a petrologic, geochemical and sr–nd isotopic study on...

22
ORIGINAL PAPER A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism and degassing of Devonian evaporites in the Norilsk aureoles, Siberia Kwan-Nang Pang Nicholas Arndt Henrik Svensen Sverre Planke Alexander Polozov Stephane Polteau Yoshiyuki Iizuka Sun-Lin Chung Received: 19 May 2012 / Accepted: 3 November 2012 Ó Springer-Verlag Berlin Heidelberg 2012 Abstract Devonian evaporites and associated sedimen- tary rocks in the Norilsk region were contact metamor- phosed during emplacement of mafic sills that form part of the end-Permian (*252 Ma) Siberian Traps. We present mineralogical, geochemical and Sr–Nd isotopic data on sedimentary rocks unaffected by metamorphism, and meta- sedimentary rocks from selected contact aureoles at Norilsk, to examine the mechanisms responsible for magma-evaporite interaction and its relation to the end- Permian environmental crisis. The sedimentary rocks include massive anhydrite, rock salt, dolostone, calcareous siltstones and shale, and the meta-sedimentary rocks comprise calcareous hornfels, siliceous hornfels and minor meta-anhydrite and meta-sandstone. Contact metamor- phism took place at low pressure and at maximum temperatures corresponding to the phlogopite-diopside stability field. Calcareous hornfels have high CaO, MgO, CO 2 ,SO 3 , low SiO 2 and initial Sr isotopic ratios of 0.7079–0.7092, features indicative of calcareous siltstone protoliths. Siliceous hornfels, in contrast, have high SiO 2 , Al 2 O 3 , Na 2 O, low in other major element oxides and initial Sr isotopic ratios of 0.7083–0.7152, consistent with pelitic or shaley protoliths. Loss of CO 2 in a subset of calcareous hornfels can be explained by decarbonation reactions dur- ing metamorphism, but release of SO 2 from evaporites cannot be accounted for by a similar mechanism. Occur- rences of wollastonite and a variety of hydrous minerals in the calcareous hornfels are consistent with equilibration with hydrous fluid, which was capable of leaching large quantities of anhydrite in the presence of dissolved NaCl. In this way, substantial sediment-derived sulfur could have been mobilized, incorporated into the magmatic system and released to the atmosphere. The release of CO 2 and SO 2 from Siberian evaporites added to the variety of toxic gases generated during metamorphism of organic matter, coal and rock salt, contributing to the end-Permian envi- ronmental crisis. Keywords Contact aureole Metamorphism End-Permian Evaporite Norilsk Siberian Traps Introduction Extensive Paleozoic evaporites, marls, organic-rich shales and coal formations in the Tunguska Basin, East Siberia, were intruded by sills related to the plumbing system of the Communicated by T. L. Grove. Electronic supplementary material The online version of this article (doi:10.1007/s00410-012-0830-9) contains supplementary material, which is available to authorized users. K.-N. Pang N. Arndt Institut des Sciences de la Terre, Universite ´ Joseph Fourier, 1381 rue de la Piscine, 38401 Grenoble, France K.-N. Pang (&) S.-L. Chung Department of Geosciences, National Taiwan University, P.O. Box 13-318, Taipei 10699, Taiwan e-mail: [email protected] H. Svensen S. Planke S. Polteau Physics of Geological Processes (PGP), University of Oslo, PO Box 1048, Blindern, 0316 Oslo, Norway A. Polozov Institute of Geology of Ore Deposits, Petrography, Mineralogy and Geochemistry, Russian Academy of Sciences, 119017 Moscow, Russia Y. Iizuka Institute of Earth Science, Academia Sinica, 128 Academia Road Section 2, Nankang Taipei 11529, Taiwan 123 Contrib Mineral Petrol DOI 10.1007/s00410-012-0830-9

Upload: others

Post on 07-Feb-2020

4 views

Category:

Documents


0 download

TRANSCRIPT

Page 1: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

ORIGINAL PAPER

A petrologic, geochemical and Sr–Nd isotopic study on contactmetamorphism and degassing of Devonian evaporitesin the Norilsk aureoles, Siberia

Kwan-Nang Pang • Nicholas Arndt • Henrik Svensen •

Sverre Planke • Alexander Polozov • Stephane Polteau •

Yoshiyuki Iizuka • Sun-Lin Chung

Received: 19 May 2012 / Accepted: 3 November 2012

� Springer-Verlag Berlin Heidelberg 2012

Abstract Devonian evaporites and associated sedimen-

tary rocks in the Norilsk region were contact metamor-

phosed during emplacement of mafic sills that form part of

the end-Permian (*252 Ma) Siberian Traps. We present

mineralogical, geochemical and Sr–Nd isotopic data on

sedimentary rocks unaffected by metamorphism, and meta-

sedimentary rocks from selected contact aureoles at

Norilsk, to examine the mechanisms responsible for

magma-evaporite interaction and its relation to the end-

Permian environmental crisis. The sedimentary rocks

include massive anhydrite, rock salt, dolostone, calcareous

siltstones and shale, and the meta-sedimentary rocks

comprise calcareous hornfels, siliceous hornfels and minor

meta-anhydrite and meta-sandstone. Contact metamor-

phism took place at low pressure and at maximum

temperatures corresponding to the phlogopite-diopside

stability field. Calcareous hornfels have high CaO, MgO,

CO2, SO3, low SiO2 and initial Sr isotopic ratios of

0.7079–0.7092, features indicative of calcareous siltstone

protoliths. Siliceous hornfels, in contrast, have high SiO2,

Al2O3, Na2O, low in other major element oxides and initial

Sr isotopic ratios of 0.7083–0.7152, consistent with pelitic

or shaley protoliths. Loss of CO2 in a subset of calcareous

hornfels can be explained by decarbonation reactions dur-

ing metamorphism, but release of SO2 from evaporites

cannot be accounted for by a similar mechanism. Occur-

rences of wollastonite and a variety of hydrous minerals in

the calcareous hornfels are consistent with equilibration

with hydrous fluid, which was capable of leaching large

quantities of anhydrite in the presence of dissolved NaCl.

In this way, substantial sediment-derived sulfur could have

been mobilized, incorporated into the magmatic system

and released to the atmosphere. The release of CO2 and

SO2 from Siberian evaporites added to the variety of toxic

gases generated during metamorphism of organic matter,

coal and rock salt, contributing to the end-Permian envi-

ronmental crisis.

Keywords Contact aureole � Metamorphism �End-Permian � Evaporite � Norilsk � Siberian Traps

Introduction

Extensive Paleozoic evaporites, marls, organic-rich shales

and coal formations in the Tunguska Basin, East Siberia,

were intruded by sills related to the plumbing system of the

Communicated by T. L. Grove.

Electronic supplementary material The online version of thisarticle (doi:10.1007/s00410-012-0830-9) contains supplementarymaterial, which is available to authorized users.

K.-N. Pang � N. Arndt

Institut des Sciences de la Terre, Universite Joseph Fourier,

1381 rue de la Piscine, 38401 Grenoble, France

K.-N. Pang (&) � S.-L. Chung

Department of Geosciences, National Taiwan University,

P.O. Box 13-318, Taipei 10699, Taiwan

e-mail: [email protected]

H. Svensen � S. Planke � S. Polteau

Physics of Geological Processes (PGP), University of Oslo,

PO Box 1048, Blindern, 0316 Oslo, Norway

A. Polozov

Institute of Geology of Ore Deposits, Petrography,

Mineralogy and Geochemistry, Russian Academy of Sciences,

119017 Moscow, Russia

Y. Iizuka

Institute of Earth Science, Academia Sinica, 128 Academia Road

Section 2, Nankang Taipei 11529, Taiwan

123

Contrib Mineral Petrol

DOI 10.1007/s00410-012-0830-9

Page 2: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

end-Permian Siberian Traps (Naldrett et al. 1995; Kont-

orovich et al. 1997; Naldrett and Lightfoot 1999; Arndt

et al. 2003). The Siberian flood basaltic volcanism was

associated with the largest known environmental crisis in

the Earth’s history, causing up to 70 % of terrestrial and

95 % of marine species to become extinct (Sharma 1997;

Wignall 2001). Recent studies propose that the crisis was

triggered by emission of sediment-derived greenhouse and

toxic gases during emplacement of the sills (Retallack and

Jahren 2008; Svensen et al. 2004, 2009a; Ganino and Arndt

2009). Other authors, however, suggest that the extinction

might have predated the main phase of volcanism and

propose that its trigger was degassing of magmatic CO2

and HCl from altered oceanic crust (Sobolev et al. 2011).

While the arguments for these competing hypotheses are

still debatable, new data and observations in this context

are important in understanding the relations between flood

basaltic volcanism and mass extinctions.

In the Norilsk region, northern Siberia, available data

and observations point to extensive magma-evaporite

interaction, including (1) development of extensive contact

aureoles surrounding the intrusions related to the Siberian

Traps (Likhachev 1994; Turovtsev 2002; Naldrett 2004),

(2) occurrence of magmatic anhydrite in the intrusions

(Li et al. 2009a; Ripley et al. 2010), (3) high 87Sr/86Sr in

the intrusions (Arndt et al. 2003), (4) high 34S in sulfides in

Ni–Cu–(PGE) sulfide ore-bearing intrusions (Gorbachev

and Grinenko 1973; Grinenko 1985; Li et al. 2003) and (5)

high Cl contents of olivine-hosted melt inclusions in the

Gudchikhinsky picrites (Sobolev et al. 2009). However,

most previous studies have focused mainly on the intru-

sions; systematic studies of the evaporitic host rocks by

modern methods have not been carried out, except for

earlier comprehensive petrographic studies in Russian that

are not generally available (e.g., Turovtsev 2002). In par-

ticular, Turovtsev (2002) focused on metamorphism of

terrigenous and carbonate rocks but did not investigate

evaporite metamorphism in detail. Further, as noted by

Walker et al. (1994) and Naldrett (2004), good Sr isotopic

analyses of anhydrite at Norilsk are not generally available

but important to evaluate magma-evaporite interaction.

Here, we present a comparative mineralogical, geochemi-

cal and Sr–Nd isotopic study on sedimentary rocks unaf-

fected by contact metamorphism, and meta-sedimentary

rocks from selected contact aureoles from boreholes and

outcrops in the Norilsk region.

Geological background

The Tunguska Basin is situated on the Siberian craton and

contains one of the oldest known petroleum systems in the

world (Frolov et al. 2011). The Precambrian basement

consists of granitoids, granitic gneisses, schists and am-

phibolites. The sedimentary rocks are Neoproterozoic to

Permian in age with total thicknesses ranging from 3 to

12.5 km (Kontorovich et al. 1997). The Neoproterozoic

strata are dominated by carbonates with minor shale,

sandstone and evaporites, overlain by thick (up to

*2.5 km) Cambrian marine evaporite deposits composed

of salt, anhydrite and carbonates in the southern parts of the

basin. In the Norilsk region, rock salt is generally absent in

the Cambrian succession, but is present locally within

Devonian sediments. The Ordovician to Devonian sequen-

ces are also dominated by the evaporitic facies consisting of

carbonates, marls, anhydrites with minor salt layers. The

Carboniferous to Lower Permian strata comprise terrige-

nous sedimentary rocks including conglomerates, sand-

stones, siltstones and coals, collectively referred to as the

Tunguska series. Sedimentation terminated in the Upper

Permian with the onset of flood basalt volcanism of the

Siberian Traps (Surkov et al. 1991; Ulmishek 2001).

The end-Permian (*252 Ma) Siberian Traps is the

world’s largest continental large igneous province (LIP)

covering an area of at least 4.5 9 106 km2 with a total

volume of *4 9 106 km3 in the northwestern part of the

Siberian craton and widespread sub-surface extension in

the West Siberian Basin (Sharma 1997; Czamanske et al.

2002; Reichow et al. 2002; Saunders et al. 2005). The

on-craton exposure of the province encompasses a central

region of flood basalts and basaltic pyroclastic rocks sug-

gested to have erupted in less than one million years (Kamo

et al. 2003). The lava pile, typically [3 km-thick in the

northwest, thinner to the southeast and absent in the south,

comprises dominantly tholeiite basalt and minor picrite

with minor alkaline rocks of more diverse compositions

(from trachyte to meimechite). The intrusive facies of the

province crop out mainly at the margins of the volcanic

pile but are penetrated by boreholes throughout the basin.

Phreatomagmatic pipes with hydrothermal magnetite

mineralization, likely rooted in Cambrian evaporites, are

abundant in the southern part of the province (Von der

Flaass and Naumov 1995; Svensen et al. 2009a, b). Basaltic

pipes are known from the northern part of the province (see

Fig. 1) but have not been subjected to detailed studies.

Norilsk lies between the Yenisey-Khatanga trough and

the West Siberian Basin in northern Siberia (Fig. 1). It is

located near the northwestern boundary of the Siberian

Traps where both extrusive and intrusive facies crop out.

The extrusive facies consists of thick piles of basaltic lavas

that erupted onto the Tunguska Basin sedimentary rocks.

The intrusive facies occurs as sills within Devonian to

Permian strata and, to a lesser extent, within the Pre-

cambrian basement. Exposure of the intrusions is con-

trolled by deep crustal faults trending in northeasterly

directions (Zen’ko and Czamanske 1994). Some intrusions

Contrib Mineral Petrol

123

Page 3: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

(i.e., Norilsk I, Talnakh and Kharaelakh) host large Ni–Cu–

(PGE) sulfide deposits, representing one of the largest

accumulations of magmatic sulfides in the world. One

unusual feature of the ore-bearing intrusions is the devel-

opment of intense metamorphic and metasomatic aureoles,

which are in many cases as thick as, or thicker than, the

intrusions (Likhachev 1994; Naldrett 2004). Sulfur isotopic

studies of the ore sulfides indicate that ore formation

involved isotopically heavy crustal S derived from the

evaporitic country rocks (Grinenko 1985; Li et al. 2003).

The presence in the Kharaelakh intrusion of magmatic

anhydrite, a rare mineral in intra-plate magmatic rocks, has

been taken as evidence of evaporite assimilation by the

ascending magma (Li et al. 2009a; Ripley et al. 2010).

Sample descriptions

During a 2006 field campaign to the Norilsk region, dia-

mond drill-cores stored at the Talnakh mine site were

investigated. Figure 1 shows the locations of boreholes.

The on-site work included borehole logging and sampling

at representative intervals (Fig. 2). The drill-cores intersect

Silurian to Permian strata almost unaffected by contact

metamorphism (MD56), meta-sedimentary rocks in the

Mikchangda area (MD48) and those occurring in the upper

aureole of the ore-bearing Talnakh intrusion (TG21).

Table 1 shows the lithology of the samples and the geo-

logical formations that they belong to. Additional samples

were collected from outcrops and underground mine

exposure in the Norilsk region.

Drill-core MD56 contains Devonian and Silurian

evaporitic strata with thicknesses of *600 and *400 m,

respectively. The Upper Devonian Nakokhoz and Lower

Devonian Zubov Formations represent sulfate-bearing

sequences, and the Middle Devonian Manturov Formation

consists of halite-bearing sequences (Zharkov 1984).

These sequences are overlain by a *200 m-thick

sequence of Carboniferous to Permian sandstone, silt-

stone, shale and coal seams intruded by minor sills. The

evaporitic strata are largely free of sills and show no

petrographic evidence of metamorphism. Most samples

appear homogeneous at the scale of hand specimen or

polished thin section; laminations or veins in some

heterogeneous samples are separated to become a sub-

sample if possible. The rocks have variable relative

abundance between chemical sedimentary and clastic

fractions and include massive anhydrite, dolostone, rock

salt, calcareous siltstones and shale (Table 2). Anhydrite,

dolomite, calcite and halite in the rocks are fine-grained

Fig. 1 Simplified geological

map of the Norilsk region,

Siberia (after Malitch et al.

1999)

Contrib Mineral Petrol

123

Page 4: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

and granular. The clastic fraction of the rocks, if present,

is composed of fine-grained mixture of quartz and clay

minerals with or without chlorite and muscovite. Sample

MD56-36 is an organic-rich shale belonging to the

Carboniferous-Permian Tunguska series. It contains rutile

and pyrite apart from the aforementioned silicate phases.

Fig. 2 Logs of drill-cores from which the majority of samples in this

study were taken, based on our logging and available logs. Note that

drill-cores MD56 and MD48 were reduced in size by 50 % compared

to TG21. Areas bounded by the green line denote portions of the

contact aureole illustrated in Fig. 9. asl above sea level

Contrib Mineral Petrol

123

Page 5: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

Drill-core MD48 was aimed for prospecting of Ni-Cu

mineralization and intersects multiple sills and the meta-

sedimentary rocks occurring between them in the

Mikchangda area. The cumulative thickness of the sills,

which are intercalated with meta-sedimentary rocks, is

*550 m (Fig. 2). The samples are taken from an interval

corresponding to the Devonian evaporitic strata of drill-

core MD56, including the high-temperature zones between

sills (MD48-1 to MD48-6) and the lower aureole of the

sills (MD48-11 to MD48-24) (Fig. 2). Samples from the

high-temperature zones occur close to the sills and some of

them even contain parts of the sills (Fig. 3a), which are

separated to become a sub-sample if possible. The meta-

sedimentary rocks (or portions of the rocks) display

heterogranular textures typical of contact metamorphic

rocks, including the development of porphyroblasts and

mineral clusters in a fine-grained matrix. The porphyro-

blasts include clinopyroxene, amphibole, phlogopite,

chlorite and anhydrite. Titanite, pyrite, calcite, Fe–Ti

oxides, Cr-spinel and Mg–Al spinel occur as accessory

minerals. The matrix contains mainly microcrystals of

similar mineralogy as the porphyroblasts and minor fine-

grained portions whose mineralogy cannot be identified

under optical microscope. Samples from the lower aureole

in general show low degrees of recrystallization hence

higher portion of the fine-grained matrix compared to those

from the high-temperature zones. They also show fine

laminations presumably corresponding to the original

bedding prior to metamorphism. Sample MD48-11, taken

at *5.2 m from the intrusive contact, is mineralogically

similar to samples present in the high-temperature zones

mentioned above, except in addition containing small

amount of apatite. Layers of massive, fine-grained gray

anhydrite are present in the aureole at *7.9 m and 18.6 m

from the sill contact (Table 2). Sample MD48-14 further

from the contact contains K-feldspar instead of phlogopite

as the major K-bearing phase. Sample MD48-17 contains

actinolite but is clinopyroxene-free. Sample MD48-23a,

taken at *69.3 m from the intrusive contact, shows no

signs of recrystallization and resembles sample MD56-22

in terms of textures. Therefore, the total thickness of the

lower Mikchangda aureole might be less than *70 m as

defined by textures and mineralogy.

Drill-core TG21 intersects the *160 m-thick Talnakh

intrusion and its contact aureole. The samples, taken along

a *230 m-thick interval from the upper aureole, are het-

erogranular meta-sedimentary rocks. Metamorphic nod-

ules, in the scale of several millimeters, and mineral

clusters occur in a finer-grained matrix in these rocks.

Chlorite, muscovite and quartz are major matrix phases;

albite is concentrated in the rims of the metamorphic

nodules. Apatite, calcite, anhydrite, K-feldspar, monazite,

Fe–Ti oxides, phlogopite, pyrite and rutile occur as

accessory minerals. Sulfide and magnetite mineralization,

and veins of calcite and gypsum are noted in some places

along this drill-core.

Additional samples were collected from underground

exposure of the Kharaelakh intrusion in the Oktyabysky

mine and outcrops of the Chernogorsk intrusion. Sample

NOR-2a and NOR-3 are fine-grained siliceous hornfels

adjacent to massive sulfide ore in the Kharaelakh intrusion.

They have a mineral assemblage consisting of albite,

chlorite, muscovite and quartz with or without amphibole

and garnet. Samples NOR-5, NOR-6, NOR-7a to NOR-7e

are meta-sedimentary rocks that are texturally similar to

those from the high-temperature zones of drill-core MD48.

A major difference is the presence of wollastonite and

garnet in these samples indicative of a relatively high

metamorphic grade. Samples NOR-14a, NOR-14b and

NOR-16 are enclaves of meta-sandstone in the Cherno-

gorsk intrusion. They contain equigranular quartz and

feldspar with minor muscovite. Samples NOR-15 and

NOR-17 are fine-grained siliceous hornfels close to the

contact of the intrusion. The texture and mineralogy of

these rocks are similar to meta-sedimentary rocks in drill-

core TG21.

Table 1 Lithology and geological formations of samples in this study

Formation Evaporites and

carbonates

Clastic rocks Calcareous hornfels

and meta-anhydrite

Siliceous

hornfels

Carboniferous-Permian Tunguska MD56-36

Upper Devonian Kalargon (D3kl) MD56-34 MD48-1, 2, 4, 6b

Upper Devonian Nakokhoz (D3nk) MD56-31

Middle Devonian Manturov (D2mt) MD56-26

Lower Devonian Razvedochnaya (D1rz) TG21-1 to 5, 7 to 10

Lower Devonian Zubov (D1zb) MD56-19, 22, 23 MD48-16,

17, 23a, 24

MD48-11 to 14

Lower Silurian Tanymen (S1tm) MD56-9a

Contrib Mineral Petrol

123

Page 6: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

Table 2 Texture and mineralogy of samples in this study

Sample Depth (m) Rock type Texture Mineral phases1 Remarks

Drill-core MD56

MD56-9a 1,178.0 Calcareous siltstone Finely laminated Cc, Qtz, Kfs Cc vein (as MD56-9b)

MD56-19 815.0 Rock salt Coarse crystalline Hl

MD56-22 744.6 Calcareous siltstone Fine granular Qtz, Kfs, Cc, Anh, Anh-Cls vein

MD56-23 742.7 Calcareous siltstone Fine granular Qtz, Kfs

MD56-26 504.5 Massive anhydrite Fine crystalline Anh

MD56-31 382.6 Massive anhydrite Fine crystalline Anh

MD56-34 323.6 Dolostone Massive Cc2

MD56-36 231.3 Shale Finely laminated, deformed Ms, Chl, Qtz, Kfs, Rt

Drill-core MD48

MD48-1 704.6 Calcareous hornfels Heterogranular crystalline Cpx, Phl, Amp, Chl,

Anh, Cc, Opa, Ttn

MD48-2 717.7 Calcareous hornfels Heterogranular crystalline Cpx, Phl, Chl, Ep, Anh,

Ttn, Py

MD48-4 735.0 Calcareous hornfels Heterogranular crystalline Cpx, Phl, Chl, Anh, Cc, Opa

MD48-6b 742.8 Calcareous hornfels Heterogranular crystalline Cpx, Phl, Chl, Anh, Cc,

Opa, Ap, Spn

MD48-11 1,257.8 Calcareous hornfels Finely laminated Cpx, Phl, Amp, Chl, Anh,

Cc, Opa, Ap

MD48-12 1,260.0 Calcareous hornfels Fine granular, spotted Cpx, Phl, Anh, Cc

MD48-13 1,260.5 Meta-anhydrite Fine crystalline Anh

MD48-14 1,262.0 Calcareous hornfels Finely laminated Cpx, Kfs, Cc, Ttn, Ap

MD48-16 1,271.2 Meta-anhydrite Fine crystalline Anh

MD48-17 1,275.2 Calcareous hornfels Finely laminated, spotted Amp, Chl, Kfs, Ab,

Cc, Ttn, Ap

MD48-23a 1,321.9 Calcareous hornfels Fine granular Qtz, Kfs, Cc, Opa, Ap Anh-Cls vein

(as MD48-23b)

MD48-24 1,338.1 Calcareous hornfels Fine granular Ms, Chl, Qtz, Cc, Kfs

Drill-core TG21

TG21-1 981.0 Siliceous hornfels Heterogranular crystalline, spotted Qtz, Chl, Ms, Ab, Cc, Ap

TG21-2 992.6 Siliceous hornfels Heterogranular crystalline Qtz, Chl, Ms, Ab, Ap

TG21-3 1,005.6 Siliceous hornfels Heterogranular crystalline, spotted Qtz, Chl, Ms, Ab, Opa,

Mnz, Rt, Cr-Spn

TG21-4 1,010.5 Siliceous hornfels Heterogranular crystalline, spotted Qtz, Chl, Ms, Opa, Mnz,

Ap, Rt, Py, Cr-Spn

TG21-5 1,070.5 Siliceous hornfels Coarsely crystalline Qtz, Chl, Ms, Ab Cc-sulfide vein

TG21-7 1,143.6 Siliceous hornfels Heterogranular crystalline Qtz, Chl, Ms, Ab, Ap

TG21-8 1,159.1 Siliceous hornfels Coarsely crystalline Qtz, Chl, Ms, Ab, Ap

TG21-9 1,165.1 Siliceous hornfels Coarsely crystalline Qtz, Chl, Ms, Ab, Ap

TG21-10 1,197.0 Siliceous hornfels Heterogranular crystalline Qtz, Chl, Ms, Ap, Rt, Cr-Spn

Samples from mine exposures

NOR-2a – Siliceous hornfels Fine crystalline Amp, Chl, Ms, Ab, Ap, Cp

NOR-3 – Siliceous hornfels Fine crystalline Grt, Chl, Ms, Ab

NOR-5 – Calcareous hornfels Heterogranular crystalline Cpx, Grt, Anh, Cc, Cp Anh vein

NOR-6 – Calcareous hornfels Heterogranular crystalline Cpx, Grt, Wo, Anh, Cc Anh vein

NOR-7a – Massive anhydrite Fine crystalline Anh

NOR-7b – Calcareous hornfels Heterogranular crystalline Cpx, Wo, Anh, Cc, Cp

NOR-7c – Calcareous hornfels Coarse crystalline Cpx, Grt, Wo, Anh, Cc, Cp

NOR-7d – Calcareous hornfels Heterogranular crystalline Cpx, Wo, Anh, Cc, Cp

NOR-7e – Calcareous hornfels Heterogranular crystalline Cpx, Grt, Wo, Anh, Cc, Cp

Contrib Mineral Petrol

123

Page 7: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

Analytical methods

Forty-three samples (8 sedimentary rocks and 35 meta-

sedimentary rocks) were collected for this study, forming a

representative collection of available sediment and hornfels

types. Rock powders for geochemical and Sr–Nd isotopic

analyses were prepared by crushing of rock slabs on a steel

plate and pulverization in an agate mill. Polished thin

sections were prepared for petrographic observation and

electron microprobe analysis.

Electron microprobe analysis

The samples were analyzed with a JEOL JXA-8500F

electron probe microanalyzer at Institute of Earth

Sciences, Academia Sinica, Taiwan. The analyses were

performed using wavelength-dispersive method at an

accelerating voltage of 12 kV, a beam current of 3 nA, a

beam diameter of 2 lm and a peak counting time of 10 s.

Accuracy of the analyses was monitored using mineral

standards, and precision was generally better than 1 % for

most elements.

Major and trace element analyses

Major element oxides and trace element abundances were

measured using routine methods by inductively coupled

plasma-atomic emission spectrometry (ICP-AES) and

inductively coupled plasma-mass spectrometry (ICP-MS),

respectively, at the University of Grenoble, France.

Analytical procedures for the trace element analysis follow

Chauvel et al. (2010), with accuracy and precision gener-

ally better than ±5 % (relative) for most trace elements as

shown by statistics of duplicate analyses of samples and of

reference material BE-N, BHVO-2, BR-24, RGM-1 and

JSd-2 (see electronic supplementary material). Loss on

ignition (LOI) was obtained by routine methods.

Light element analyses

Measurements of total organic carbon and total inorganic

carbon were conducted by a Carbon Analyzer LECO

(CR-412) instrument at the Department of Geosciences,

University of Oslo. Sample powders weighing 350 mg

were loaded into combustible crucible boats. Aliquots of

inorganic carbon were released by addition of HCl at

40–50 �C. All crucibles with samples were washed, dried

and combusted in pure oxygen at 1,350 �C in the LECO

instrument. Analyses for H and S were performed at OEA

Laboratories Limited, Callington, UK. Sample powders

and V2O5 were loaded into tin capsules using a Mettler

ultra-microbalance. The sample capsules were dropped

sequentially into a reaction furnace packed with pure

tungsten oxide and Cu held at 1,000 �C with He as a carrier

gas. They were then flash combusted by a pulse of oxygen

at *1,700 �C. The resultant gases were purified and

separated on a packed GC column before flowing to the

detector for quantification on a CE instruments (Thermo)

EA1110 elemental analyzer. The light element data were

expressed as total organic C (TOC), CO2 (carbonates), H2O

and SO3 for the ease of comparison with other major

element data.

Sr–Nd isotopic analyses

Measurements of Sr–Nd isotopes were performed by a

ThermoFinnigan Neptune Multi-collector ICP-MS at

Department of Geosciences, National Taiwan University,

Taiwan. Analytical procedures are the same as in Lee et al.

(2012). Within-run isotopic fractionation was corrected for88Sr/86Sr = 8.375209 and 146Nd/144Nd = 0.7219. The87Sr/86Sr ratio of the Sr standard SRM987 was

0.71029 ± 1, and the 143Nd/144Nd ratio of the La Jolla

standard JNdi-1 was 0.512122 ± 7 through the course of

the measurements. The data were calculated as initial87Sr/86Sr and eNd values relative to an age of 251 Ma,

Table 2 continued

Sample Depth (m) Rock type Texture Mineral phases1 Remarks

NOR-14a – Meta-sandstone Nodular Qtz, Chl, Ab

NOR-14b – Meta-sandstone Nodular Qtz, Chl, Ab

NOR-15 – Siliceous hornfels Finely laminated Qtz, Chl, Ms, Ab, Opa

NOR-16 – Meta-sandstone Nodular Qtz, Chl, Ab

NOR-17 – Siliceous hornfels Finely laminated Qtz, Chl, Ms, Ab

1 Ab albite, Amp amphibole, Anh anhydrite, Ap apatite, Cc calcite-dolomite, Chl chlorite, Cls celestine, Cp chalcopyrite, Cpx clinopyroxene, Cr-

Spn chrome spinel, Ep epidote, Grt garnet, Hl halite, Kfs K-feldspar, Mnz monazite, Ms muscovite, Opa opaque Fe–Ti oxides, Phl phlogopite, Pypyrite, Qtz quartz, Rt rutile, Spn spinel, Ttn titanite, Wo wollastonite

Contrib Mineral Petrol

123

Page 8: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

Fig. 3 Scans of thin sections, photomicrographs and backscattered

electron images of representative samples from the Norilsk contact

aureoles, Siberia. a Contact between dolerite and calcareous hornfels

(sample MD48-1); the grain size of the hornfels is coarsened toward

the contact as a result of contact metamorphism. b Metamorphic

nodules rich in albite in a fine-grained matrix in siliceous hornfels

(sample TG21-3). c Chlorite and clinopyroxene crystals surrounded

by anhydrite porphyroblast in calcareous hornfels (sample NOR-7c,

crossed polars). d Fine crystals of muscovite and albite, and fibrous

chlorite in siliceous hornfels (sample NOR-2a, crossed polars).

e Chlorite, either fibrous or crystalline, and fine clinopyroxene grains

surrounded by coarse anhydrite and phlogopite crystals in calcareous

hornfels (sample MD48-4). f Fibrous chlorite and muscovite, and fine

quartz grains in siliceous hornfels (sample TG21-10). Ab albite, Anhanhydrite, Chl(c/f) chlorite (crystalline/fibrous), Cpx clinopyroxene,

Ms muscovite, Qtz quartz

Contrib Mineral Petrol

123

Page 9: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

decay constants of 1.42 9 10-11 year-1 for 87Rb, 6.54 9

10-12 year-1 for 147Sm, and present day chondritic values

of 143Nd/144Nd = 0.512638, 147Sm/144Nd = 0.1967,87Sr/86Sr = 0.7045 and 87Rb/86Sr = 0.0827 (Faure and

Mensing 2005).

Results

Mineral compositions

Representative analyses of minerals from the Norilsk

aureoles are listed in Table 3. The full dataset, together

with mineral chemical data presented by Turovtsev (2002),

is provided as an electronic supplement. Data for clino-

pyroxene, phlogopite and amphibole are calculated using

the programs PYROX (Yavuz 2001), MICA ? (Yavuz

2003) and WinAmphcal (Yavuz 2007), respectively. Min-

erals indicative of peak metamorphic conditions of the

Mikchangda aureole include clinopyroxene and phlogopite.

Clinopyroxene has compositions between augite and

diopside with variable degrees of Tschermak substitution

(Fig. 4a). This is reflected in the highly variable Al2O3

content of clinopyroxene ranging from less than 1 to *13

wt% (see supplementary material). Within-sample differ-

ence of several weight percent is common. The Mg# of

clinopyroxene ranges from 61 to 97 with the majority

between 78 and 85. Its TiO2 content is generally low

(\1 wt%), and Cr is mostly below detection limit. Some

analyses plot outside the pyroxene quadrilateral toward the

wollastonite apex, compared to those from the sills that are

dominated by augite (Fig. 4a). Phlogopite in the aureole

has low TiO2 (\0.5 wt%) and high Mg# (73–97, with the

majority [85). It contains H2O as the dominant volatile

species (3.5–4.5 wt%) and minor F (below detection limit

to 2 wt%) (see electronic supplementary material). Other

minerals from the aureole include chlorite (clinochlore-

chamosite solid solution), amphibole (magnesiotaramite),

albite, orthoclase (Fig. 4b), titanite and apatite (Table 3).

The major minerals from the Talnakh aureole include

muscovite, chlorite, albite and apatite (Table 3). The

muscovite has high Al2O3 (*28 to 35 wt%) and moderate

Mg# (38–80). Biotite containing up to *7 wt% F occurs as

patches associated with apatite, chlorite, rutile and pyrite in

sample TG21-4 (Table 3). Apatite contains F as the dom-

inant volatile species (4.1–5.4 wt%, see supplementary

material), in contrast with that in the Mikchangda aureole

containing substantial Cl apart from F (Fig. 4c).

Major, trace and light elements

Major, trace and light element data for sedimentary rocks

in the Norilsk region and meta-sedimentary rocks from the

Norilsk aureoles are given as an electronic supplementary

material. Sedimentary rocks from drill-core MD56 display

wide compositional variations indicative of the relative

abundance of a chemical sedimentary and a detrital,

silty fraction (Figs. 5, 6). In a SiO2–(CaO ? MgO)–

(Al2O3 ? Na2O ? K2O) ternary diagram (Fig. 5), these

rocks fall on a linear trend between massive anhydrite and

dolostone near the (MgO ? CaO) apex and the shale

sample near the SiO2–(Al2O3 ? Na2O ? K2O) line. The

only exception is sample MD56-19, an impure rock salt

containing *6.3 wt% SiO2 and *30 wt% Na2O. Its Na2O

content implies *56 % halite by weight. Positive trends of

Al2O3, TiO2, Na2O, Cr, La, Zr and H2O with SiO2 suggest

that these components are controlled primarily by the

detrital fraction in the rocks (Figs. 6a, b, d–g, 7a). The

negative trend of (CaO ? MgO) versus SiO2 is consistent

with control by anhydrite and carbonates (Fig. 6c). The

lack of systematic variation between TOC and SiO2 indi-

cates that the distribution of organic carbon is mostly

random (Fig. 7b). No correlations between CO2 or SO3 and

SiO2 suggest the relative abundance between anhydrite and

carbonates is variable in the chemical sedimentary fraction

(Fig. 7c, d). The sedimentary rocks display modest frac-

tionation between light and heavy REE (e.g., La/Yb =

5.7–27.3). In mantle-normalized trace element diagrams,

they show consistent patterns marked by negative Ba, Nb,

Ta and Ti anomalies (Fig. 8a).

Samples from drill-core MD48 consist of massive

anhydrite and calcareous hornfels. The massive anhydrite

is compositionally similar to those from the nearby drill-

core MD56, except for higher absolute abundance of most

trace elements (Fig. 8b). Calcareous hornfels have SiO2

(22.9–46.8 wt%), Al2O3 (5.0–13.9 wt%), Fe2O3 (3.0–6.1

wt%), CaO (9.4–28.8 wt%), MgO (6.6–22.8 wt%), CO2

(0.2–20.5 wt%), H2O (1.7–10.0 wt%) and SO3 (0.1–20.8

wt%) as major element oxides. The calcareous hornfels

tend to follow the major element trends shown by the

sedimentary rocks (Figs. 5, 6), except H2O extending to

much higher values (Fig. 7a). Like the sedimentary rocks,

massive anhydrite and calcareous hornfels from drill-core

MD48 also show negative Ba, Nb, Ta and Ti anomalies

(Fig. 8b). In addition, these rocks exhibit marked negative

Eu anomaly. Samples taken close to the intrusive contact

have low TOC and CO2 compared to those occurring at

distances greater than *60 m from the contact (Fig. 9a).

Drill-core TG21 consists entirely of siliceous hornfels

that have SiO2 (53.3–75.2 wt%), Al2O3 (13.8–24.9 wt%),

Fe2O3 (0.8–10.6 wt%), CaO (0.2–5.3 wt%), MgO (0.1–4.0

wt%), Na2O (0.4–10.8 wt%) and K2O (below detection

limit to 4.8 wt%) as major element oxides. The siliceous

hornfels do not follow the major element trends shown

by the sedimentary rocks (Figs. 5, 6). They display

slight fractionation between light and heavy REE (e.g.,

Contrib Mineral Petrol

123

Page 10: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

Table 3 Representative electron microprobe analyses of minerals from the Norilsk contact aureoles, Siberia

Sample Lab ID SiO2 TiO2 Al2O3 Cr2O3 FeO MnO MgO

Mikchangda aureole

Clinopyroxene

MD48-1 ES-10 50.10 1.01 3.30 0.30 10.57 0.14 14.16

MD48-2 Cs-2 46.44 0.00 10.25 0.00 5.89 0.00 12.26

MD48-4 C48 44.84 1.18 13.14 0.03 2.12 0.00 13.32

MD48-6 E97 48.84 0.41 6.36 0.13 4.30 0.16 14.74

MD48-11 Bs-7 46.50 1.18 7.91 0.11 5.64 0.26 13.03

Phlogopite

MD48-1 C-20 38.10 0.21 20.84 bdl3 4.66 0.00 21.94

MD48-2 A16 36.52 0.08 21.02 bdl 6.56 0.00 23.26

MD48-4 A11 40.08 0.15 17.68 bdl 2.25 0.00 25.44

MD48-6 E91 39.32 0.17 16.26 bdl 2.56 0.03 25.57

MD48-11 C28 38.59 0.00 18.52 bdl 5.16 0.00 23.38

Chlorite

MD48-2 B46 28.83 0.17 20.25 bdl 16.89 0.00 21.93

MD48-4 C58 32.02 bdl 19.60 bdl 1.88 0.13 32.71

MD48-11 C35 40.96 0.02 10.41 bdl 4.78 0.08 29.60

MD48-17 F68 31.66 0.09 19.55 bdl 10.09 0.14 25.57

Amphibole

MD48-1 D-37 37.80 0.59 21.76 bdl 6.41 0.00 14.68

MD48-11 C24 40.66 0.69 15.74 bdl 8.28 0.00 16.12

MD48-11 D42 41.61 0.11 15.78 bdl 7.58 0.25 16.49

MD48-17 A5 54.18 0.09 6.14 bdl 5.21 0.02 18.48

Feldspar

MD48-14 A2-31 65.40 bdl 17.60 bdl 0.13 bdl bdl

MD48-17 F73 65.06 bdl 18.17 bdl 0.30 bdl bdl

MD48-17 D42 68.88 bdl 19.88 bdl 0.02 bdl bdl

MD48-23 C6 65.41 bdl 18.21 bdl 0.01 bdl bdl

Titanite

MD48-1 A-5 31.49 32.02 3.95 bdl 2.36 bdl 0.16

MD48-2 A11 31.33 33.41 2.68 bdl 1.12 0.01 0.14

MD48-14 A2-4 31.22 36.44 1.64 bdl 1.33 0.21 bdl

Apatite

MD48-11 C40 0.86 bdl bdl bdl 0.43 0.05 0.16

MD48-14 A2-22 0.41 bdl bdl bdl 0.32 0.00 0.08

MD48-17 C27 0.24 bdl bdl bdl 0.49 0.21 0.35

Talnakh aureole

Muscovite

TG21-3 A2-13 44.42 0.49 29.51 bdl 7.31 0.04 3.79

TG21-4 B-19 49.34 0.34 32.63 bdl 3.59 bdl 1.07

TG21-10 RR-24 46.84 bdl 32.57 bdl 4.41 0.04 1.78

TG21-10 Map1-59 46.03 0.06 32.51 bdl 4.15 0.15 1.91

Phlogopite

TG21-4 A-83 43.41 0.57 14.25 bdl 7.96 bdl 16.86

TG21-4 A-85 44.35 0.44 16.59 bdl 7.15 0.00 14.22

Chlorite

TG21-3 A2-15 28.60 0.18 24.25 bdl 25.72 0.13 8.32

TG21-3 Mat-54 24.87 0.19 23.58 bdl 29.23 0.38 10.24

TG21-4 A-90 25.56 0.72 18.00 bdl 41.55 0.03 3.04

Contrib Mineral Petrol

123

Page 11: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

Table 3 continued

Sample Lab ID SiO2 TiO2 Al2O3 Cr2O3 FeO MnO MgO

TG21-4 B-14 39.67 0.28 19.18 bdl 22.23 bdl 5.56

TG21-10 R-17 24.88 bdl 22.89 bdl 35.30 0.04 5.35

Feldspar

TG21-3 Mat-60 68.28 bdl 20.00 bdl 0.22 bdl bdl

TG21-3 Mat-63 67.95 bdl 20.39 bdl 0.00 bdl bdl

Apatite

TG21-4 A-5 0.20 bdl bdl bdl 0.78 0.06 0.02

TG21-4 A-87 0.35 bdl bdl bdl 0.72 bdl 0.03

Sample Lab ID CaO Na2O K2O P2O5 F Cl H2O1 Total Mg#2

Mikchangda aureole

Clinopyroxene

MD48-1 ES-10 20.47 0.31 0.02 – – – – 100.38 70.5

MD48-2 Cs-2 25.87 0.05 0.01 – – – – 100.77 78.8

MD48-4 C48 24.98 0.76 0.12 – – – – 100.49 91.8

MD48-6 E97 25.37 0.04 0.13 – – – – 100.48 86.0

MD48-11 Bs-7 24.91 0.15 0.06 – – – – 99.73 80.5

Phlogopite

MD48-1 C-20 0.00 0.25 9.60 – 0.23 0.03 4.15 100.01 89.3

MD48-2 A16 0.20 0.44 7.49 – 0.00 0.02 4.24 99.83 86.3

MD48-4 A11 0.02 0.82 9.24 – 1.20 0.02 3.79 100.69 95.3

MD48-6 E91 0.00 0.36 10.38 – 1.13 0.05 3.72 99.54 94.7

MD48-11 C28 0.08 0.97 9.56 – 0.08 0.07 4.20 100.60 89.0

Chlorite

MD48-2 B46 0.16 0.00 0.13 – 0.05 0.00 12.03 100.43 69.8

MD48-4 C58 0.82 0.08 bdl – 0.05 0.37 12.76 100.41 96.9

MD48-11 C35 1.32 0.01 0.12 – 0.12 0.23 12.76 100.41 91.7

MD48-17 F68 0.24 0.04 0.07 – 0.06 0.01 12.39 99.91 81.9

Amphibole

MD48-1 D-37 13.68 2.38 1.37 – 0.42 0.05 1.88 101.02 80.3

MD48-11 C24 12.67 2.77 1.05 – 0.26 0.18 1.90 100.31 77.6

MD48-11 D42 13.04 2.88 0.64 – 0.00 0.14 2.05 100.56 79.5

MD48-17 A5 11.90 0.47 1.44 – 0.11 0.04 2.09 100.18 86.3

Feldspar

MD48-14 A2-31 0.76 0.09 16.75 – – – – 100.73 –

MD48-17 F73 0.16 0.13 16.33 – – – – 100.15 –

MD48-17 D42 0.32 10.92 0.10 – – – – 100.12 –

MD48-23 C6 0.06 0.17 16.32 – – – – 100.18 –

Titanite

MD48-1 A-5 28.34 0.06 bdl – 0.23 0.02 1.02 99.66 –

MD48-2 A11 28.27 0.06 0.03 – 0.00 0.04 1.11 98.19 –

MD48-14 A2-4 27.80 bdl 0.24 – bdl bdl 1.13 100.00 –

Apatite

MD48-11 C40 53.50 0.10 0.00 39.60 0.89 3.66 0.42 99.66 –

MD48-14 A2-22 54.14 0.12 0.15 41.31 2.33 2.51 0.09 101.45 –

MD48-17 C27 54.72 0.00 0.07 42.08 3.15 0.15 0.32 101.78 –

Talnakh aureole

Muscovite

TG21-3 A2-13 0.00 0.26 10.22 – 0.22 0.28 4.21 100.75 48.0

Contrib Mineral Petrol

123

Page 12: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

Table 3 continued

Sample Lab ID CaO Na2O K2O P2O5 F Cl H2O1 Total Mg#2

TG21-4 B-19 0.37 0.07 8.58 – bdl 0.02 4.55 100.56 34.7

TG21-10 RR-24 0.04 0.23 9.51 – 0.18 0.15 4.35 100.11 41.9

TG21-10 Map1-59 0.08 0.42 9.70 – bdl 0.23 4.38 99.60 45.1

Phlogopite

TG21-4 A-83 0.51 0.22 9.72 – 7.31 0.29 0.91 102.02 79.0

TG21-4 A-85 0.70 0.20 9.85 – 4.65 0.26 2.11 98.76 78.0

Chlorite

TG21-3 A2-15 0.14 0.14 1.39 – bdl 0.03 11.60 100.50 36.6

TG21-3 Mat-54 0.05 0.02 0.01 – 0.02 bdl 11.27 99.87 38.4

TG21-4 A-90 0.33 0.00 0.19 – 0.00 0.00 10.60 100.03 11.5

TG21-4 B-14 0.25 0.08 0.67 – 0.04 0.10 12.06 100.12 30.8

TG21-10 R-17 0.09 bdl 0.19 – bdl 0.05 10.94 99.73 21.3

Feldspar

TG21-3 Mat-60 0.54 10.99 0.07 – – – – 100.10 –

TG21-3 Mat-63 0.82 10.68 0.10 – – – – 99.94 –

Apatite

TG21-4 A-5 54.98 0.12 0.07 41.03 5.37 0.13 – 102.76 –

TG21-4 A-87 53.61 0.29 0.09 41.38 5.12 0.12 – 101.69 –

1 H2O calculated on the basis of ideal mineral formulae2 Mg# = molar 100 9 Mg/(Mg ? Fe2?)3 bdl = below detection limit

AnAb

Or

Cpx from sills

Plagioclasefrom sills

Fs

Wo

En

a

b

Sanidine

Anorthoclase

AlbiteOligoclase

Andesine Labradorite Bytownite Anorthite

Diopside

Augite

Pigeonite

Hedenbergite

HedenbergiteEnstatite

OHCl

Fc

Apatite fromlayered intrusions

Drill-core MD56 (sedimentary rocks)Drill-core MD48 (calcareous hornfelsand meta-evaporites)Drill-core TG21 (siliceous hornfels)

Fig. 4 Compositions of

a clinopyroxene, b feldspars and

c apatite in Paleozoic

sedimentary rocks and in meta-

sedimentary rocks from the

Norilsk contact aureoles,

Siberia. Gray fields in a and

b denote our unpublished data

from the sills, whereas in

c denotes compositions of

igneous apatite in major layered

intrusions (after Boudreau et al.

1995)

Contrib Mineral Petrol

123

Page 13: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

La/Yb = 3.6–8.1). In mantle-normalized trace element

diagrams, most siliceous hornfels show negative Ba, Nb,

Pb, Sr anomalies (Fig. 8c). Also, a subset of samples is

much richer in large ion lithophile elements (LILE) than

the others. Concentrations of TOC, CO2 and SO3 are low at

intervals *200 m from the intrusive contact (Fig. 9b).

Sample TG21-1 collected at *230 m from the contact has

*1 wt% TOC.

Samples from mine exposure comprise massive anhy-

drite, calcareous hornfels, siliceous hornfels and meta-

sandstone. The former three rock types are geochemically

similar to their counterparts in drill-cores MD48 and TG21

(Figs. 5, 6, 7, 8d, e). Meta-sandstones have SiO2

(86.1–89.0 wt%), Al2O3 (6.8–7.6 wt%) and Na2O (3.2–3.6

wt%) as the only major element oxides. Their trace element

patterns are marked by negative Ba and Ti anomalies and

positive Pb, Zr and Hf anomalies (Fig. 8f).

Sr–Nd isotopes

Sr–Nd isotopic data for sedimentary rocks in the Norilsk

region and meta-sedimentary rocks from the Norilsk

aureoles are listed in Table 4. All samples are character-

ized by high initial Sr isotopic ratios ranging from 0.7079

to 0.7154 (Table 4). The lowest value of 0.7079 for mas-

sive anhydrite from drill-core MD56 is similar to that of

Devonian seawater (Veizer et al. 1999). The calcareous

hornfels have a relatively restricted range of (87Sr/86Sr)i

(0.7079–0.7092), whereas siliceous hornfels have a slightly

higher and wider range of (87Sr/86Sr)i (0.7083–0.7152). In

the Mikchangda aureole, (87Sr/86Sr)i tends to increase with

increasing distance away from the intrusive contact

(Fig. 9a). The meta-sandstone (sample NOR-14a) has

(87Sr/86Sr)i of 0.7088. The Nd isotopic compositions of the

samples are highly variable, with eNd(t) from -8.0 to ?4.3

for sedimentary rocks, -1.1 to ?9.6 for calcareous

hornfels and -4.8 to ?10.2 for siliceous hornfels

(Table 4). The meta-sandstone has eNd(t) of -6.4.

On the (87Sr/86Sr)i–eNd(t) diagram, the samples have

high initial Sr isotopic ratios compared to flood basalts and

the related intrusive rocks of the Siberian Traps (Fig. 10a).

The isotopic variations of the intrusive rocks can be

explained in terms of two end-members: shale (sample

MD56-36) and impure evaporites (see Arndt et al. 2003).

Some samples have exceptionally high eNd(t) (?8.8 to

?10.2), even higher than the highest value of ?7 reported

for the flood basalts (Sharma 1997). However, there is no

evidence that these samples formed from mafic and isoto-

pically depleted protoliths. We thus speculate that the high

eNd(t) values are due to disturbance of the Sm–Nd isotopic

system during contact metamorphism (see Polat et al.

2008). On a (87Sr/86Sr)i–Sr diagram, the data of the intru-

sive rocks fall roughly on trends toward contamination by

either shale or impure evaporites, but not toward that by

pure anhydrite (Fig. 10b).

Discussion

Protoliths and metamorphic conditions

Four types of meta-sedimentary rocks are recognized in

this study, that is, calcareous hornfels, siliceous hornfels,

meta-anhydrite and meta-sandstones. The fact that they

have different mineralogical, geochemical and Sr–Nd iso-

topic compositions, as illustrated above, is best understood

in terms of different protoliths. The relatively low SiO2,

Al2O3, Na2O and high CaO, MgO, CO2 and SO3 in cal-

careous hornfels are indicative of impure evaporite proto-

liths, such as the calcareous siltstone in drill-core MD56.

This interpretation is supported by the fact that these rocks

are intermediate between massive anhydrite (or dolostone)

Sills

Al O +2 3

SiO2

MgO +OK+OaNCaO 2 2

Drill-core MD56 (sedimentary rocks)Drill-core MD48 (calcareous hornfelsand meta-evaporites)

Samples from mine exposure(calcareous and siliceous hornfels,and meta-sandstone)

Drill-core TG21 (siliceous hornfels)

Fig. 5 A ternary diagram

SiO2–(CaO ? MgO)–

(Al2O3 ? Na2O ? K2O) of

bulk-rock compositions for

Paleozoic sedimentary rocks

and meta-sedimentary rocks

from the Norilsk contact

aureoles, Siberia. Gray fielddenotes our unpublished data

from the sills

Contrib Mineral Petrol

123

Page 14: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

and shale for most major elements (Figs. 7, 8) and Sr

isotopic ratios (Fig. 10). In contrast, siliceous hornfels have

high SiO2, Al2O3, Na2O and low CaO, MgO, CO2 and SO3

(Figs. 7, 8), features consistent with pelitic or shaley pro-

toliths. The different protoliths suggested for calcareous

and siliceous hornfels are also consistent with their dif-

ferent mineral compositions. Meta-anhydrite has very

similar composition as and thus likely formed from mas-

sive anhydrite protoliths. The very high SiO2, Al2O3 and

Na2O in meta-sandstones are indicative of quartzo-feld-

spathic protoliths.

The lithostatic pressure during contact metamorphism in

the Norilsk aureoles can be deduced from depths at which

the intrusions emplaced. The trace element and isotopic

compositions of the ore-bearing sills can be matched with

those of distinctive units in the volcanic sequence (Arndt

et al. 2003), and the vertical distance between the intrusive

and volcanic units is *1.5 km. Assuming the overburden

has an average density similar to the continental crust

(2.7 g cm-3), the pressure at which the intrusions were

emplaced was likely to be *0.4 kbar or less.

The peak temperature of metamorphism can be esti-

mated by mineral assemblages of rocks in the aureoles. The

peak metamorphic assemblage consists of phlogopite and

clinopyroxene indicated by the samples in the high-tem-

perature zones in the Mikchangda intrusion (Fig. 2). In the

Talnakh intrusion, the peak assemblage might have been

obscured by retrograde metamorphism resulting in an

30

Al

O(w

t.%)

23

20

10

0

b

a

0.8

0.4

40

Mg

O+

Ca

O(w

t.%

)

1.2T

iO(w

t.%

)2

0

60

20

0

ed

Cr

(pp

m)

102

Na

O(w

t.%

)2

0

100

50

10

40

150

200

250

101

100

10-1

10-2

gf

SiO (wt.%)2 SiO (wt.%)2

Zr

(pp

m)

50

La

(pp

m)

400 60

600

0 20 6020 80

30

20

0

400

040 80

200

c

Drill-core MD56 (sedimentary rocks)Drill-core MD48 (calcareous hornfelsand meta-evaporites)

Samples from mine exposure(calcareous and siliceous hornfels)

Drill-core TG21 (siliceous hornfels)

Fig. 6 Binary plots of bulk-

rock concentrations of selected

major and trace elements versus

SiO2 for Paleozoic sedimentary

rocks and meta-sedimentary

rocks from the Norilsk contact

aureoles, Siberia. a Al2O3.

b TiO2. c MgO ? CaO.

d Na2O. e Cr. f La. g Zr. Data

for meta-sandstone are not

plotted

Contrib Mineral Petrol

123

Page 15: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

assemblage of quartz, chlorite, muscovite and alkali feld-

spars (Turovtsev 2002; this study). Aarnes et al. (2010)

modeled the mineral assemblages of an average pelite with

increasing grade of metamorphism. Their results indicate

that phlogopite is stable at temperatures \750 �C and

muscovite at temperatures \500 �C. As pointed out by

these authors and Aarnes et al. (2011), the maximum

temperature that can be attained in contact aureoles is a

function of (1) the size of the intrusion, (2) the temperature

of magma, (3) the distance away from the intrusive contact,

(4) the geothermal gradient and (5) the lithology of host

rocks. In general, the temperature of wallrocks adjacent to

the intrusive contact is roughly half of the liquidus tem-

perature of the magma and decreases exponentially with

increasing distance from the contact. Assuming a liquidus

of *1,200 �C for the sills, their contact aureoles probably

attained maximum temperatures of \600 �C (Carlsaw and

Jaeger 1959). This is generally in line with the absence of

very high-grade metamorphic assemblages in the Norilsk

aureoles.

Mechanisms of magma-evaporite interaction

The evaporite country rocks at Norilsk might interact with

the intruding magmas in various ways: (1) wholesale or

partial melting, (2) elemental transfer via hydrous fluid

(Li et al. 2003, 2009b; Ripley et al. 2003) and (3) meta-

morphic devolatilization (Ganino and Arndt 2009). In this

section, these mechanisms are examined in light of our

new data.

Melting of evaporites theoretically produces sulfate-rich

melts that are readily incorporated into the magmatic sys-

tem, in a way similar to crustal contamination of mantle-

derived magmas. The melting point of anhydrite is

*1,450 �C (http://www.mindat.org/min-234.html), which

led Li et al. (2003) and Ripley et al. (2003) to suggest that

evaporite melting probably did not take place at Norilsk

due to the lack of potential agents that may lower its

melting point. Experiments indicate that partial melting of

anhydrite-dolomite mixtures occurs at *900 to 1,000 �C

(van der Sluis 2010) and probably at lower temperatures in

the presence of impurities such as silt horizons or frag-

ments. Our findings confirm the presence of carbonates and

siliceous impurities in Devonian evaporites at Norilsk.

Assuming the basaltic magma intruding the evaporites has

a liquidus of *1,200 �C, their assimilation through partial

melting may not be completed precluded. However, this

should occur locally along the contacts against the country

rocks, and its role in causing extensive magma-evaporite

interaction is uncertain.

ba

)%.t

w(C

OT

)%.t

w(O

H2

0 0

30

2

4

6

1

2

3

4

5

40

60dc

2SiO (wt.%) SiO (wt.%)2

)%.t

w(O

S3

40

)%.t

w(O

C2

40 060 0 20 600802

20

10

0 040 80

20

Fig. 7 Binary plots of bulk-rock concentrations of light elements versus SiO2 for Paleozoic sedimentary rocks and meta-sedimentary rocks from

the Norilsk contact aureoles, Siberia. a H2O. b TOC. c CO2. d SO3. Data for meta-sandstone are not plotted. Legend is the same as in Fig. 6

Contrib Mineral Petrol

123

Page 16: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

Transfer of elements from evaporites to magma via

circulating hydrothermal fluid merits consideration in

shallow magmatic systems like Norilsk. In this study,

several observations from the aureoles are consistent

with the presence of hydrous fluid during contact meta-

morphism: (1) the abundance of hydrothermal veins of

carbonates and/or sulfates in drill-cores of aureole rocks in

this study, (2) the occurrence of wollastonite in calcareous

hornfels (Li et al. 2009b; this study) indicating equilibra-

tion with hydrous fluid (Greenwood 1967; Ferry et al.

2001), (3) the abundance of hydrous phases in the aureoles,

including chlorite, hydrogrossular, muscovite, pectolite,

phengite, phlogopite, thomsonite and xonotlite (Li et al.

2009b; this study). Dehydration of chlorite, muscovite and

clay minerals in sedimentary rocks during contact meta-

morphism likely result in a hydrous fluid, percolating and

reacting with evaporites in the aureoles. Experiments by

Newton and Manning (2005) demonstrated that the solu-

bility of anhydrite increases enormously with NaCl activity

in hydrothermal solutions at *600 to 800 �C. In view of

this, the presence of salt horizons in the Tunguska sedi-

mentary sequence is noteworthy (Matukhin 1978; Zharkov

1984; Svensen et al. 2009a). There are two observations

consistent with participation of the salt horizons during

metamorphism: (1) most siliceous hornfels in this study

contain high Na2O (0.42–10.8 wt%; with the majority

[3 wt%), a feature that, according to van de Kamp and

Leake (1996), is best explained by addition of Na from

salts or brines, and (2) high Cl in apatite from the aureole

(Fig. 4c) and in melt inclusions in some Siberian magmatic

rocks (Sobolev et al. 2009) points to formation of a Cl-rich

fluid and addition of Cl derived from the salt horizons,

respectively. Based on the above arguments, we suggest

that elemental transfer via a hydrous fluid, together with

the presence of dissolved salts, likely contributed to

extensive magma-evaporite interaction at Norilsk.

Devolatilization of calcareous sedimentary rocks during

metamorphism directly generates fluids of CO2 (i.e.,

decarbonation) and SO2 (i.e., desulfatation), which in the-

ory are able to enter the magmatic system. For example,

the release of CO2 by decarbonation reactions during

progressive metamorphism of siliceous dolomites is well

known (Bowen 1940). Degassing of SO2 from anhydrite in

an analogous manner was proposed by Gorman et al.

(1984). Figure 11 is a plot of (CO2 ? SO3) versus CaO of

samples in this study illustrating devolatilization. Pure

Calcareous siltstone

Rock salt

Shale

Dolostone

d Mine exposure(calcareous hornfels)

c TG21

103

10-1

102

100

eltn

am

evit imir

P/el

pm

aS

100

a MD56

101

10-1

CsRb Er

f Mine exposure(meta-sandstone)

e Mine exposure(siliceous hornfels)

b MD48eltn

am

evitimir

P/el

pm

aS

CsRb

Ba U Ta Ce Sr Zr Sm Ti Tb Y LuTh Nb La Pb Nd Hf Eu Gd Dy

Ba U Ta Ce Sr Zr Sm Ti Tb Y LuTh Nb La Pb Nd Hf Eu Gd Dy Er

101

102

102

100

101

10-1

eltn

am

evitimi r

P/el

pm

aS

Fig. 8 Primitive mantle-

normalized trace element

diagram for Paleozoic

sedimentary rocks and meta-

sedimentary rocks from the

Norilsk contact aureoles,

Siberia. a Samples in drill-core

MD56. b Samples in drill-core

MD48. c Samples in drill-

core TG21. d Calcareous

hornfels from mine exposure.

e Siliceous hornfels from mine

exposure. f Meta-sandstone

from mine exposure.

Normalizing values are after

McDonough and Sun (1995)

Contrib Mineral Petrol

123

Page 17: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

Ta

ble

4R

b-S

ran

dS

m–

Nd

iso

top

icd

ata

for

un

met

amo

rph

ose

dse

dim

enta

ryro

cks

and

met

a-se

dim

enta

ryro

cks

fro

mth

eN

ori

lsk

con

tact

aure

ole

s,S

iber

ia

Sam

ple

Rb

(pp

m)

Sr

(pp

m)

87R

b/8

6S

r87S

r/86S

r2r

(87S

r/86S

r)i1

Sm

(pp

m)

Nd

(pp

m)

147S

m/1

44N

d143N

d/1

44N

d2r

(143N

d/1

44N

d) i

eNd

(t)

Dri

ll-c

ore

MD

56

MD

56

-9a

11

41

64

0.2

40

0.7

18

17

30

.000

01

70

.711

04

.12

18

.30

.136

0.5

12

75

70

.000

00

40

.512

54

.3

MD

56

-9b

16

.85

63

0.0

86

0.7

08

89

40

.000

01

00

.708

68

.50

28

.70

.179

0.5

12

68

40

.000

00

50

.512

41

.5

MD

56

-19

19

.03

89

0.1

41

0.7

09

35

60

.000

00

50

.708

91

.03

4.0

20

.155

0.5

12

50

30

.000

00

90

.512

2-

1.3

MD

56

-22

94

.14

54

0.6

00

0.7

11

17

40

.000

01

20

.709

02

.65

13

.00

.123

0.5

12

52

40

.000

00

60

.512

30

.1

MD

56

-23

56

.02

69

60

.00

70

.70

89

58

0.0

00

00

50

.708

71

.86

8.6

50

.130

0.5

12

48

90

.000

00

30

.512

3-

0.8

MD

56

-23

(du

p)

56

.02

,696

0.0

07

0.7

08

93

70

.000

00

30

.708

71

.86

8.6

50

.130

0.5

12

48

90

.000

00

80

.512

3-0

.8

MD

56

-26

20

.30

1,4

49

0.0

00

0.7

07

86

60

.000

00

60

.707

9–

––

––

––

MD

56

-31

0.1

01

82

90

.00

00

.70

78

72

0.0

00

00

70

.707

9–

––

––

––

MD

56

-34

3.4

01

08

0.0

11

0.7

08

70

70

.000

00

80

.708

40

.26

1.3

90

.113

0.5

12

16

30

.000

00

60

.512

0-

6.6

MD

56

-36

12

09

1.0

0.4

55

0.7

28

97

20

.000

00

70

.715

43

.27

22

.10

.089

0.5

12

05

10

.000

00

10

.511

9-

8.0

Dri

ll-c

ore

MD

48

MD

48

-14

0.6

47

80

.02

90

.70

87

34

0.0

00

00

70

.707

97

.01

27

.50

.154

0.5

12

53

00

.000

00

70

.512

3-

0.8

MD

48

-20

.90

39

60

.00

10

.70

81

14

0.0

00

00

50

.708

15

.79

26

.60

.132

0.5

12

47

50

.000

00

40

.512

3-

1.1

MD

48

-43

1.0

22

60

.04

70

.70

93

09

0.0

00

00

80

.707

94

.63

24

.00

.117

0.5

12

52

10

.000

00

20

.512

30

.3

MD

48

-12

34

.36

90

0.0

17

0.7

08

95

50

.000

00

60

.708

42

.38

9.5

30

.151

0.5

13

01

50

.000

00

50

.512

88

.8

MD

48

-13

6.4

02

49

80

.00

10

.70

85

85

0.0

00

00

80

.708

6–

––

––

––

MD

48

-17

72

.57

64

0.0

33

0.7

09

74

30

.000

00

70

.708

83

.01

12

.20

.149

0.5

12

71

60

.000

00

30

.512

53

.0

MD

48

-23

a7

5.9

24

00

.10

90

.71

23

53

0.0

00

01

00

.709

13

.40

16

.10

.128

0.5

13

01

90

.000

00

90

.512

89

.6

MD

48

-23

b0

.90

27

96

0.0

01

0.7

08

65

50

.000

00

50

.708

7–

––

––

––

MD

48

-24

48

.61

97

0.7

14

0.7

11

77

50

.000

00

60

.709

22

.33

9.4

60

.149

0.5

12

65

70

.000

00

30

.512

41

.9

Dri

ll-c

ore

TG

21

TG

21-1

0.3

06

1.0

0.0

02

0.7

09

78

60

.000

00

60

.709

76

.26

25

.80

.147

0.5

12

48

10

.000

00

20

.512

2-

1.5

TG

21-2

56

.52

46

0.6

65

0.7

11

94

70

.000

00

90

.709

62

.69

12

.50

.130

0.5

12

51

30

.000

00

20

.512

3-

0.3

TG

21-3

93

.91

30

0.2

49

0.7

16

20

30

.000

00

80

.708

77

.37

35

.00

.127

0.5

13

04

40

.000

00

60

.512

81

0.2

TG

21-4

94

.16

2.0

0.5

24

0.7

30

86

80

.000

00

40

.715

23

.73

17

.90

.126

0.5

12

57

40

.000

00

30

.512

41

.0

TG

21-7

56

.53

49

0.4

69

0.7

10

96

40

.000

01

00

.709

31

2.0

43

.20

.168

0.5

12

63

30

.000

00

30

.512

40

.8

TG

21-8

1.7

01

06

0.0

06

0.7

09

88

40

.000

00

80

.709

72

.50

11

.70

.129

0.5

12

48

40

.000

00

20

.512

3-

0.8

TG

21-1

01

27

89

.00

.49

30

.72

62

32

0.0

00

00

30

.711

55

.62

35

.20

.097

0.5

12

54

60

.000

00

20

.512

41

.4

Sam

ple

sfr

om

min

eex

po

sure

NO

R-3

88

.52

80

0.9

15

0.7

14

38

30

.000

00

90

.711

14

.69

22

.10

0.1

28

0.5

12

60

60

.000

00

10

.512

41

.6

NO

R-5

5.2

03

33

0.0

45

0.7

08

41

60

.000

01

00

.708

32

.50

9.9

90

.151

0.5

12

52

40

.000

00

40

.512

3-

0.8

NO

R-7

b1

.00

27

30

.01

10

.70

86

30

0.0

00

00

20

.708

63

.52

15

.10

0.1

41

0.5

12

51

70

.000

00

20

.512

3-

0.6

NO

R-1

4a

2.7

05

6.0

0.0

17

0.7

09

28

90

.000

00

90

.708

80

.67

2.5

80

.157

0.5

12

24

60

.000

00

80

.512

0-

6.4

NO

R-1

51

71

23

92

.07

20

.71

56

47

0.0

00

00

40

.708

35

.71

34

.60

0.1

00

0.5

12

31

20

.000

00

50

.512

1-

3.2

NO

R-1

74

1.4

50

20

.02

80

.70

94

84

0.0

00

00

90

.708

64

.69

22

.30

.127

0.5

12

27

90

.000

00

20

.512

1-

4.8

1(8

7S

r/86S

r)i

and

eNd

(t)

val

ues

wer

eca

lcula

ted

bas

edon

anag

eof

251

Ma,

k(87R

b)

=1

.42

91

0-

11

yea

r-1,

k(1

47S

m)

=6

.54

91

0-

12

yea

r-1,

and

pre

sen

td

aych

on

dri

tic

val

ues

of

143N

d/1

44N

d=

0.5

12

63

8,

147S

m/1

44N

d=

0.1

96

7,

87S

r/86S

r=

0.7

04

5an

d87R

b/8

6S

r=

0.0

82

7(F

aure

and

Men

sin

g2

00

5)

2S

amp

les

MD

56-2

6,

MD

56-3

1an

dM

D4

8-1

3w

ere

no

tan

aly

zed

for

Nd

iso

top

esd

ue

tolo

wN

dco

nte

nts

Contrib Mineral Petrol

123

Page 18: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

evaporites composed of anhydrite, dolomite and calcite plot

in the shaded area and shale plot near the origin. Calcareous

siltstones (i.e., impure evaporites) and any metamorphic

rocks that do not undergo extensive devolatilization should

plot in arrays between the origin and the shaded area. Here,

two assumptions are relevant: (1) Ca in the protoliths is

present exclusively in anhydrite and carbonates and (2) Ca is

neither added nor removed to the aureole rocks during

metamorphism. Rocks that plot below these arrays indicate

significant devolatilization due to preferential loss of CO2

and/or SO3 relative to CaO. Figure 11 shows that a subset of

calcareous hornfels exhibits devolatilization in various

degrees. The majority of them have less than *2.5 wt%

CO2 but *4.5–21 wt% SO3. As a result, we argue that

devolatilization is mainly brought about by loss of CO2 and

sulfate minerals are largely unaffected by this process. The

decarbonation reactions likely caused the formation of

clinopyroxene and phlogopite in calcareous hornfels at the

expense of dolomite (Rice 1977; Tracy and Frost 1991):

5 CaMg CO3ð Þ2 dolomiteð Þ þ 8SiO2 þ H2O

¼ Ca2Mg5Si8O22 OHð Þ2 tremoliteð Þ þ 3 CaCO3 calciteð Þþ 7 CO2

Ca2Mg5Si8O22 OHð Þ2 tremoliteð Þþ KAlSi3O8 K-feldsparð Þ þ 2 CaMg CO3ð Þ2 dolomiteð Þ¼ 4 CaMgSi2O6 diopsideð Þþ KMg3AlSi3O10 OHð Þ2 phlogopiteð Þ þ 4 CO2

The latter reaction occurs at *460 to 500 �C for a wide

range of mole fractions of CO2 in the fluid (Tracy and Frost

1991), temperatures that can be reached according to our

temperature estimates based on mineral assemblage.

Gas release and the end-Permian environmental crisis

As mentioned above, the release of CO2 and SO2 from the

aureoles during contact metamorphism most likely

involves hydrothermal leaching of evaporites and decar-

bonation of impure evaporites, respectively. Here, we

estimate the generation potentials of these gases in a LIP

context.

We estimate CO2 production potential using decarbon-

ation reactions and the volume of the aureole rocks that

underwent partial degassing. Based on molar volume, the

aforementioned clinopyroxene- and phlogopite-forming

20

40

60

80

200

150

100

50

0

a Mikchangda

b Talnakh

(wt.%) (wt.%) (wt.%)

morf

ya

wa

ecn

atsiD

)m(tc

atn

ocevis

urtni

CO2 SO3

Cpx Phl Kfs Chl AnhCc+

0.5 1 1.5 0 1 4Qtz Chl Mus Ab Ap

20

TOC

20 40

0 3 1

0m

orfy

aw

aec

natsi

D)

m(tcat

noc

e visurt

niAnhydritelayers

Sill

Hornfels

Sediments

(?)

Sill

Hornfels

Sills (minor)

Metasomatichornfels

0 1 2 3 100 30 0 60 0.709 0.710

( Sr/ Sr)87 86i

0 0.5 1.5 0.710 0.7142

Fig. 9 Simplified column sections of the Mikchangda and Talnakh aureoles showing variations of mineralogy, TOC, CO2, SO3 and (87Sr/86Sr)i

with distance away from the intrusive contact. The color scheme of the sections is the same as in Fig. 2

Contrib Mineral Petrol

123

Page 19: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

reactions produce 375–430 g CO2 per kilogram of dolo-

mite, or 188–215 g CO2 per kilogram of impure evaporite

with 50 % dolomite. If we assume the volume of the

metamorphosed rock in the lower Mikchangda aureole to

be 0.5 km3 [5 km (length) 9 500 m (breadth) 9 200 m

(aureole thickness)], a density of 2,500 kg m-3 and 80 %

of dolomite was transformed to clinopyroxene and phlog-

opite, the total amount of CO2 produced is about 0.4 Gt.

With reference to estimates of CO2 released from the

Deccan volcanism (Self et al. 2006), the amount of mag-

matic CO2 released from the Mikchangda intrusion [5 km

(length) 9 500 m (breadth) 9 550 m (sill thickness)]

would be *0.015 Gt, much less than the above estimate of

metamorphic CO2. Scaling the above estimates to a LIP

scale is somewhat speculative, but the present day out-

cropping area of the intrusions is at least 1.6 9 106 km2

and they most frequently intruded Paleozoic sedimentary

rocks (Kontorovich et al. 1997). These values imply that

the total amount of metamorphic CO2 generated by

decarbonation would be in the order of several tens of

thousand Gt or above and is not trivial compared to esti-

mates in earlier studies (Table 5).

The SO2 production potential cannot be estimated using

the above method because it was not released directly from

heating of evaporites as for CO2 (see earlier discussion). In

the Norilsk region, the source of sulfides in the Ni-Cu-

(PGE) deposits is generally considered to be the reduced

form of sulfates in evaporites (Li et al. 2003, 2009a, b;

Ripley et al. 2003; Arndt et al. 2003; Naldrett 2004),

providing an indirect means to estimate SO2 release. These

deposits contain *1,300 mT of ore (Naldrett 2004) sug-

gested to have formed from immiscible sulfide melts

equilibrated with basaltic magma belonging to the intrusive

portion of the Siberian Traps. Assuming magma/sulfide

mass ratios (R factors) of 100–400 (Li et al. 2009b), the

mass of magma was *130 to 520 Gt. The maximum

concentration of S dissolved in a basaltic magma at

1,300 �C, and 1 GPa is *0.18 wt% under reducing con-

ditions and *1.8 wt% under oxidizing conditions (Jugo

et al. 2005). If 70 % of the S was degassed, the total

amount of SO2 produced ranges from 0.03 to 1.3 Gt. This is

a minimum estimate because it only accounts for the S

dissolved in the magma and neglects any SO2 potentially

occurring as a separate fluid phase in the magmatic system.

In addition, total amount of metamorphic SO2 on a LIP

scale would be in the order of several hundreds or thou-

sands Gt (Table 5).

Recent studies emphasize the role of volatile release in

triggering the end-Permian environmental crisis (Berner

2002; Self et al. 2006; Beerling et al. 2007; Retallack and

Jahren 2008; Svensen et al. 2009a; Li et al. 2009a; Sobolev

et al. 2011; Black et al. 2012; Tang et al. 2012). However,

diverse opinions still exist about the source of volatiles

15

10

5

0

-10

-150.704 0.708 0.712

)(

dN

t

( Sr/ Sr)87 86i

0.716

a

b

101 102 104

)rS

/rS

(6

87

8i

Sr (ppm)103

0.716

0.712

0.708

0.704

-5

Disturbanceof Nd isotopes(?)

Crustalcontamination

Evaporitecontamination

Crustalcontamination

Evaporitecontamination

Fig. 10 Binary plots of Sr–Nd isotopic compositions for Paleozoic

sedimentary rocks and meta-sedimentary rocks from the Norilsk

contact aureoles, Siberia. a eNd(t) versus (87Sr/86Sr)i. b (87Sr/86Sr)i

versus Sr concentrations. The isotopic data were calculated at

t = 252 Ma. Gray fields and white diamonds denote flood basalts

and intrusive rocks, respectively, from the Siberian Traps after

Sharma et al. (1992), Lightfoot et al. (1993), Hawkesworth et al.

(1995) and Arndt et al. (2003). Legend is the same as in Fig. 6

60

060200

)%.t

w(O

S+

OC

32

CaO (wt.%)

40

40

20

Cc

Anh

Dol

80

60

40

20

80

60

40

20

80

60

40

20

Degassing

Ca-poorsulfate

Assimilation

Fig. 11 A binary plot of (CO2 ? SO3) versus CaO for Paleozoic

sedimentary rocks and meta-sedimentary rocks from the Norilsk

contact aureoles, Siberia (see text for discussion). Data for samples in

drill-core TG21 are not plotted. Legend is the same as in Fig. 6

Contrib Mineral Petrol

123

Page 20: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

(e.g., magmatic vs. sediment-derived, mantle vs. crust).

Our results show that contact metamorphism of impure

evaporites could have generated abundant CO2 in addition

to that of organic matter and coal (Svensen et al. 2009a)

which, when emitted to the atmosphere, can be one of the

main contributor to the end-Permian global warming. We

also note that anhydrite can be mobilized by leaching

associated with magmatic-hydrothermal activity, releasing

SO2 to the magmatic system and eventually the atmo-

sphere. The SO2 has harmful effects on respiratory systems

of organisms and it might form acid rain. These gases,

together with other greenhouse gases like CH4 or toxic

gases of halocarbons released by magmatic or sediment

degassing (Table 5), likely contributed to the end-Permian

crisis.

Concluding remarks

Contact metamorphism in the Norilsk aureoles occurs at

low pressure and moderate peak metamorphic tempera-

tures. Calcareous hornfels from the Mikchangda aureole

formed by calcareous siltstone protoliths, whereas siliceous

hornfels from the Talnakh aureole formed by pelitic or

shaley protoliths. Decarbonation during metamorphism

resulted in loss of CO2 from the aureole rocks. Hydro-

thermal leaching of sulfates from evaporites produced SO2

that subsequently enters the magmatic system. The release

of these gases into the atmosphere provides a viable

explanation for the end-Permian environmental crisis and

mass extinctions.

Acknowledgments We thank Francis Coeur for assistance in sam-

ple preparation, Catherine Chauvel, Sarah Bureau and Christele Poggi

in major and trace element analyses, and Hao-Yang Lee and Chiu-

Hong Chu for Sr–Nd isotopic analyses. We acknowledge funding

granted to NTA from the French ANR (BEGDy project) and the

American NSF (continental geodynamics program) and to HS and

others from PGP and the Norwegian Research Council (YFF and SFF

grants). Logistic support and access to drill-cores provided by Norilsk

Nickel are gratefully acknowledged. We express special thanks to

Valery Fedorenko, former Norilsk Nickel chief geologist, for the

assistance in the field trip and sample delivery. Comments by two

anonymous reviewers and the editor Tim Grove improved the quality

of the manuscript.

References

Aarnes I, Svensen H, Connolly JAD, Podladchikov YY (2010) How

contact metamorphism can trigger global climate changes:

modeling gas generation around igneous sills in sedimentary

basins. Geochim Cosmochim Acta 74:7179–7195

Aarnes I, Fristad K, Planke S, Svensen H (2011) The impact of host-

rock composition on devolatilization of sedimentary rocks

during contact metamorphism around mafic sheet intrusions.

Geochem Geophy Geosy 12:Q10019. doi:10.1029/2011GC

003636

Arndt NT, Czamanske GK, Walker RJ, Chauvel C, Fedorenko VA

(2003) Geochemistry and origin of the intrusive hosts of the

Norilsk-Talnakh Cu-Ni-PGE sulfide deposits. Econ Geol

98:495–515

Table 5 Estimates of gas generation potential for the Siberian Traps

Method Carbon Sulfur Halogens Reference

Bulk-rock volatile data

of magmatic rocks

4400 Gt CO 7000 Gt H2S – Tang et al. (2012)

85000 Gt CO2 68000 Gt SO2

Melt inclusions – 6300 to 7800 Gt S 3400 to 8,700 Gt Cl Black et al. (2012)

7,100 to 13,600 Gt F

Melt inclusions 170000 Gt CO2 – 18000 Gt HCl Sobolev et al. (2011)

S-isotopes – 20000 to 30000 Gt

SO2

– Li et al. (2009a, b)

Bulk-rock volatile data of rock salt 10700 to 31200 Gt C – 5200 to 15300 Gt

CH3Cl

Svensen et al.

(2009a)

39000 to 114000 Gt

CO2

87 to 255 Gt CH3Br

14300 to 41900 Gt CH4

Inference from degassing rate of the

Columbia River Basalts and the volume

of the Siberian Traps

– 38000 Gt SO2 2200 Gt HCl Beerling et al.

(2007)0.0636 Gt CH3Cl

0.0008 Gt CH3Br

Inference from degassing rate of modern

basalts and the volume of the Siberian

Traps

2000 to 13000 CO2 – – Berner (2002)

* Conversion factors: 1 gigatonne (Gt) = 1000 teragram (Tg) = 1015 gram

^To compare different species of the same element (e.g., C and CO2), conversion factors of atomic/molecular masses are required

Contrib Mineral Petrol

123

Page 21: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

Beerling DJ, Harfoot M, Lomax B, Pyle JA (2007) The stability of the

stratospheric ozone layer during the end-Permain eruption of the

Siberian Traps. Philos Trans Royal Soc Math Phys Eng Sci

365:1843–1866

Berner RA (2002) Examination of hypotheses for the Permo-Triassic

boundary extinction by carbon cyclemodeling. Proc Natl Acad

Sci USA 99:4172–4177

Black BA, Elkins-Tanton LT, Rowe MC, Ukstins Peate I (2012)

Magnitude and consequences of volatile release from the

Siberian Traps. Earth Planet Sci Lett 317–318:363–373

Boudreau AE, Love C, Prendergast MD (1995) Halogen geochem-

istry of the Great Dyke, Zimbabwe. Contrib Mineral Petrol

122:289–300

Bowen NL (1940) Progressive metamorphism of siliceous limestone

and dolomite. J Geol 48:225–274

Carlsaw HS, Jaeger JC (1959) Conduction of heat in solids. Oxford

University Press, London

Chauvel C, Bureau S, Poggi C (2010) Comprehensive chemical and

isotopic analyses of basalt and sediment reference materials.

Geostand Geoanal Res 35:125–143

Czamanske GK, Zen’ko TE, Fedorenko VA, Calk LC, Budahn JR,

Bullock JH Jr, Fries TL, King BW, Siems DF (2002)

Petrographic and geochemical characterization of ore-bearing

intrusions of the Norilsk-type, Siberia; with discussion of their

origin. United States Geological Survey Open-file Report

02-074. http://geopubs.wr.usgs.gov/open-file/of02-074/

Faure G, Mensing TM (2005) Isotopes: principles and applications.

Wiley, New Jersey

Ferry JM, Wing BA, Rumble D (2001) Formation of wollastonite by

chemically reactive fluid flow during contact metamorphism, Mt.

Morrison pendant, Sierra Nevada, California, USA. J Petrol

42:1705–1728

Frolov SV, Akhmanov GG, Kozlova EV, Krylov OV, Sitar KA,

Galushkin YI (2011) Riphean basins of the central and western

Siberian Platform. Mar Petrol Geol 28:906–920

Ganino C, Arndt NT (2009) Climate changes caused by degassing of

sediments during the emplacement of large igneous provinces.

Geology 37:323–326

Gorbachev NS, Grinenko LN (1973) The sulfur-isotope ratios of the

sulfides and sulfates of the Oktyabr’sky sulfide deposit, Norilsk

region, and the problem of its origin. Geokhimiya 8:1127–1136

Gorman JA, Peterson EU, Essene EJ (1984) Anhydrite equilibria and

sulfide zonation in the Fowler massive sulfide body, NY. EOS

Trans Am Geophys Union 65:293

Greenwood HJ (1967) Wollastonite: stability in H2O-CO2 mixtures

and occurrence in a contact-metamorphic aureole near Salmo,

British Columbia, Canada. Am Mineral 52:1669–1680

Grinenko LN (1985) Sources of sulfur of the nickeliferous and barren

gabbro-dolerite intrusions of the northwest Siberian platform. Int

Geol Rev 28:695–708

Hawkesworth CJ, Lightfoot PC, Fedorenko VA, Blake S, Naldrett AJ,

Doherty W, Gorbachev NS (1995) Magma differentiation and

mineralisation in the Siberian continental flood basalts. Lithos

34:61–88

Jugo PJ, Luth RW, Richards JP (2005) An experimental study of the

sulfur content in basaltic melts saturated with immiscible sulfide

or sulfate liquids at 1300�C and 1.0 GPa. J Petrol 46:783–798

Kamo SL, Czamanske GK, Amelin Y, Fedorenko A, Davis DW,

Trofimov VR (2003) Rapid eruption of Siberian floodvolcanic rocks

and evidence for coincidence with the Permian-Triassic boundary

and mass extinction at 251 Ma. Earth Planet Sci Lett 214:75–91

Kontorovich AE, Khomenko AV, Burshtein LM, Likhanov II, Pavlov

AL, Staroseltsev VS, Ten AA (1997) Intense basic magmatism

in the Tunguska petroleum basin, eastern Siberia, Russia. Petrol

Geosci 3:359–369

Lee H-Y, Chung S-L, Ji J, Qian Q, Gallet S, Lo C-H, Lee T-Y, Zhang

Q (2012) Geochemical and Sr-Nd isotopic constraints on the

genesis of the Cenozoic Linzizong volcanic successions, south-

ern Tibet. J Asian Earth Sci 53:96–114

Li C, Ripley EM, Naldrett AJ (2003) Compositional variations of

olivine and sulfur isotopes in the Norilsk and Talnakh intrusions,

Siberia: implications for ore-forming processes in dynamic

magma conduits. Econ Geol 98:69–86

Li C, Ripley EM, Naldrett AJ, Schmitt AK, Moore CH (2009a)

Magmatic anhydrite-sulfide assemblages in the plumbing system

of the Siberian Traps. Geology 37:259–262

Li C, Ripley EM, Naldrett AJ (2009b) A new genetic model for the

giant Ni-Cu-PGE sulfide deposits associated with the Siberian

flood basalts. Econ Geol 104:291–301

Lightfoot PC, Hawkesworth CJ, Hergt J, Naldrett AJ, Gorbachev NS,

Fedorenko VA, Doherty W (1993) Remobilisation of the

continental lithosphere by a mantle plume: major-, trace-

element, and Sr-, Nd-, Pb-isotope evidence from picritic and

tholeiitic lavas of the Noril’sk District, Siberian Trap, Russia.

Contrib Mineral Petrol 114:171–188

Likhachev AP (1994) Ore-bearing intrusions of the Norilsk region. In:

Lightfoot PC, Naldrett AJ (eds.) Proceedings of the Sudbury-

Norilsk symposium. Ontario Geological Survey Special Publi-

cation, vol 5, pp 185–202

Malitch NS et al (ed) (1999) Geological map of Siberian platform and

adjoining areas, 1:1 500 000. Ministry of Natural Resources of

Russian Federation

Matukhin RG (1978) Salt potential of the Devonian sedimentary

rocks in the Siberia. Review. Geol Prospecting and exploratory

methods of non-metal deposits. Moscow. VIEMS. 39 pp (in

Russian)

McDonough WF, Sun S–S (1995) The composition of the earth.

Chem Geol 120:223–253

Naldrett AJ (2004) Magmatic sulfide deposits. Springer, Berlin

Naldrett AJ, Lightfoot PC (1999) Ni-Cu-PGE deposits of the Norilsk

region, Siberia: their formation in conduits for flood basalt

volcanism. Geological Association of Canada Short Course

Notes, vol 13, pp 195–250

Naldrett AJ, Fedorenko VA, Lightfoot PC, Kunilov E, Gorbachev NS,

Doherty W, Johan Z (1995) Ni-Cu-PGE deposits of the Norilsk

region, Siberia: their formation in conduits for flood basalt

volcanism. Trans Inst Min Metall 104:B18–B36

Newton RC, Manning CE (2005) Solubility of anhydrite, CaSO4, in

NaCl-H2O solutions at high pressures and temperatures: appli-

cations to fluid-rock interaction. J Petrol 46:701–716

Polat A, Frei R, Appel PWU, Dilek Y, Fryer B, Ordonez-Calderon JC,

Yang Z (2008) The origin and compositions of Mezoarchean

oceanic crust: evidence from the 3075 Ma Ivisaartoq greenstone

belt, SW Greenland. Lithos 100:293–321

Reichow MK, Saunders AD, White RV, Pringle MS, Al’Mukham-

edov AI, Medvedev AI, Kirda NP (2002) 40Ar/39Ar dates from

the West Siberian Basin: siberian flood basalt province doubled.

Science 296:1846–1849

Retallack G, Jahren AH (2008) Methane release from igneous

intrusion of coal during Late Permian extinction events. J Geol

116:1–20

Rice JM (1977) Contact metamorphism of impure dolomitic

limestone in the Boulder aureole, Montana. Contrib Mineral

Petrol 59:237–259

Ripley EM, Lightfoot PC, Li C, Elswick ER (2003) Sulfur isotopic

studies of continental flood basalts in the Norilsk region:

implications for the association between lavas and ore-bearing

intrusions. Geochim Cosmochim Acta 67:2805–2817

Ripley EM, Li C, Moore CH, Schmidt AK (2010) Micro-scale S

isotope studies of the Kharaelakh intrusion, Norilsk region,

Contrib Mineral Petrol

123

Page 22: A petrologic, geochemical and Sr–Nd isotopic study on ...folk.uio.no/hensven/Pang_CMP2012_Norilsk.pdf · A petrologic, geochemical and Sr–Nd isotopic study on contact metamorphism

Siberia: constraints on the genesis of coexisting anhydrite and

sulfide minerals. Geochim Cosmochim Acta 74:634–644

Saunders AD, England RW, Reichow MK, White RV (2005) A

mantle plume origin for the Siberian traps: uplift and extension

in the West Siberian Basin, Russia. Lithos 79:407–424

Self S, Widdowson M, Thordarson T, Jay AE (2006) Volatile fluxes

during flood basalt eruptions and potential effects on the global

environment: a Deccan perspective. Earth Planet Sci Lett 248:

518–532

Sharma M (1997) Siberian traps. In: Mahoney JJ, Coffin MF (eds)

Large igneous provinces: continental, oceanic and planetary

flood volcanism. Geophysical Monograph 100, American Geo-

physical Union, Washington, pp 273–295

Sharma M, Basu AR, Nesterenko GV (1992) Temporal Sr-, Nd- and

Pb-isotopic variations in the Siberian flood basalts: implications

for the plume-source characteristics. Earth Planet Sci Lett 113:

365–381

Sobolev AV, Krivolutskaya NA, Kuzmin DV (2009) Petrology of the

parental melts and mantle sources of Siberian trap magmatism.

Petrology 17:253–286

Sobolev SV, Sobolev AV, Kuzmin DV, Krivolutskaya NA, Petrunin

AG, Arndt NT, Radko VA, Vasiliev YR (2011) Linking mantle

plumes, large igneous provinces and environmental catastrophes.

Nature 477:312–316

Surkov VS, Grishin MP, Larichev AI, Lotyshev VI, Melnikov NV,

Kontorovich AE, Trofimuk AA, Zolotov AN (1991) The

Riphean sedimentary basins of the Eastern Siberia Province

and their petroleum potential. Precambrian Res 54:37–44

Svensen H, Planke S, Malthe-Sorenssen A, Jamtveit B, Myklebust R,

Eidem TR, Rey SS (2004) Release of methane from a volcanic

basin as a mechanism for initial Eocene global warming. Nature

429:542–545

Svensen H, Planke S, Polozov AG, Schmidbauer N, Corfu F,

Podladchikov YY, Jamtveit B (2009a) Siberian gas venting and

the end-Permian environmental crisis. Earth Planet Sci Lett 277:

490–500

Svensen H, Schmidbauer N, Roscher M, Stordal F, Planke S (2009b)

Contact metamorphism, halocarbons, and environmental crises

of the past. Environ Chem 6:466–471

Tang Q, Zhang M, Li C, Yu M, Li L (2012) The chemical

compositions and abundances of volatiles in the Siberian large

igneous province: constraints on magmatic CO2 and SO2

emissions into the atmosphere. Chem Geol. doi:10.1016/

j.chemgeo.2012.08.031

Tracy RJ, Frost BR (1991) Phase equilibria and thermobarometry of

calcareous, ultramafic and mafic rocks, and iron formations. In:

Kerrick DM (ed.) Contact Metamorphism. Mineralogical Society

of America, Reviews in Mineralogy 26, Washington, pp 207–

290

Turovtsev DM (2002) Contact metamorphism of the Noril’sk

intrusions. Scientific World, Moscow, p 319 in Russian

Ulmishek GF (2001) Petroleum Geology and Resources of the Baykit

High Province, East Siberia, Russia. US Geological Survey

Bulletin. 2201-F

van de Kamp PC, Leake BE (1996) Petrology, geochemistry, and Na

metasomatism of Triassic-Jurassic non-marine clastic sediments

in the Newark, Hartford, and Deerfield rift basins, northeastern

USA. Chem Geol 133:89–124

van der Sluis ML (2010) Melting relations in the anhydrite-dolomite

system. Unpublished Master thesis, Universiteit Utrecht. (http://

igitur-archive.library.uu.nl/student-theses/2010-0828-200201/

UUindex.html)

Veizer J, Ala D, Azmy K, Bruckschen P, Buhl D, Bruhn F, Carden

GAF, Diener A, Ebneth S, Godderis Y, Jasper T, Korte C,

Pawellek F, Podlaha OG, Strauss H (1999) 87Sr/86Sr, d13C and

d18O evolution of Phanerozoic seawater. Chem Geol 161:59–88

Von der Flaass GS, Naumov VA (1995) Cup-shaped structures of iron

ore deposits in the South of the Siberian Platform (Russia). Geol

Ore Depos 37:340–350

Walker RJ, Morgan JW, Horan MF, Czamanske GK, Krogstad EJ,

Fedorenko VA, Kunilov VE (1994) Re-Os isotopic evidence for

an enriched-mantle source for the Norilsk-type, ore-bearing

intrusions, Siberia. Geochim Cosmochim Acta 58:4179–4197

Wignall PB (2001) Large igneous provinces and mass extinctions.

Earth-Sci Rev 53:1–33

Yavuz F (2001) PYROX: a computer program for the IMA pyroxene

classification and calculation scheme. Comput Geosci 27:97–107

Yavuz F (2003) Evaluating micas in petrologic and metallogenic

aspect: i-definitions and structure of the computer program

MICA?. Comput Geosci 29:1203–1213

Yavuz F (2007) WinAmphcal: a Windows program for the IMA-04

amphibole classification. Geochem Geophy Geosy 8:Q01004.

doi:10.1029/2006GC001391

Zen’ko T, Czamanske GK (1994) Tectonic controls on ore-bearing

intrusions of the Talnakh ore junction: position, morphology, and

ore distribution. Int Geol Rev 36:1033–1057

Zharkov MA (1984) Paleozoic salt bearing formations of the world.

Springer, Berlin

Contrib Mineral Petrol

123