0.01 0.25 0.91 0.%).021 Unit formulas based on six oxygens for pyroxenes and four oxygens for olivine.054 0.02 0.60 23. orthopyroxene.018 0.79 0. 10 and 12 in Table 2) Sample Iv175. In the absence of rehomogenization data.74 0. MgO (0– 20 wt.88 2.28 0. voids which probably represent former liquid or gaseous bubbles (Fig.% recalculated on anhydrous basis from a set of four analyses from Ivanovka and seven analyses from Ishkinino).50 2 cpx 53.000 – 4.%) and FeO (0.15 0. micron-sized (Fe. ol. sometimes.00 n.16 0.a.026 0. 0.05 wt.000 0.63 0.G.070 0.000 0.033 0.2 wt.012 Iv175. Cu.02 0.%) and Na2O (4 –10 wt.00 0.844 0.5 wt.63 0. augitic clinopyroxenes (Fig. 100.34 0.07 0.020 0.00 20.51 0. Ni)-sulfide blebs occur in the glass.038 0.002 0.000 0. low CaO (0 –6 wt.8 7 cpx 54.000 0. Silicate daughter minerals comprise irregular.004 1. Occasionally.03 17.05 17. very low K2O ( V 0.053 0.12 0.64 0.%) and usually significant Cr2O3 ( V 1.00 20.a.a. 99.54 0.162 0. 5d and e).823 0.005 3.34 101.074 0.80 1. The occurrence of sulfide blebs and former gaseous or liquid bubbles suggests that the original inclusions consisted of either a homogenous (H2O + S)-bearing silicate melt or a supercritical silicarich fluid (Schiano et al.49 1.10 19. b Calculated as Cr2 +.95 0.038 0.006 Ish610-11 4 Glassa 70. with one exception at 0.01 n.02 0.01 9.02 0.915 0. 5d and e).a.26 0.047 0.01 0. Tesalina et al.25 5 ol 41.87 0.07 1.96 0.43 4.003 1.05 1. The residual glasses are characterized by high SiO2 (63 – 76 wt.14 35. / Lithos 70 (2003) 39–59 53 sometimes.968 0.001 0. The subcalcic augites have Al2O3.00 1.958 0.057 0.038 0. round or rarely euhedral crystals of enstatitic orthopyroxene and diopsidic to subcalcic.05 0. Labels: cpx.002 0.%.000 – 4. olivine. 1995). n.051 0. Representative analyses of glass and daughter minerals in melt inclusions are reported in Table 4.%) and TiO2 ( V 0.000 0. These features are typical of quench subcalcic clinopyroxenes formed under nonequilibrium conditions in subalkaline basalts (e.%).a.73 0. opx. variable Al2O3 (9 – 19 wt.08 0.87 1.96 5.: not analyzed.a. Smith and Lindsley. High-quality analyses were often difficult to obtain owing to the small size of the inclusions and to the presence of voids.951 0.g.05 10.010 6 opx 57.001 0.00 0.136 0.94 0. Intergrowths of diopside with enstatite or subcalcic augite are common.000 – 0.000 0.

rather. the compositions of the residual glasses and the absence of daughter minerals other than pyroxenes suggest that the original melt compositions had SiO2 greater than ca.1. Dick. growth patterns expressed by Co and Ni zoning in cobaltite are cut by the chromite inclusions. melt-free inclusions (Table 4). Melekestseva et al. Highly magnesian (Fo92 – 95). are typical of cumulate mafic and ultra- . This implies that the sulfide inclusions may be secondary and that at least some of them may not be true inclusions but. 4e). Li et al.% (maximum measured value in the residual glasses). Morphological and compositional data Indications about the origin of the studied chromites are provided by morphological and compositional data.7 – 1. a syngenetic relation between the inclusions and their hosts remains questionable. (2001) reported pyrite + chalcopyrite inclusions in chromites as well as chromite inclusions in different sulfide minerals from Ishkinino. euhedral chromites. whereas the opposite relation is common. 1995). Tesalina et al. such as those commonly found in some other studied serpentinites or in association with the Ivanovka and Ishkinino sulfide ores. However. 0. sulfide inclusions in chromite are often located near the altered chromite rims or along partially healed cracks and usually have the same composition and optical orientation as the host sulfide. First. chromite inclusions in sulfides often occur as broken fragments.7 wt. are rare.3 wt.54 S.. Cr-rich (Cr2O3 = 0. In fact. they were part of clastic materials that were introduced mechanically into discontinuities of fractured sulfide ores. However.2. Bulanova. Discussion 7. Fig. Second. and chromian diopside have also been rarely found as isolated.g. we must conclude that there is no textural evidence that the formation of Ivanovka and Ishkinino chromites was contemporaneous to the deposition of the sulfides. Irregular. 4c). By contrast. clearly indicating that formation and disruption of the chromite crystals predated the deposition of the sulfides. sulfide inclusions in chromite. contamination of electron microprobe analyses by the host chromite may as well in part explain the measured Cr contents and may perhaps account for the apparent slight cation excess and Si deficiency of the analyses (Table 4). however. are typical of upper mantle peridotites that are believed to represent residues after partial melting (e. 7. rather. Other textural features. (2001) invariably exhibit their own euhedral habit (cf.% (mean composition of daughter pyroxenes) and K2O lesser than ca. therefore. As for the relations between chromite inclusions and zoning patterns in cobaltite. 1995). 7. Third. where the fraction of the reduced species Cr2 + becomes significant. and are also favored by high activities of silica in the melt and of MgCr2O4 component in the coexisting spinel (Lehman. the chromite inclusions in cobaltite described by Melekestseva et al. This observation suggests that these chromites do not belong to late mineral parageneses but. (2001) interpreted these particular textural relations as reflecting a possible formation of chromite during deposition of the sulfide ores. In some cases. Chromite – sulfide textural relations Melekestseva et al. 4c). / Lithos 70 (2003) 39–59 minerals volume ratios do not allow a quantitative estimate of the original compositions of the melts. these veins are filled by a mixture of chromite crystals and fragments of host rocks (see chloritite clasts in Fig. we note that the interruption of zoning bands at the host – inclusion interface cannot be taken as an index of contemporaneous growth. portions of late sulfides surrounding irregularly shaped chromite grains. Concentrations of euhedral chromite crystals in veins cutting earlier sulfides are problematic (Fig. 55 wt.%) olivine. According to these authors. whereas those in arsenopyrite surround the chromite inclusions. do not support a syngenetic relation between chromites and sulfides at Ivanovka and Ishkinino. 1983. unless the inclusion exhibits a negative crystal shape or the inclusion and the host show evidence of mutual growth interference (cf.G. The unusually high measured contents of chromium in olivine are possible at very high temperature or at very low oxygen fugacities. whatever their nature. Although the mere textural relations between the chromites and the sulfides are not always unequivocal. round or subround. 1977). such as those found in some of the studied serpentinites and talc-rich rocks. amoeboid chromites interstitial to olivine and pyroxene. sometimes in association with chromian enstatite.

6a. In terms of chemical composition.65 wt. Euhedral and melt inclusion-bearing chromites from the Ishkinino ores show a . back-arc volcanic rocks (cf. while relative proportions of trivalent ions remain virtually unchanged up to low-amphibolite facies conditions (below f 500 –550 jC. Chromites from chloritites after mafic protoliths are particularly enriched in Fe2 +. 7a). Kamenetsky et al. Euhedral chromites from olivine-rich melagabbroids and.7 wt. Johnson et al. the absence of any correlation between Mg# and TiO2 suggests that lowgrade alteration is at least in part responsible for the observed Fe enrichment. The presence of primary melt 1982. suggesting derivation from more fractionated melts or an evolution towards higher-Ti tholeiitic or calcalkaline types (Fig. 4a and b).G.%) and low-K2O ( < 0. Dick. These must have included both mantle melting residues and mantle or crust cumulates.% (Fig.2 wt. Section 6). Types II and III of Dick and Bullen. This observation suggests that the orehosted chromites have the same origin as those in the associated hydrothermally altered magmatic rocks and mantle melting residues. combined with the relatively high-SiO2 (>55 wt. the very high Cr# values and low TiO2 contents ( V 0.%) character of the melt inclusions (cf. The inverse correlations between TiO2 contents and Mg# and Cr# numbers shown by high-Cr# (>80) magmatic chromites from other Ivanovka talc-rich rocks are consistent with crystallization from melts that underwent variable degrees of olivine F pyroxeneF spinel fractionation (Fig. Barnes. These processes may induce an increase in Zn (Mn) contents and a decrease in Mg# values. Thus. The above relations are not significantly modified by subsolidus reequilibration and low-grade alteration.. serpentinites are enriched in TiO2 (up to 0. 1977. 7a).%) suggest that the parent melts had an arc tholeiitic or boninitic affinity.%.g.. but still within the field of typical SSZ peridotites (Fig. compare well with those of postulated boninitic primary magmas (e. 20 wt. The compositions of amoeboid chromites in Ishkinino serpentinites are well within the field of SSZ mantle peridotites (Fig. 2001. the most iron-rich among these samples resemble some of the chromites from forearc highMg andesites (e. Bamus volcano. discriminatory plots that use highly charged cations should be more robust to subsolidus reequilibration and alteration than those based on Mg and Fe contents (cf. Kamenetsky et al.S. 7b). 6a and b).%) imply high degrees of mantle melting and are typical of spinels from supra-subduction zone (SSZ) mantle peridotites and island arc or. talc-rich rocks from Ivanovka clearly indicates the heterogeneous nature of their protoliths. Cr# values in the range 70 – 80 appear in less than 2% of the samples and no sample with Cr# >80 is reported. (Al2O3)melt systematics in low-Al spinels (cf. In a compilation of 1265 analyses of spinels from MORB basalts by Barnes and Roeder (2001). In particular.%) compared to chromites in both talc-rich rocks and chloritites. Moreover. ´ . These values. Type I of Dick and Bullen.%) chromites in some talc-rich rocks indicate lower degrees of mantle melting.% and Al2O3 contents of 8 – 11 wt. 1987).. 1983). 2001). their Fig. especially. 7). / Lithos 70 (2003) 39–59 55 mafic rocks and podiform chromitites in ophiolitic sequences and are considered to reflect crystal growth ´ from a free melt (e. Tesalina et al. For these highly chromiferous spinels. Auge and Roberts.g. Auge inclusions in many of these euhedral chromites unambiguously demonstrates their magmatic origin. 1984) and Al2O3 contents higher than ca.3 wt. b and 7a). the occurrence of chromites with either euhedral or amoeboid shapes in several hydrothermally altered. chromian spinels in abyssal peridotites and MORB basalts related to the oceanic ridge system typically have Cr# < 60 (cf. 0. respectively.g. 6a and b). The compositions of amoeboid chromites from Ivanovka serpentinites and of detrital chromites in the breccia capping the main massive sulfide orebody strictly resemble those of chromites in SSZ mantle peridotites (Fig. 1984) (Fig. The estimated compositions have TiO2 contents of less than ca. More Al-rich (Al2O3 = 15 – 22 wt. Cr# values greater than 60 (or Al2O3 < 20 wt. 7). The approximate TiO2 and Al2O3 contents of the melts parent to these chromites can be estimated from (TiO2)spinel vs. The compositions of ore-hosted chromites from Ivanovka are scattered across the whole range of compositions of euhedral and amoeboid chromites in associated talc-rich and serpentinitic rocks and of detrital chromites in the hanging wall breccia (Figs. 2000). (TiO2)melt and (Al2O3)spinel vs. less commonly. 7a). Papua New Guinea. 1983). In this group. although their Cr# values and TiO2 contents remain comparable with those of the high-Cr# magmatic chromites in talc-rich rocks (Fig. Walker and Cameron.

2000) and as a primary phase in association with magmatic Fe –Ni – Cu sulfide ores.%. Groves et al. Highly chromian. calculated according to spinel –melt systematics (Kamenetsky et al. 6c. Ti)-poor spinels such as those studied here have never been found in abyssal peridotites and volcanics.6 at. most aluminiferous of these chromites approach in composition the euhedral chromites that occur in Ishkinino serpentinized harzburgites and dunites and in Ivanovka melagabbroids (Figs. analysis 7).%). but are not so poor in TiO2 (0. Dick and Bullen.. in press). Zaykov et al. 2001). 1984. indicating a stronger degree of magmatic fractionation or an evolution towards more tholeiitic or calcalkaline compositions compared with the majority of Ivanovka samples. Geodynamic setting and mode of chromite and sulfide formation Textural and compositional data on sulfide minerals as well as host-rock alteration sequences indicate that the Ivanovka and Ishkinino ore deposits formed by seafloor or subseafloor hydrothermal processes (Wipfler et al.g. 7.3.4. are characterized by low Al2O3 contents (8 – 12 wt.8).g. At Ishkinino.56 S. 2001. 6c.. Barnes. 1983). the original hydrothermal textures and parageneses have been partly modified by later remobilization.%). which do not exist in the ‘‘ferritchromits’’ studied here nor in any of the studied chromites. TiO2 and TiO2 vs. ironenriched rims. we are forced to conclude that the chromites in the Ishkinino and Ivanovka deposits represent relicts derived from the ore-hosting rocks and have no genetic relationship with the associated ores. 2001). Cumulates potentially included both silicatic rocks and chromitites. / Lithos 70 (2003) 39–59 large scatter in Mg# values (Fig. apparently isolated clinopyroxene (Table 4. be excluded. In the Cr# vs. which can primarily be ascribed to low-grade alteration.. The least chromiferous. Barnes and Roeder. which was included in a millimetric chromite rich in melt inclusions and hosted in an ore-bearing talc –chlorite –carbonate rock from Ivanovka (Iv175. Burkhard. .19 –0. Al and Fe contents suggest that this clinopyroxene is not a ‘‘quench’’ mineral. The development of the ‘‘ferritchromit’’ and magnetite rims in the studied chromites is ascribed to reactions with silicate minerals and oxidizing hydrous fluids during early oceanic alteration or during subsequent hydrothermal circulation and sulfide deposition. The absence of coexisting low-Ca pyroxene and the armor effect operated by the host chromite probably prevented this clinopyroxene from significant subsolidus reequilibration. if not exclusive.G.. Kamenetsky et al. at Ishkinino.. Estimated crystallization temperatures Pyroxene temperatures based on the graphic thermometer of Lindsley (1983) and compositions of coexisting clino.6 wt.. these values can be considered as minimum estimates for the temperatures of the melts at the time of entrapment and chromite crystallization. d and 7b). which precludes a midocean ridge origin for the studied mafic –ultramafic rocks of the MUFZ (e. The estimated compositions of the melts parent to Ishkinino chromites. 1993.3 –0.%) than those of most Ivanovka samples (Figs. yielded a temperature of 1260 jC. A single. while at Ivanovka they have been almost entirely preserved. As for the significance of the oxidized. 6d). therefore.and orthopyroxene included in chromites from Ivanovka and Ishkinino (excluding subcalcic and highly aluminous ‘‘quench’’ compositions) are in the range 930– 1170 jC at a nominal pressure of 1 GPa. The latter is characterized by distinctively high contents of Zn (>0. A magmatic origin for the ‘‘ferritchromits’’ can. Al2O3 plots. and appear to have been dominant. compositional and morphological data and the presence of high-temperature melt inclusions in many crystals indicate that the ore-associated chromites consisted of a mixed population of spinels derived from mantle melting residues and cumulates of mantle and/or crustal origin. By contrast. 2000a. Tesalina et al.48 wt. The high and little varied Fe3 +/Fe2 + ratios indicate relatively uniform values of oxygen fugacity for all Ishkinino chromites of magmatic origin. (Al. 7. d and 7b). we recall that ‘‘ferritchromit’’ is found both as an alteration product of chromites that forms during serpentinization and greenschist– amphibolitefacies metamorphism of ultramafic rocks (e. Nimis et al. the compositions of these chromites are more uniform and displaced to slightly higher TiO2 contents (0. Given the contrasting origin of and the textural relationships between the sulfides and the chromites. 1999. Because of thermal relaxation during pyroxene crystallization and potential subsolidus reequilibration between the two pyroxenes. The relatively low Na.

4c) suggests that mechanical injection of altered and disrupted mafic –ultramafic materials through the sulfide ores.. The most probable time window for sulfide ore deposition is to be found between the onset of boninitic island arc magmatism in the Southern Urals. 3. High proportions of chromite in brecciated lithologies can also in part be explained by erosion of altered mantle and lower-crust rocks exposed on an uneven seafloor. Tatarko (Bashkirgeologia..-J. The chromite-bearing protoliths included mantle melting residues and mantle or crust cumulates that formed in a supra-subduction zone. and references therein). Miass) is thanked for help in field work and her preliminary study of Cr-spinels from Ishkinino. followed by gravitative concentration during transport prior to sulfide mineralization. / Lithos 70 (2003) 39–59 57 The likely boninitic to low-Ti tholeiitic affinity of the melts parental to the studied spinels suggests formation in an early arc or forearc setting (e. to their entrainment in the rim portions of the growing sulfide crystals. The occasional occurrence of chromite + monazite ‘‘heavy-mineral’’ concentrations at Ishkinino may also have a detrital origin.S.G. 1998.. also point to a boninitic to island arc tholeiitic affinity (Simonov et al. 380 – 370 Ma. Circulation of hydrothermal fluids through cracks and discontinuities of tectonic and/or sedimentary breccias could promote the deposition of disseminated to massive Fe – Cu –(Ni – Co) sulfide ores by metasomatic substitution. and to N. 8. The locally high proportion of chromites suggests that the protoliths of the sulfide host-rocks may have included chromitites. Acknowledgements The authors are indebted to P. 1992. J. and biostratigraphic data by Maslov et al. This may account for the widespread occurrence of brecciated. Zaykov et al. The presence of inclusions of relict chromite in the massive sulfides restrains the timing of sulfide deposition to after the formation of the chromite. may locally have played a significant role. be excluded. The occurrence of chromite crystals and chloritite fragments in Mg-saponite-carbonate matrix as filling of fractures in some ore samples (Fig. 2002. I. Carampin and L.g. 1995).. Tectonic activity within the arc – forearc system could favor exposure and brecciation of crust and mantle materials. the geochemistry of variously altered rocks from both Ivanovka and Ishkinino deposits. Omenetto (Padova) for his invaluable suggestions and comments.. 1993) and the age of continent – arc collision. Orleans) is thanked for help during the 2001 Urals trip. 2000a).. 400 Ma based on the new time scale of Tucker et al. maf´ ic – ultramafic lithologies (olistostromes? tectonic melange?) and the frequent fragmented appearance of the chromite crystals in the studied ore-bearing sequences and in their surroundings. such as those occurring occasionally in serpentinites from the Ishkinino area. Orgev´ al (BRGM. Conclusions The main conclusions of the present work can be summarized as follows: 1. In spite of the strong analogies between sulfide mineralogy in the studied deposits and in counterparts on modern oceanic spreading centers (e. and work in progress). The chromites occurring in VHMS deposits of the southern MUFZ represent refractory relicts of hydrothermally altered and metasomatically replaced mafic –ultramafic rocks. possibly. The chromite-bearing VHMS deposits did not form on a mid-ocean ridge but in an early-arc or forearc setting characterized by abundant brecciated serpentinites and island arc tholeiitic to.. as well as the compositions of surrounding mafic volcanics and of melt inclusions found in some igneous pyroxenes. This process may also have led to selective concentration of high-density components such as chromite in preferential sites. R. marked by volcanic rocks in the Baimak – Buribai region (ca. Scarrow et al. in part. Ufa) for access to the ˇ Sibay lithotheque and Ivanovka drillhole. a mid-ocean ridge origin of the Ishkinino and Ivanovka deposits can. Consistently. driven by circula- tion of pressured hydrothermal media. 2002.g. therefore. sometimes polygenic. Bloomer et al. marked by highpressure subduction metamorphism of the East European continental margin (Maksyutov Complex. although a hydrothermal origin of monazite cannot be excluded. Pearce et al. The refractory nature of the chromites led to their accumulation in the residual silicaterich matrix and. Melekestseva (IMIN. Tesalina et al. Peruzzo (CNR-IGG Padova) are thanked for . boninitic igneous rocks. 2.

1 – 23. Puchkov.-P..J.J. Cr-spinel and melt inclusions from primitive rocks. Tesalina et al. 72. S. 2000. and their significance for the petrochemistry of chromium. Cosmochim. 1982. In: Petrascheck. Taylor. Kamenetsky. Early arc volcanism and the ophiolite problem: a perspective from drilling in the Western Pacific. Miass. Arculus. Omenetto. 1983. 1999. 42. Processes of forearc and accretionary complex formation during arc – continent collision in the southern Urals. Johnson.. Auge. Z. Johnson.. 132.58 S. J. Ufa Institute of Geology Publications..G. Chromite in komatiites: II. Am..). Zaykov gratefully acknowledge the support of Russian Foundations RFFI no. D. Petrol.. 105 – 107. In Russian.S.V.Yu.J. 1995. The Urals Mineralogical Collection... Nimis gratefully acknowledges the financial support of the CNR-IGG (Padova) and Italian MURST ex 60% grants.. P.B. 1989. Zaykov. Acta 57. 11. Petrol. Miner.. In Russian. Bamus volcano. Partial melting in the Josephine peridotite: I. 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