Economic Geology Vol.90, 1995,pp.

676-689

The Tomtor Alkaline Ultrabasic Massif andRelated REE-Nb Deposits,

Northern Siberia
S. M. KRAVCHENKO

Institute of OreDeposit Geology, Petrography, Mineralogy andGeochemistry, Russian Academy of Science,

Staromonetny per. 35, 109017Moscow, Russia
AND t3.(;. POKROVSKY

Geological Institute of theRussian Academy of Sciences, Pyzhevski 7, 109017 Moscow, Russia

Abstract

Nb-REEoredeposits related toweathered carbonatite within theTomtor massif, northern Siberia, contain theworld's largest carbonatite-related concentrations of Nb andREE. Despite itsremote location, economic exploitation of thedeposit wasmade possible by thediscovery of richSc-REE-Y-Nb ore.

The300-km 2Tomtor massif isa ring complex inwhich theNb-REE deposits aresituated within and above
a central carbonatite stock. Thedeposits include: (1) pyrochlore-bearing carbonatite, (2) a lower orehorizon, and(3) anupper orehorizon. Theaverage concentration of niobium increases froma fewtenths of a percent in thecarbonatite, to a fewpercent in thelower orehorizon, andupto 12percent in theupper orehorizon. REE contents range from0.5 to 0.7 percent in carbonatite, 4 to 6 percent in the lowerorehorizon, and11 to 30 percent in the upperorehorizon.

In a plotof 6sO vs.63C, the Tomtor carbonates plotalong a trendfromthe Okaboxfor magmatic carbonates tothefield ofsedimentary carbonates. TheTomtor carbonatites have initial S7Sr/S6Sr ratios ranging
from0.70346 to 0.70374, a range consistent withmantle derivation for themagmas. The lowerore horizon, whichis up to 300 m thick,consists of niobium (Nb205content 1-2%) and phosphorus oresthatoccur in a variety of original rocktypes (carbonatites, volcanics, picritic dikes, and country rocks) which have undergone several types ofalteration including weathering, hydrothermal alteration,

andlow-temperature sideritization. S7Sr/86Sr ratios of thelower orehorizon range from 0.70421 to 0.70374
andsuggest a dominantly mantle source for Srwitha veryminor addition of crustal Sr. Theupper orehorizon isa placer deposit 3 to 25 m thick which has been partly affected byhydrothermal alteration. Richores oftheupper orehorizon arecomposed mainly ofpyrochlore, phosphates andalumophosphates of REE, Sr andBa (florencite, monazite, gorceixite, goyazite), rutfie, andpyrite. Nb in theTomtor deposits occurs principally in pyrochlore, columbite, rutfie, andihnenorutile. REE and Y occur in fiorencite, monazite, rhabdophane, xenotime, andbastnasite, andScoccurs in monazite, rhabdophane (0.55-0.95%), minerals of the crandallite group (0.017-0.030%), rutfie, andasa thinfihnof Sc(OH)3 on phosphates.
Introduction

THE Tomtordeposit, together with deposits suchasAraxa

(Brazil) and Mount Weld (Western Australia),containsone

opment of pyrochlore placers in local karst depressions (Konoplev et al., 1992).

Since the Tomtor carbonatite is remote from modern trans-

portroutes andis almost completely covered by sedimentary of the largest concentrations of Nb andREE in weathered rocks, it hadbeen poorly investigated untilrecently. However, carbonatite. The deposit occurs in theTomtor massif, which detailed studies of drill corehavenowshown that, asprehas many similarities withtheKhibina (Russia) andLovozero viously suggested (Kravchenko, 1982), Tomtor is oneof the (Russia) massifs. Thisfamily of giantmassifs shows a regular world's largest Nb (morethanAraxa) andREE (moreREE combination of favorable features which led to the develop- thanMountWeld) deposits. The mostimportant result of mentof large deposits of phosphorus andrareelements dur- the recent workhasprobably beenthe discovery of a rich ingdifferent stages of theirevolution. These features include Sc-REE-Y-Nb ore (Kravchenkoet al., 1990b) which made a kimberlitelike composition of mantle-derived parent melts economic exploitation of the deposit possible in spiteof its (Kravchenko andRass, 1985), anability toextract phosphorus remote location. andrareelements fromthemantle, very large heatcapacities, andlarge magma chambers which allow extended crystallizaAnalytical Techniques tion-differentiation. The massifs havealso beenaffected by intense postmagmatic alteration processes (Kravchenko et al., REE, Sc,Sr,Ba,andTh concentrations wereobtained by
1992b).
instrumental neutron activation.Standard deviationsfor La,

5 to 8 percent, for Sr,Ba,Ce, Yb,and The large alkaline-ultramafic complexes are composedSin,Eu, andScequal andfor Th, 20 percent. Y, Zr, Nb, La, mainly of the end members of comagmatic igneous series Lu, 10 to 15percent, such assyenites, andin the case of Tomtor, of carbonatites. andCe concentrations weredetermined by XRF. Standard A favorable factor in the formation of Tomtor ores was also deviations are 10 to 15 percent. thelarge size of thecarbonatite stock vhich ledto thedevelSr isotope analyses were obtained on a MAT-260mass
0361-0128/95/1698/676-1454.00 676

TOMTORREE-NbDEPOSITS, N SIBERIA

677
126' 72'

2,00m

71'

116

NNW

m B

200

Fro.1. A. Simplifed geologic scheme oftheTomtor massif. 1 = Permian coal-bearing deposits: conglomerate, sandstone, andargillite; 2 = maginatie andinetasomatie rocks ofthecentral earbonatite stock; 3 = nepheline andnepheline-bearing syenites; 4 = altered jaeupirangite-urtite; 5 = mainly carbonate deposits andsandstone-siltstone of theRhiphean UlaehanKurung andUnguoehtaeh suites andtheVendian Tomtor suite. Insetfrommap(Orlova andKrasnoff, 1978): 6 = folded complex; 7 = orogenie-stage complex intra-andmarginal depressions; 8 = crystalline rocks of theAnabar shield. B. Cross sections modified afterLapin andTolstov (1993). 1 = Mesozoic-Cenozoic deposits; 2 = Permian coal-bearing deposits; 3 = upper orehorizon (afterLapin andTolstov, 1993; "epigenetie altered products ofwethering"); 4 = kaolinite-hydromiea weathering crust onsilicate rocks; 5 = lower orehorizon: a = siderite rocks, b = limonitie weathering crust, e = limonitefrancolite rocks; 6 = ijolite-melteigite rocks; 7 = metasomatie rocks: a = apatite-potassium feldspar-ehlorite rocks, b= calcite-potassium feldspar-phlogopite rocks; 8 = ore-bearing calcite-dolomite earbonatite; 9a = ankerite-ehamozite rocks; 9b = ore-bearing mkerite earbonatite; 10 = early, unmineralized calcite-dolomite earbonatite.

spectrometer. Accuracy ofthe87Sr/86Sr determination isbet- 93C arein permil relative thePDBstandard. Theresults ter than0.001.The isotopic compositions of O andC xvere for534S arein perrailrelative to theSikhote-Alin standard. measured on an MU-1201B mass spectrometer. The SlsOAccuracy of thedeterminations is 0.2 per mil for 93C and results aregiven in per mil relative to SMOWandthose for 9s0and 0.3permilfor54S.

678

KRAVCHENKO AND POKROVSKY

Geologic Features of the TomtorMassifand Associated Ore Deposits

The Tomtor massif is located in northern Siberia between

TABLE 1. Ages in Magmatic andMetasomatic Rocks fromTomtor

(Entin et al., 1990)

Ages

the AnabarShieldto the westand the Olenyoc uplift to theeast (Fig.1). It occurs onthemeridional Udgy palcorift (Shpunt et al., 1991)whichis the boundary between basementcrystalline rocks of different ages (Egoroy et al.,1985). Thepalcorift canbetraced for400kmusing geophysical and morphostructural data.The depthof the Mohois 30 to 35 km in the palcorift zone.The Tomtormassif is located on thewest shoulder oftherift.Riphean sedimentary rocks crop
out in a meridional zone within the dominant Cambrian de-

Magmatie rocks

Metasomatie rocks andores

Metasomatic K feldspar in nepheline pegmatoid syenite
Lower ore horizon calcite-

(Ma)
240?
340-320

chlorite-serpentine
metasomatites

Upperorehorizon REEphosphate metasomatites

Nepheline syenite dike
Pierifle dikes and diatremes

<400
410
430-470

posits. A present-day dome morphostructure 20 kmin diameter corresponds to the Tomtormassif. The Tomtormassif intrudes Riphean dolomite, siltstone, Subalkaline gabbro syenite dike andsandstone of the Ulachan-Kurung suite, shale, siltstone, Nepheline dolomite, andtuffaceous deposits of the Unguochtach suite, Central stock carbonatite
and Vendian siltstone and sandstone of the Tomtor suite. The
and carbonatite

Lowerorehorizon K feldspar, 450-440

calcite, and chloritic
metasomatites

592-528 614
660510

Centralstock phoscorite

660-650

massif is overlain by a layerof Permian conglomerate and Nepheline syenite dike 675 sandstone which contains interbedded coal in theupper part. Ringzonenepheline and 700-800 syenite Theyoungest units include Lower Jurassic argillo-arenaceousnepheline-bearing 700-800 marine sediments andNeogene-Quaternary alluvial sands. Jacupirangite-urtite TheTomtor massif isatypical ring complex (more 300km 2) andhasa relatively simple structure. Predominant biotite-, biotite-pyroxenemepheline-, andnepheline-bearing alkaline mite-calcite-phlogopite rocks whichare locally transitional syenites (morethan60%of the areaof the massif) compose into micaceous rocks. Apatite-feldspar-chlorite and calcitea peripheral zone2 to 6 km wide.The central stock crops francolite-chlorite carbonatites werealso formed bycarbonatization. outover a total area of40 km 2ofwhich 12km iscomposed of carbonatite. The orezones consist of: (1) pyrochlore-bearing carbonaMuchof thecarbonatite stock iscovered byrocks interpre- tire,(2) a lower orehorizon upto 300m thickcontaining ore tedto bevolcanics including melanephelenite, phonolite, tra- lodes richin niobium andphosphorus, and(3) a 3- to 25-mchyte, andtheeffusive equivalent of phoscorite (Entinet al., thickupperore horizon whichis a buriedplacerdeposit 1990).However, recognition of theserocks asvolcanics is containing rich fiorencite-monazite-pyrochlore ore (Kravbased mainly on structural features andthe mineralogical chenko et al., 1990; Konoplev et al., 1992). The average confeatures of intensely altered rocks andremains speculativecentration of economic components increases from a few (Entin et al., 1990). tenths of a percent in the carbonatite, to a few percent in The stock andthe peripheral syenite ringzoneare sepa- thelowerorehorizon, to a fewtensof percent REE andto rated by ajacupirangite-urtite ringdikei to 3 kmwide.The morethan12 percent Nb in the upperorehorizon. carbonatite stock is intruded by a dike complex of picrite, The K/Ar andRb/Srages of ErlichandZagruzina (1981) alnoite, nepheline syenite, melilitite, tinguaite, alkali trachyte, andEntin et al. (1991)indicate two majorevents at about and dolerite. The jaeupirangite-urtite ring dike is intruded 700 Ma and 400 Ma, but Entin et al. (1991) recognize a by ringdikes of magnetitite, apatitite, andotherphoseorites. number of stages (Table1). The K/Arageof potash feldspar The earbonatite stock hasa rhomblike shape andincludes mayhave beenaffected by argon loss. intrusive rocks, possible metasomatie earbonatite, and in- Lower ore horizon tensely earbonatized ijolite. The oldest earbonatites aredolomite-calcite andcalcite rocks which formmeridionally elonRocks and oresof the lowerore horizon are composed gated bodies. According toLapin and Tolstov (1993) there are mainly of carbonates (calcite, dolomite, ankerite, siderite, early,unmineralized calcite-dolomite earbonatites andore- rhodochrosite, magnesite, manganosiderite, etc.), phosphates bearing calcite-dolomite andankeritie earbonatites (Fig.lB). (predominantly francolite, apatite, strontium apatite, monaDolomite-calcite and calcite earbonatites are medium to fine zite,florencite, crandallite, gorceixite, goyazite, etc.),oxides grained, massive, andsporadically banded rocks withhypidio- andhydroxides (goethite, hydrogoethite, magnetite, groutitc, morphie textures. Interstitial pyroehlore contains significantmanganite, pyrochlore, columbite, rutfie,anatase, etc.),and uranium andzireonium, a featurenot foundin otherpyro- silicates (chlorite,hydromica, kaolinitc,montmorillonite, ehloregenerations. The accessory minerals include apatite, feldspar, garnet, harmotome, natrolite, etc.)(Fig.2). phlogopite, magnetite, andpyrite. High-grade phosphate ores of thelower orehorizon (avg Younger ankerite earbonatites arelocalized in the central 12.5%PO.) occur essentially aslenses or bedsup to 50 m is composed of various original partof thestock; theyhave granoblastie textures andcontain thick.The lowerorehorizon including carbonatite, volcanics, picrite, andother accessory minerals including pyroehlore, apatite, magnetite, rocktypes andrichteritc. Carbonatization of ijolitehasproduced dolo- dikerocks andpossibly some country rocks asinferred from

TOMTOR REE-Nb DEPOSITS, N SIBERIA

679

Pc

Ca

Fe

Nb

Ce

Fro.2. Cross section of thelower orehorizon (drillhole104)in thenorthern partof thecentral carbonatite stock. 1 = eruptive breeeia of pierite andother rocks, 2 = rocks withpoq)hyritie textures (dikes, probably partly effusive), 3= mainly geothitie, sideritie, limonitie, andother highironrocks, 4 = mainly francolite rocks, 5 = metasomatie earbonatite, 6 = Permian conglomerate, 7 = quartz veins, 8 = rocks altered by sideritization, 9 = rocks altered by kaolinization. Pc
= porosity.

Some investigators (e.g.,LapinandTolstov, 1991)have suggested that the lowerore horizon exhibits a regular sequence of weathering zones above the carbonatite. Thisincludes francolite, goethite (richin ironandmanganese), siderite,andhydromica-kaolinite zones. The firsttwozones are thought to havebeencreated by oxidation, with goethite ma) (Table 1). representing a zoneof leaching andfrancolite a zoneof cePyrochlore andpyrochlore-columbite Nb orescontain a menration. The formation of morehighly dispersed zones of variety of assemblages, including francolite-siderite, goethite- sideritization andhydromica-kaolinite maybe relatedto a hydrogoethite-francolite-siderite, and chlorite-goethite-hyreduction stage. However, thissequence is seen onlyin the partof thecarbonatite stock. Elsewhere, some zones drogoethite. Thealtered carbonatites arecrosscut bynumer- central belacking, orthesequence may beinverted or repeated. ous veins containing rhodochrosite, chicrite, quartz, albite, K may feldspar, goethite, andmagnetite. The weathering crust of thelowerorehorizon occurs asa Upperorehorizon whichincludes the higher grade blanket up to 10 m thick,andlargebodies of weathered The upperore horizon, material, upto 300m thick, arelocalized in circular structures ore,lieson topof the altered carbonatites andbeneath the upto3.5kmin diameter in thesouthern partofthecarbona- mainly sandy, coal-bearing Permian strata. In plan thedistritire stock. Thesemayrepresent cauldron subsidence struc- butionof the upperore horizon coincides with that of the deposits (around 8 km 2,Fig.1).Thehigh-grade Sctures based ontheirrounded shape, large size, andthepres- Permian ence of rocks interpreted asvolcanics overlying thecarbona- REE-Y-Nboresare recognized as a buriedplacerdeposit theirverylightcarbon isotope composition (Pokrovsky et al., 1990).Theserocks haveundergone several stages of alteration including weathering, hydrothermal alteration, andlowtemperature sideritization. Some of the alteration hasbeen dated, including calcite andchlorite alteration (450-440Ma), serpentinization (340-320Ma), andK feldspathization (240
tire stock (Erlich, 1964; Entin et al., 1990). However, these which formed in a lacustrine environment (Kravchenko et

al., 1990).Interbeds of siltandfine-grained sand havealso circular features could also be formed by solution-collapse processes. been identified within theupper orehorizon. Thelacustrine-

680

KRAVCHENKO AND POKROVSKY

,,,g ;

25
WD: 8 " RG:

kV

A further oretypein theupper orehorizon contains fluida] andbreccia textures, in which fragments of pyrochlore crystalsarecemented byflorencite. Thepyrochlore ispalerthan thatin bedded ores, whereas fiorencite appears isotropic in
thin section.

1888

18

Important Mineralogical Features of the TomtorComplex Theformation of theweathered zoneoccurred predominantly before theCarboniferous (more than345Ma ago) but also included a weathering period during theJurassic. Several
alterationeventshavealsobeen dated (Table 1): francolitiza11

'k

PHOTO:

IGEM

C--13.2.9

. PTOH
. SM 96e

A
HU.

tionandformation ofpotash feldspar (450-440 Ma),carbonatization (439-332Ma), metasomatic alteration of the upper orehorizon (less than 400Ma),formation oflow-temperature calcite-chlorite-serpentine metasomatic rocks (340-320Ma), andformation of potash feldspar in a dykeof nepheline syenite(240Ma). Thiscomplicated history of formation is reflected in the features and relations of mineral and element

2 5 HD:

kU

ratios fromdifferent parts of the complex. In thispaper we discuss onlythe composition of pyrochlore andthe mineral associations of thelower andtheupper orehorizons.

Pyrochlore Pyrochlore occurring in carbonatite, thelower orehorizon, 7513 andsometimes in theupper orehorizon canbe divided into fivemaingroups (Table2; Belyakov et al., 1989,1990):(1) transparent, black, brown, red,orange, and yellow octahedral andrarely cubic-octahedral, stoichiometric; (2) nontransparPHOTO: ent,paleyellow in thelower orehorizon andyellow-gray in lO carbonatite, Sr- andBa-rich withsome cation deficiency in theA site; (3) transparent gray in carbonatite, thehighest Ba IGEtl 19.2.89 content, with a largercation deficiency in the A site;(4) aPTON nontransparent, octahedral in the lower ore horizon andcarDSM 96 ' bonatite withthehighest Sr content andlargest cation deftciency in theA site; and(5)white and beige, rounded, shelly, strongly altered in the lowerandupperorehorizon. FIG.3. Scanning electron micrographs of thesurface of an REEphosThe first four groups ofpyrochlore wereformed asa result phate fromtheupper orehorizon. A andB have different magnifications.
!'1A6
! !
'e
..

type oreisclearly stratified, withgray, lightgray, andyellow, fine-grained layers 0.5to 1.5mmthick.In therichest sector,
leucocratic and melanocratic bands are seen to alternate. The

leucocratic bands consist of finely dispersed, earthy monazite (rhabdophanite) with florencite, siderite, dolomite, quartz, andfeldspar. Themelanocratic bands consist of pyrite, anatase, and oxides and hydroxides ofiron(Figs. 3 and 4).Within
the individualleucocratic bands,there are euhedraland octa-

hedral crystals of pyrochlore which sometimes occur in cavities. Thelayers often formsmall folds, which areapparently of secondary origin.
In addition, talusores(2-15 m thick) and brow ores(2-

15 m thick)havebeendistinguished by Konoplev et al. (1992). These are coarser grained thanthe lacustrine-type oreandarecomposed predominantly of earthy phosphates. Theygenerally contain pyrochlore only in discrete horizons. Theformation of REE phosphate in the upper orehorizon has been ascribed to theinfiltration of ground water byKo- FIG.4. Photomicrograph of high-grade Sc-REE-Y-Nb ore.Transmitted noplev et al. (1992). light.P = pyrochlore crystal.

TOMTOR REE-Nb DEPOSITS, N SIBERIA TABLE 2. Composition of Pyrochlore fromtheTomtor Phosphorus-Rare Element Deposits
Wt %
Carbonatite

681

Nb2Os
67.68 66.92 65.67

TiO2
1.88 4.15 2.15

Ta2s
1.15 2.64 1.42

Fe2Oa
0.10 0.72 0.91

CaO
15.81 14.63 15.44

Na20
5.77 4.43 5.04

K2
0.02 0.03 0.04

BaO
0.10 0.49 0.11

SrO
0.45 1.86 1.24 3.20

Ce2Oa
0.41 1.47 1.62 0.78

Black Brown Red Yellow White

Orange

63.65
68.64 67.41

3.33
3.76 3.47

0.02
0.20

0.40
0.04

16.00
14.77

5.3

6.10

0.03
0.11 0.02

0.02
0.75 9.38

0.00

1.70

Yellow-gray
Black Brown Red

68.87
63.50 65.81 63.38

3.76
1.26 1.39 1.39

2.15
0.20
0.13 0.56 0.14

1.55
1.35
1.01 1.13 0.99

9.35
1.79
16.35 17.7 15.77

2.28
1.33
6.06 16.79 5.87

0.01

7.43

10.59
0.89 0.57 0.57

2.23

0.72
1.27
2.01 0.90 3.18

Lower ore horizon

0.16 0.03 0.18

0.06 0.00 0.17

Yellow

Orange
Pale-yellow Beige

64.33
64.33

2.82
2.82

0.34
0.34

0.70
0.70

14.90
14.90

7.93
7.93

0.17

0.17

0.00

0.00

1.74

1.74

0.59
0.59

57.18 61.20
57.03

3.06 2.70
3.29

0.20 0.07
trace

0.59 0.70
0.82

8.00 4.00
0.99

2.10 3.60
1.71

0.02 0.03
0.01

8.86 5.30
5.52

3.60 14.50
15.2

3.90 0.75
3.93

White

Microprobe analyses by O.M. Georgievskaia.

in thinveins are strongly phosphatic of hydrothermal-metasomatic processes andasa product of pyrochlore-columbite 3B),andsometimes reach oregrade. TheFe203/FeO eationexchange duringlow-temperature processes. The (Table with the ratioof siderite to Fe oxides rounded, shelly variety was probably formed during laterear- ratio(6.2-0.4) correlates bonatization, evidence ofwhich may beseen in thinsections.andhydroxides. The Tomtor complex is richin manganese like the Oka Theactivities of BEE, Ba,Sr,andPbsubstituting forCaand in Canada (MeMahon andHaggarry, 1979). The conNain group A pyroehlore, increased progressively during low- massif oxides in the lower orehorizon is up to andmiddle-temperature processes. PbOcontents in Tomtor tentof manganese We have investigated a zonerichin Mn in the pyroehlore range up to 36 percent (Entinet al., 1991). The 30 percent. partof theearbonatite stock. A newvariety of serdiminishing colorintensity of pyroehlore corresponds to a northern mineral named A1 eariopelite was found atadepth diminishing content ofiron. Almost allvarieties ofpyroehlorepentinelike withbrownire, hausmannite, arepresent inallsamples butin different ratios. Therounded, of100to 150minanassemblage monazite, rhodoehrosite, BEEsvanbergite, barshelly pyroehlore is the predominant typein the upper ore Mngoethite, andBEE goyazite. The composition of one horizon. Thepresence atTomtor of Ce-Ba-Sr pyroehlore and ite, pyrolusite, structural hexagon is (Mn46 Mg2)4s (8i25.5 Ai14.5)(OH48,O8)56 Pbpyroehlore appears toresult fromthespatial superposition et al., 1993). of different processes thatled to the formation of the five (Organova varieties of pyroehlore. Theratio of sO ealeite-pyroehlore composition of upperorehorizon in thelower orehorizon probably reflects hydrothermal tem- Mineral peratures (Pokrovsky et al., 1990). The upperorehorizon is essentially a buried fioreneitemonazite-pyroehlore placer which wasformed by redeposiMineralcomposition of thelowerorehorizon tion of weathered earbonatite (Fig.4). It is considered by Themineral composition ofthelower orehorizon has been Konoplev et al. (1992)that BEE, Ba, and Sr phosphates investigated in thenorthern partofthecarbonatite stock (Fig. belonging totheerandallite group formed after placer forma2; Table 3). The main mineralsare francolite(19.45-64.56%) tion. The main minerals, besides pyroehlore (up to 20%) andsiderite (10.86-60.38%) to a depthof 200 m, where car- include fioreneite, rhabdophanite, goreeixite, and goyazite bonarite is encountered. These two minerals were formed at (Figs. 3 and 4; Table 4A and B). All phosphates andalumodifferent times as a result of different P-T-Eh conditions. phosphates areSeandY bearing andveryfinegrained. The formation of siderite is interpreted to haveoccurred Threetypes of pyroehlore aredistinguished in theupper under reducing conditions (partly bypercolation ofrainwater ore horizon(Table4): predominantly yellow,transparent; thathadbeen reduced byinteraction withcoal), whereas the beige, rounded, and shelly, and intensely altered byearbonatiformation of francolite is interpreted to havetakenplace zation;and eolloform, observed asthin veinsin carbonate. underoxidizing conditions (Lapinand Tolstov, 1991)and Geochemical Features of the Carbonatite at least partly underhydrothermal conditions (Aplonov and and Nb-REE Deposits Erlich, 1980). Themineral composition ofthelower orehorizonin thispart of the complex wascreated by the spatial Isotopic geochemistry superposition of at leastthreeprocesses mentioned above: compositions ofcarbonate, pyrochlore, and weathering, hydrothermal metasomatic processes as estab- TheSrisotope (Table 5) areuseful genetic indicators because of the lished by isotope geothermometry (Pokrovsky et al.,1990), apatite minerals' verylowRb/Sr ratios (less 0.01). Initial S7Sr/S6Sr andlow-temperature sideritization. for these minerals in Tomtorcarbonatites range from Lowerore horizon rocks whichcontain pyrochlore and ratios

682

KRAVCHENKO AND POKROVSKY

TABLE 3. A. Mineralogical Composition (mass %) of Rocks andOres

from the Lower Ore Horizon (drill hole 104)

Interval (m)

92-113

118-128

177-197

199-206

237-249

0.70346 to 0.70374. Thisinterval corresponds to the modal mean of a large selection (n = 118)of carbonatites compiled by Samoilov (1984)andis consistent with a mantleorigin for the magmas. However, the range is higher thanthatfor
carbonatites from the Guli massif located west of the Anabar

Wt percent of 0.05
mm fraction 66 83 76 69

Shield. Theobserved range islarger than theanalytical uncer0.48

27.07

F apatite
Francolite

3.80
64.56
0.06

10.72
37.94

tr
19.45
tr

36.19

Svanbergite
Monazite

tr
tr

tainty. Carbonates from the lower ore horizon(calcite+ dolomite)

Pyrochlore
Columbite Ilmenorutile Rutile
Brucite Anatase Priderite

0.76
0.44 0.06 0.04
,0.47

0.08
0.87 0.04 0.01

2.55
tr 0.23
0.23

0.08
1.04

0.10
tr

arenoticeably richer in SVSr and have a wider range ofS7Sr/ S6Sr initial rtios (0.70374-0.70421) thanis observed in the
carbonatites. However, pyroehlore fromthe lowerore horizonhas anSrisotope composition similar tothatofpyroehlore
from the the carbonatites.

0.01

0.08

Fe oxides and

hydroxides
Hematite, martRe

0.91
0.82

tr
4.58 0.52

28.83
0.05

One sample from the outercontact of Ripbean marble (dolomitic limestone) hasan S7Srff6Sr ratioof 0.70667. As a wholethe Anabar Ripbean sedimentary deposits arecharac-

terized byrelatively lowS7Sr/S6Sr ratios (0.7048-0.7064, Pokrovsky andVinogradov, 1991). The Sr isotope inhomogeneity in the Tomforrocks and oressuggests thatat least twoSr reservoirs wereinvolved in their formation. One reservoir wasdepleted mantlerepre-

Pyrite Sphalerite
Galena
Mica

0.12 0.01
0.03

0.47 tr
0.01

6.00 tr
0.01
tr

6.24
0.01
1.31

0.10 0.01
tr

Clayaggregate with
limonite Calcite

0.36

0.04

0.02

0.08

19.66 0.03

sented bythecarbonatites. Thecorrelation of S7Sr/86Sr' and 8sO shows that sedimentary country rocks were probably the

second source of Sr. However, Sr concentrations are very highin the carbonatites andthe weathered rocks, whereas those in thesedimentary limestone areanorder of magnitude Tr = traceminerals including sphene, zircon, garnet, barite,thaumasite, lower.Mixing of mantle andcrustal Srwas probably carried fluorite, moissonite, cinnabar, ilmenite, chalcopyrite, pyrrhotite, hydromica, out by high Sr brines which are a common feature of sedimenchlorite, halloysite, Sr apatite, braunate, hausmannite, Mn goethite, pyrolusite, and kaolinitc tarybasins.
Siderite, rhodochrosite 12.67 44.45 60.38 35.91 10.86

Quartz+ feldspar

14.88

5.37

4.70

18.38

12.86

The8sO values in carbonates from thecarbonatites range from8.9 to 14.0per mil andthe 8aC values range from -4.6 to -3.0 permil(Table 6).In 8sO-8aC coordinates the
TABLE 3. B. Chemical Composition (mass %) of Rocks andOresfromthe LowerOre Horizon (drillhole104), Together withAverage DatafromLapinandTolstov (1991)
Interval(m)
92-113 117-128 177-197 199-206 237-249 i 2

Averages
3 4 5

SiO2 TiO2 A1203 Fe203

FeO MnO CaO

12.06 1.64 1.96 10.40

3.59 1.56 30.70

5.67 1.28 1.00 4.33

12.93 3.53 26.45

5.76 1.96 0.92 22.38

17.96 3.92 14.87

13.59 0.74 2.96 7.03

16.8 4.39 16.56

14.43 0.48 0.60 33.03

5.32 0.74 17.48

5.04 0.14 0.10 4.72

2.10 0.90 45.50

2.17 0.70 0.35 59.02

2.37 6.00 3.74

5.90 0.25 0.10 19.08

1.15 3.92 34.75

7.84 8.86 11.79 6.15

1.62 0.08 2.79

0.98 1.18 3.58 5.96

35.78 8.00 3.43

MgO
NaaO K20 PO5 COa HO + HaOF S

0.50
0.30 0.70 20.40 3.52 0.38 2.24
2.10 0.17

0.20
0.20 0.15 19.44 10.12 0.24 1.30
2.00 0.41

0.50
0.20 0.30 12.01 11.66 0.16 1.38
1.58 2.31

1.70
0.10 2.30 10.67 13.86 0.26 1.54
1.54 2.08

0.35
0.15 0.10 11.42 3.74 0.54 1.45
1.45 0.21

1.06
0.12 0.11 3.16 33.59

0.40
0.12 0.04 4.26 4.74

0.26
0.13 0.05 25.02 4.00

0.09
0.22 0.10 16.73 0.31

0.68
0.07 0.07 3.62 25.62

0.27

0.25

0.25

0.32

1.62

OF2
TotM

0.88
91.32

0.84
88.41

0.67
97.20

0.65
94.8

0.61
94.83

Analyst K. Poljacova
REE, Sr, and Ba not determined.

Samples: 1 = calcitic carbonatite (n = 2), 2 = goethitic ocher (n = 2), 3 = goethite-francolite rocks (n = 2), 4 = kaolinite-crandallite rocks (n = 3), 5
= sideritic rocks (n = 2).

TOMTOR REE-Nb DEPOSITS, N SIBERIA

683

TABLE 4. A. Mineralogical Composition (mass %) of theUpper Ore Horizon (sample 5649-83, 0.05-ram fraction)
F apatite 0.20

TABLE 5. Strontium Isotope Composition of Tomtor Carbonate andPyrochlore

Fe oxides andhydroxides
Francolite

0.24
0.32

Sample no.

Mineral, rock
Carbonatite

SVSr/S*Sr

Sr(ppm)

Pyrite

19.60

Monazite, fiorencite, gorceixite, goyzite

Galena

27.83
0.03

103/80 103/113
103/202

Calcite + dolomite Calcite + dolomite

Calcite + dolomite

0.70362 0.70347
0.70346

3,400 4,700 2,900

Svanbergite
Calcite

1.27
0.28

103/213

Calcite + dolomite

0.70355

Pyrochlore
Siderite,rhodochrosite, rutfie
Dolomite
Anatase

7.26
16.13
10.08
6.05

103/185

Pyrochlore
Lower ore horizon

0.70374

3,500

Quartz andfeldspar

9.27

107/172

Calcite + dolomite

0.70374

107/202 107/228 107/292

Calcite + dolomite Calcite + dolomite Calcite + dolomite

0.70374 0.70421 0.70395

4,700 4,300 2,100

Tomtor carbonatites define a trendlinking normal carbonatitessuch asOka(Convey andTaylor, 1969) or Guli(PokrovskyandVinogradov, 1987)andsedimentary carbonate rocks (Fig.5). Thistrendcanbe attributed to fraetionation between CO2-rieh fluidandearbonatite meltaswell asto mixing of
mantle and crustal material. The correlation between 9sO

111/58

Pyrochlore

0.70371

7,000

Riphean sediments
F-2A/86 Marble 0.70667 170

and 87Sr/86Sr supports mixing rather than differentiation, but -3.4 to -15.8 permil (-59.9%0in onespecimen). Carbonwecannot exclude acombination ofcrystallization differentia- ates from theupper orehorizon have 9So (10.5-21.6%o) and
tion of the earbonatite melt and interaction with crustal mate-

orehorizon. On thewhole, carbonates fromthe upperand Carbonates ofthelower ore horizon have 51sO values rang- lower orehorizons areenriched in so anddepleted in 3C ingfrom11.0 to 23.1perrailand93C values ranging from compared withthecarbonatites. Thelow93C values indicate thatthe rocks wereformed notonlyfrommantle CO2and sedimentary carbon but also withanimportant contribution TABLE 4. B. Chemical Composition (mass %) of Minerals fromtheUpper Ore Horizon (sample 5649-83) of CO.,derived from the oxidation of organic matterand methane. Bothcarbon andoxygen isotope fractionation val1 2 3 4 5 6 ues between dolomite and calcite vary widely (Fig. 5). In (7) (3) (4) themajority of specimens these minerals arenotin isotopic equilibrium. SiO2 0.05 0.57 0.08 0.5 1.2 0.3 TiO2 4.21 2.97 The range in the oxygen isotope composition of quartz
ZrO2 0.21

rial during formation of the metasomatie earbonatites.

93C(-3.2 to -19.9) values similar to thosefromthe lower

NbzO5 LazO3
CeOa Pr2Oa

13.18 33.79 0.67

63.55 0.32
0.68

54.31
1.76

0.9 2.2 0.3

0.8 1.3 0.4

3.8 5.65

from carbonatites (9so = 11.3-17.2%o) and the lower ore horizon(51so = 10.2 -16.3%o) is similar. Thesevalues are

Nd2Oa
SmOa Gd203 ScO, UOz ThO,2 Fe2Oa
FeO

11.59
1.12 0.43 0.65 0.07 0.00 0.00

0.04

0.18

0.6

0.4

1.45

unusually high forplutonic rocks and suggest formation under hydrothermal conditions. Magnetite and pyrochlore from carbonatite and thelower orehorizon have very low51SO values, from -9.4 to 0.0 per mil, alsoindicating a hydrothermal
origin.

0.18

0.90
0.8 2.6 0.8

AlcOa
SrO BaO CaO NaO K20 P205
F

0.00
2.46 1.18 15.10 7.42 0.07
4.86

32.0
15.92 5.59 0.50 1.58 10.6 6.5 2.7

28.3
0.0 11.0 3.1

26.4
4.8 4.6 0.9

If it is assumed thatcalcite andmagnetite arein isotopic equilibrium, the oxygen isotope fraetionation between these minerals canbe used to determine the temperatures of ore formation. The temperatures calculated for the lowerore horizon using theequation ofConvey and Taylor (1969) range from131 to 267C (Fig.6).

The534S values in sulfide minerals (Table 7, Fig.7) show

a very widerange from-33.9 to28.8permil.Thesulfides in
the lower ore horizon are therefore not derived from mantle

32.46
0.86 1.08

26.1
99.68 2.04 97.64 92.74 0.45 92.29

26.4

28.3

magmatie sulfur. It is also veryunlikely thatsulfur in pyrite

origin. A mantle source for sulfur in galena andpyritefrom 99.05 the carbonatites canalsobe ruledout andtheyare very much outof equilibrium withthepyrite.Sulfate reduction, (1)monazite, (2)yellow pyrochlore, (3)beige pyroehlore, (4)goyazite, (5) at lowtemperatures, is accompanied by a very gorceixite, (6) florencite; 1-3, microprobe analyses (analyst O.M.Georgiev- particularly fractionation of sulfur isotopes. Nevertheless, evenexskaia); 4-6, averages fromKonoplev et al. (1992): number of samples in large parentheses tremeevolution of a single solution cannot explain theheavi-

Sum O---F Total

((53zfS = -5.4 to+2.8%0) from the carbonatites isofmagmatic

684

KRAVCHENKO AND POKROVSKY

TABLE 6. Oxygen andCarbon Isotope Composition

of Tomtor Calcite and Dolomite Dolomite

Calcite

(_+MnCO3 + FeCO3)

Sample
no.

6'3C
(%o)

6180
(%o)

613C
(%o)

ilS
<%o)

Upperorehorizon
4825/77 4075/45
4068/128

-- 16.0 -5.6
-9.6

mm

- 14.0
- 10.6

21.6
13.4

19.9 10.5
15.1
21.5

-0

Lb,

--

4825/153 4829/135 4071/149 110/47 5650/95 5648/69

4009/49

- 17.5 - 12.8 - 11.3 - 12.9

15.4 16.2 16.6 15.2

- 19.9 -3.2 - 18.4 -4.5 - 12.9 - 12.9

-9.8

13.1
14.5
12.5
16.9

10.9
12.6

5650/81 5651/64 4825/83

-7.7
- 13.8

18.4
18.1

-9.9 -7.8 - 15.3

12.8
20.8 ,

Lower ore horizon

104/118 107/118 107/172a -7.5 -4.8 -6.4 15.0 16.5 17.5

FIc. 5. 63C-6sO relationships of Tomtor carbonates. 1 = carbonatite,

-4.5
12.4

107/172b
106/202 107/228 107/247 107/292 111/159 111/215 113/145 113/185

-5.2
-4.5 -5.8 -4.3 -4.0 -5.0 -3.3 -15.8

12.9
14.8 15.9 17.3 12.0 19.7 22.4 19.4

2 = lower orehorizon, 3 = upper orehorizon, 4 = Guly carbonatite (PokrovskyandVinogradov, 1987), 5 = sedimentary rocks. Opensymbols = dolomite,filledsymbols = calcite.

-3.4 -3.3 -59.9

11.9
11.0

23.1lower ore horizon were formed partly under hydrothermal

,mO, % Oka
20
Tomtor

On thewhole, sulfur andoxygen isotope temperatures are in goodagreement. Theyshow that isotopic systems of the

Carbonatite
104/118
103/116 103/133

-4.2
-4.3 -4.6

10.5
10.0

-3.9

9.2 8.9

103/172 103/185 103/202 103/213

-4.3 -3.0 -3.8 -3.8

10.2 14.0 11.6 13.8

16

Riphean marble
F-2A/86 F-2B/86 -3.4 -2.2 20.8 23.3 -2.1 -2.0 22.4 23.0

12

estandlightest sulfide values for the Tomtor rocks. At least threesources of sulfur may be suggested forTomtor sulfides:

heavy seawater sulfate, 64S values morethan20 per mil; light diagenetic H2S, 64S values less than-20 permil;and magmatic S,634S near 0. The634S fractionation between sphalerite andgalena in thelower orehorizon ranges from3.0to 4.0 permil (Fig.7) andcorresponds to temperatures of 135 to 245C using the equations collected by Friedman and O'Neil (1977).Two pyrite-galena pairsgivehigher temperatures (272-313C), [ 0-1 $-2 whereas twoother pairs appear nottobein equilibrium. One sphalerite-galena pairfromcarbonatite gives an improbably FIc. 6. 6180 fractionation between equilibrium minerals. 1 = calcite, 2 lowtemperature (50-60C), suggesting a lackof equilibrium = magnetite, 3 = pyrochlore. Temperatures calculated afterthe equation
between the two minerals.

of Pokrovsky et al. (1991).

TOMTORREE-NbDEPOSITS, N SIBERIA

685

TABLE 7. Isotopic Composition of Sulfurin TomtorSulfides

6a4S (%)

Sample no.

Pyrite

Galena

Sphalerite
CaO

Lower ore horizon 107/172 107/202 107/228 107/277 19.4 -7.7 28.8 - 7.3 Carbonafire
103/277 0.3 -33.9 -26.5
Cl

-0.9 - 11.4 - 17.3 - 10.5

3.0 - 13.25 - 7.5

103/80 103/101 103/213 103/133 103/172

0.0 2.8 -0.8 -5.4 -3.8

iI
o 50 Mg0

FIG. 8. Geochemistry of carbonatites in the CaO-MgO-FeO diagram (mass percent). Thelines approximate chemical trends forTomtor andother carbonatites. C = Chilva, F = Fen,K = Kangankunde, T = Tundulu; circles = single carbonatite compositions fromNelson et al. (1988). i = Lokupoi,
calcite; 2 = Suculu,dolomite;3 = Nachendaz,calcite; 4 = Goudini,ankerite-

conditions at mean temperatures of 200 to 250C. A single dolomite; 5 = Goudini, ankerite-dolomite; 6 = Wallouway, calcite; 7= measurement ofthehydrogen isotope composition ofchlorite Mudtank, dolomite;8 = Mount Weld, calcite;9 = Mount Weld, calcite;10 calcite; 11 = Jacupiranga, calcite; 12 = Magnet Cove, calcite; fromthelower orehorizon (tD = -135%o) suggests surface = Jacupiranga,
water as the main source of the solutions.
13 = Kaiserstuhl,calcite.

Geochemistry of majorandtraceelements sideritecarbonatites of the Tundulu massif(Africa). There is The composition of the carbonatite varies fromdolomite- a trendtoward increasing Mg in the middlestage, andincalcite andcalcitic to ankeritic. Ascanbe seen in Figure 8, creasing Fe in the late evolution of the carbonatite melt. thecomposition of theankerite carbonatite isverysimilar to The same Mg trendis a feature of the carbonatite series of that ofankerite carbonatite from Gudini (Africa). Thecompo- Kangancunde (Africa), Fen (Norway), andTundulu (Africa). sitional trend forcarbonatites in theCaO-MgO-FeO diagram The REE patterns for carbonatites aresimilar to those of shows anintermediate position between thecalcite-dolomite other Tomtor rocks and ores (Fig. 9) and show an enrichment carbonatites of the Chilwa massif(Africa) and the calcitein lightlanthanoids andan absence of Eu anomalies. The relationships between Nb andCe in carbonatites containing pyrochlore and phosphates have been investigated in Tomtor samples (n = 88). Nb and Ce have a high correlation coeffis carbonatites L OH cientof 0.56(Table8), but Sr andBa,which aredispersed in carbonatites, arepoorly correlated with Nb, Ce, andY. The Tomtor ores typically havea higheffective porosity, upto47 5 percent in highrade sectors Their s ecific ravi 3 g ' P g ty is2.24 g/cmcompared with 4.18g/cm 3forthesame material without pores. Theporosity ofthelower orehorizon has been
o

o
I0s

.-3

-_

I0a

i l

La Ce

Nd SmEu

Tb

Yb tu

FIG.7. Sulfur isotope compositions of sulfides fromcarbonatite andthe FIG. 9. Chondrite-normalized patternof lanthanides (Evensen et al., 2 = rocksand ores of the lower ore horizon,3 = lower orehorizon. Minerals in equilibrium areconnected withsolid lines, 1978). i = carbonatite, nonequilibrrum minerals withdotted lines. i = pyrite, 2 = sphalerite, 3 = ores oftheupper orehorizon, 4 = Middle Permian sedimentary rocks above
galena. the upperore horizon.

686

KRAVCHENKO AND POKROVSK

TABLE 8.

Correlation Coefficients(X100) of Concentrations of Rare Elementsin Carbonatite(n = 88)

Nb Ce
65 56

andupper orehorizons (0.06-0.07). Thenearly constant Ce/ Nb ratioin different Tomtorrocks andoresis probably a consequence of buffering by the mineral association. Mineralogieal data show thatNb iscontained inpyroehlore,
eolumbite,rutfie, and ilmenorutile,and REE and Y in fioren-

cite,monazite, rhabdophane, bastnisite, xenotime, etc.,Sein monazite, rhabdophane (0.55-0.95%), minerals of the erandallite group (0.017-0.030%), ruffle, andfilms of Se(OH)a on examined in detailin the north-central part of the massif phosphates (discovered by Y. P. Diekovusingthe X-ray (drill hole 104,Table9A). The effective porosity correlates photo-electron method). positively only withtheBacontent andwas probably formed Discussion and Conclusions aftergeneration of pyroehlore andfrancolite, because of the a voleano-plutonie complex withanexnegative correlation between porosity andNb andP (Table Tomtorrepresents weathering capdeveloped onthe earbonatites andis 9A). As canbe seenfromthe typeof correlations between tensive to deposits such asAraxa andSeis Lagos in Brazil and effective porosity andthe contents of minorandtraceele- similar whichare important deposits of ments, theyare different fromtypical weathering crusts in MountWeld in Australia, SeandY). In theTomtor oredeposwhich, asa rule,anincrease in porosity increases thecontents Nb andREE (including different processes weresuperimposed in space of theinertcomponents. Thecorrelation of elements in sam- its,several during their geologic history. This led to the development of plescollected fromdifferent parts of the lowerorehorizon of mineral development, particularly for (Table 9B) issimilar to thatforsamples fromtheonevertical manygenerations (Belyaeov et al.,1989, 1990). Several types of ores section. The good correlation between Nb andCe(Y)proba- pyroehlore including Se-REE-Y-Nb and Nb (Kravblymeans thatin rocks andores containing lowREE andP, were developed et al., 1990,1992b; Konoplev et al., 1992),P andFe the REE arecontained mainly in pyroehlore. The REE pat- ehenko tern for the lower ore horizon is similar to that of other rocks (Egorov et al., 1985),andmanganese (Entinet al., 1990). oftenhaveveryhighconcentrations of ecoof the massif andshows an enrichment in lightlanthanidesThesedeposits nomic components. andlackof an Eu anomaly. TheTomtor earbonatites contain magmatie calcite anddoDifferentiation of lanthanides duringformation of the carbonates, whose range of Tomtor massif (Fig.9) was notasintense asduring theforma- lomite,aswell asmetasomatie

Y Nb

57

tion of weathered earbonatitesat Mount Weld in Australia, Fecontent isvery wide. Theinitial 87Sr/S6Sr provides evidence where ehurehitehasbeen observed (Lottermoser,1990).The of a mantle source forthe magmas, witha minor addition of ratio of REEce/REEin weatheredmaterial at Mount Weld radiogenic Sr from the hostsedimentary rocks. However,

of the hostsedimentary rocks appears unlikely ranges up to 40, whereas that at Tomtorranges up to 20. assimilation REE contentsin Se-REE-Y-Nb ores at Tomtor (Table 10) because of theirverylow Sr content. The addition of Sr is dueto the effectof brines witha highSr content. areverysimilar to those in Lovozero loparite in which the probably The lowerore horizon developed on earbonatite, rocks contents of Nb andREE range from4.24to 8.25and25.58 asvoleanies, andprobably alsoin sedimentary to 30.81percent, respectively. TheTomtor ores area natural interpreted concentrate of pyroehlore andREE (Sr,Ba)phosphates and are threetimesricherin pyroehlore thanoresfromAraxa TABLE 9. A. Correlation Coefficients (X100)of Porosity andRare in Brazil,and an orderof magnitude richerin rare-earth Elementsin a Sectionof the Lower Ore Horizon (drill hole 104, n = 12) phosphates (Table 4A andB).TheREE pattern issimilar to that in Khibina apatite, but the REEcdREEyratiois twice PsOs Nb Sr La Ce Ba Y ashighat Tomtor andthe REE content an orderof magni-35 -35 -31 -28 -25 54 tudehigher (Table 11).Khibina apatite also has a small nega- Porosity 63 44 57 59 PsOs tiveEu anomaly. 62 Nb 34 95 96 REE concentrations at Tomtorare highest in the upper Sr 56 98 71 orehorizon andthe REE pattern is verysimilar to thatin La 80 earbonatite andijolite. Thecorrelations between elements in Ce 37 Ba the upperorehorizon aredifferent fromthose in the lower ore horizon (Tables 9 and 12). This results fromthe high content of REE-(Sr-Ba)-Se-Y-bearing phosphates: Bain rich TABLE9. B. CorrelationCoefficients (X100) of Rare Element ores correlates withY, Se,andSr.The Nb/Ceratiowas nearly Concentrations in the Lower Ore Horizon (n = 27) constant (0.6-0.7)duringformation of the Tomtormassif (Fig.10,Table13).Only thePermian sedimentary rocks have Sr Y Nb Ba Ce Th higher Nb/Ce ratios and these probably result fromredepositionof oreminerals fromthe upperorehorizon since frag- Sc 24 47 52 52 73 25 52 45 ments of crystals of pyroehlore havebeenobserved in thin Sr
sections of the Permian rocks. Sr/Ba ratios decrease from
Y

83

73
43

76
40 66

0.072in ijoliteto 0.013and0.010in lowerandupperore horizons, respectively. The maximum Y/Cevalues arefound in earbonatite andijolite(0.12), withlower values in thelower

Nb
Ba

Ce

TOMTORREE-NbDEPOSITS, N SIBERIA

687

TABLE 10. Concentrations (mass %) of Economic andOtherConponents in Ores of the UpperOre Horizon
Sc
Mean concentration

RE E

Nb

Th

Reference

0.039 0.039 0.038

0.62 0.79 0.30

11.00 13.82 8.34

4.20 5.40 3.01

0.61 0.68

0.01

0.11

4.97

0.12

(Konoplev et al., 1992) (Lapin andTolstoy, 1993) Thispaper

Sample 5649/83
0.085 0.70 31.49 8.72

6.98

(Kravchenko et al., 1990)

rocks dueto a combination of hydrothermal alteration, low- of heavy minerals in an aqueous environment. In addition temperature sideritization, andweathering. Konoplev et al. (1992)attribute the development of REE Thereis agreement thatthe formation of the lowerand phosphate minerals to ground-water infiltration. upper orehorizons was a complex process. Lapin andTolstoy In the upperore horizon, several periods of weathering (1991, 1993) have described twoprocesses: upper orehorizon andhydrothermal alteration (including sideritization) probaenrichment dueto removal of mobile components, andto blyoccurred following deposition ofearly, weathered material accumulation of inertconstituents during oxidation andre- in an aqueous environment. The possible role of bacterial duction. Entinet al. (1991)considers onlythe addition of growth anddecay in changing water pH andpromoting the material during development of the upperore horizon by precipitation ofphosphates in theupper orehorizon has been discussed by Zhmuret al. (1994). metasomatism of rocks interpreted to have been phosphatic lavas. Kravchenko et al. (1990)andKonoplev et al. (1992) The Tomtor massif is composed mainly of latedifferentihave described the redeposition of weathered material and ates including nepheline andnepheline-bearing syenites and enrichment in heavy minerals (pyrochlore, monazite, etc.) earbonatites. This possibly indicates a substantial roleforcrysduring erosion of the ore-bearing sequence anddepositiontallization differentiation asa precursor to mineralization. A correlation between Nb resources andthearea of syenite and earbonatite in alkaline-ultrabasie massifs hasbeennoted by TABLE 11. Concentrations of MajorElements andREE (mass %)
andREE in Apatite froInthe Khibina Massif

Kravehenko(1982).

Upper orehorizon (Sample 5649/83)

SiO2 TiO2 3.11 5.54

Khibina massif apatite (n = 5)

Nb205 Fe203 A1203

PeO MnO

12.47 7.40 1.14

1.61 0.02

MgO
CaO

1.5
2.63

Na,20 KO P205 CO
F

0.15 0.1 18.24 0.88

0.62

1.0

H,20 La20 Ce2Oa PrO3

1.12 9.75 17.81 1.64

0.28

Nd203
Sm203 Eu20

5.69
0.61 0.14

Gd,20 Tb203 Dy203

HoO3 ErgO3 Tm203

0.40 0.07 0.21

0.04 0.09 0.03

Yb203 Lu.203 YO3 ScO3

0.007 0.002 1.36 0.13

0.43 0.04 0.14 0.02 0.005 0.0015 0.002 0.083 0.0015 0.0034 0.0009 0.0016 0.0005

Francolite zones areusual in weathering crusts formed on earbonatites. Homogenization temperatures of vapor-liquid inclusions (Aplonov and Erlieh,1980)suggest that at least some of the francolite maybe hydrothermal in origin. According to deerepitation temperatures, Aplonov andErlieh (1980)propose a stage of hydrothermal alteration at 500 to 300C based on quartz, hematite, andfrancolite data.Most francolite, whichforms a net of veins with associated pyrite andhematite, mayhaveformed in the temperature interval between 310 and350C (main deerepitation peak). Zones of sideritization areusually developed vialow-temperature fluidinteraction in a reducing environment. The H isotope composition in sample 111/125 fromthe lowerore horizon (tSD = -135%o;Pokrovsky et al., 1990)maygivean indication of the palcoclimate. Fractionation in the system chlorite-water at 200 to 250C is 40 per mil andthepalcowaterin equilibrium withchlorite hadtSD= -90 per mil, similar tothatofmodern waters in temperate climatic regions
(Maruto et al., 1980).
TABLE 12. Correlation Coefficients (X100)of Upper Ore Horizon
Rare Element Concentrations (n = 90)
Sr Sc Sr
Y

Y 71 16

Nb 49 62
33

Ba 33 42 18

Ce 49 22
68

Th 74 28 53

24

Nb
Ba Ce

24

34
16
52

688

KRAVCHENKO AND POKROVSKY

TABLE 13. Range (in parentheses) andAverage Concentration (ppm) of RareElements in Rocks andOresfromtheTomtor Massif
Ijolite
n 11

Carbonatite
86

Lowerorehorizon
26

Upperorehorizon
92

Permian sediments
27

La Ce Sm Eu Yb Lu Se Y Sr Ba Zr Nb Th

536 (115-3,140) 1,027 (254-5,295) 60 (6-313) 23 (3-127)

1,396 (20-12,610) 2,606 (260-12,610)

74 (13-332) 75 (2-556) 4,786 (1,273-12,372) 3,003 (508-16,695) 670 (2-3,393) 743 (65-5,199) 90 (6-664)

285 (20-2,300) 4,018 (1,260-28,000) 3,429 (150-17,000) 41 (1-600) 1,500 (20-8,540)

4,043 (358-15,928) 7,561 (280-38,158) 377 (21-1,582) 156 (19-797) 75 (6-497) 9 (1-80) 89 (16-358) 528 (2-3,680) 6,367 (610-20,007) 7,542 (1,066-20,604) 338 (2-2,330) 4,435 (60-40,749) 248 (14-1,495)

21,851 (874-126,744) 41,150 (2,123-210,584) 2,304 (40-10,690) 702 (33-7,319) 283 (15-1,876) 35 (0.5.260) 390 (39-2,214) 2,969 (58-25,288) 19,521(907-62,748) 20,119 (518-141,291) 121 (2-3,213) 30,102 (1,190-144,578) 1,155 (14-9,209)

5,264 (323-40,130) 10,997 (182-72,531) 664 (6-7,571) 257 (5-3,252)

9 (1.24) 204 (4-1,918) 1,520 (2-25,288) 10,948(1,009-51,117) 10,739 (1,176-30,295) 769 (2-2,186) 12,573 (2-91,470) 571 (6-3,467)

Average concentrations arelower than oregrades because they include low-grade rocks; analysts: V.I. Kaluzny, J.V.Terechov, andB.A.Ziskin

ofthelarge carbonatite stock asa result ofcrystallization The(180 values in Tomtor carbonatites arevery high and ment and metasomatism, weathering and hydrothersuggest the existence of at least twosources of oxygen (Fig. differentiation of thelower orehorizon, erosion andredeposi5). In rocks andoresof the upperandlowerore horizons, malalteration andmonazite. The development of REE 980 values are higher still and overlap therange forsedimen-tionof pyrochlore in the upperorehorizon maybe a consequence tary carbonates. The53C values in carbonatites are high and phosphates ground waterandat lastpartly dueto hydroareverylowin rocks andores of thelower orehorizon, and of percolating processes andlow-temperature, possibly repeated, especially theupperorehorizon. The latterpossibly reflects thermal sideritization. theinfluence of organic matter during the Permian. at Tomtor of large P, REE, andNb ore A good correlation between Nb andREE in carbonatites The development wasnotaccidental but,aswithothergiant massifs andthe lowerorehorizon mayindicate thatthese elements deposits Khibina andLovozero), was theresult of a regular arecontained mainly in pyrochlore. Correlation of lower ore (including of features favorable for development of the horizon porosity onlywith Ba is not characteristic of typical combination ore deposits of P, Nb(-Ta),REE, Sc,andY during weathering crusts. Asnoted above, a small change in theNb/ largest et al., 1992b). Ce ratioin different rocks andoresduring superposition in their evolution(Kravchenko space of several processes (Fig.9) maybe dueto buffering Acknowledgments by the mineral association. These process include developWe thank Economic Geology reviewers for helpwiththe manuscript, I.N. Kigai forhelpin translation, andA.V.Zharikovfor helpin transferring the manuscript to disk. We also thankthe manager of geology of the Tomtordeposit, A.I. Kubishev, geologist A.V.Tolstov, and themanager ofgeology of the Chernishevsky Expedition of theYacutian Geological Survey, A.T. Vasilyev, for helpduring fieldinvestigations.

-' III I IIIII

--

REFERENCES

Aplonov, V.S.,andErlich,E.N., 1980,The temperatures of the Tomtor miner'ds, rocks andores generation, in Alkaline magmatism andapatitebearing of northern Siberia: Leningrad, Arcticgeology Institute, p. 112123 (in Russian).

Belyakov, A.Y.,Georgievskaj, O.M., andGrjaznova, J.A.,1989,Chemistry of Tomformassif pyrochlore: VUZ'ov Izvestia SeriiaGeologicheskia Razvedca Rudnich Mestorogdenii, no.8, p. 33-39 (in Russian).
LI

Convey, C.M.,and Taylor, H.P., 1969, SO/60 and 3C/2C ratio ofcoexisting
minerals in the OkaandMagnet Covecarbonafire bodies: Journal of Geology, v. 77,p. 618-626. Egorov, L.S., Surina, L.S., and Porshnev, G.J., 1985, Oremagmatic ultrabasic alkaline rocks andcarbonatites complex of Udgy, in Ore-magmatic complexes in north-west Siberia platform andTaymyr: Leningrad, Nedra, p.
138-154 (in Russian).

t:0,47

Fro. 10. Average concentration of Nb vs.Ce. 1, Tomfor massif.' J= ijolite-urtite, K = carbonatite, LOH = lower orehorizon, NS = nepheline (in Russian). A.R.,Eremenko, G.K.,andTjan,O.A.,1991, About alteration ranges syenite, P = Permian rocks, UOH = upper orehorizon; 2, Kh = Khibiny, Entin, of the parentpyrochlores: Akademiia NaukSSSR Doklady, v. 319, p. L1-3 = first,second, andthirdphases of Lovozero; 3, K = kimberlites, N 1218-1221 (in Russian). = nephelenites, afterWedepohl andMuramatsu (1979).

Entin, A.R.,Zaitzev, A.J., andNenashev, N.J.,1990, About therange of the geological events related to theultramafic alkaline rocks intrusion of the Tomtor massif (NM Yakutija): Geology andGeophysics, v. 12,p. 42.51

TOMTORREE-NbDEPOSITS, N SIBERIA

689

Erlich,E.N., 1964, Thenewprovince of alkali rocks onthenorthof Siberian McMahon, B.M., andHaggerty, S.E.,1979, The Okacarbonatate complex: platformand its geological aspects: Zapisky Vsesoiuznogo MineraloMagnetite composition andrelated roleof the titanium in pyrochlore: International Kimbedite Conference, 2nd,Proceedings, v. 1, p. 382-392. gicheskogo Obshestva, v. 93, p. 6824393 (in Russian). Erlich,E.N., andZagrusina, J.A.,1981,Geochronology of the north partof Nelson, D.R., Chivas, A.R.,Chappell, B.W.,andMcCulloch, M.T., 1988, Geochemical andisotopic systematics in carbonatites andimplications for the Siberia platform andits geological aspects: Akademiia NaukSSSR the evolutionof ocean-island sources: Geochimicaet Cosmochimica Acta, Izvestiya, Seriia Geologicheskia, no.9, p. 3-13 (in Russian). Evensen, N.M., Hamilton, P.J.,andO'Nions,R.K.,1978,Rare-earth abunv. 52, p. 1-17. dancesin chondriticmeteorites:Geochimicaet Cosmochimica Acta, v. Organova, N.I., Gorshkov, A.I., Zhuchlistov, A.P., Kuzmina, O.K., Sivzov, 42, p. 1199-1212. A.V.,andKravchenko, S.M.,1993, Al-cariopelite from theweathered carbonatites of theTomfor(northSiberian platform): Akademiia NaukRAN Friedman, J.,andO'Neil,J.R.,1977, Compilation of stable isotope fractionationfactors of geochemical interest, in Fleischer, M., ed.,Dataof geoDoklady, v. 328,p. 234-238(in Russian). Orlova, M.P.,andKrasnov, V.I., 1978,Mapof alkaline magmatic association chemistry, 6th ed.:Washington, D.C., U.S.Printing Office,116p. Konoplev, A.D., Kuzmin, V.I., andEpshtein, E.M., 1992,Geological and and their ore specialization's of USSR:Leningrad, VSEGEI, scale 1:10,000,000(in Russian). geochemical peculiarities talus-lake placer above theweathering crust of G.S.,Sanoilov, V.S.,andGlishev, s.J.,1980, Isotopic pairs (5Cthe rare-elements-bearing carbonatites, in Mineralogy andgeochemistryPlusnin, of placers: Moscow, Nauka, p. 111-123 (in Russian). (SXSO method and temperatures carbonatite facies: Akademiia Nauk SSSR Kravchenko, S.M., 1982,Correlation of the Nb resources of the carbonatitic Doklady, v. 254,p. 1241-1245 (in Russian). complexes with their geological peculiarities: Akademiia Nauk SSSR Pokrovsky, B.G.,and Vinogradov, V.I., 1987, Some elements isotope compositions of ultrabasic-alkaline rocks, Maimecha-Kotuy province: Sovetskaja Doklady, v. 263,p. 168-71(in Russian). Kravchenko, S.M., and Rass,I.T., 1985,The alkaline-ultramafic association-geologija, no.5, p. 81-90 (in Russian). 1991,Strontium, oxygen and carbon isotope composition in upper theparagenesis oftwocomagmatic series: Akademiia Nauk SSSR Doklady, -Precambrian carbonates of Ahabarian rise: Akademiia Nauk SSSR v. 283, p. 973-978 (in Russian). Kravchenko, S.M., Belyakov, A.Y.,Tolstov, A.V.,andKubishev, A.I., 1990, Doklady, v. 320,p. 1245-1250 (in Russian). Sc-REE-Y-Nb ores a newtypeof rareelement economic resource: Inter- Pokrovsky, B.G.,Belyakov, A.Y.,Kravchenko, S.M., andGryaznova, Y.A., national Geology Reviews, v. 33, p. 280-284. 1990,Isotope dataonthe origin of carbonatites andmineraized strata in Kravchenko, S.M., Belyakov, A.Y., Babushkin, P.N., et al., 1992a,Sodium the Tomtorintrusion, NW Yakutia: Geochemistry International, v. 33, p. 93-101. nepheline syenites of Khibina massif arethepossible derivates fromhigh V.S.,1984, Geochemistry of carbonatites: Moscow, Nauka, 190p. calcium alkaline-ultrabasic magma: Geochemistry, no.5, p. 6854396 (in Samoilov,
Russian). (in Russian).

Kravchenko, S.M.,Belyakov, A.Y., andPokrovsky, B.G.,1992b GeochemistryShpunt, B.R.,Shamshina, E.A.,Brachfogel, F.F., andFilipov, N.D., 1991, andgenesis ofTomtor massif (north of Siberian platform): Geochemistry, Composition and petrochemical peculiarities ofthealkaline-utrabasic rock no. 8, p: 1094-1110(in Russian). from Udzhauplift (northof Siberia platform): Akademiia Nauk SSSR Lapin, A.V.,andTolstov, A.V.,1991, Oxidizing andreduclfon stages formaIzvestija, Seriia Geologicheskia, no.8, p. 68-80 (in Russian). tionof zonecarbonatites epygenesis andtheirore-content: Geology of Taylor, H.P.,Fuchen, J.,andDegens, E.T.,1967, Oxygen and carbon isotope Ore Deposits, v. 33, no. 4, p. 81-92 (in Russian). studies of carbonatites fromLaacher See district, WestGermany andAlno -1993,A newunique raremetals ore deposit in the carbonatitic crust district, Sweden: Geochimica et Cosmochimica Acta,v. 31, p. 407430. weathering: Razvedca i Ochrana Nedr,no.3, p. 7-11 (in Russian). Wedepohl, K.H., andMuramatsu, J., 1979,The chemical composition of Lottermoser, B.G., 1990, Rare-earth element mineralizationwithin the Mr. kimberlites compared with the average composition of three basaltic Weldcarbonatite laterite, Western Australia: Lithos, v. 24, p. 151-167. magma types: International Kimberlite Conference, 2nd,Proceedings, v. Maruto, K., Nagasawa, K., andKuroda, Y., 1980,Mineralogy andhydrogen 1, p. 300-312. isotope geochemistry of clayminerals in the Ohnuma geothermal area, Zhmur,S.Y.,Kravchenko, S.M., Rosanov, A.Y., and Zhegallo, E.A, 1994, northeastern Japan: EarthandPlanetary Science Letters, v. 47, p. 25On the richores origin fromTomtor massif (north of Siberia platform): 262. Rossiiskia Akademiia NaukDoklady, v. 336,p. 372-375(in Russian).