.~------.--------.

JOURNAL OF THE MINERALOGICAL SOCIETY OF INDIA

(Affiliated to the International Mineralogical Association)

VOLUME 42, N(). 1 JANUARY 2008

Mineraloglcal'rJ11~f!il)

Society
of

~ifi!ll-~1

INDIA

l\-IYSORE

2008

The Indian.Mineralogist, Vol.42,.No.l,Januaiy2D08,Pp.62-70

© 2008 The Mineralogical Society ofIndia, Mysore, ISSN :0019-5928 .

PGE MINERALIZATION INKATHPAL CHRO:MlTES~ SuKrNDAULTRAMAFIC COMPLEX, ORISSA,lNDIA' .. .. D.

MOHANTY1,2 and

A.K~ SENt

'Department of Earth Sciences, IIT Roorkee, Roorkee~247667, Uttatakhand. 2Department of Mining & Mineral Resources Engineering; Southern IIlinois University, Carbondale, Illinois 62901. e-mail: drddmohantytarediffmail.com, senakfes@iitr.emet.in
A:SSTRA.CT Kathpal chromite bodies are located in the western-most extreme of Sukinda ultramafic complex and emplaced within Iron. Ore Group of rocks. The chromite ore occurs as randomly oriented Iensoid bodies within serpentinized ultramafic rocks. but preserves the primary .igneous features. Gradational variation in Cr-spinel proportion from ore to ihosr rock with agenenH low Cd %) concentration of sulfide minerals is characteristics. of these ores, the PCE concentration.fn the chrornite ores and the associated rocks is in sub-chondritic level with dominance Of IPGE (Os;. Ir & Ru) and the chrornite ore is enriched inPGE concentration compared to the associated rocks, It indicates strong partitioning of POE into crystallizing- Cr-spinels at high temperature (high Mg#) and .relatively higher fa, (IbwFe2t/[Fe2++Fe3+]). Sulfide-PGM association is rare and. only fewextrem~iy fine grains (0.5-2. 'flni) of PGM could he detected in one sample from foorwall contact of chromite ore. Heazlewoodite and Ni-rich pentlandite are the main sulfide minerals and they occur as bi-mineraIic intergrowths. Millerite is present as secondary alteration product. Sulfides are relatively abundant in the contact zones. than that of ores. PGM is present as native alloys ofOs-Jr-Ru, metallic solid solutions of Pt-I! and sulfides of Os-Ir-Ru Le., minerals of Iaurite-erlichmanite series. The presence of Ir-Pt-alloy seems to be very important and interesting feature of PGEmineralization in Kathpal chromite deposit. Based on both mineralogical and geochemical .data on PGE, it is concluded that the Kathpal chromite deposits are much similar to. that of Uralian type chromite deposits.

1NTRODUCfION
Motivated by the global attractiveness for POE values of economic importance from chromite hosted ultramafic complexes, the present work is taken up to study the primary mineralization pattern and POE potentiality of the chrornitites and-the host rocks of the Kathpal chromite deposit. Platinum. group of elements (POE) behave as chalcophiles and majority of the known POE prospects are associated with different Ni-Cu sulfide mineralization connected to the mafic-ultramafic complexes. Such deposits are classified broadly into two main categories (Naldrett, 1981) i. Ultramafic rocks of layered complexes mined mainly for POE and chromite with Ni-Cu base metal sulfides as by-product and, may be 'reef type' (Merensky reef, Bushveld complex, RSA) or 'chromitite hosted type' (U02 chromitites, Bushveld complex, RSA) (Naldrett, 1989). ii, Base metal sulfide deposits mainly mined for Ni-Cu (pOE as by-product) e.g, Noril'skTalnak,Russia and Thompson Nickel Belt, Canada.

PGE MINERALIZATION IN KATIlI'AL CHROMIJES, ORISSA

6.3

Layered ultramafic com'p1.excontribute 90% of the global ·PGE resource of which 75% is locked trp inthe UG~2 chromititel~yer;Merensky Reef and Plat Reef of Bushveld Complex, South Africa (Misra; 1998) and hence 'chromiteand the associated ultramafic rocks'arethe global targets for POE. Su1cindalJ1tralllafic omplex (SUC) of Orissa contributes about "",95% to the chromite C reserve of the Indian subcontinent and needs special attention as regards to its POE potentiality.The duniticperidotites hosting the chrornitites (>70% Cr-spinel, by volume) are extensively serpentinized and limonitized. The primal)' nature of any mineralization could best be traced from the serpentinized hostultrarnafics and associated grey chromite ores compared to the brown ores or lirnonitized hosts. Kathpal chromite ores are mostly of grey variety. The chromite deposit of Kathpal areais of peculiar .natureand' represents a distinct zone of intense geologicdistutballce compared to that of the main Sukinda Valleyand virtually separated from it by a concealed contact of unknown nature, The Kathpalarea has been chosen for the present study. GEOLOGY Sukinda ultratn#k complex extends from Tomka (85°55'E 21°7'N) in the east to Kathpal.(85°41'E 2101'N) on the west (Banerjee, 1972)spreadirtgover an area.of 40 sq km in NE::'SWdirectiollin Jaipur and Dhel:ll(a.nal districts of Orissa, It is flanked by the 'Ibmka~Daitarirange to the .north and Ma.hagirirange tothesouth (Fig.I).Tectonically sue had tindergonerelativ¢lysimpkdef6rmationpha.ses mostly of post-emplacement and post-consolidation in nature, resulting a broadly westerly plunging fold with steeply dippinglimbsclosure towards eastern side (Chakraborty et aI., 1980)~ Kathpalchromites and associated ultramafics located in the southwestern quadrant of the Complex occur as'a detached patch from the main Sukinda Valley. Kathpal represents a zone of intense geological disturbance as indicated by tectonically detached slabs of the ohromites whereas banded nature of chrome ore from th~ main Valley apparentlyilldicates their similarityto that of layered complexes in terms of the stratiform nature of the deposit. The ehromites of the main Valley are distinctly and conspicuously banded on regional scale. Kathpal ultrarnafics. fn contrast, show irregular orientation of small lensoid bodies of chromite seemingly embedded in a host of serpentinized dunite and perid()tites. Banerjee (1912) identified this as a melange type deposit and suggested thatthe irregular orientation of the blocks ofchromite and pyroxenites is due to their emplacement essentially in a solid state associated with some tectonic movement. Samples of grey chromite ores and associated serpentinized host rocks are collected from two mining levels of Kathpal underground.mines to understand their geochemistry and to ~orrunent on the magmatic evolution of the ultramafics.
I.,.

Ind. Mineral., v,42, no.l, January 2008

---------------~-----------------------

6-1

MOHANTY AND SEN

II>

.ce

1llf

••

~ c
0

Ji => -e .,
E

.. "" ~ E
.

.., '"

u::

:::;

:; 1il !i: "g

(i)

.':~

.. "" .. "
"0

e
lI;

'"

Co

'"

Ind. Mineral., v.42, no.I, January 2008

-----~------------------------------- --------------- -----------

PGE MINERALIZATION IN KATHPAL CHROMITES, ORISSA

65

ANALYTICAL PROCEDURE
The composition of Cr-spinel is obtained using JEOLmake JXA-8600 M WDS-EPMA instrument at the Institute Instrumentation Centre, TIT, Roorkee. The operatibrla:lconditions were maintained at an acceleration voltage of 15 kv with a beam current of 20 nAand a counting time of lOs per element and calibrations were performed bySPI rnulti-standarda-Total Fe-calculatedas-Pefrand-Fe" value are obtained from stochiometrlc recalculation as described by Carmichael (1967). The cations are calculated on four oxygen atom basis and values are presentedin Table-I. Table 1. ComposHionof SampleNo. 1 2 60.71 11.47 2.88 16.65 8.32 0.10 0.23 100.36 11.20 massive chromite 3 60.23 11.94 3;64 17.61 7.40 0:2S 0:23 101.34 11.04 4 59.24 12;02 3.01 16.90 7.52 0.05 0.26 9§.00 10.53

ore
Cations Cr Al Pel. Mg Fez+ Ti Mn Total At.Ratios C'r#
Mg#

1 1.43 0.46 0.11 0.80 0.19 0.00 0.Q1 3:00

2 1.50 0.42

3 1.47 0.43 0.08 0.81 0.19 0.01 0.01 3.00 0;77 0.81

4 1.48 0.45 0.07 0.80 0.20 0.00 0.01 3.00

c-.o,
AIZOj Pep3 MgO FeO TiOz MnO Total FeOt *Cr#=

58.56 12.73 4.71 17A5 7.57 0.09 0.25 101.35 12.28

om
0.78 0.22 0.00 0.01 3.00

*
0.76 0.80 0.78 0.78 0.77 0.80

Cr/[Cr+Al], Mg# =.Mg/[Mg+Fe"]

Whole rock POE concentrations were obtainedby fire assay followed by tellurium copreclpitation technique in combination with ICP-MS (perkin-Elmer Sciex, Elan DRC II make) at National-Geophysical Research Institute (NGRI), Hyderabad. A total of 8 samples including host rockserpentinites, spotted/semi-massive ores and massive ores from both the mining levels i.e., Level ..I&U are analyzed for precious metal concentrations. The details of the instrument and operating parameters are described byBalaram-and Rao (2003) and the procedurefollowedis discussed by Mathur etal., (2003) and Balaram etal., (2006). The standard used forthe calibration of the instrument for the samples is SARM-7. The internal standard used. is ·O.2pJlm Cd+Tl solution to correct for signal drift during analysis: The conceIitr~iion range bf Os, Jr, .Ru, Rh,Pt and Pd are 3;40-121.40 ppb, 7.80-38.20 ppb, 25.60-116.20 ppb, 2:00-11.20 pPb, 2.80-9.40 ppb and 1.00-8.00 ppb, respectively. This is to mention th.at the data his been used with the reservation _ that the values for Os and Ruare semi-quantitative owing to their loss as voiatile oxides during the fire assaying. However, in~lllikelihood the actual values must be higher than the values determined.

Ind. Mineral., v.42, no.I, January 2008

66

MOHANTY AND S~N

RESULTS AND DISCUSSION

Dasgupta (1959) reported the occurrence ofplatiilUIrt in the$ukinda valley for the first time followed by the pioneering work produced. by Page et al., (1985). This work presents the nature of fractionation of PGE and the mode of occurrence of PaM in the Kathpalchromites and host ultramafics andhence gives better understanding about their paragenesis furelation to the magmatic evolution 'of the deposit in the •. ighrof l compositions of associated Cr-spinels (Sen et al., 2005), sulfides (Sen & Mphanty 2005, Sen & Mohanty, under preparation).
,.ur---.,---."..----,---,.----,

0.'

x~.
\

,,'

tJj
r: ,--:~""
.

Mg#-Cr#

MasSive chiOrTiltites (A.2)from Level-l

"lnne
I

.'. .............,/KomatIites ---', .

'

"

"

"

/--~---, ,,

,.,
,

,1

i
I

~.'

·2
N

\l,:
I)

o
1=

0.'

\
\_

I·-----------_-----.l

Alkaline

./
chrcmltltes

~ . phiolitic

~
+

Mantle

LEVEL~

LEVEL~(

$C1Chondrlte

A A-1

&. Avg. Bushveld

Avg;Kemplrsai ~. Great Dyke

•
•

Y 0

8·'
B~~ B-4

A'2 A·~ A-4

IJ B·2

I!I Stillwater

Fig.2.a. Mg#-Cr# plot of Cr-splnel from massive ore compared to different magmatic varieties (fields after Barnes and Roeder, 2001). b. Cr#-TiOz plot. of Cr-spinels from massive ores (fields from Arai, 1992). c. Triangular variation diagram showing plot of Pt+Pd-Ir+Rh-Os+Ru, See details in the text. d. Triangular variation diagram showing p(ot of Pt·Pd+Rh-Os+Ru+lr. See details in the text.

Ind. Mineral., v,42, no.I, January 2008

--_._---_._._. ----

PGE

MINERALIZATION

IN

KATHJ'.-\L

CHW)'.q'C'c::'

."';.'::--~.",

67

The Cr-spinels are the best petrogenetic indicator, fer tne ",;,,('CiaeD ultramafic complexes (Dick & Bullen, 1984; Arai, 1992: Arai, 199-+: Barnes and Roeder. 2001 I. In the mere absence of any unaltered phases, the Cr-spineis used as the petrogenetic indicator to study the nature of the parent melt. The Cr-spinels from massive chrornitites have likely to suffer least subsolidus reequilibration in the mere absence of olivine and hence chosen for the study of the parent melt composition. The plot of Cr# vs. ]'vlg# shows that the Cr-spinel compositions represents the melt composition is similar to that of the Mg-rich magmatic varieties like komatiires, boninires ere. and is within the range of values for pediform chromitites (Fig.Za, Barnes & Roeder. 20CJl). The C1'# \IS. TiO, for the Cr-spinels of chromitite also indicates a boninitic affinity of the parent melt- (Fig.2b. Arai 1992). The sub-chondritic total POE concentrations (55.0-311.2 ppb) with enrichment in IPOE compared to the PPGE. The proportions of the PGE closely resemble to that of the Kempirsai chromitite deposits (Fig.Zc & d, Mantle values: Barnes et al., 1987, Cl chondrite: McDonough & Sun, 1995, global data: Distler unpub).

Fig.3.a. Photomicrograph showing sulfide mineral within the interstitial spaces of chromite (Reflected light, PPL). h. Photomicrograph showing sulfide mineral as pit-filling within chromite (Reflected light, PPL). c. Photomicrograph of sulfide mineral within serpentine mass (Reflected light, PPL). d. SEM-BSE image showing three very minute grains of' PGM (A, B & C) occurring within Ni-rich pentlandlte and heazlewoodite, and two grains of' PGM (D&E) within silicate matrix.

Ind. Mineral., v.4l, no.l, January 2008

68

MOHANTY AND SEN

The microscopic observations and subsequent SEM-EDS studies had shown low proportion. of modal sufi des. Sulfides mostly occur in the interstitial spaces between chromite grains (Fig.3a), asmicro~pitfillil1.gs (Fig.3b) or 'as specks and fines in the silicate matrix. (Fig.pc), Heazlewoodite and Ni-rich pentlandite are l11ainsulfide minerals and occur as bi-mineralic intergrowths. Millerite is present as secondary alteration product, Sulfides are relatively abundant in t~e contact zones than that of-ores. Sulfide. PGMassodition rare and only few extreme1yfine (O.5":2,.un) or POMcou,ld be detected in one sample from. footwallcontact of ohromiteore. The POE mineralogy is dominated by Os-Ir-Ru alloys of variable ratio and laurite (RuS2)-erlichmanite (OSS2) solid solution series (Fig.Sd; Mohanty Z007, .Sen etal., under 'preparation). Sarkar et al., 2003) has also. reported the inclusion of Os~Ir-(Ru) alloys within the chromites from the Kathpalbreccia zone. Such assemblages of PGE phases are pronounced in many of the ophiolitic complexes.

is.

grains'

CONCLUSIONS

.:

'IheCr-spinelcomposition, whole rock PGE. concentr~tion ;:tl1.dhePGE:rni~erai()gy t overwhelmingly incli(;ate~a high·:Mgsiliceousparentmelt.fraction for the.6hromite depositssirtrilar to that of the ultramafic complexes Iikethoseof Urals, 'rheconc¢ntration range.'of Os, Ir,.Ru. ']lli, Pt and Pd are3AO-12L40. ppp, 7.80-38.20 ppP.2S;60416.20 pp1?, 2.00-11.20ppb, 2.80-9.40ppb and LOO-8.00 ppb, respectively. the concentrliti0l1 values of PGE clearly indicate dominanceofIPGE oyeri?PGE, characteristic of POE assoCiated with Mg~rich CNpineL ThePGE mineralogy fs clpminateqby IPOE,mostly'asalloys with minor sulfide. ACKNOWLEDGEMENT CSIR, New Delhi is duly acknowledged for the financial sUJ?port '.toDM as CSIR-NET fellowship to carry' out the work-Prof. V. V. Distler and Dr..V. Balaramare sincerely acknowledged for providing the SEM-EDS·.and ICP-MSanalyticalfacilities, respectively.

REFERENCES
Arai, S .• (1992). Chemistry of chromiumspinel in volcanic rocks as a potential guide to magma chemistry. Min. M<l:g.,v.56.pp: 173-184. Arai, S., (1994). Characterization ofspineI peridotite~ by olivine-spinel compositional relationships: Review and interpretation. Chern. Geo1.,v.! 1:3,no.3-4, pp.19b204. Balaram, V.,Mathur.R, Banakar, V.K.,Hein, lR., Rao, C.R.M" Rao, T.G. andDasaram, B .• (2006). Determination of platinum-group elements (PGE) and gold (Au) ill manganese nodule reference samples by nickel sulfide fire-assay and Te coprecipitation with rCP-MS. Ind. Jour. Marine ScL, v.35, no.l, pp..7-16. Balaram, V. and Rao, T.G., (2003). Rapiddetermination ofREEs and other traceelements in geological samples by microwave acid digestion and ICP-MS. Atomic Spectroscopy, v.24, no.6, pp.206-211.

Ind. Mineral., v,42, no. 1, January 2008

POE MINERALIZATION IN KATHPi\L CHR.OMITES, ORISSA

69

Banerjee,p:K" (1972). 'Geology al1dgeoche.!Ilistryofthe Sukinda ultramafic field, Cnnack district, Orissa, Me:in. OeoI.SurY.lndia, no.103, pp.1-I7. Barnes, SJ., Boyd. R, Korneliussen, A"NHlson, L.R, Often, M., Pedersen, RB. and Robins, B.,( 1987). The use of mantle normalization and metal ratios-in discriminating between the effects of partial melting, crystal fractionation and sulphide segregation 011 platinum.-groupelel11entsi gold, nlpkeland coppenexamplesfromNorway, In.Priehard; H;M~,Potts,P.J., Bowles. J.F.W. and Crlbb.SJ.(eds.) .Geo-Platinum, Elsevier.Amsterdam, pp.113-143.·· . . Barnes, SJ.and Roeder,P.L" (2,OOD. The ran.geof~pillel compositions in terrestrial mafic andultramaficrocks.}.Petrol., vA2, pp.2279"2302. Carmichael,I,S.E., (1967).Theiron~titanium oxides of salic volcanicrocks and their associated ferromagnesiarrsillcates. Contrib, Mineral. Petrol., v.14,pp.36~64. Chakraborty, KL. andChakraborty,T.L.,(1984). Geologicalfeatures and origin of the.chromite deposits of Sukinda yalley, Orissa, India. Mineral. Deposita, v.19, J?P;256.,.265. Chakraborty, 1<:.L.,Chakraborty, T.L. and Majumder, T., (1980). Stratigraphy and structure of the Precambrian Banded Iron Formation .andchromite bearing ultramafic rocks of Sukinda valley, Orissa. Jour. Geol, Soc., India,v.21, pp.398A04. Dasgupta, S., (1959). Chromite deposits near Sukinda, Cuttack district, Orissa. Quat Jour. Geol. Mining and Metal, Soc., India, v.31,pp.227-232. Dick, HJ.B. and Bullen, T., (1984). Chromian.spinel as a'petrogenetic.mdicatorin abyssal and alpine-type peridotites and spatially associated lavas.Contrib. Mineral. Petrol., v.86, pp.54-76. Mathur, R, Balaram, v; Rao,C.RM., Rao, T.G:, Ramesh, S.L., Charan, S.N., Dasaram, B., Anjaiah, K.V.and Rajashekhar, V.B., (2003). Fire-assay methods in combination with ICP-MS for determination of PGE and Au in geological materials. In: National training courseon .11 Inductivelycoupledplasma mass spectrometry and associated .analytical techniques for·geophemical,mineral exploration. and environmental studies & Workshop VI- "Trendsin Geochemistry" , NORI, India, pp.81-94. Me Donough, W.E and Sun, S.S., (1995). The composition of the Earth. Chem. Geol., v.l20, pp.223~253. Misra, KC., (1998). Platinum-Group Element (PGE) deposits. In: Understanding mineral deposits, 1st ed, Kluwer Acad. Pub., 845p. Mohanty, D., (2007). Ore genesis of PGE mineralization in the Sukinda.chromite deposit, Orissa, India, Ph ,D. Thesis (Unpubl.), Indian Institute of Technology, Roorkee, India, 213p. Naldrett, A.J.,(198 l), Platinum-group element deposits. In: Cabri, L.J. (ed.) Platinum-group elements: Mineralogy, Geology, Recovery. Canadian Institute of Mining and Metallurgy SpI. PubL, v.23, pp.l97-232.

Ind. Mineral., ".42, no.!, January 2008

iO

MOHANTY AND SEN

Naldrett, A.J., (1989). Magmaticsulphidedeposits, Oxford Monograph in Geology and Geophysics, no.l4,186p.. . . Page, N.J.,.BaneJ.ji,P.K. and Hafety, J., (198~). Characterization of the Suldndaand Nausahi .ultramafic: complexes, Orissa, India by Platinum-Group element geochemistry.Precamb, Res., v;30,pp.27Al. . Sarkar,N..I(., Panigrahi, D., Ghosh, S.N., Mallik,AI<:. .an.d- home.S; (2003).Anote on the S incidenceofgold.-PGM in the breccia zone ofKatpal chromite.quarry, Sukindaultramafic complex, Dhenkanal district, Orissa. Indian Minerals, v.57, pp.85-92. Sen, A.K.andMohanty, D., (2005). PGE Mineralization.asaociatedwith Sukinda chromite deposit, Orissa, India ~An:ore genetic model.In: lQthlntemationalplatil1umsymposium, Platinum-group elements - from genesis to beneficiation and. environmental impact, Oulu.Finland, August 2005, pp.566~569. Sen,A.K., Sharma, P.K.,Mohanty,D. and Ghosh, T.K., (2005). Compositionofer-spinel ~an oregenericIndicator ofr<athpal chromite deposit, Sukindauitramafic complex. Orissa, Iadia.CumSci., v.88,rlo.lO,pp.1547-1550. (Received: August 2007; Revised form accepted: December 2007)

Ind. Mineral., v.42, no. 1, January 2008

(Abstracted in Chemical Abstracts and Mineralogical Abstracts)

The Indian Mineralogist

No.1

Journal of The Mineralogical Society of India

VOLUME 42,
JANUARY

2008.

CONTENts
REsEARCH PAPERS Geochemical characteristics zone, western Iran of the granitoid complex QfBoroujerd, Sanandaj-Sirjan R.
ZAREI SAHAMEIH AND A.AHMADI KHALAJI

Fluid inclllsioll study and hydrothermal source characterization sulfide deposit, eastern Dharwar craton
B.C. PRABHAKAR, MOHAMEDSirAREEF?R.V

of Thinthini copper
RASHMI

GIREESH ANDB.N.

20

Petrological and geochemicalcharacteristicsofdunites and associated granulites Salem and Nagaramalal areas in 'Iamilnadu, Southern India
M. SATYANi\RAYANAN, D.V.SUBBARAo,S. A.KARTHIKEYAN,S.NARSING NIRMALCHARAN, KANBARAS(!, RAo, B.DAsARAM, S.S.SAWANTAND

of

V.BALARAM

33

Improvement in characterization of Crosta technique for porphyry copper alteration mapping using 1M data in Varzag!in,Azarhaijan, Iran

H.
PGEtarriers at Boula-Nausahi igneous complex, Orissa J.K. MOHANTY, A..K. Pxutr

SHAHINFAR

44 53 62 71

AND N. CHARCHI

PGE mineralization in Kathpal chromites, Sukinda uItramaficcomplex,Orissa, Spinifex textured metabasalt ofSonakhan greenstone belt, centralIndia
S.D. DESHMUK,K.R.

India
BEN

D. MOHANTY AND AK.

Solid inclusions of magmatic halite and CO2 - H2 Ramanagaram; Dharwar Craton, India

IfARf,P.

DIWAN AND

H.T.

BASAVARAJAPPA

inclusions in Closepet granite from

C. SRIKANTAPPA AND M.N. MALATHI

84

REVlEWPAPER Does geophysics help locatediamond,

Gold-and Platinum?
Y.L.S. BHIMASANKARAM

99 127
130

NOTES
Annual report for the year 2006·07 Report on IX convention ofMSI and National Seminar
C. SRTKANTAPPA

S.

GOVTNOAIAH

OBITUARY ,
Prof. M.G. ChakrapaniNaidu "ISSN 0019-5928 (1916-2007) S.M.
RAMANANDA SETTY

135

Registered under Karnataka Society's Act

Registration No.: 194/1997-98