First Report of Florencite from the Singhbhum Shear Zone of the East Indian Craton.
9
Research Article First Report of Florencite from the Singhbhum Shear Zone of the East Indian Craton Maitrayee Chakraborty, 1 Sayan Biswas, 1 Nandini Sengupta, 2 and Pulak Sengupta 1 1 Department of Geological Sciences, Jadavpur University, Raja SC Mullick Road, Kolkata 700032, India 2 Department of Geology, University of Calcutta, 35 Ballygunge Circular Road, Kolkata 700019, India Correspondence should be addressed to Pulak Sengupta; [email protected] Received 29 June 2013; Accepted 6 November 2013; Published 3 February 2014 Academic Editors: M. Arima, E. Belluso, M. M. Jord´ an Vidal, and L. N. Warr Copyright © 2014 Maitrayee Chakraborty et al. is is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Metamorphic florencite is being reported from kyanite-rich rocks from the eastern part of the Palaeo- to Mesoproterozoic Singhbhum shear zone. is is the first report of florencite from the Precambrian rocks of the Indian Shield. Host rock of florencite is a kyanite-rich rock (>80 vol%) with small and variable amounts of quartz, lazulite, augelite, and rutile. Florencite forms small (<20microns) idioblastic-to-subhedral crystals that are included in large kyanite grains. Rarely, florencite replaces kyanite. e florencite has small proportion of crandallite (8.7–11.8 mol%) and goyazite (<2 mol%) components. Florencite of this study is dominated by Ce (∼49 mol%) with significant La (∼30 mol%) and Nd (∼21 mol%). Compared to other florencite occurrences of the world, florencite of the studied rock is impoverished in S, Sr, and Ba and rich in P. Stability of the assemblage florencite- kyanite-augelite-lazulite and the quantitative thermobarometry in the adjoining rocks suggest that florencite was formed during Palaeoproterozoic metamorphism that culminated at the - range of 490 ± 40 ∘ C and 6.3 ± 1 kbar. Integrating all the geological features it is postulated that florencite was formed due to metasomatism of some aluminous protolith by infiltration of acidic fluids charged with PO 4 −3 and LREE. 1. Introduction Florencite is a rare but important mineral in the alunite super group with the general formula of AB 3 (XO 4 ) 2 (OH) 6 , where A-site filled with Ce, La, and Nd, B-site with Al and X-site with P (Bayliss et al. [1]). e structure of florencite also accommodates variable amounts of Ca 2+ , Pb 2+ , Hg 2+ , K + , Ba 2+ , Sr 2+ , Rb + (in A-site), Fe 3+ , Cu 2+ , Zn 2+ , Sn 2+ , V 3+ , Cr 3+ , and Ga 3+ (in B-site) (Bayliss et al. [1], Dill [2]). Florencite is commonly associated in hydrothermally altered rock (Dill [2], Gaboreau et al. [3], Hikov et al. [4], and Repina [5], among others) and less commonly in metamorphic rocks (Nagy et al. [6], Izbrodin et al. [7], and Janots et al. [8]). Because of its open structure that can accommodate a large number of cations and anions including the REE, the composition of florencite provides a wealth of information about the source and composition of the metamorphic and hydrothermal fluids (Visser et al. [9], Nagy et al. [6], Dill [2], Gaboreau et al. [3], Hikov et al. [4], Izbrodin et al. [7], Repina [5], and Janots et al. [8]). Once formed florencite is very difficult to be destroyed even in the weathering profile and hence controls the mobility of LREE over a wide range of geological conditions (Gaboreau et al. [3], Izbrodin et al. [7], and Repina [5]). Florencite is associated with different types of hydrothermal or deposits including unconformity type uranium deposits and thus the presence of this mineral can be used as a pathfinder mineral in exploration of these deposits (Gaboreau et al. [3]). Singhbhum shear zone (SSZ) of the East Indian shield separates the Palaeo- to Meso- to Neo Archaean Singhb- hum craton from Palaeoproterozoic metamorphosed vol- cano sedimentary pile, known as North Singhbhum Fold Belt (NSFB, Figure 1 aſter Dunn and Dey [10] and Saha [11]). It is generally agreed upon that Palaeoproterozoic tectonism led to thrusting of the NSFB over the Archaen Singhbhum craton along the SSZ (discussed in Sarkar and Gupta [12]). Multitudes of rocks are intermingled, intensely sheared and hydrothermally altered along the SSZ. Repeated Hindawi Publishing Corporation International Journal of Mineralogy Volume 2014, Article ID 978793, 8 pages http://dx.doi.org/10.1155/2014/978793
Transcript of First Report of Florencite from the Singhbhum Shear Zone of the East Indian Craton.
Research ArticleFirst Report of Florencite from the Singhbhum Shear Zone ofthe East Indian Craton
Maitrayee Chakraborty1 Sayan Biswas1 Nandini Sengupta2 and Pulak Sengupta1
1 Department of Geological Sciences Jadavpur University Raja SC Mullick Road Kolkata 700032 India2Department of Geology University of Calcutta 35 Ballygunge Circular Road Kolkata 700019 India
Correspondence should be addressed to Pulak Sengupta pulaksggmailcom
Received 29 June 2013 Accepted 6 November 2013 Published 3 February 2014
Academic Editors M Arima E Belluso M M Jordan Vidal and L N Warr
Copyright copy 2014 Maitrayee Chakraborty et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited
Metamorphic florencite is being reported from kyanite-rich rocks from the eastern part of the Palaeo- to MesoproterozoicSinghbhum shear zoneThis is the first report of florencite from the Precambrian rocks of the Indian Shield Host rock of florenciteis a kyanite-rich rock (gt80 vol) with small and variable amounts of quartz lazulite augelite and rutile Florencite forms small(lt20microns) idioblastic-to-subhedral crystals that are included in large kyanite grains Rarely florencite replaces kyanite Theflorencite has small proportion of crandallite (87ndash118mol) and goyazite (lt2mol) components Florencite of this study isdominated by Ce (sim49mol) with significant La (sim30mol) and Nd (sim21mol) Compared to other florencite occurrences ofthe world florencite of the studied rock is impoverished in S Sr and Ba and rich in P Stability of the assemblage florencite-kyanite-augelite-lazulite and the quantitative thermobarometry in the adjoining rocks suggest that florencite was formed duringPalaeoproterozoic metamorphism that culminated at the 119875-119879 range of 490 plusmn 40∘C and 63 plusmn 1 kbar Integrating all the geologicalfeatures it is postulated that florencite was formed due to metasomatism of some aluminous protolith by infiltration of acidic fluidscharged with PO
4
minus3 and LREE
1 Introduction
Florencite is a rare but important mineral in the alunitesuper group with the general formula of AB
3(XO4)2(OH)6
where A-site filled with Ce La and Nd B-site with Al andX-site with P (Bayliss et al [1]) The structure of florencitealso accommodates variable amounts of Ca2+ Pb2+ Hg2+K+ Ba2+ Sr2+ Rb+ (in A-site) Fe3+ Cu2+ Zn2+ Sn2+V3+ Cr3+ and Ga3+ (in B-site) (Bayliss et al [1] Dill [2])Florencite is commonly associated in hydrothermally alteredrock (Dill [2] Gaboreau et al [3] Hikov et al [4] and Repina[5] among others) and less commonly in metamorphicrocks (Nagy et al [6] Izbrodin et al [7] and Janots et al[8]) Because of its open structure that can accommodate alarge number of cations and anions including the REE thecomposition of florencite provides a wealth of informationabout the source and composition of the metamorphic andhydrothermal fluids (Visser et al [9] Nagy et al [6] Dill[2] Gaboreau et al [3] Hikov et al [4] Izbrodin et al [7]
Repina [5] and Janots et al [8]) Once formed florencite isvery difficult to be destroyed even in the weathering profileand hence controls the mobility of LREE over a wide rangeof geological conditions (Gaboreau et al [3] Izbrodin et al[7] and Repina [5]) Florencite is associated with differenttypes of hydrothermal or deposits including unconformitytype uranium deposits and thus the presence of this mineralcan be used as a pathfinder mineral in exploration of thesedeposits (Gaboreau et al [3])
Singhbhum shear zone (SSZ) of the East Indian shieldseparates the Palaeo- to Meso- to Neo Archaean Singhb-hum craton from Palaeoproterozoic metamorphosed vol-cano sedimentary pile known as North Singhbhum FoldBelt (NSFB Figure 1 after Dunn and Dey [10] and Saha[11]) It is generally agreed upon that Palaeoproterozoictectonism led to thrusting of the NSFB over the ArchaenSinghbhum craton along the SSZ (discussed in Sarkar andGupta [12]) Multitudes of rocks are intermingled intenselysheared and hydrothermally altered along the SSZ Repeated
Hindawi Publishing CorporationInternational Journal of MineralogyVolume 2014 Article ID 978793 8 pageshttpdxdoiorg1011552014978793
2 International Journal of Mineralogy
Tatanagar
Jaduguda
Ghatshila
MG
S
Chakradharpurgranite gneiss N N
1050
(scale in km)
DelhiSSZN N
E E
EE
Mayurbhanj granite
N
SSZSSZ
SSZ
SSZ
Singhbhum graniteIOGsediments
IOGsediments
Dalma volcanics
Arkasani granophyre
Soda granite
Soda granite
KanyalukaDhanjorivolcanics
IOG metavolcanicsDhanjorisediments
Singhbhum groupof metapelites
KolhanGroup ofvolcanics
NSFB
Ongarbirametavolcanics
85∘ 45998400 86∘ 0998400 1599840086∘ 86∘
76∘
76∘
30998400 86∘ 45998400
23∘
24∘24∘
0998400
22∘
92∘
92∘ 45998400
22∘
30998400
22∘
86∘ 4599840015998400
1599840015998400
86∘ 3099840086∘ 86∘099840085∘ 45998400
22∘
22∘
30998400
22∘
459984008∘8∘
099840023∘
lowast
Figure 1 Geologic map showing the distribution of stratigraphic units in a part of eastern India After Dunn and Dey [10] and Saha [11] SSZSinghbhum shear zone NSFB North Singhbhum Fold Belt IOG Iron Ore GroupThe rectangle around Kanyaluka (marked by red asterisk)is blown up in Figure 2
hydrothermal activities developed different types of Cu-Fe-U-P deposits that are associated with tourmalinizationmuscovitization and ferruginization (discussed in Senguptaet al [13] and Sarkar and Gupta [12]) Infiltration-drivenmetamorphism in the SSZ produced a number of exotic rocksincluding per-aluminous kyanite-quartz rocks that fringe thenorthern boundary of the SSZ (Figures 1 and 2 Figure 2partly after Mukhopadhyay and Deb [14]) In the easternpart where the SSZ takes a bend towards south (Figure 1)kyanite-quartz rock is spatially associated with chloritoid-bearing schist pssammopelites mica schist and bands oftourmalinite (Figure 2) All these rocks share a commonhistory of deformation and metamorphism that culminatedat 490 plusmn 40∘C and 63 plusmn 1 kbar (Sengupta [15]) In thiscommunication we are describing themode of occurrence offlorencite in the host of kyanite-rich rock (gt80 vol kyanite)that is exposed near the village of Kanyaluka (Figure 2)Integrating all the petrological data we demonstrate thatflorencite was developed due to infiltration of acidic fluidcharged with P and LREE into the per-aluminous kyanite-rich rock at the culmination of metamorphism and deforma-tion Incidentally this is the first report of florencite from anyPrecambrian rocks of India
2 Petrography and Mineral Chemistry
In domains of minimum strain kyanite-rich rock developsrandomly oriented blades of kyanite that occupy more than80 vol of the rock (Figure 3(a) abbreviations after Kretz[16]) Grains of quartz and rutile occupy the interstitialspace of the mesh formed by the kyanite blades (Figures3(a) and 3(b)) The kyanite-rich rock develops centimeter todecimeter thick bands of intense shearing In the shear bandskyanite blades are kinked bent and fractured (Figure 3(b))and the quartz grains show undulose extinction Locallydeformed kyanite blades are extensively replaced by augeliteand lazulite (Figure 4(a)) Unlike kyanite lazulite andaugelite do not show any deformation (static growth) Inthe backscattered electron (BSE) images florencite grainsappear as numerous small bright spots in the dull backgroundcomposed of lazulite kyanite and quartz (Figure 4(b)) Smalldisseminated idioblastic subhedral to anhedral crystals (lt20microns) of florencite are included in kyanite quartz andlazulite (Figures 4(c) and 4(d)) Rarely florencite replaceskyanite (Figure 4(c)) Textural features attest to the view thatflorencite crystals are left stranded within lazulite when thelatter mineral replaced kyanite (Figure 4(d)) This featuresuggests equilibrium coexistence of florencite and lazulite
International Journal of Mineralogy 3
Kanyaluka
Bhalki
Mica schist (NSFB)Banded ferruginousquartziteKyanite quartzitekyanite mica schistChloritoid schistSoda graniteFeldspathic schistQuartz mica schistTourmalinitetourmaline schist
Sankh
Nala
h
Subarnarekha
Chlorite quartz schist(granular rock)QuartziteMetabasic rocksBanded psammopelitesBiotite muscovite schistFaultRiver
N
22∘
22∘
86∘30998400
86∘
30998400
30998400
30998400
lowast
Figure 2 Lithological map of the South Eastern sector of Singhbhum shear zone (SSZ) around Kanyaluka (Partly after Mukhopadhyay andDeb [14]) The location from where the samples have been collected is marked with red asterisk
Ky
Rt
Qtz
Ky
50120583m
(a)
Rt Qtz
Ky
50120583m
(b)
Figure 3 (a) Randomly oriented kyanite grains forming a mesh-like appearance Some corroded rutile grains and quartz are also seen in theinterstitial spaces and (b) Kyanite poor zone in the host rock showing the presence of deformed (kinked) kyanite Mineral abbreviations usedare after Kretz [16]
4 International Journal of Mineralogy
Ky
LazAug
(a)
Laz
Fl
Ky
Ky
Qtz
(b)
Ky Fl
Laz
(c)
Laz
FlQtz
(d)
Figure 4 BSE images showing (a) Kyanite blades replaced by augelite and lazulite (b) overall view of the lazulite rich zone relicts ofkyanite showing corroded boundary are sparsely distributed here The small bright spots seen here are florencite (c) florencite grain withprotruding grain boundary inside kyanite showing that florencite replaces kyanite (d) florencite grain stranded within lazulite Aug augeliteFl florencite All other mineral abbreviations are after Kretz [16]
Electron microprobe analyses and WDS spectrum of theflorencite are presented in Table 1 and Figure 5 respectivelyAlso included in Table 1 are the representative analysesof kyanite lazulite and rutile For comparison florenciteanalyses from somewell-known localities are also included inTable 1 Chemical compositions of florencite and the adjacentminerals were determined from carbon-coated thin sectionsby electron microprobe analysis (EMPA) with a CAMECASX100 electron microprobe at the Central PetrologicalLaboratory Geological Survey of India Kolkata For elementsother than Sr Ba and the REE the accelerating voltage usedwas 15 kVwith a 12 nA current Elements were analyzed usingnatural standards except for Mn and Ti for which syntheticstandards were used For the heavy metals (Ba Sr and REE)20 kV and 20 nA were usedThe following standards are usedfor REE (REE glass) Sr (celestite) and Ba (barite) The rawdata were processed using the PAP procedure (Pouchou andPichoir [17]) The composition of florencite is recalculatedon 11 oxygen basis and the nomenclature of the differentspecies is according to Bayliss et al [1] Compositionallyflorencite is essentially a solid solution of the speciesFlorencite-(Ce) (487mol) Florencite-(La) (299mol)and Florencite-(Nd) (213mol) (Table 1) Similar to othernatural florencite compositions concentrations of LREE
outweigh the concentrations of HREE The concentrationsof HREE S and As are below the detection limit of electronmicroprobe Concentrations of Sr (0002 to 0008 apfu) Ba(sim000003 apfu) Ca (0040 to 0062 apfu) and K (0001 to0012 apfu) are low Concentration of ThO
2varies between
sim05 and 12 wt (001ndash0024 apfu) The WDS spectrumsuggests that the elements that are not measured do nothave any significant concentrations Lazulite is dominated byMg (9806mol lazulite) with a small amount of scorzalite(194mol Fe-Lazulite Table 1) Kyanite rutile and quartzhave essentially the end member compositions
Entry of small amount of Th and Ca in the structure offlorencite can be explained by the substitution REE3+ harrTh + Ca (Nagy et al [6] Georgieva and Velinova [18] andGaboreau et al [3]) Compared to the florencite compositionsreported from many florencite occurrences in the worldflorencite compositions of this study are depleted in Sr CaBa and S whereas they are enriched in P
2O5(Table 1)
3 Discussion
Florencite in the kyanite rich rock of the Singhbhum shearzone records the first occurrence of this mineral from any
International Journal of Mineralogy 5Ta
ble1Re
presentativ
eanalyses
offlo
rencitelazuliteaugelitekyaniteand
rutilemineralfro
mstu
died
areaF
lorencite
mineralcompo
sitionhasb
eencomparedwith
compo
sitions
from
different
localities
Elem
ents
Locatio
n
Florencite(calculated
on11oxygen
basis
Valuesinwt
)
Florencitedata
byNagyetal
2002
[6](values
inwt
)
Florencitedata
byJano
tsetal
2006
[8](values
inwt
)
Florencitedataby
Doroshk
evichetal
2009
[19](values
inwt
)
Lazulite(values
inwt
)Au
gelite(
values
inwt
)Ky
anite
(values
inwt
)Ru
tile(values
inwt
)
Sing
hbhu
mshearz
one(SSZ)
Sopron
Hills
Easte
rnAlps
Hun
gary
Sebtide
complexR
ifMorocco
Amba-D
ongar
GujaratInd
iaSing
hbhu
mshearz
one(SSZ)
SiO
2000
006
001
na
024ndash4
2gt075
001
023
3669
000
TiO
2007
000
004
na
na
na
003
006
002
10090
Al 2O
32847
2737
2728
2866ndash
3189
2710
ndash319
22786ndash
3067
3349
4930
6245
006
Cr2O
3000
000
000
na
na
na
000
008
004
013
FeO
000
001
000
na
017ndash14
na
000
000
003
010
MnO
000
000
000
na
na
na
043
004
002
000
CaO
042
064
054
072ndash144
042ndash0
69
023ndash0
81
001
000
000
001
MgO
001
005
010
na
002ndash0
70
na
1332
003
001
000
Na 2O
009
009
011
na
001ndash0
06
na
003
000
006
000
K 2O
000
000
001
na
na
na
000
000
002
001
P 2O
53081
3072
3084
2697ndash2893
224ndash264
2608ndash2856
4844
3709
000
000
ZrO
2000
000
000
na
na
na
mdashmdash
mdashmdash
Nb 2O
5000
000
004
na
na
na
mdashmdash
mdashmdash
La2O
3683
769
712
646
ndash866
422ndash4
25
391ndash1264
mdashmdash
mdashmdash
Ce 2O
31093
1215
1178
1091ndash1433
837ndash926
494ndash1232
mdashmdash
mdashmdash
PbO
000
000
000
na
na
na
mdashmdash
mdashmdash
ThO
2049
118
118
055ndash994
059ndash109
na
mdashmdash
mdashmdash
U2O
3004
002
002
na
007ndash0
17na
mdashmdash
mdashmdash
BaO
000
000
000
na
na
na
mdashmdash
mdashmdash
SrO
012
015
010
016ndash0
67
132ndash591
447ndash1336
mdashmdash
mdashmdash
Nd 2O
3270
261
269
165ndash500
396ndash4
80
102ndash291
mdashmdash
mdashmdash
Sm2O
3110
106
109
010ndash0
92
055ndash0
60
na
mdashmdash
mdashmdash
SO3
000
000
000
na
021ndash0
59
108ndash
471
mdashmdash
mdashmdash
Total
8208
8381
8295
8769ndash
9036
7821ndash86
35
7140ndash
7898
9576
8683
9940
1012
5ap
fu
apfu
apfu
apfu
apfu
apfu
apfu
apfu
apfu
apfu
Si000
001
000
na
0020ndash
0379
006
0ndash0170
000
002
100
000
Ti000
000
000
na
na
na
000
000
000
100
Al
299
290
289
3203ndash3360
2880ndash
3131
2710ndash
2950
195
384
200
000
Cr000
000
000
na
na
na
001
000
000
000
Fe000
000
000
na
0012ndash0107
0020ndash
0333
002
000
000
000
Mn
000
000
000
na
na
na
000
000
000
000
Ca004
006
005
006
8ndash0105
0038ndash
0067
0020ndash
0070
000
000
000
000
Mg
000
001
001
na
0003ndash0095
na
098
000
000
000
Na
002
002
002
na
0002ndash0012
na
000
000
000
000
K000
000
000
na
na
na
000
000
000
000
6 International Journal of Mineralogy
Table1Con
tinued
Elem
ents
Locatio
n
Florencite(calculated
on11oxygen
basis
Valuesinwt
)
Florencitedata
byNagyetal
2002
[6](values
inwt
)
Florencitedata
byJano
tsetal
2006
[8](values
inwt
)
Florencitedataby
Doroshk
evichetal
2009
[19](values
inwt
)
Lazulite(values
inwt
)Au
gelite(
values
inwt
)Ky
anite
(values
inwt
)Ru
tile(values
inwt
)
Sing
hbhu
mshearz
one(SSZ)
Sopron
Hills
Easte
rnAlps
Hun
gary
Sebtide
complexR
ifMorocco
Amba-D
ongar
GujaratInd
iaSing
hbhu
mshearz
one(SSZ)
P233
234
235
2041ndash2117
1710ndash1863
1770ndash2001
203
208
000
000
Zr000
000
000
na
na
na
mdashmdash
mdashmdash
Nb
000
000
000
na
na
na
mdashmdash
mdashmdash
La011
013
012
0104ndash
0106
0131ndash0140
0110ndash
0340
mdashmdash
mdashmdash
Ce
018
020
019
0204ndash
0213
0277ndash0282
0140ndash
0392
mdashmdash
mdashmdash
Pb000
000
000
na
na
na
mdashmdash
mdashmdash
Th001
002
002
na
0022ndash0011
na
mdashmdash
mdashmdash
U000
000
000
na
0001ndash000
4na
mdashmdash
mdashmdash
Ba000
000
000
na
na
na
mdashmdash
mdashmdash
Sr001
001
001
0011ndash0035
na
na
mdashmdash
mdashmdash
Nd
009
008
009
0142ndash0156
0128ndash
0143
0030ndash
0071
mdashmdash
mdashmdash
Sm003
003
003
0023ndash0027
0018ndash
0019
na
mdashmdash
mdashmdash
Sbdl
bdl
bdl
na
0069ndash
0285
0070ndash
0273
mdashmdash
mdashmdash
Totalcation
580
580
579
589
2ndash599
25763ndash
594
55637ndash
583
4498
595
300
100
sumRE
E042
045
044
0484ndash
0537
0603ndash0612
0300ndash
0603
Florencite
(mol)
8994
8669
8845
Goyazite
(mol)
136
147
103
Crandallite
(mol)
870
1184
1052
Noten
anot
availablebdlbelowdetectionlim
it
International Journal of Mineralogy 7
Cps
5000
4000
3000
2000
1000
020000 30000 40000 50000 60000 70000 80000 90000
S In
P Ka
P Ka
Al Ka
Ce La
Ce Lb
La La
TAPPET
Figure 5 WDS of florencite showing Al P Ce and La TAP and PET are crystals of the electron microprobe machine
Precambrian rocks of the peninsular India The only otherlocality of florencite in India is the carbonatite complex ofAmba Dongar Gujarat (Doroshkevich et al [19])
Textural features suggest that florencite was formed dur-ing and after the growth of kyanite and hence originatedduringmetamorphism that accompanied the ductile shearingof the studied rock Florencite remained stable during theformation of lazulite and augelite that replaced kyanite understatic condition (post-shearing) Experimental study in theAl-P-O-H system and the observations from natural rocksshow that the assemblage augelite + kyanite is stable at con-ditions 380∘ndash475∘C and pressure gt2 kbar (Wise and Loh [20]andVisser et al [9])The assemblage kyanite + lazulite on theother hand has a wide thermal and baric stability (gt400∘Cand gt2 kbar Schmid-Beurmann et al [21] andMorteani et al[22]) Stability of florencite at high temperature (up to 550∘C)is reported from the eastern Alps (Nagy et al [6]) and fromAfrican carbonatites (Mckie [23]) Briefly the assemblagekyanite + augelite + lazulite + florencite appears to form attemperature and pressure that exceeded 400∘C and 2 kbarThis is in a good agreement with the calculated 119875-119879 valuesof 490 plusmn 40∘C and sim6 plusmn 1 kbar from the adjoining chloritoidgarnet bearing schist (Sengupta [15])
Origin of florencite in kyanite-quartz rock requires advec-tive transport of LREE and P presumably by infiltrationof aqueous fluids Singhbhum shear zone is characterizedby repeated infiltrations of aqueous fluids that resulted inmineralization ofCu-Fe-U-P and tourmalinization (reviewedin Sengupta et al [13] and Sarkar and Gupta [12]) In thisstudy we document phosphate REE and Mg-metasomatismwhich developed end member lazulite (very low content ofscorzalite) in kyanite-rich rock Several studies have demon-strated that florencite develops in hydrothermally altered(sensu lato) rock in which themetasomatic fluids are oxidizedand have acidic pH (Visser et al [9] Nagy et al [6] Gaboreau
et al [3] Hikov et al [4] and Georgieva and Velinova [18]) Inview of this we envisage that infiltration of acidic fluid froman extraneous source to be responsible for the developmentof florencite Absence ofmuscovitization of kyanite in kyanitequartz rock of this particular studied area and extensivetourmalinization of the adjoining rocks (Sengupta et al [13])supports that acidic metasomatic fluids infiltrated the rocksof the area Studies have shown that acidic fluids can dissolvea large amount of PO
4
minus3 and LREE as these chemical speciesform the ligand (REE (PO
4)∘
aq) (Ayers and Watson [24]cf Jones et al [25]) This fluid upon interacting with per-aluminous host rock stabilized florencite (Nagy et al [6])
4 Conclusion
(1) Florencite a REE-Al phosphate has been reportedfrom a metamorphosed kyanite-rich rock from theSinghbhum shear zone of the east Indian Shield
(2) Petrology of the florencite-bearing mineral associa-tion suggests metamorphic growth of florencite in the119875-119879 range of sim6 plusmn 1 kbar and 490∘plusmn 40∘C This is thefirst report of florencite from Precambrian rocks ofIndia
(3) Florencite was formed due to interaction of acidicaqueous fluids charged with PO4minus and REE and alu-minous country rock during regional metamorphismand ductile shearing in the Singhbhum shear zone
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
8 International Journal of Mineralogy
Acknowledgments
Maitrayee Chakraborty and Sayan Biswas acknowledge theresearch grants sanctioned by the CSIR New Delhi andUGC New Delhi respectively Nandini Sengupta acknowl-edges the financial assistance from project WOS-A DST(Department of Science and Technology New Delhi) PulakSengupta acknowledges the financial assistance from theCAS Department of Geological Sciences and UPE-II Jadav-pur University They thank Mr Priyadarshi Chowdhuryand Dr A Gupta for their assistance during the fieldworkThey also thank two anonymous reviewers for their helpfulcomments that improved the clarity of the paper
References
[1] P Bayliss U Kolitsch EHNickel andA Pring ldquoAlunite super-group recommended nomenclaturerdquo Mineralogical Magazinevol 74 no 5 pp 919ndash927 2010
[2] H G Dill ldquoThe geology of Aluminium Phosphates and sulfatesof the alunite supergouprdquo Earth-Science Reviews vol 53 pp 35ndash93 2001
[3] S Gaboreau D Beaufort P Vieillard P Patrier and P Brune-ton ldquoAluminum phosphate-sulfate minerals associated withProterozoic unconformity-type uranium deposits in the EastAlligator River Uranium Field Northern Territories AustraliardquoCanadian Mineralogist vol 43 no 2 pp 813ndash827 2005
[4] AHikovC Lerouge andNVelinova ldquoGeochemistry of alunitegroupminerals in hydrothermally altered rocks from the Asarelporphyry copper deposit Central Srednogorierdquo Review of theBulgarian Geological Society vol 71 no 1ndash3 pp 133ndash148 2010
[5] S A Repina ldquoFractionation of REE in the xenotime andflorencite paragenetic association fromAu-REEmineral occur-rences of the Nether-Polar Uralsrdquo Geochemistry Internationalvol 49 no 9 pp 868ndash887 2011
[6] G Nagy E Draganits A Demeny G Panto and P ArkaildquoGenesis and transformations of monazite florencite and rhab-dophane duringmedium grademetamorphism examples fromthe Sopron Hills Eastern Alpsrdquo Chemical Geology vol 191 no1ndash3 pp 25ndash46 2002
[7] I A Izbrodin G S Ripp and A G Doroshkevich ldquoAluminiumphosphate and phosphate-sulphate minerals in kyanite schistsof the Ichetuyskoye area West Transbaikalia Russia crystalchemistry and evolutionrdquoMineralogy and Petrology vol 101 no1 pp 81ndash96 2011
[8] E Janots F Negro F Brunet B Goffe M Engi and M LBouybaouene ldquoEvolution of the REE mineralogy in HP-LTmetapelites of the Sebtide complex Rif Morocco monazitestability and geochronologyrdquo Lithos vol 87 no 3-4 pp 214ndash234 2006
[9] D Visser R O Felius andMMoree ldquoAugelite and cerian cran-dallite in dumortierite quartzites Vaca Morta quarry Veredarange Macaubas Bahia Brazilrdquo Mineralogical Magazine vol61 no 4 pp 607ndash609 1997
[10] J A Dunn and A K Dey ldquoGeology and petrology of EasternSinghbhum and surrounding areasrdquo Memoirs of the GeologicalSurvey of India vol 69 no 2 1942
[11] A K Saha ldquoCrustal evolution of Singhbhum North OrissaEastern IndiardquoGeological Society of IndiaMemoir vol 27 article341 1994
[12] S C Sarkar and A Gupta Crustal Evolution andMetallogeny inIndia vol 741 Cambridge University Press 2012
[13] N Sengupta P Sengupta and H K Sachan ldquoAluminous andalkali-deficient tourmaline from the Singhbhum Shear ZoneEast Indian shield insight for polyphase boron infiltrationduring regional metamorphismrdquo American Mineralogist vol96 no 5-6 pp 752ndash767 2011
[14] D Mukhopadhyay and G K Deb ldquoStructural and texturaldevelopment in Singhbhum shear zone eastern Indiardquo Proceed-ings of the Indian Academy of Sciences vol 104 no 3 pp 385ndash405 1995
[15] N Sengupta ldquoStability of chloritoid + biotite-bearing assem-blages in some metapelites from the Palaeoproterozoic Singhb-hum Shear Zone eastern India and their implicationsrdquo Geolog-ical Society LondonmdashSpecial Publications vol 365 pp 91ndash1162012
[16] R Kretz ldquoSymbols for rock-forming mineralsrdquo American Min-eralogist vol 68 no 1-2 pp 277ndash279 1983
[17] J L Pouchou and F Pichoir ldquoA new model for quantitativeX-ray microanalysismdashpart-I application to the analysis ofhomogeneous samplesrdquo La Recherche Aerospatiale no 3 pp167ndash192 1984
[18] S Georgieva and N Velinova ldquoFlorencite-(Ce La Nd) fromthe advanced argillic alterations in the Chelopech high-sulphidation epithermal Cu-Au deposit Bulgariardquo in Proceed-ings of the National Conference with International Participation(GEOSCIENCES rsquo12) Bulgarian Geological Society 2012
[19] A G Doroshkevich S G Viladkar G S Ripp and M V Burt-seva ldquoHydrothermal REE mineralization in the Amba Dongarcarbonatite complex Gujarat Indiardquo Canadian Mineralogistvol 47 no 5 pp 1105ndash1116 2009
[20] W S Wise and S E Loh ldquoEquilibria and origin of minerals inthe system Al
2
O-AlPO4
-H2
Ordquo American Mineralogist vol 61pp 409ndash413 1976
[21] P Schmid-Beurmann G Morteani and L Cemic ldquoExper-imental determination of the upper stability of scorzaliteFeAl2
[OHPO4
]2
and the occurrence of minerals with a com-position intermediate between scorzalite and lazulite(ss) upto the conditions of the amphibolite faciesrdquo Mineralogy andPetrology vol 61 no 1ndash4 pp 211ndash222 1998
[22] G Morteani D Ackermand and H A Horn ldquoAluminum-phosphates and borosilicates in muscovite-kyanite metaquar-tzites near Diamantina (Minas Gerais Brazil) petrogeneticimplicationsrdquo Periodico diMineralogia vol 70 pp 111ndash129 2001
[23] D Mckie ldquoGoyazite and florencite from two African carbon-atitesrdquoMineralogical Magazine vol 33 pp 281ndash297 1962
[24] J C Ayers and E B Watson ldquoSolubility of apatite mon-azite zircon and rutile in supercritical aqueous fluids withimplications for subduction zone geochemistryrdquo PhilosophicalTransactionsmdashRoyal Society of London A vol 335 no 1638 pp365ndash375 1991
[25] A P Jones F Wall and C T Williams Eds Rare EarthMinerals Chemistry Origin and Ore Deposits vol 357 of TheMineralogical Society Series 7 Chapman and Hall 1996
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Mining
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Journal of
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Geochemistry
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OceanographyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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MineralogyInternational Journal of
Meteorology
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ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom
Volume 2014
Geological ResearchJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Geology Advances in
2 International Journal of Mineralogy
Tatanagar
Jaduguda
Ghatshila
MG
S
Chakradharpurgranite gneiss N N
1050
(scale in km)
DelhiSSZN N
E E
EE
Mayurbhanj granite
N
SSZSSZ
SSZ
SSZ
Singhbhum graniteIOGsediments
IOGsediments
Dalma volcanics
Arkasani granophyre
Soda granite
Soda granite
KanyalukaDhanjorivolcanics
IOG metavolcanicsDhanjorisediments
Singhbhum groupof metapelites
KolhanGroup ofvolcanics
NSFB
Ongarbirametavolcanics
85∘ 45998400 86∘ 0998400 1599840086∘ 86∘
76∘
76∘
30998400 86∘ 45998400
23∘
24∘24∘
0998400
22∘
92∘
92∘ 45998400
22∘
30998400
22∘
86∘ 4599840015998400
1599840015998400
86∘ 3099840086∘ 86∘099840085∘ 45998400
22∘
22∘
30998400
22∘
459984008∘8∘
099840023∘
lowast
Figure 1 Geologic map showing the distribution of stratigraphic units in a part of eastern India After Dunn and Dey [10] and Saha [11] SSZSinghbhum shear zone NSFB North Singhbhum Fold Belt IOG Iron Ore GroupThe rectangle around Kanyaluka (marked by red asterisk)is blown up in Figure 2
hydrothermal activities developed different types of Cu-Fe-U-P deposits that are associated with tourmalinizationmuscovitization and ferruginization (discussed in Senguptaet al [13] and Sarkar and Gupta [12]) Infiltration-drivenmetamorphism in the SSZ produced a number of exotic rocksincluding per-aluminous kyanite-quartz rocks that fringe thenorthern boundary of the SSZ (Figures 1 and 2 Figure 2partly after Mukhopadhyay and Deb [14]) In the easternpart where the SSZ takes a bend towards south (Figure 1)kyanite-quartz rock is spatially associated with chloritoid-bearing schist pssammopelites mica schist and bands oftourmalinite (Figure 2) All these rocks share a commonhistory of deformation and metamorphism that culminatedat 490 plusmn 40∘C and 63 plusmn 1 kbar (Sengupta [15]) In thiscommunication we are describing themode of occurrence offlorencite in the host of kyanite-rich rock (gt80 vol kyanite)that is exposed near the village of Kanyaluka (Figure 2)Integrating all the petrological data we demonstrate thatflorencite was developed due to infiltration of acidic fluidcharged with P and LREE into the per-aluminous kyanite-rich rock at the culmination of metamorphism and deforma-tion Incidentally this is the first report of florencite from anyPrecambrian rocks of India
2 Petrography and Mineral Chemistry
In domains of minimum strain kyanite-rich rock developsrandomly oriented blades of kyanite that occupy more than80 vol of the rock (Figure 3(a) abbreviations after Kretz[16]) Grains of quartz and rutile occupy the interstitialspace of the mesh formed by the kyanite blades (Figures3(a) and 3(b)) The kyanite-rich rock develops centimeter todecimeter thick bands of intense shearing In the shear bandskyanite blades are kinked bent and fractured (Figure 3(b))and the quartz grains show undulose extinction Locallydeformed kyanite blades are extensively replaced by augeliteand lazulite (Figure 4(a)) Unlike kyanite lazulite andaugelite do not show any deformation (static growth) Inthe backscattered electron (BSE) images florencite grainsappear as numerous small bright spots in the dull backgroundcomposed of lazulite kyanite and quartz (Figure 4(b)) Smalldisseminated idioblastic subhedral to anhedral crystals (lt20microns) of florencite are included in kyanite quartz andlazulite (Figures 4(c) and 4(d)) Rarely florencite replaceskyanite (Figure 4(c)) Textural features attest to the view thatflorencite crystals are left stranded within lazulite when thelatter mineral replaced kyanite (Figure 4(d)) This featuresuggests equilibrium coexistence of florencite and lazulite
International Journal of Mineralogy 3
Kanyaluka
Bhalki
Mica schist (NSFB)Banded ferruginousquartziteKyanite quartzitekyanite mica schistChloritoid schistSoda graniteFeldspathic schistQuartz mica schistTourmalinitetourmaline schist
Sankh
Nala
h
Subarnarekha
Chlorite quartz schist(granular rock)QuartziteMetabasic rocksBanded psammopelitesBiotite muscovite schistFaultRiver
N
22∘
22∘
86∘30998400
86∘
30998400
30998400
30998400
lowast
Figure 2 Lithological map of the South Eastern sector of Singhbhum shear zone (SSZ) around Kanyaluka (Partly after Mukhopadhyay andDeb [14]) The location from where the samples have been collected is marked with red asterisk
Ky
Rt
Qtz
Ky
50120583m
(a)
Rt Qtz
Ky
50120583m
(b)
Figure 3 (a) Randomly oriented kyanite grains forming a mesh-like appearance Some corroded rutile grains and quartz are also seen in theinterstitial spaces and (b) Kyanite poor zone in the host rock showing the presence of deformed (kinked) kyanite Mineral abbreviations usedare after Kretz [16]
4 International Journal of Mineralogy
Ky
LazAug
(a)
Laz
Fl
Ky
Ky
Qtz
(b)
Ky Fl
Laz
(c)
Laz
FlQtz
(d)
Figure 4 BSE images showing (a) Kyanite blades replaced by augelite and lazulite (b) overall view of the lazulite rich zone relicts ofkyanite showing corroded boundary are sparsely distributed here The small bright spots seen here are florencite (c) florencite grain withprotruding grain boundary inside kyanite showing that florencite replaces kyanite (d) florencite grain stranded within lazulite Aug augeliteFl florencite All other mineral abbreviations are after Kretz [16]
Electron microprobe analyses and WDS spectrum of theflorencite are presented in Table 1 and Figure 5 respectivelyAlso included in Table 1 are the representative analysesof kyanite lazulite and rutile For comparison florenciteanalyses from somewell-known localities are also included inTable 1 Chemical compositions of florencite and the adjacentminerals were determined from carbon-coated thin sectionsby electron microprobe analysis (EMPA) with a CAMECASX100 electron microprobe at the Central PetrologicalLaboratory Geological Survey of India Kolkata For elementsother than Sr Ba and the REE the accelerating voltage usedwas 15 kVwith a 12 nA current Elements were analyzed usingnatural standards except for Mn and Ti for which syntheticstandards were used For the heavy metals (Ba Sr and REE)20 kV and 20 nA were usedThe following standards are usedfor REE (REE glass) Sr (celestite) and Ba (barite) The rawdata were processed using the PAP procedure (Pouchou andPichoir [17]) The composition of florencite is recalculatedon 11 oxygen basis and the nomenclature of the differentspecies is according to Bayliss et al [1] Compositionallyflorencite is essentially a solid solution of the speciesFlorencite-(Ce) (487mol) Florencite-(La) (299mol)and Florencite-(Nd) (213mol) (Table 1) Similar to othernatural florencite compositions concentrations of LREE
outweigh the concentrations of HREE The concentrationsof HREE S and As are below the detection limit of electronmicroprobe Concentrations of Sr (0002 to 0008 apfu) Ba(sim000003 apfu) Ca (0040 to 0062 apfu) and K (0001 to0012 apfu) are low Concentration of ThO
2varies between
sim05 and 12 wt (001ndash0024 apfu) The WDS spectrumsuggests that the elements that are not measured do nothave any significant concentrations Lazulite is dominated byMg (9806mol lazulite) with a small amount of scorzalite(194mol Fe-Lazulite Table 1) Kyanite rutile and quartzhave essentially the end member compositions
Entry of small amount of Th and Ca in the structure offlorencite can be explained by the substitution REE3+ harrTh + Ca (Nagy et al [6] Georgieva and Velinova [18] andGaboreau et al [3]) Compared to the florencite compositionsreported from many florencite occurrences in the worldflorencite compositions of this study are depleted in Sr CaBa and S whereas they are enriched in P
2O5(Table 1)
3 Discussion
Florencite in the kyanite rich rock of the Singhbhum shearzone records the first occurrence of this mineral from any
International Journal of Mineralogy 5Ta
ble1Re
presentativ
eanalyses
offlo
rencitelazuliteaugelitekyaniteand
rutilemineralfro
mstu
died
areaF
lorencite
mineralcompo
sitionhasb
eencomparedwith
compo
sitions
from
different
localities
Elem
ents
Locatio
n
Florencite(calculated
on11oxygen
basis
Valuesinwt
)
Florencitedata
byNagyetal
2002
[6](values
inwt
)
Florencitedata
byJano
tsetal
2006
[8](values
inwt
)
Florencitedataby
Doroshk
evichetal
2009
[19](values
inwt
)
Lazulite(values
inwt
)Au
gelite(
values
inwt
)Ky
anite
(values
inwt
)Ru
tile(values
inwt
)
Sing
hbhu
mshearz
one(SSZ)
Sopron
Hills
Easte
rnAlps
Hun
gary
Sebtide
complexR
ifMorocco
Amba-D
ongar
GujaratInd
iaSing
hbhu
mshearz
one(SSZ)
SiO
2000
006
001
na
024ndash4
2gt075
001
023
3669
000
TiO
2007
000
004
na
na
na
003
006
002
10090
Al 2O
32847
2737
2728
2866ndash
3189
2710
ndash319
22786ndash
3067
3349
4930
6245
006
Cr2O
3000
000
000
na
na
na
000
008
004
013
FeO
000
001
000
na
017ndash14
na
000
000
003
010
MnO
000
000
000
na
na
na
043
004
002
000
CaO
042
064
054
072ndash144
042ndash0
69
023ndash0
81
001
000
000
001
MgO
001
005
010
na
002ndash0
70
na
1332
003
001
000
Na 2O
009
009
011
na
001ndash0
06
na
003
000
006
000
K 2O
000
000
001
na
na
na
000
000
002
001
P 2O
53081
3072
3084
2697ndash2893
224ndash264
2608ndash2856
4844
3709
000
000
ZrO
2000
000
000
na
na
na
mdashmdash
mdashmdash
Nb 2O
5000
000
004
na
na
na
mdashmdash
mdashmdash
La2O
3683
769
712
646
ndash866
422ndash4
25
391ndash1264
mdashmdash
mdashmdash
Ce 2O
31093
1215
1178
1091ndash1433
837ndash926
494ndash1232
mdashmdash
mdashmdash
PbO
000
000
000
na
na
na
mdashmdash
mdashmdash
ThO
2049
118
118
055ndash994
059ndash109
na
mdashmdash
mdashmdash
U2O
3004
002
002
na
007ndash0
17na
mdashmdash
mdashmdash
BaO
000
000
000
na
na
na
mdashmdash
mdashmdash
SrO
012
015
010
016ndash0
67
132ndash591
447ndash1336
mdashmdash
mdashmdash
Nd 2O
3270
261
269
165ndash500
396ndash4
80
102ndash291
mdashmdash
mdashmdash
Sm2O
3110
106
109
010ndash0
92
055ndash0
60
na
mdashmdash
mdashmdash
SO3
000
000
000
na
021ndash0
59
108ndash
471
mdashmdash
mdashmdash
Total
8208
8381
8295
8769ndash
9036
7821ndash86
35
7140ndash
7898
9576
8683
9940
1012
5ap
fu
apfu
apfu
apfu
apfu
apfu
apfu
apfu
apfu
apfu
Si000
001
000
na
0020ndash
0379
006
0ndash0170
000
002
100
000
Ti000
000
000
na
na
na
000
000
000
100
Al
299
290
289
3203ndash3360
2880ndash
3131
2710ndash
2950
195
384
200
000
Cr000
000
000
na
na
na
001
000
000
000
Fe000
000
000
na
0012ndash0107
0020ndash
0333
002
000
000
000
Mn
000
000
000
na
na
na
000
000
000
000
Ca004
006
005
006
8ndash0105
0038ndash
0067
0020ndash
0070
000
000
000
000
Mg
000
001
001
na
0003ndash0095
na
098
000
000
000
Na
002
002
002
na
0002ndash0012
na
000
000
000
000
K000
000
000
na
na
na
000
000
000
000
6 International Journal of Mineralogy
Table1Con
tinued
Elem
ents
Locatio
n
Florencite(calculated
on11oxygen
basis
Valuesinwt
)
Florencitedata
byNagyetal
2002
[6](values
inwt
)
Florencitedata
byJano
tsetal
2006
[8](values
inwt
)
Florencitedataby
Doroshk
evichetal
2009
[19](values
inwt
)
Lazulite(values
inwt
)Au
gelite(
values
inwt
)Ky
anite
(values
inwt
)Ru
tile(values
inwt
)
Sing
hbhu
mshearz
one(SSZ)
Sopron
Hills
Easte
rnAlps
Hun
gary
Sebtide
complexR
ifMorocco
Amba-D
ongar
GujaratInd
iaSing
hbhu
mshearz
one(SSZ)
P233
234
235
2041ndash2117
1710ndash1863
1770ndash2001
203
208
000
000
Zr000
000
000
na
na
na
mdashmdash
mdashmdash
Nb
000
000
000
na
na
na
mdashmdash
mdashmdash
La011
013
012
0104ndash
0106
0131ndash0140
0110ndash
0340
mdashmdash
mdashmdash
Ce
018
020
019
0204ndash
0213
0277ndash0282
0140ndash
0392
mdashmdash
mdashmdash
Pb000
000
000
na
na
na
mdashmdash
mdashmdash
Th001
002
002
na
0022ndash0011
na
mdashmdash
mdashmdash
U000
000
000
na
0001ndash000
4na
mdashmdash
mdashmdash
Ba000
000
000
na
na
na
mdashmdash
mdashmdash
Sr001
001
001
0011ndash0035
na
na
mdashmdash
mdashmdash
Nd
009
008
009
0142ndash0156
0128ndash
0143
0030ndash
0071
mdashmdash
mdashmdash
Sm003
003
003
0023ndash0027
0018ndash
0019
na
mdashmdash
mdashmdash
Sbdl
bdl
bdl
na
0069ndash
0285
0070ndash
0273
mdashmdash
mdashmdash
Totalcation
580
580
579
589
2ndash599
25763ndash
594
55637ndash
583
4498
595
300
100
sumRE
E042
045
044
0484ndash
0537
0603ndash0612
0300ndash
0603
Florencite
(mol)
8994
8669
8845
Goyazite
(mol)
136
147
103
Crandallite
(mol)
870
1184
1052
Noten
anot
availablebdlbelowdetectionlim
it
International Journal of Mineralogy 7
Cps
5000
4000
3000
2000
1000
020000 30000 40000 50000 60000 70000 80000 90000
S In
P Ka
P Ka
Al Ka
Ce La
Ce Lb
La La
TAPPET
Figure 5 WDS of florencite showing Al P Ce and La TAP and PET are crystals of the electron microprobe machine
Precambrian rocks of the peninsular India The only otherlocality of florencite in India is the carbonatite complex ofAmba Dongar Gujarat (Doroshkevich et al [19])
Textural features suggest that florencite was formed dur-ing and after the growth of kyanite and hence originatedduringmetamorphism that accompanied the ductile shearingof the studied rock Florencite remained stable during theformation of lazulite and augelite that replaced kyanite understatic condition (post-shearing) Experimental study in theAl-P-O-H system and the observations from natural rocksshow that the assemblage augelite + kyanite is stable at con-ditions 380∘ndash475∘C and pressure gt2 kbar (Wise and Loh [20]andVisser et al [9])The assemblage kyanite + lazulite on theother hand has a wide thermal and baric stability (gt400∘Cand gt2 kbar Schmid-Beurmann et al [21] andMorteani et al[22]) Stability of florencite at high temperature (up to 550∘C)is reported from the eastern Alps (Nagy et al [6]) and fromAfrican carbonatites (Mckie [23]) Briefly the assemblagekyanite + augelite + lazulite + florencite appears to form attemperature and pressure that exceeded 400∘C and 2 kbarThis is in a good agreement with the calculated 119875-119879 valuesof 490 plusmn 40∘C and sim6 plusmn 1 kbar from the adjoining chloritoidgarnet bearing schist (Sengupta [15])
Origin of florencite in kyanite-quartz rock requires advec-tive transport of LREE and P presumably by infiltrationof aqueous fluids Singhbhum shear zone is characterizedby repeated infiltrations of aqueous fluids that resulted inmineralization ofCu-Fe-U-P and tourmalinization (reviewedin Sengupta et al [13] and Sarkar and Gupta [12]) In thisstudy we document phosphate REE and Mg-metasomatismwhich developed end member lazulite (very low content ofscorzalite) in kyanite-rich rock Several studies have demon-strated that florencite develops in hydrothermally altered(sensu lato) rock in which themetasomatic fluids are oxidizedand have acidic pH (Visser et al [9] Nagy et al [6] Gaboreau
et al [3] Hikov et al [4] and Georgieva and Velinova [18]) Inview of this we envisage that infiltration of acidic fluid froman extraneous source to be responsible for the developmentof florencite Absence ofmuscovitization of kyanite in kyanitequartz rock of this particular studied area and extensivetourmalinization of the adjoining rocks (Sengupta et al [13])supports that acidic metasomatic fluids infiltrated the rocksof the area Studies have shown that acidic fluids can dissolvea large amount of PO
4
minus3 and LREE as these chemical speciesform the ligand (REE (PO
4)∘
aq) (Ayers and Watson [24]cf Jones et al [25]) This fluid upon interacting with per-aluminous host rock stabilized florencite (Nagy et al [6])
4 Conclusion
(1) Florencite a REE-Al phosphate has been reportedfrom a metamorphosed kyanite-rich rock from theSinghbhum shear zone of the east Indian Shield
(2) Petrology of the florencite-bearing mineral associa-tion suggests metamorphic growth of florencite in the119875-119879 range of sim6 plusmn 1 kbar and 490∘plusmn 40∘C This is thefirst report of florencite from Precambrian rocks ofIndia
(3) Florencite was formed due to interaction of acidicaqueous fluids charged with PO4minus and REE and alu-minous country rock during regional metamorphismand ductile shearing in the Singhbhum shear zone
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
8 International Journal of Mineralogy
Acknowledgments
Maitrayee Chakraborty and Sayan Biswas acknowledge theresearch grants sanctioned by the CSIR New Delhi andUGC New Delhi respectively Nandini Sengupta acknowl-edges the financial assistance from project WOS-A DST(Department of Science and Technology New Delhi) PulakSengupta acknowledges the financial assistance from theCAS Department of Geological Sciences and UPE-II Jadav-pur University They thank Mr Priyadarshi Chowdhuryand Dr A Gupta for their assistance during the fieldworkThey also thank two anonymous reviewers for their helpfulcomments that improved the clarity of the paper
References
[1] P Bayliss U Kolitsch EHNickel andA Pring ldquoAlunite super-group recommended nomenclaturerdquo Mineralogical Magazinevol 74 no 5 pp 919ndash927 2010
[2] H G Dill ldquoThe geology of Aluminium Phosphates and sulfatesof the alunite supergouprdquo Earth-Science Reviews vol 53 pp 35ndash93 2001
[3] S Gaboreau D Beaufort P Vieillard P Patrier and P Brune-ton ldquoAluminum phosphate-sulfate minerals associated withProterozoic unconformity-type uranium deposits in the EastAlligator River Uranium Field Northern Territories AustraliardquoCanadian Mineralogist vol 43 no 2 pp 813ndash827 2005
[4] AHikovC Lerouge andNVelinova ldquoGeochemistry of alunitegroupminerals in hydrothermally altered rocks from the Asarelporphyry copper deposit Central Srednogorierdquo Review of theBulgarian Geological Society vol 71 no 1ndash3 pp 133ndash148 2010
[5] S A Repina ldquoFractionation of REE in the xenotime andflorencite paragenetic association fromAu-REEmineral occur-rences of the Nether-Polar Uralsrdquo Geochemistry Internationalvol 49 no 9 pp 868ndash887 2011
[6] G Nagy E Draganits A Demeny G Panto and P ArkaildquoGenesis and transformations of monazite florencite and rhab-dophane duringmedium grademetamorphism examples fromthe Sopron Hills Eastern Alpsrdquo Chemical Geology vol 191 no1ndash3 pp 25ndash46 2002
[7] I A Izbrodin G S Ripp and A G Doroshkevich ldquoAluminiumphosphate and phosphate-sulphate minerals in kyanite schistsof the Ichetuyskoye area West Transbaikalia Russia crystalchemistry and evolutionrdquoMineralogy and Petrology vol 101 no1 pp 81ndash96 2011
[8] E Janots F Negro F Brunet B Goffe M Engi and M LBouybaouene ldquoEvolution of the REE mineralogy in HP-LTmetapelites of the Sebtide complex Rif Morocco monazitestability and geochronologyrdquo Lithos vol 87 no 3-4 pp 214ndash234 2006
[9] D Visser R O Felius andMMoree ldquoAugelite and cerian cran-dallite in dumortierite quartzites Vaca Morta quarry Veredarange Macaubas Bahia Brazilrdquo Mineralogical Magazine vol61 no 4 pp 607ndash609 1997
[10] J A Dunn and A K Dey ldquoGeology and petrology of EasternSinghbhum and surrounding areasrdquo Memoirs of the GeologicalSurvey of India vol 69 no 2 1942
[11] A K Saha ldquoCrustal evolution of Singhbhum North OrissaEastern IndiardquoGeological Society of IndiaMemoir vol 27 article341 1994
[12] S C Sarkar and A Gupta Crustal Evolution andMetallogeny inIndia vol 741 Cambridge University Press 2012
[13] N Sengupta P Sengupta and H K Sachan ldquoAluminous andalkali-deficient tourmaline from the Singhbhum Shear ZoneEast Indian shield insight for polyphase boron infiltrationduring regional metamorphismrdquo American Mineralogist vol96 no 5-6 pp 752ndash767 2011
[14] D Mukhopadhyay and G K Deb ldquoStructural and texturaldevelopment in Singhbhum shear zone eastern Indiardquo Proceed-ings of the Indian Academy of Sciences vol 104 no 3 pp 385ndash405 1995
[15] N Sengupta ldquoStability of chloritoid + biotite-bearing assem-blages in some metapelites from the Palaeoproterozoic Singhb-hum Shear Zone eastern India and their implicationsrdquo Geolog-ical Society LondonmdashSpecial Publications vol 365 pp 91ndash1162012
[16] R Kretz ldquoSymbols for rock-forming mineralsrdquo American Min-eralogist vol 68 no 1-2 pp 277ndash279 1983
[17] J L Pouchou and F Pichoir ldquoA new model for quantitativeX-ray microanalysismdashpart-I application to the analysis ofhomogeneous samplesrdquo La Recherche Aerospatiale no 3 pp167ndash192 1984
[18] S Georgieva and N Velinova ldquoFlorencite-(Ce La Nd) fromthe advanced argillic alterations in the Chelopech high-sulphidation epithermal Cu-Au deposit Bulgariardquo in Proceed-ings of the National Conference with International Participation(GEOSCIENCES rsquo12) Bulgarian Geological Society 2012
[19] A G Doroshkevich S G Viladkar G S Ripp and M V Burt-seva ldquoHydrothermal REE mineralization in the Amba Dongarcarbonatite complex Gujarat Indiardquo Canadian Mineralogistvol 47 no 5 pp 1105ndash1116 2009
[20] W S Wise and S E Loh ldquoEquilibria and origin of minerals inthe system Al
2
O-AlPO4
-H2
Ordquo American Mineralogist vol 61pp 409ndash413 1976
[21] P Schmid-Beurmann G Morteani and L Cemic ldquoExper-imental determination of the upper stability of scorzaliteFeAl2
[OHPO4
]2
and the occurrence of minerals with a com-position intermediate between scorzalite and lazulite(ss) upto the conditions of the amphibolite faciesrdquo Mineralogy andPetrology vol 61 no 1ndash4 pp 211ndash222 1998
[22] G Morteani D Ackermand and H A Horn ldquoAluminum-phosphates and borosilicates in muscovite-kyanite metaquar-tzites near Diamantina (Minas Gerais Brazil) petrogeneticimplicationsrdquo Periodico diMineralogia vol 70 pp 111ndash129 2001
[23] D Mckie ldquoGoyazite and florencite from two African carbon-atitesrdquoMineralogical Magazine vol 33 pp 281ndash297 1962
[24] J C Ayers and E B Watson ldquoSolubility of apatite mon-azite zircon and rutile in supercritical aqueous fluids withimplications for subduction zone geochemistryrdquo PhilosophicalTransactionsmdashRoyal Society of London A vol 335 no 1638 pp365ndash375 1991
[25] A P Jones F Wall and C T Williams Eds Rare EarthMinerals Chemistry Origin and Ore Deposits vol 357 of TheMineralogical Society Series 7 Chapman and Hall 1996
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Geochemistry
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MineralogyInternational Journal of
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Volume 2014
Geological ResearchJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Geology Advances in
International Journal of Mineralogy 3
Kanyaluka
Bhalki
Mica schist (NSFB)Banded ferruginousquartziteKyanite quartzitekyanite mica schistChloritoid schistSoda graniteFeldspathic schistQuartz mica schistTourmalinitetourmaline schist
Sankh
Nala
h
Subarnarekha
Chlorite quartz schist(granular rock)QuartziteMetabasic rocksBanded psammopelitesBiotite muscovite schistFaultRiver
N
22∘
22∘
86∘30998400
86∘
30998400
30998400
30998400
lowast
Figure 2 Lithological map of the South Eastern sector of Singhbhum shear zone (SSZ) around Kanyaluka (Partly after Mukhopadhyay andDeb [14]) The location from where the samples have been collected is marked with red asterisk
Ky
Rt
Qtz
Ky
50120583m
(a)
Rt Qtz
Ky
50120583m
(b)
Figure 3 (a) Randomly oriented kyanite grains forming a mesh-like appearance Some corroded rutile grains and quartz are also seen in theinterstitial spaces and (b) Kyanite poor zone in the host rock showing the presence of deformed (kinked) kyanite Mineral abbreviations usedare after Kretz [16]
4 International Journal of Mineralogy
Ky
LazAug
(a)
Laz
Fl
Ky
Ky
Qtz
(b)
Ky Fl
Laz
(c)
Laz
FlQtz
(d)
Figure 4 BSE images showing (a) Kyanite blades replaced by augelite and lazulite (b) overall view of the lazulite rich zone relicts ofkyanite showing corroded boundary are sparsely distributed here The small bright spots seen here are florencite (c) florencite grain withprotruding grain boundary inside kyanite showing that florencite replaces kyanite (d) florencite grain stranded within lazulite Aug augeliteFl florencite All other mineral abbreviations are after Kretz [16]
Electron microprobe analyses and WDS spectrum of theflorencite are presented in Table 1 and Figure 5 respectivelyAlso included in Table 1 are the representative analysesof kyanite lazulite and rutile For comparison florenciteanalyses from somewell-known localities are also included inTable 1 Chemical compositions of florencite and the adjacentminerals were determined from carbon-coated thin sectionsby electron microprobe analysis (EMPA) with a CAMECASX100 electron microprobe at the Central PetrologicalLaboratory Geological Survey of India Kolkata For elementsother than Sr Ba and the REE the accelerating voltage usedwas 15 kVwith a 12 nA current Elements were analyzed usingnatural standards except for Mn and Ti for which syntheticstandards were used For the heavy metals (Ba Sr and REE)20 kV and 20 nA were usedThe following standards are usedfor REE (REE glass) Sr (celestite) and Ba (barite) The rawdata were processed using the PAP procedure (Pouchou andPichoir [17]) The composition of florencite is recalculatedon 11 oxygen basis and the nomenclature of the differentspecies is according to Bayliss et al [1] Compositionallyflorencite is essentially a solid solution of the speciesFlorencite-(Ce) (487mol) Florencite-(La) (299mol)and Florencite-(Nd) (213mol) (Table 1) Similar to othernatural florencite compositions concentrations of LREE
outweigh the concentrations of HREE The concentrationsof HREE S and As are below the detection limit of electronmicroprobe Concentrations of Sr (0002 to 0008 apfu) Ba(sim000003 apfu) Ca (0040 to 0062 apfu) and K (0001 to0012 apfu) are low Concentration of ThO
2varies between
sim05 and 12 wt (001ndash0024 apfu) The WDS spectrumsuggests that the elements that are not measured do nothave any significant concentrations Lazulite is dominated byMg (9806mol lazulite) with a small amount of scorzalite(194mol Fe-Lazulite Table 1) Kyanite rutile and quartzhave essentially the end member compositions
Entry of small amount of Th and Ca in the structure offlorencite can be explained by the substitution REE3+ harrTh + Ca (Nagy et al [6] Georgieva and Velinova [18] andGaboreau et al [3]) Compared to the florencite compositionsreported from many florencite occurrences in the worldflorencite compositions of this study are depleted in Sr CaBa and S whereas they are enriched in P
2O5(Table 1)
3 Discussion
Florencite in the kyanite rich rock of the Singhbhum shearzone records the first occurrence of this mineral from any
International Journal of Mineralogy 5Ta
ble1Re
presentativ
eanalyses
offlo
rencitelazuliteaugelitekyaniteand
rutilemineralfro
mstu
died
areaF
lorencite
mineralcompo
sitionhasb
eencomparedwith
compo
sitions
from
different
localities
Elem
ents
Locatio
n
Florencite(calculated
on11oxygen
basis
Valuesinwt
)
Florencitedata
byNagyetal
2002
[6](values
inwt
)
Florencitedata
byJano
tsetal
2006
[8](values
inwt
)
Florencitedataby
Doroshk
evichetal
2009
[19](values
inwt
)
Lazulite(values
inwt
)Au
gelite(
values
inwt
)Ky
anite
(values
inwt
)Ru
tile(values
inwt
)
Sing
hbhu
mshearz
one(SSZ)
Sopron
Hills
Easte
rnAlps
Hun
gary
Sebtide
complexR
ifMorocco
Amba-D
ongar
GujaratInd
iaSing
hbhu
mshearz
one(SSZ)
SiO
2000
006
001
na
024ndash4
2gt075
001
023
3669
000
TiO
2007
000
004
na
na
na
003
006
002
10090
Al 2O
32847
2737
2728
2866ndash
3189
2710
ndash319
22786ndash
3067
3349
4930
6245
006
Cr2O
3000
000
000
na
na
na
000
008
004
013
FeO
000
001
000
na
017ndash14
na
000
000
003
010
MnO
000
000
000
na
na
na
043
004
002
000
CaO
042
064
054
072ndash144
042ndash0
69
023ndash0
81
001
000
000
001
MgO
001
005
010
na
002ndash0
70
na
1332
003
001
000
Na 2O
009
009
011
na
001ndash0
06
na
003
000
006
000
K 2O
000
000
001
na
na
na
000
000
002
001
P 2O
53081
3072
3084
2697ndash2893
224ndash264
2608ndash2856
4844
3709
000
000
ZrO
2000
000
000
na
na
na
mdashmdash
mdashmdash
Nb 2O
5000
000
004
na
na
na
mdashmdash
mdashmdash
La2O
3683
769
712
646
ndash866
422ndash4
25
391ndash1264
mdashmdash
mdashmdash
Ce 2O
31093
1215
1178
1091ndash1433
837ndash926
494ndash1232
mdashmdash
mdashmdash
PbO
000
000
000
na
na
na
mdashmdash
mdashmdash
ThO
2049
118
118
055ndash994
059ndash109
na
mdashmdash
mdashmdash
U2O
3004
002
002
na
007ndash0
17na
mdashmdash
mdashmdash
BaO
000
000
000
na
na
na
mdashmdash
mdashmdash
SrO
012
015
010
016ndash0
67
132ndash591
447ndash1336
mdashmdash
mdashmdash
Nd 2O
3270
261
269
165ndash500
396ndash4
80
102ndash291
mdashmdash
mdashmdash
Sm2O
3110
106
109
010ndash0
92
055ndash0
60
na
mdashmdash
mdashmdash
SO3
000
000
000
na
021ndash0
59
108ndash
471
mdashmdash
mdashmdash
Total
8208
8381
8295
8769ndash
9036
7821ndash86
35
7140ndash
7898
9576
8683
9940
1012
5ap
fu
apfu
apfu
apfu
apfu
apfu
apfu
apfu
apfu
apfu
Si000
001
000
na
0020ndash
0379
006
0ndash0170
000
002
100
000
Ti000
000
000
na
na
na
000
000
000
100
Al
299
290
289
3203ndash3360
2880ndash
3131
2710ndash
2950
195
384
200
000
Cr000
000
000
na
na
na
001
000
000
000
Fe000
000
000
na
0012ndash0107
0020ndash
0333
002
000
000
000
Mn
000
000
000
na
na
na
000
000
000
000
Ca004
006
005
006
8ndash0105
0038ndash
0067
0020ndash
0070
000
000
000
000
Mg
000
001
001
na
0003ndash0095
na
098
000
000
000
Na
002
002
002
na
0002ndash0012
na
000
000
000
000
K000
000
000
na
na
na
000
000
000
000
6 International Journal of Mineralogy
Table1Con
tinued
Elem
ents
Locatio
n
Florencite(calculated
on11oxygen
basis
Valuesinwt
)
Florencitedata
byNagyetal
2002
[6](values
inwt
)
Florencitedata
byJano
tsetal
2006
[8](values
inwt
)
Florencitedataby
Doroshk
evichetal
2009
[19](values
inwt
)
Lazulite(values
inwt
)Au
gelite(
values
inwt
)Ky
anite
(values
inwt
)Ru
tile(values
inwt
)
Sing
hbhu
mshearz
one(SSZ)
Sopron
Hills
Easte
rnAlps
Hun
gary
Sebtide
complexR
ifMorocco
Amba-D
ongar
GujaratInd
iaSing
hbhu
mshearz
one(SSZ)
P233
234
235
2041ndash2117
1710ndash1863
1770ndash2001
203
208
000
000
Zr000
000
000
na
na
na
mdashmdash
mdashmdash
Nb
000
000
000
na
na
na
mdashmdash
mdashmdash
La011
013
012
0104ndash
0106
0131ndash0140
0110ndash
0340
mdashmdash
mdashmdash
Ce
018
020
019
0204ndash
0213
0277ndash0282
0140ndash
0392
mdashmdash
mdashmdash
Pb000
000
000
na
na
na
mdashmdash
mdashmdash
Th001
002
002
na
0022ndash0011
na
mdashmdash
mdashmdash
U000
000
000
na
0001ndash000
4na
mdashmdash
mdashmdash
Ba000
000
000
na
na
na
mdashmdash
mdashmdash
Sr001
001
001
0011ndash0035
na
na
mdashmdash
mdashmdash
Nd
009
008
009
0142ndash0156
0128ndash
0143
0030ndash
0071
mdashmdash
mdashmdash
Sm003
003
003
0023ndash0027
0018ndash
0019
na
mdashmdash
mdashmdash
Sbdl
bdl
bdl
na
0069ndash
0285
0070ndash
0273
mdashmdash
mdashmdash
Totalcation
580
580
579
589
2ndash599
25763ndash
594
55637ndash
583
4498
595
300
100
sumRE
E042
045
044
0484ndash
0537
0603ndash0612
0300ndash
0603
Florencite
(mol)
8994
8669
8845
Goyazite
(mol)
136
147
103
Crandallite
(mol)
870
1184
1052
Noten
anot
availablebdlbelowdetectionlim
it
International Journal of Mineralogy 7
Cps
5000
4000
3000
2000
1000
020000 30000 40000 50000 60000 70000 80000 90000
S In
P Ka
P Ka
Al Ka
Ce La
Ce Lb
La La
TAPPET
Figure 5 WDS of florencite showing Al P Ce and La TAP and PET are crystals of the electron microprobe machine
Precambrian rocks of the peninsular India The only otherlocality of florencite in India is the carbonatite complex ofAmba Dongar Gujarat (Doroshkevich et al [19])
Textural features suggest that florencite was formed dur-ing and after the growth of kyanite and hence originatedduringmetamorphism that accompanied the ductile shearingof the studied rock Florencite remained stable during theformation of lazulite and augelite that replaced kyanite understatic condition (post-shearing) Experimental study in theAl-P-O-H system and the observations from natural rocksshow that the assemblage augelite + kyanite is stable at con-ditions 380∘ndash475∘C and pressure gt2 kbar (Wise and Loh [20]andVisser et al [9])The assemblage kyanite + lazulite on theother hand has a wide thermal and baric stability (gt400∘Cand gt2 kbar Schmid-Beurmann et al [21] andMorteani et al[22]) Stability of florencite at high temperature (up to 550∘C)is reported from the eastern Alps (Nagy et al [6]) and fromAfrican carbonatites (Mckie [23]) Briefly the assemblagekyanite + augelite + lazulite + florencite appears to form attemperature and pressure that exceeded 400∘C and 2 kbarThis is in a good agreement with the calculated 119875-119879 valuesof 490 plusmn 40∘C and sim6 plusmn 1 kbar from the adjoining chloritoidgarnet bearing schist (Sengupta [15])
Origin of florencite in kyanite-quartz rock requires advec-tive transport of LREE and P presumably by infiltrationof aqueous fluids Singhbhum shear zone is characterizedby repeated infiltrations of aqueous fluids that resulted inmineralization ofCu-Fe-U-P and tourmalinization (reviewedin Sengupta et al [13] and Sarkar and Gupta [12]) In thisstudy we document phosphate REE and Mg-metasomatismwhich developed end member lazulite (very low content ofscorzalite) in kyanite-rich rock Several studies have demon-strated that florencite develops in hydrothermally altered(sensu lato) rock in which themetasomatic fluids are oxidizedand have acidic pH (Visser et al [9] Nagy et al [6] Gaboreau
et al [3] Hikov et al [4] and Georgieva and Velinova [18]) Inview of this we envisage that infiltration of acidic fluid froman extraneous source to be responsible for the developmentof florencite Absence ofmuscovitization of kyanite in kyanitequartz rock of this particular studied area and extensivetourmalinization of the adjoining rocks (Sengupta et al [13])supports that acidic metasomatic fluids infiltrated the rocksof the area Studies have shown that acidic fluids can dissolvea large amount of PO
4
minus3 and LREE as these chemical speciesform the ligand (REE (PO
4)∘
aq) (Ayers and Watson [24]cf Jones et al [25]) This fluid upon interacting with per-aluminous host rock stabilized florencite (Nagy et al [6])
4 Conclusion
(1) Florencite a REE-Al phosphate has been reportedfrom a metamorphosed kyanite-rich rock from theSinghbhum shear zone of the east Indian Shield
(2) Petrology of the florencite-bearing mineral associa-tion suggests metamorphic growth of florencite in the119875-119879 range of sim6 plusmn 1 kbar and 490∘plusmn 40∘C This is thefirst report of florencite from Precambrian rocks ofIndia
(3) Florencite was formed due to interaction of acidicaqueous fluids charged with PO4minus and REE and alu-minous country rock during regional metamorphismand ductile shearing in the Singhbhum shear zone
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
8 International Journal of Mineralogy
Acknowledgments
Maitrayee Chakraborty and Sayan Biswas acknowledge theresearch grants sanctioned by the CSIR New Delhi andUGC New Delhi respectively Nandini Sengupta acknowl-edges the financial assistance from project WOS-A DST(Department of Science and Technology New Delhi) PulakSengupta acknowledges the financial assistance from theCAS Department of Geological Sciences and UPE-II Jadav-pur University They thank Mr Priyadarshi Chowdhuryand Dr A Gupta for their assistance during the fieldworkThey also thank two anonymous reviewers for their helpfulcomments that improved the clarity of the paper
References
[1] P Bayliss U Kolitsch EHNickel andA Pring ldquoAlunite super-group recommended nomenclaturerdquo Mineralogical Magazinevol 74 no 5 pp 919ndash927 2010
[2] H G Dill ldquoThe geology of Aluminium Phosphates and sulfatesof the alunite supergouprdquo Earth-Science Reviews vol 53 pp 35ndash93 2001
[3] S Gaboreau D Beaufort P Vieillard P Patrier and P Brune-ton ldquoAluminum phosphate-sulfate minerals associated withProterozoic unconformity-type uranium deposits in the EastAlligator River Uranium Field Northern Territories AustraliardquoCanadian Mineralogist vol 43 no 2 pp 813ndash827 2005
[4] AHikovC Lerouge andNVelinova ldquoGeochemistry of alunitegroupminerals in hydrothermally altered rocks from the Asarelporphyry copper deposit Central Srednogorierdquo Review of theBulgarian Geological Society vol 71 no 1ndash3 pp 133ndash148 2010
[5] S A Repina ldquoFractionation of REE in the xenotime andflorencite paragenetic association fromAu-REEmineral occur-rences of the Nether-Polar Uralsrdquo Geochemistry Internationalvol 49 no 9 pp 868ndash887 2011
[6] G Nagy E Draganits A Demeny G Panto and P ArkaildquoGenesis and transformations of monazite florencite and rhab-dophane duringmedium grademetamorphism examples fromthe Sopron Hills Eastern Alpsrdquo Chemical Geology vol 191 no1ndash3 pp 25ndash46 2002
[7] I A Izbrodin G S Ripp and A G Doroshkevich ldquoAluminiumphosphate and phosphate-sulphate minerals in kyanite schistsof the Ichetuyskoye area West Transbaikalia Russia crystalchemistry and evolutionrdquoMineralogy and Petrology vol 101 no1 pp 81ndash96 2011
[8] E Janots F Negro F Brunet B Goffe M Engi and M LBouybaouene ldquoEvolution of the REE mineralogy in HP-LTmetapelites of the Sebtide complex Rif Morocco monazitestability and geochronologyrdquo Lithos vol 87 no 3-4 pp 214ndash234 2006
[9] D Visser R O Felius andMMoree ldquoAugelite and cerian cran-dallite in dumortierite quartzites Vaca Morta quarry Veredarange Macaubas Bahia Brazilrdquo Mineralogical Magazine vol61 no 4 pp 607ndash609 1997
[10] J A Dunn and A K Dey ldquoGeology and petrology of EasternSinghbhum and surrounding areasrdquo Memoirs of the GeologicalSurvey of India vol 69 no 2 1942
[11] A K Saha ldquoCrustal evolution of Singhbhum North OrissaEastern IndiardquoGeological Society of IndiaMemoir vol 27 article341 1994
[12] S C Sarkar and A Gupta Crustal Evolution andMetallogeny inIndia vol 741 Cambridge University Press 2012
[13] N Sengupta P Sengupta and H K Sachan ldquoAluminous andalkali-deficient tourmaline from the Singhbhum Shear ZoneEast Indian shield insight for polyphase boron infiltrationduring regional metamorphismrdquo American Mineralogist vol96 no 5-6 pp 752ndash767 2011
[14] D Mukhopadhyay and G K Deb ldquoStructural and texturaldevelopment in Singhbhum shear zone eastern Indiardquo Proceed-ings of the Indian Academy of Sciences vol 104 no 3 pp 385ndash405 1995
[15] N Sengupta ldquoStability of chloritoid + biotite-bearing assem-blages in some metapelites from the Palaeoproterozoic Singhb-hum Shear Zone eastern India and their implicationsrdquo Geolog-ical Society LondonmdashSpecial Publications vol 365 pp 91ndash1162012
[16] R Kretz ldquoSymbols for rock-forming mineralsrdquo American Min-eralogist vol 68 no 1-2 pp 277ndash279 1983
[17] J L Pouchou and F Pichoir ldquoA new model for quantitativeX-ray microanalysismdashpart-I application to the analysis ofhomogeneous samplesrdquo La Recherche Aerospatiale no 3 pp167ndash192 1984
[18] S Georgieva and N Velinova ldquoFlorencite-(Ce La Nd) fromthe advanced argillic alterations in the Chelopech high-sulphidation epithermal Cu-Au deposit Bulgariardquo in Proceed-ings of the National Conference with International Participation(GEOSCIENCES rsquo12) Bulgarian Geological Society 2012
[19] A G Doroshkevich S G Viladkar G S Ripp and M V Burt-seva ldquoHydrothermal REE mineralization in the Amba Dongarcarbonatite complex Gujarat Indiardquo Canadian Mineralogistvol 47 no 5 pp 1105ndash1116 2009
[20] W S Wise and S E Loh ldquoEquilibria and origin of minerals inthe system Al
2
O-AlPO4
-H2
Ordquo American Mineralogist vol 61pp 409ndash413 1976
[21] P Schmid-Beurmann G Morteani and L Cemic ldquoExper-imental determination of the upper stability of scorzaliteFeAl2
[OHPO4
]2
and the occurrence of minerals with a com-position intermediate between scorzalite and lazulite(ss) upto the conditions of the amphibolite faciesrdquo Mineralogy andPetrology vol 61 no 1ndash4 pp 211ndash222 1998
[22] G Morteani D Ackermand and H A Horn ldquoAluminum-phosphates and borosilicates in muscovite-kyanite metaquar-tzites near Diamantina (Minas Gerais Brazil) petrogeneticimplicationsrdquo Periodico diMineralogia vol 70 pp 111ndash129 2001
[23] D Mckie ldquoGoyazite and florencite from two African carbon-atitesrdquoMineralogical Magazine vol 33 pp 281ndash297 1962
[24] J C Ayers and E B Watson ldquoSolubility of apatite mon-azite zircon and rutile in supercritical aqueous fluids withimplications for subduction zone geochemistryrdquo PhilosophicalTransactionsmdashRoyal Society of London A vol 335 no 1638 pp365ndash375 1991
[25] A P Jones F Wall and C T Williams Eds Rare EarthMinerals Chemistry Origin and Ore Deposits vol 357 of TheMineralogical Society Series 7 Chapman and Hall 1996
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Geochemistry
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MineralogyInternational Journal of
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ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Volume 2014
Geological ResearchJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Geology Advances in
4 International Journal of Mineralogy
Ky
LazAug
(a)
Laz
Fl
Ky
Ky
Qtz
(b)
Ky Fl
Laz
(c)
Laz
FlQtz
(d)
Figure 4 BSE images showing (a) Kyanite blades replaced by augelite and lazulite (b) overall view of the lazulite rich zone relicts ofkyanite showing corroded boundary are sparsely distributed here The small bright spots seen here are florencite (c) florencite grain withprotruding grain boundary inside kyanite showing that florencite replaces kyanite (d) florencite grain stranded within lazulite Aug augeliteFl florencite All other mineral abbreviations are after Kretz [16]
Electron microprobe analyses and WDS spectrum of theflorencite are presented in Table 1 and Figure 5 respectivelyAlso included in Table 1 are the representative analysesof kyanite lazulite and rutile For comparison florenciteanalyses from somewell-known localities are also included inTable 1 Chemical compositions of florencite and the adjacentminerals were determined from carbon-coated thin sectionsby electron microprobe analysis (EMPA) with a CAMECASX100 electron microprobe at the Central PetrologicalLaboratory Geological Survey of India Kolkata For elementsother than Sr Ba and the REE the accelerating voltage usedwas 15 kVwith a 12 nA current Elements were analyzed usingnatural standards except for Mn and Ti for which syntheticstandards were used For the heavy metals (Ba Sr and REE)20 kV and 20 nA were usedThe following standards are usedfor REE (REE glass) Sr (celestite) and Ba (barite) The rawdata were processed using the PAP procedure (Pouchou andPichoir [17]) The composition of florencite is recalculatedon 11 oxygen basis and the nomenclature of the differentspecies is according to Bayliss et al [1] Compositionallyflorencite is essentially a solid solution of the speciesFlorencite-(Ce) (487mol) Florencite-(La) (299mol)and Florencite-(Nd) (213mol) (Table 1) Similar to othernatural florencite compositions concentrations of LREE
outweigh the concentrations of HREE The concentrationsof HREE S and As are below the detection limit of electronmicroprobe Concentrations of Sr (0002 to 0008 apfu) Ba(sim000003 apfu) Ca (0040 to 0062 apfu) and K (0001 to0012 apfu) are low Concentration of ThO
2varies between
sim05 and 12 wt (001ndash0024 apfu) The WDS spectrumsuggests that the elements that are not measured do nothave any significant concentrations Lazulite is dominated byMg (9806mol lazulite) with a small amount of scorzalite(194mol Fe-Lazulite Table 1) Kyanite rutile and quartzhave essentially the end member compositions
Entry of small amount of Th and Ca in the structure offlorencite can be explained by the substitution REE3+ harrTh + Ca (Nagy et al [6] Georgieva and Velinova [18] andGaboreau et al [3]) Compared to the florencite compositionsreported from many florencite occurrences in the worldflorencite compositions of this study are depleted in Sr CaBa and S whereas they are enriched in P
2O5(Table 1)
3 Discussion
Florencite in the kyanite rich rock of the Singhbhum shearzone records the first occurrence of this mineral from any
International Journal of Mineralogy 5Ta
ble1Re
presentativ
eanalyses
offlo
rencitelazuliteaugelitekyaniteand
rutilemineralfro
mstu
died
areaF
lorencite
mineralcompo
sitionhasb
eencomparedwith
compo
sitions
from
different
localities
Elem
ents
Locatio
n
Florencite(calculated
on11oxygen
basis
Valuesinwt
)
Florencitedata
byNagyetal
2002
[6](values
inwt
)
Florencitedata
byJano
tsetal
2006
[8](values
inwt
)
Florencitedataby
Doroshk
evichetal
2009
[19](values
inwt
)
Lazulite(values
inwt
)Au
gelite(
values
inwt
)Ky
anite
(values
inwt
)Ru
tile(values
inwt
)
Sing
hbhu
mshearz
one(SSZ)
Sopron
Hills
Easte
rnAlps
Hun
gary
Sebtide
complexR
ifMorocco
Amba-D
ongar
GujaratInd
iaSing
hbhu
mshearz
one(SSZ)
SiO
2000
006
001
na
024ndash4
2gt075
001
023
3669
000
TiO
2007
000
004
na
na
na
003
006
002
10090
Al 2O
32847
2737
2728
2866ndash
3189
2710
ndash319
22786ndash
3067
3349
4930
6245
006
Cr2O
3000
000
000
na
na
na
000
008
004
013
FeO
000
001
000
na
017ndash14
na
000
000
003
010
MnO
000
000
000
na
na
na
043
004
002
000
CaO
042
064
054
072ndash144
042ndash0
69
023ndash0
81
001
000
000
001
MgO
001
005
010
na
002ndash0
70
na
1332
003
001
000
Na 2O
009
009
011
na
001ndash0
06
na
003
000
006
000
K 2O
000
000
001
na
na
na
000
000
002
001
P 2O
53081
3072
3084
2697ndash2893
224ndash264
2608ndash2856
4844
3709
000
000
ZrO
2000
000
000
na
na
na
mdashmdash
mdashmdash
Nb 2O
5000
000
004
na
na
na
mdashmdash
mdashmdash
La2O
3683
769
712
646
ndash866
422ndash4
25
391ndash1264
mdashmdash
mdashmdash
Ce 2O
31093
1215
1178
1091ndash1433
837ndash926
494ndash1232
mdashmdash
mdashmdash
PbO
000
000
000
na
na
na
mdashmdash
mdashmdash
ThO
2049
118
118
055ndash994
059ndash109
na
mdashmdash
mdashmdash
U2O
3004
002
002
na
007ndash0
17na
mdashmdash
mdashmdash
BaO
000
000
000
na
na
na
mdashmdash
mdashmdash
SrO
012
015
010
016ndash0
67
132ndash591
447ndash1336
mdashmdash
mdashmdash
Nd 2O
3270
261
269
165ndash500
396ndash4
80
102ndash291
mdashmdash
mdashmdash
Sm2O
3110
106
109
010ndash0
92
055ndash0
60
na
mdashmdash
mdashmdash
SO3
000
000
000
na
021ndash0
59
108ndash
471
mdashmdash
mdashmdash
Total
8208
8381
8295
8769ndash
9036
7821ndash86
35
7140ndash
7898
9576
8683
9940
1012
5ap
fu
apfu
apfu
apfu
apfu
apfu
apfu
apfu
apfu
apfu
Si000
001
000
na
0020ndash
0379
006
0ndash0170
000
002
100
000
Ti000
000
000
na
na
na
000
000
000
100
Al
299
290
289
3203ndash3360
2880ndash
3131
2710ndash
2950
195
384
200
000
Cr000
000
000
na
na
na
001
000
000
000
Fe000
000
000
na
0012ndash0107
0020ndash
0333
002
000
000
000
Mn
000
000
000
na
na
na
000
000
000
000
Ca004
006
005
006
8ndash0105
0038ndash
0067
0020ndash
0070
000
000
000
000
Mg
000
001
001
na
0003ndash0095
na
098
000
000
000
Na
002
002
002
na
0002ndash0012
na
000
000
000
000
K000
000
000
na
na
na
000
000
000
000
6 International Journal of Mineralogy
Table1Con
tinued
Elem
ents
Locatio
n
Florencite(calculated
on11oxygen
basis
Valuesinwt
)
Florencitedata
byNagyetal
2002
[6](values
inwt
)
Florencitedata
byJano
tsetal
2006
[8](values
inwt
)
Florencitedataby
Doroshk
evichetal
2009
[19](values
inwt
)
Lazulite(values
inwt
)Au
gelite(
values
inwt
)Ky
anite
(values
inwt
)Ru
tile(values
inwt
)
Sing
hbhu
mshearz
one(SSZ)
Sopron
Hills
Easte
rnAlps
Hun
gary
Sebtide
complexR
ifMorocco
Amba-D
ongar
GujaratInd
iaSing
hbhu
mshearz
one(SSZ)
P233
234
235
2041ndash2117
1710ndash1863
1770ndash2001
203
208
000
000
Zr000
000
000
na
na
na
mdashmdash
mdashmdash
Nb
000
000
000
na
na
na
mdashmdash
mdashmdash
La011
013
012
0104ndash
0106
0131ndash0140
0110ndash
0340
mdashmdash
mdashmdash
Ce
018
020
019
0204ndash
0213
0277ndash0282
0140ndash
0392
mdashmdash
mdashmdash
Pb000
000
000
na
na
na
mdashmdash
mdashmdash
Th001
002
002
na
0022ndash0011
na
mdashmdash
mdashmdash
U000
000
000
na
0001ndash000
4na
mdashmdash
mdashmdash
Ba000
000
000
na
na
na
mdashmdash
mdashmdash
Sr001
001
001
0011ndash0035
na
na
mdashmdash
mdashmdash
Nd
009
008
009
0142ndash0156
0128ndash
0143
0030ndash
0071
mdashmdash
mdashmdash
Sm003
003
003
0023ndash0027
0018ndash
0019
na
mdashmdash
mdashmdash
Sbdl
bdl
bdl
na
0069ndash
0285
0070ndash
0273
mdashmdash
mdashmdash
Totalcation
580
580
579
589
2ndash599
25763ndash
594
55637ndash
583
4498
595
300
100
sumRE
E042
045
044
0484ndash
0537
0603ndash0612
0300ndash
0603
Florencite
(mol)
8994
8669
8845
Goyazite
(mol)
136
147
103
Crandallite
(mol)
870
1184
1052
Noten
anot
availablebdlbelowdetectionlim
it
International Journal of Mineralogy 7
Cps
5000
4000
3000
2000
1000
020000 30000 40000 50000 60000 70000 80000 90000
S In
P Ka
P Ka
Al Ka
Ce La
Ce Lb
La La
TAPPET
Figure 5 WDS of florencite showing Al P Ce and La TAP and PET are crystals of the electron microprobe machine
Precambrian rocks of the peninsular India The only otherlocality of florencite in India is the carbonatite complex ofAmba Dongar Gujarat (Doroshkevich et al [19])
Textural features suggest that florencite was formed dur-ing and after the growth of kyanite and hence originatedduringmetamorphism that accompanied the ductile shearingof the studied rock Florencite remained stable during theformation of lazulite and augelite that replaced kyanite understatic condition (post-shearing) Experimental study in theAl-P-O-H system and the observations from natural rocksshow that the assemblage augelite + kyanite is stable at con-ditions 380∘ndash475∘C and pressure gt2 kbar (Wise and Loh [20]andVisser et al [9])The assemblage kyanite + lazulite on theother hand has a wide thermal and baric stability (gt400∘Cand gt2 kbar Schmid-Beurmann et al [21] andMorteani et al[22]) Stability of florencite at high temperature (up to 550∘C)is reported from the eastern Alps (Nagy et al [6]) and fromAfrican carbonatites (Mckie [23]) Briefly the assemblagekyanite + augelite + lazulite + florencite appears to form attemperature and pressure that exceeded 400∘C and 2 kbarThis is in a good agreement with the calculated 119875-119879 valuesof 490 plusmn 40∘C and sim6 plusmn 1 kbar from the adjoining chloritoidgarnet bearing schist (Sengupta [15])
Origin of florencite in kyanite-quartz rock requires advec-tive transport of LREE and P presumably by infiltrationof aqueous fluids Singhbhum shear zone is characterizedby repeated infiltrations of aqueous fluids that resulted inmineralization ofCu-Fe-U-P and tourmalinization (reviewedin Sengupta et al [13] and Sarkar and Gupta [12]) In thisstudy we document phosphate REE and Mg-metasomatismwhich developed end member lazulite (very low content ofscorzalite) in kyanite-rich rock Several studies have demon-strated that florencite develops in hydrothermally altered(sensu lato) rock in which themetasomatic fluids are oxidizedand have acidic pH (Visser et al [9] Nagy et al [6] Gaboreau
et al [3] Hikov et al [4] and Georgieva and Velinova [18]) Inview of this we envisage that infiltration of acidic fluid froman extraneous source to be responsible for the developmentof florencite Absence ofmuscovitization of kyanite in kyanitequartz rock of this particular studied area and extensivetourmalinization of the adjoining rocks (Sengupta et al [13])supports that acidic metasomatic fluids infiltrated the rocksof the area Studies have shown that acidic fluids can dissolvea large amount of PO
4
minus3 and LREE as these chemical speciesform the ligand (REE (PO
4)∘
aq) (Ayers and Watson [24]cf Jones et al [25]) This fluid upon interacting with per-aluminous host rock stabilized florencite (Nagy et al [6])
4 Conclusion
(1) Florencite a REE-Al phosphate has been reportedfrom a metamorphosed kyanite-rich rock from theSinghbhum shear zone of the east Indian Shield
(2) Petrology of the florencite-bearing mineral associa-tion suggests metamorphic growth of florencite in the119875-119879 range of sim6 plusmn 1 kbar and 490∘plusmn 40∘C This is thefirst report of florencite from Precambrian rocks ofIndia
(3) Florencite was formed due to interaction of acidicaqueous fluids charged with PO4minus and REE and alu-minous country rock during regional metamorphismand ductile shearing in the Singhbhum shear zone
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
8 International Journal of Mineralogy
Acknowledgments
Maitrayee Chakraborty and Sayan Biswas acknowledge theresearch grants sanctioned by the CSIR New Delhi andUGC New Delhi respectively Nandini Sengupta acknowl-edges the financial assistance from project WOS-A DST(Department of Science and Technology New Delhi) PulakSengupta acknowledges the financial assistance from theCAS Department of Geological Sciences and UPE-II Jadav-pur University They thank Mr Priyadarshi Chowdhuryand Dr A Gupta for their assistance during the fieldworkThey also thank two anonymous reviewers for their helpfulcomments that improved the clarity of the paper
References
[1] P Bayliss U Kolitsch EHNickel andA Pring ldquoAlunite super-group recommended nomenclaturerdquo Mineralogical Magazinevol 74 no 5 pp 919ndash927 2010
[2] H G Dill ldquoThe geology of Aluminium Phosphates and sulfatesof the alunite supergouprdquo Earth-Science Reviews vol 53 pp 35ndash93 2001
[3] S Gaboreau D Beaufort P Vieillard P Patrier and P Brune-ton ldquoAluminum phosphate-sulfate minerals associated withProterozoic unconformity-type uranium deposits in the EastAlligator River Uranium Field Northern Territories AustraliardquoCanadian Mineralogist vol 43 no 2 pp 813ndash827 2005
[4] AHikovC Lerouge andNVelinova ldquoGeochemistry of alunitegroupminerals in hydrothermally altered rocks from the Asarelporphyry copper deposit Central Srednogorierdquo Review of theBulgarian Geological Society vol 71 no 1ndash3 pp 133ndash148 2010
[5] S A Repina ldquoFractionation of REE in the xenotime andflorencite paragenetic association fromAu-REEmineral occur-rences of the Nether-Polar Uralsrdquo Geochemistry Internationalvol 49 no 9 pp 868ndash887 2011
[6] G Nagy E Draganits A Demeny G Panto and P ArkaildquoGenesis and transformations of monazite florencite and rhab-dophane duringmedium grademetamorphism examples fromthe Sopron Hills Eastern Alpsrdquo Chemical Geology vol 191 no1ndash3 pp 25ndash46 2002
[7] I A Izbrodin G S Ripp and A G Doroshkevich ldquoAluminiumphosphate and phosphate-sulphate minerals in kyanite schistsof the Ichetuyskoye area West Transbaikalia Russia crystalchemistry and evolutionrdquoMineralogy and Petrology vol 101 no1 pp 81ndash96 2011
[8] E Janots F Negro F Brunet B Goffe M Engi and M LBouybaouene ldquoEvolution of the REE mineralogy in HP-LTmetapelites of the Sebtide complex Rif Morocco monazitestability and geochronologyrdquo Lithos vol 87 no 3-4 pp 214ndash234 2006
[9] D Visser R O Felius andMMoree ldquoAugelite and cerian cran-dallite in dumortierite quartzites Vaca Morta quarry Veredarange Macaubas Bahia Brazilrdquo Mineralogical Magazine vol61 no 4 pp 607ndash609 1997
[10] J A Dunn and A K Dey ldquoGeology and petrology of EasternSinghbhum and surrounding areasrdquo Memoirs of the GeologicalSurvey of India vol 69 no 2 1942
[11] A K Saha ldquoCrustal evolution of Singhbhum North OrissaEastern IndiardquoGeological Society of IndiaMemoir vol 27 article341 1994
[12] S C Sarkar and A Gupta Crustal Evolution andMetallogeny inIndia vol 741 Cambridge University Press 2012
[13] N Sengupta P Sengupta and H K Sachan ldquoAluminous andalkali-deficient tourmaline from the Singhbhum Shear ZoneEast Indian shield insight for polyphase boron infiltrationduring regional metamorphismrdquo American Mineralogist vol96 no 5-6 pp 752ndash767 2011
[14] D Mukhopadhyay and G K Deb ldquoStructural and texturaldevelopment in Singhbhum shear zone eastern Indiardquo Proceed-ings of the Indian Academy of Sciences vol 104 no 3 pp 385ndash405 1995
[15] N Sengupta ldquoStability of chloritoid + biotite-bearing assem-blages in some metapelites from the Palaeoproterozoic Singhb-hum Shear Zone eastern India and their implicationsrdquo Geolog-ical Society LondonmdashSpecial Publications vol 365 pp 91ndash1162012
[16] R Kretz ldquoSymbols for rock-forming mineralsrdquo American Min-eralogist vol 68 no 1-2 pp 277ndash279 1983
[17] J L Pouchou and F Pichoir ldquoA new model for quantitativeX-ray microanalysismdashpart-I application to the analysis ofhomogeneous samplesrdquo La Recherche Aerospatiale no 3 pp167ndash192 1984
[18] S Georgieva and N Velinova ldquoFlorencite-(Ce La Nd) fromthe advanced argillic alterations in the Chelopech high-sulphidation epithermal Cu-Au deposit Bulgariardquo in Proceed-ings of the National Conference with International Participation(GEOSCIENCES rsquo12) Bulgarian Geological Society 2012
[19] A G Doroshkevich S G Viladkar G S Ripp and M V Burt-seva ldquoHydrothermal REE mineralization in the Amba Dongarcarbonatite complex Gujarat Indiardquo Canadian Mineralogistvol 47 no 5 pp 1105ndash1116 2009
[20] W S Wise and S E Loh ldquoEquilibria and origin of minerals inthe system Al
2
O-AlPO4
-H2
Ordquo American Mineralogist vol 61pp 409ndash413 1976
[21] P Schmid-Beurmann G Morteani and L Cemic ldquoExper-imental determination of the upper stability of scorzaliteFeAl2
[OHPO4
]2
and the occurrence of minerals with a com-position intermediate between scorzalite and lazulite(ss) upto the conditions of the amphibolite faciesrdquo Mineralogy andPetrology vol 61 no 1ndash4 pp 211ndash222 1998
[22] G Morteani D Ackermand and H A Horn ldquoAluminum-phosphates and borosilicates in muscovite-kyanite metaquar-tzites near Diamantina (Minas Gerais Brazil) petrogeneticimplicationsrdquo Periodico diMineralogia vol 70 pp 111ndash129 2001
[23] D Mckie ldquoGoyazite and florencite from two African carbon-atitesrdquoMineralogical Magazine vol 33 pp 281ndash297 1962
[24] J C Ayers and E B Watson ldquoSolubility of apatite mon-azite zircon and rutile in supercritical aqueous fluids withimplications for subduction zone geochemistryrdquo PhilosophicalTransactionsmdashRoyal Society of London A vol 335 no 1638 pp365ndash375 1991
[25] A P Jones F Wall and C T Williams Eds Rare EarthMinerals Chemistry Origin and Ore Deposits vol 357 of TheMineralogical Society Series 7 Chapman and Hall 1996
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
ClimatologyJournal of
EcologyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
EarthquakesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom
Applied ampEnvironmentalSoil Science
Volume 2014
Mining
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal of
Geophysics
OceanographyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of Computational Environmental SciencesHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofPetroleum Engineering
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Geochemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Atmospheric SciencesInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
OceanographyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MineralogyInternational Journal of
Meteorology
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Paleontology JournalHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom
Volume 2014
Geological ResearchJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Geology Advances in
International Journal of Mineralogy 5Ta
ble1Re
presentativ
eanalyses
offlo
rencitelazuliteaugelitekyaniteand
rutilemineralfro
mstu
died
areaF
lorencite
mineralcompo
sitionhasb
eencomparedwith
compo
sitions
from
different
localities
Elem
ents
Locatio
n
Florencite(calculated
on11oxygen
basis
Valuesinwt
)
Florencitedata
byNagyetal
2002
[6](values
inwt
)
Florencitedata
byJano
tsetal
2006
[8](values
inwt
)
Florencitedataby
Doroshk
evichetal
2009
[19](values
inwt
)
Lazulite(values
inwt
)Au
gelite(
values
inwt
)Ky
anite
(values
inwt
)Ru
tile(values
inwt
)
Sing
hbhu
mshearz
one(SSZ)
Sopron
Hills
Easte
rnAlps
Hun
gary
Sebtide
complexR
ifMorocco
Amba-D
ongar
GujaratInd
iaSing
hbhu
mshearz
one(SSZ)
SiO
2000
006
001
na
024ndash4
2gt075
001
023
3669
000
TiO
2007
000
004
na
na
na
003
006
002
10090
Al 2O
32847
2737
2728
2866ndash
3189
2710
ndash319
22786ndash
3067
3349
4930
6245
006
Cr2O
3000
000
000
na
na
na
000
008
004
013
FeO
000
001
000
na
017ndash14
na
000
000
003
010
MnO
000
000
000
na
na
na
043
004
002
000
CaO
042
064
054
072ndash144
042ndash0
69
023ndash0
81
001
000
000
001
MgO
001
005
010
na
002ndash0
70
na
1332
003
001
000
Na 2O
009
009
011
na
001ndash0
06
na
003
000
006
000
K 2O
000
000
001
na
na
na
000
000
002
001
P 2O
53081
3072
3084
2697ndash2893
224ndash264
2608ndash2856
4844
3709
000
000
ZrO
2000
000
000
na
na
na
mdashmdash
mdashmdash
Nb 2O
5000
000
004
na
na
na
mdashmdash
mdashmdash
La2O
3683
769
712
646
ndash866
422ndash4
25
391ndash1264
mdashmdash
mdashmdash
Ce 2O
31093
1215
1178
1091ndash1433
837ndash926
494ndash1232
mdashmdash
mdashmdash
PbO
000
000
000
na
na
na
mdashmdash
mdashmdash
ThO
2049
118
118
055ndash994
059ndash109
na
mdashmdash
mdashmdash
U2O
3004
002
002
na
007ndash0
17na
mdashmdash
mdashmdash
BaO
000
000
000
na
na
na
mdashmdash
mdashmdash
SrO
012
015
010
016ndash0
67
132ndash591
447ndash1336
mdashmdash
mdashmdash
Nd 2O
3270
261
269
165ndash500
396ndash4
80
102ndash291
mdashmdash
mdashmdash
Sm2O
3110
106
109
010ndash0
92
055ndash0
60
na
mdashmdash
mdashmdash
SO3
000
000
000
na
021ndash0
59
108ndash
471
mdashmdash
mdashmdash
Total
8208
8381
8295
8769ndash
9036
7821ndash86
35
7140ndash
7898
9576
8683
9940
1012
5ap
fu
apfu
apfu
apfu
apfu
apfu
apfu
apfu
apfu
apfu
Si000
001
000
na
0020ndash
0379
006
0ndash0170
000
002
100
000
Ti000
000
000
na
na
na
000
000
000
100
Al
299
290
289
3203ndash3360
2880ndash
3131
2710ndash
2950
195
384
200
000
Cr000
000
000
na
na
na
001
000
000
000
Fe000
000
000
na
0012ndash0107
0020ndash
0333
002
000
000
000
Mn
000
000
000
na
na
na
000
000
000
000
Ca004
006
005
006
8ndash0105
0038ndash
0067
0020ndash
0070
000
000
000
000
Mg
000
001
001
na
0003ndash0095
na
098
000
000
000
Na
002
002
002
na
0002ndash0012
na
000
000
000
000
K000
000
000
na
na
na
000
000
000
000
6 International Journal of Mineralogy
Table1Con
tinued
Elem
ents
Locatio
n
Florencite(calculated
on11oxygen
basis
Valuesinwt
)
Florencitedata
byNagyetal
2002
[6](values
inwt
)
Florencitedata
byJano
tsetal
2006
[8](values
inwt
)
Florencitedataby
Doroshk
evichetal
2009
[19](values
inwt
)
Lazulite(values
inwt
)Au
gelite(
values
inwt
)Ky
anite
(values
inwt
)Ru
tile(values
inwt
)
Sing
hbhu
mshearz
one(SSZ)
Sopron
Hills
Easte
rnAlps
Hun
gary
Sebtide
complexR
ifMorocco
Amba-D
ongar
GujaratInd
iaSing
hbhu
mshearz
one(SSZ)
P233
234
235
2041ndash2117
1710ndash1863
1770ndash2001
203
208
000
000
Zr000
000
000
na
na
na
mdashmdash
mdashmdash
Nb
000
000
000
na
na
na
mdashmdash
mdashmdash
La011
013
012
0104ndash
0106
0131ndash0140
0110ndash
0340
mdashmdash
mdashmdash
Ce
018
020
019
0204ndash
0213
0277ndash0282
0140ndash
0392
mdashmdash
mdashmdash
Pb000
000
000
na
na
na
mdashmdash
mdashmdash
Th001
002
002
na
0022ndash0011
na
mdashmdash
mdashmdash
U000
000
000
na
0001ndash000
4na
mdashmdash
mdashmdash
Ba000
000
000
na
na
na
mdashmdash
mdashmdash
Sr001
001
001
0011ndash0035
na
na
mdashmdash
mdashmdash
Nd
009
008
009
0142ndash0156
0128ndash
0143
0030ndash
0071
mdashmdash
mdashmdash
Sm003
003
003
0023ndash0027
0018ndash
0019
na
mdashmdash
mdashmdash
Sbdl
bdl
bdl
na
0069ndash
0285
0070ndash
0273
mdashmdash
mdashmdash
Totalcation
580
580
579
589
2ndash599
25763ndash
594
55637ndash
583
4498
595
300
100
sumRE
E042
045
044
0484ndash
0537
0603ndash0612
0300ndash
0603
Florencite
(mol)
8994
8669
8845
Goyazite
(mol)
136
147
103
Crandallite
(mol)
870
1184
1052
Noten
anot
availablebdlbelowdetectionlim
it
International Journal of Mineralogy 7
Cps
5000
4000
3000
2000
1000
020000 30000 40000 50000 60000 70000 80000 90000
S In
P Ka
P Ka
Al Ka
Ce La
Ce Lb
La La
TAPPET
Figure 5 WDS of florencite showing Al P Ce and La TAP and PET are crystals of the electron microprobe machine
Precambrian rocks of the peninsular India The only otherlocality of florencite in India is the carbonatite complex ofAmba Dongar Gujarat (Doroshkevich et al [19])
Textural features suggest that florencite was formed dur-ing and after the growth of kyanite and hence originatedduringmetamorphism that accompanied the ductile shearingof the studied rock Florencite remained stable during theformation of lazulite and augelite that replaced kyanite understatic condition (post-shearing) Experimental study in theAl-P-O-H system and the observations from natural rocksshow that the assemblage augelite + kyanite is stable at con-ditions 380∘ndash475∘C and pressure gt2 kbar (Wise and Loh [20]andVisser et al [9])The assemblage kyanite + lazulite on theother hand has a wide thermal and baric stability (gt400∘Cand gt2 kbar Schmid-Beurmann et al [21] andMorteani et al[22]) Stability of florencite at high temperature (up to 550∘C)is reported from the eastern Alps (Nagy et al [6]) and fromAfrican carbonatites (Mckie [23]) Briefly the assemblagekyanite + augelite + lazulite + florencite appears to form attemperature and pressure that exceeded 400∘C and 2 kbarThis is in a good agreement with the calculated 119875-119879 valuesof 490 plusmn 40∘C and sim6 plusmn 1 kbar from the adjoining chloritoidgarnet bearing schist (Sengupta [15])
Origin of florencite in kyanite-quartz rock requires advec-tive transport of LREE and P presumably by infiltrationof aqueous fluids Singhbhum shear zone is characterizedby repeated infiltrations of aqueous fluids that resulted inmineralization ofCu-Fe-U-P and tourmalinization (reviewedin Sengupta et al [13] and Sarkar and Gupta [12]) In thisstudy we document phosphate REE and Mg-metasomatismwhich developed end member lazulite (very low content ofscorzalite) in kyanite-rich rock Several studies have demon-strated that florencite develops in hydrothermally altered(sensu lato) rock in which themetasomatic fluids are oxidizedand have acidic pH (Visser et al [9] Nagy et al [6] Gaboreau
et al [3] Hikov et al [4] and Georgieva and Velinova [18]) Inview of this we envisage that infiltration of acidic fluid froman extraneous source to be responsible for the developmentof florencite Absence ofmuscovitization of kyanite in kyanitequartz rock of this particular studied area and extensivetourmalinization of the adjoining rocks (Sengupta et al [13])supports that acidic metasomatic fluids infiltrated the rocksof the area Studies have shown that acidic fluids can dissolvea large amount of PO
4
minus3 and LREE as these chemical speciesform the ligand (REE (PO
4)∘
aq) (Ayers and Watson [24]cf Jones et al [25]) This fluid upon interacting with per-aluminous host rock stabilized florencite (Nagy et al [6])
4 Conclusion
(1) Florencite a REE-Al phosphate has been reportedfrom a metamorphosed kyanite-rich rock from theSinghbhum shear zone of the east Indian Shield
(2) Petrology of the florencite-bearing mineral associa-tion suggests metamorphic growth of florencite in the119875-119879 range of sim6 plusmn 1 kbar and 490∘plusmn 40∘C This is thefirst report of florencite from Precambrian rocks ofIndia
(3) Florencite was formed due to interaction of acidicaqueous fluids charged with PO4minus and REE and alu-minous country rock during regional metamorphismand ductile shearing in the Singhbhum shear zone
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
8 International Journal of Mineralogy
Acknowledgments
Maitrayee Chakraborty and Sayan Biswas acknowledge theresearch grants sanctioned by the CSIR New Delhi andUGC New Delhi respectively Nandini Sengupta acknowl-edges the financial assistance from project WOS-A DST(Department of Science and Technology New Delhi) PulakSengupta acknowledges the financial assistance from theCAS Department of Geological Sciences and UPE-II Jadav-pur University They thank Mr Priyadarshi Chowdhuryand Dr A Gupta for their assistance during the fieldworkThey also thank two anonymous reviewers for their helpfulcomments that improved the clarity of the paper
References
[1] P Bayliss U Kolitsch EHNickel andA Pring ldquoAlunite super-group recommended nomenclaturerdquo Mineralogical Magazinevol 74 no 5 pp 919ndash927 2010
[2] H G Dill ldquoThe geology of Aluminium Phosphates and sulfatesof the alunite supergouprdquo Earth-Science Reviews vol 53 pp 35ndash93 2001
[3] S Gaboreau D Beaufort P Vieillard P Patrier and P Brune-ton ldquoAluminum phosphate-sulfate minerals associated withProterozoic unconformity-type uranium deposits in the EastAlligator River Uranium Field Northern Territories AustraliardquoCanadian Mineralogist vol 43 no 2 pp 813ndash827 2005
[4] AHikovC Lerouge andNVelinova ldquoGeochemistry of alunitegroupminerals in hydrothermally altered rocks from the Asarelporphyry copper deposit Central Srednogorierdquo Review of theBulgarian Geological Society vol 71 no 1ndash3 pp 133ndash148 2010
[5] S A Repina ldquoFractionation of REE in the xenotime andflorencite paragenetic association fromAu-REEmineral occur-rences of the Nether-Polar Uralsrdquo Geochemistry Internationalvol 49 no 9 pp 868ndash887 2011
[6] G Nagy E Draganits A Demeny G Panto and P ArkaildquoGenesis and transformations of monazite florencite and rhab-dophane duringmedium grademetamorphism examples fromthe Sopron Hills Eastern Alpsrdquo Chemical Geology vol 191 no1ndash3 pp 25ndash46 2002
[7] I A Izbrodin G S Ripp and A G Doroshkevich ldquoAluminiumphosphate and phosphate-sulphate minerals in kyanite schistsof the Ichetuyskoye area West Transbaikalia Russia crystalchemistry and evolutionrdquoMineralogy and Petrology vol 101 no1 pp 81ndash96 2011
[8] E Janots F Negro F Brunet B Goffe M Engi and M LBouybaouene ldquoEvolution of the REE mineralogy in HP-LTmetapelites of the Sebtide complex Rif Morocco monazitestability and geochronologyrdquo Lithos vol 87 no 3-4 pp 214ndash234 2006
[9] D Visser R O Felius andMMoree ldquoAugelite and cerian cran-dallite in dumortierite quartzites Vaca Morta quarry Veredarange Macaubas Bahia Brazilrdquo Mineralogical Magazine vol61 no 4 pp 607ndash609 1997
[10] J A Dunn and A K Dey ldquoGeology and petrology of EasternSinghbhum and surrounding areasrdquo Memoirs of the GeologicalSurvey of India vol 69 no 2 1942
[11] A K Saha ldquoCrustal evolution of Singhbhum North OrissaEastern IndiardquoGeological Society of IndiaMemoir vol 27 article341 1994
[12] S C Sarkar and A Gupta Crustal Evolution andMetallogeny inIndia vol 741 Cambridge University Press 2012
[13] N Sengupta P Sengupta and H K Sachan ldquoAluminous andalkali-deficient tourmaline from the Singhbhum Shear ZoneEast Indian shield insight for polyphase boron infiltrationduring regional metamorphismrdquo American Mineralogist vol96 no 5-6 pp 752ndash767 2011
[14] D Mukhopadhyay and G K Deb ldquoStructural and texturaldevelopment in Singhbhum shear zone eastern Indiardquo Proceed-ings of the Indian Academy of Sciences vol 104 no 3 pp 385ndash405 1995
[15] N Sengupta ldquoStability of chloritoid + biotite-bearing assem-blages in some metapelites from the Palaeoproterozoic Singhb-hum Shear Zone eastern India and their implicationsrdquo Geolog-ical Society LondonmdashSpecial Publications vol 365 pp 91ndash1162012
[16] R Kretz ldquoSymbols for rock-forming mineralsrdquo American Min-eralogist vol 68 no 1-2 pp 277ndash279 1983
[17] J L Pouchou and F Pichoir ldquoA new model for quantitativeX-ray microanalysismdashpart-I application to the analysis ofhomogeneous samplesrdquo La Recherche Aerospatiale no 3 pp167ndash192 1984
[18] S Georgieva and N Velinova ldquoFlorencite-(Ce La Nd) fromthe advanced argillic alterations in the Chelopech high-sulphidation epithermal Cu-Au deposit Bulgariardquo in Proceed-ings of the National Conference with International Participation(GEOSCIENCES rsquo12) Bulgarian Geological Society 2012
[19] A G Doroshkevich S G Viladkar G S Ripp and M V Burt-seva ldquoHydrothermal REE mineralization in the Amba Dongarcarbonatite complex Gujarat Indiardquo Canadian Mineralogistvol 47 no 5 pp 1105ndash1116 2009
[20] W S Wise and S E Loh ldquoEquilibria and origin of minerals inthe system Al
2
O-AlPO4
-H2
Ordquo American Mineralogist vol 61pp 409ndash413 1976
[21] P Schmid-Beurmann G Morteani and L Cemic ldquoExper-imental determination of the upper stability of scorzaliteFeAl2
[OHPO4
]2
and the occurrence of minerals with a com-position intermediate between scorzalite and lazulite(ss) upto the conditions of the amphibolite faciesrdquo Mineralogy andPetrology vol 61 no 1ndash4 pp 211ndash222 1998
[22] G Morteani D Ackermand and H A Horn ldquoAluminum-phosphates and borosilicates in muscovite-kyanite metaquar-tzites near Diamantina (Minas Gerais Brazil) petrogeneticimplicationsrdquo Periodico diMineralogia vol 70 pp 111ndash129 2001
[23] D Mckie ldquoGoyazite and florencite from two African carbon-atitesrdquoMineralogical Magazine vol 33 pp 281ndash297 1962
[24] J C Ayers and E B Watson ldquoSolubility of apatite mon-azite zircon and rutile in supercritical aqueous fluids withimplications for subduction zone geochemistryrdquo PhilosophicalTransactionsmdashRoyal Society of London A vol 335 no 1638 pp365ndash375 1991
[25] A P Jones F Wall and C T Williams Eds Rare EarthMinerals Chemistry Origin and Ore Deposits vol 357 of TheMineralogical Society Series 7 Chapman and Hall 1996
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
ClimatologyJournal of
EcologyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
EarthquakesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom
Applied ampEnvironmentalSoil Science
Volume 2014
Mining
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal of
Geophysics
OceanographyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of Computational Environmental SciencesHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofPetroleum Engineering
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Geochemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Atmospheric SciencesInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
OceanographyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MineralogyInternational Journal of
Meteorology
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Paleontology JournalHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom
Volume 2014
Geological ResearchJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Geology Advances in
6 International Journal of Mineralogy
Table1Con
tinued
Elem
ents
Locatio
n
Florencite(calculated
on11oxygen
basis
Valuesinwt
)
Florencitedata
byNagyetal
2002
[6](values
inwt
)
Florencitedata
byJano
tsetal
2006
[8](values
inwt
)
Florencitedataby
Doroshk
evichetal
2009
[19](values
inwt
)
Lazulite(values
inwt
)Au
gelite(
values
inwt
)Ky
anite
(values
inwt
)Ru
tile(values
inwt
)
Sing
hbhu
mshearz
one(SSZ)
Sopron
Hills
Easte
rnAlps
Hun
gary
Sebtide
complexR
ifMorocco
Amba-D
ongar
GujaratInd
iaSing
hbhu
mshearz
one(SSZ)
P233
234
235
2041ndash2117
1710ndash1863
1770ndash2001
203
208
000
000
Zr000
000
000
na
na
na
mdashmdash
mdashmdash
Nb
000
000
000
na
na
na
mdashmdash
mdashmdash
La011
013
012
0104ndash
0106
0131ndash0140
0110ndash
0340
mdashmdash
mdashmdash
Ce
018
020
019
0204ndash
0213
0277ndash0282
0140ndash
0392
mdashmdash
mdashmdash
Pb000
000
000
na
na
na
mdashmdash
mdashmdash
Th001
002
002
na
0022ndash0011
na
mdashmdash
mdashmdash
U000
000
000
na
0001ndash000
4na
mdashmdash
mdashmdash
Ba000
000
000
na
na
na
mdashmdash
mdashmdash
Sr001
001
001
0011ndash0035
na
na
mdashmdash
mdashmdash
Nd
009
008
009
0142ndash0156
0128ndash
0143
0030ndash
0071
mdashmdash
mdashmdash
Sm003
003
003
0023ndash0027
0018ndash
0019
na
mdashmdash
mdashmdash
Sbdl
bdl
bdl
na
0069ndash
0285
0070ndash
0273
mdashmdash
mdashmdash
Totalcation
580
580
579
589
2ndash599
25763ndash
594
55637ndash
583
4498
595
300
100
sumRE
E042
045
044
0484ndash
0537
0603ndash0612
0300ndash
0603
Florencite
(mol)
8994
8669
8845
Goyazite
(mol)
136
147
103
Crandallite
(mol)
870
1184
1052
Noten
anot
availablebdlbelowdetectionlim
it
International Journal of Mineralogy 7
Cps
5000
4000
3000
2000
1000
020000 30000 40000 50000 60000 70000 80000 90000
S In
P Ka
P Ka
Al Ka
Ce La
Ce Lb
La La
TAPPET
Figure 5 WDS of florencite showing Al P Ce and La TAP and PET are crystals of the electron microprobe machine
Precambrian rocks of the peninsular India The only otherlocality of florencite in India is the carbonatite complex ofAmba Dongar Gujarat (Doroshkevich et al [19])
Textural features suggest that florencite was formed dur-ing and after the growth of kyanite and hence originatedduringmetamorphism that accompanied the ductile shearingof the studied rock Florencite remained stable during theformation of lazulite and augelite that replaced kyanite understatic condition (post-shearing) Experimental study in theAl-P-O-H system and the observations from natural rocksshow that the assemblage augelite + kyanite is stable at con-ditions 380∘ndash475∘C and pressure gt2 kbar (Wise and Loh [20]andVisser et al [9])The assemblage kyanite + lazulite on theother hand has a wide thermal and baric stability (gt400∘Cand gt2 kbar Schmid-Beurmann et al [21] andMorteani et al[22]) Stability of florencite at high temperature (up to 550∘C)is reported from the eastern Alps (Nagy et al [6]) and fromAfrican carbonatites (Mckie [23]) Briefly the assemblagekyanite + augelite + lazulite + florencite appears to form attemperature and pressure that exceeded 400∘C and 2 kbarThis is in a good agreement with the calculated 119875-119879 valuesof 490 plusmn 40∘C and sim6 plusmn 1 kbar from the adjoining chloritoidgarnet bearing schist (Sengupta [15])
Origin of florencite in kyanite-quartz rock requires advec-tive transport of LREE and P presumably by infiltrationof aqueous fluids Singhbhum shear zone is characterizedby repeated infiltrations of aqueous fluids that resulted inmineralization ofCu-Fe-U-P and tourmalinization (reviewedin Sengupta et al [13] and Sarkar and Gupta [12]) In thisstudy we document phosphate REE and Mg-metasomatismwhich developed end member lazulite (very low content ofscorzalite) in kyanite-rich rock Several studies have demon-strated that florencite develops in hydrothermally altered(sensu lato) rock in which themetasomatic fluids are oxidizedand have acidic pH (Visser et al [9] Nagy et al [6] Gaboreau
et al [3] Hikov et al [4] and Georgieva and Velinova [18]) Inview of this we envisage that infiltration of acidic fluid froman extraneous source to be responsible for the developmentof florencite Absence ofmuscovitization of kyanite in kyanitequartz rock of this particular studied area and extensivetourmalinization of the adjoining rocks (Sengupta et al [13])supports that acidic metasomatic fluids infiltrated the rocksof the area Studies have shown that acidic fluids can dissolvea large amount of PO
4
minus3 and LREE as these chemical speciesform the ligand (REE (PO
4)∘
aq) (Ayers and Watson [24]cf Jones et al [25]) This fluid upon interacting with per-aluminous host rock stabilized florencite (Nagy et al [6])
4 Conclusion
(1) Florencite a REE-Al phosphate has been reportedfrom a metamorphosed kyanite-rich rock from theSinghbhum shear zone of the east Indian Shield
(2) Petrology of the florencite-bearing mineral associa-tion suggests metamorphic growth of florencite in the119875-119879 range of sim6 plusmn 1 kbar and 490∘plusmn 40∘C This is thefirst report of florencite from Precambrian rocks ofIndia
(3) Florencite was formed due to interaction of acidicaqueous fluids charged with PO4minus and REE and alu-minous country rock during regional metamorphismand ductile shearing in the Singhbhum shear zone
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
8 International Journal of Mineralogy
Acknowledgments
Maitrayee Chakraborty and Sayan Biswas acknowledge theresearch grants sanctioned by the CSIR New Delhi andUGC New Delhi respectively Nandini Sengupta acknowl-edges the financial assistance from project WOS-A DST(Department of Science and Technology New Delhi) PulakSengupta acknowledges the financial assistance from theCAS Department of Geological Sciences and UPE-II Jadav-pur University They thank Mr Priyadarshi Chowdhuryand Dr A Gupta for their assistance during the fieldworkThey also thank two anonymous reviewers for their helpfulcomments that improved the clarity of the paper
References
[1] P Bayliss U Kolitsch EHNickel andA Pring ldquoAlunite super-group recommended nomenclaturerdquo Mineralogical Magazinevol 74 no 5 pp 919ndash927 2010
[2] H G Dill ldquoThe geology of Aluminium Phosphates and sulfatesof the alunite supergouprdquo Earth-Science Reviews vol 53 pp 35ndash93 2001
[3] S Gaboreau D Beaufort P Vieillard P Patrier and P Brune-ton ldquoAluminum phosphate-sulfate minerals associated withProterozoic unconformity-type uranium deposits in the EastAlligator River Uranium Field Northern Territories AustraliardquoCanadian Mineralogist vol 43 no 2 pp 813ndash827 2005
[4] AHikovC Lerouge andNVelinova ldquoGeochemistry of alunitegroupminerals in hydrothermally altered rocks from the Asarelporphyry copper deposit Central Srednogorierdquo Review of theBulgarian Geological Society vol 71 no 1ndash3 pp 133ndash148 2010
[5] S A Repina ldquoFractionation of REE in the xenotime andflorencite paragenetic association fromAu-REEmineral occur-rences of the Nether-Polar Uralsrdquo Geochemistry Internationalvol 49 no 9 pp 868ndash887 2011
[6] G Nagy E Draganits A Demeny G Panto and P ArkaildquoGenesis and transformations of monazite florencite and rhab-dophane duringmedium grademetamorphism examples fromthe Sopron Hills Eastern Alpsrdquo Chemical Geology vol 191 no1ndash3 pp 25ndash46 2002
[7] I A Izbrodin G S Ripp and A G Doroshkevich ldquoAluminiumphosphate and phosphate-sulphate minerals in kyanite schistsof the Ichetuyskoye area West Transbaikalia Russia crystalchemistry and evolutionrdquoMineralogy and Petrology vol 101 no1 pp 81ndash96 2011
[8] E Janots F Negro F Brunet B Goffe M Engi and M LBouybaouene ldquoEvolution of the REE mineralogy in HP-LTmetapelites of the Sebtide complex Rif Morocco monazitestability and geochronologyrdquo Lithos vol 87 no 3-4 pp 214ndash234 2006
[9] D Visser R O Felius andMMoree ldquoAugelite and cerian cran-dallite in dumortierite quartzites Vaca Morta quarry Veredarange Macaubas Bahia Brazilrdquo Mineralogical Magazine vol61 no 4 pp 607ndash609 1997
[10] J A Dunn and A K Dey ldquoGeology and petrology of EasternSinghbhum and surrounding areasrdquo Memoirs of the GeologicalSurvey of India vol 69 no 2 1942
[11] A K Saha ldquoCrustal evolution of Singhbhum North OrissaEastern IndiardquoGeological Society of IndiaMemoir vol 27 article341 1994
[12] S C Sarkar and A Gupta Crustal Evolution andMetallogeny inIndia vol 741 Cambridge University Press 2012
[13] N Sengupta P Sengupta and H K Sachan ldquoAluminous andalkali-deficient tourmaline from the Singhbhum Shear ZoneEast Indian shield insight for polyphase boron infiltrationduring regional metamorphismrdquo American Mineralogist vol96 no 5-6 pp 752ndash767 2011
[14] D Mukhopadhyay and G K Deb ldquoStructural and texturaldevelopment in Singhbhum shear zone eastern Indiardquo Proceed-ings of the Indian Academy of Sciences vol 104 no 3 pp 385ndash405 1995
[15] N Sengupta ldquoStability of chloritoid + biotite-bearing assem-blages in some metapelites from the Palaeoproterozoic Singhb-hum Shear Zone eastern India and their implicationsrdquo Geolog-ical Society LondonmdashSpecial Publications vol 365 pp 91ndash1162012
[16] R Kretz ldquoSymbols for rock-forming mineralsrdquo American Min-eralogist vol 68 no 1-2 pp 277ndash279 1983
[17] J L Pouchou and F Pichoir ldquoA new model for quantitativeX-ray microanalysismdashpart-I application to the analysis ofhomogeneous samplesrdquo La Recherche Aerospatiale no 3 pp167ndash192 1984
[18] S Georgieva and N Velinova ldquoFlorencite-(Ce La Nd) fromthe advanced argillic alterations in the Chelopech high-sulphidation epithermal Cu-Au deposit Bulgariardquo in Proceed-ings of the National Conference with International Participation(GEOSCIENCES rsquo12) Bulgarian Geological Society 2012
[19] A G Doroshkevich S G Viladkar G S Ripp and M V Burt-seva ldquoHydrothermal REE mineralization in the Amba Dongarcarbonatite complex Gujarat Indiardquo Canadian Mineralogistvol 47 no 5 pp 1105ndash1116 2009
[20] W S Wise and S E Loh ldquoEquilibria and origin of minerals inthe system Al
2
O-AlPO4
-H2
Ordquo American Mineralogist vol 61pp 409ndash413 1976
[21] P Schmid-Beurmann G Morteani and L Cemic ldquoExper-imental determination of the upper stability of scorzaliteFeAl2
[OHPO4
]2
and the occurrence of minerals with a com-position intermediate between scorzalite and lazulite(ss) upto the conditions of the amphibolite faciesrdquo Mineralogy andPetrology vol 61 no 1ndash4 pp 211ndash222 1998
[22] G Morteani D Ackermand and H A Horn ldquoAluminum-phosphates and borosilicates in muscovite-kyanite metaquar-tzites near Diamantina (Minas Gerais Brazil) petrogeneticimplicationsrdquo Periodico diMineralogia vol 70 pp 111ndash129 2001
[23] D Mckie ldquoGoyazite and florencite from two African carbon-atitesrdquoMineralogical Magazine vol 33 pp 281ndash297 1962
[24] J C Ayers and E B Watson ldquoSolubility of apatite mon-azite zircon and rutile in supercritical aqueous fluids withimplications for subduction zone geochemistryrdquo PhilosophicalTransactionsmdashRoyal Society of London A vol 335 no 1638 pp365ndash375 1991
[25] A P Jones F Wall and C T Williams Eds Rare EarthMinerals Chemistry Origin and Ore Deposits vol 357 of TheMineralogical Society Series 7 Chapman and Hall 1996
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
ClimatologyJournal of
EcologyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
EarthquakesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom
Applied ampEnvironmentalSoil Science
Volume 2014
Mining
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal of
Geophysics
OceanographyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of Computational Environmental SciencesHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofPetroleum Engineering
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Geochemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Atmospheric SciencesInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
OceanographyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MineralogyInternational Journal of
Meteorology
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Paleontology JournalHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom
Volume 2014
Geological ResearchJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Geology Advances in
International Journal of Mineralogy 7
Cps
5000
4000
3000
2000
1000
020000 30000 40000 50000 60000 70000 80000 90000
S In
P Ka
P Ka
Al Ka
Ce La
Ce Lb
La La
TAPPET
Figure 5 WDS of florencite showing Al P Ce and La TAP and PET are crystals of the electron microprobe machine
Precambrian rocks of the peninsular India The only otherlocality of florencite in India is the carbonatite complex ofAmba Dongar Gujarat (Doroshkevich et al [19])
Textural features suggest that florencite was formed dur-ing and after the growth of kyanite and hence originatedduringmetamorphism that accompanied the ductile shearingof the studied rock Florencite remained stable during theformation of lazulite and augelite that replaced kyanite understatic condition (post-shearing) Experimental study in theAl-P-O-H system and the observations from natural rocksshow that the assemblage augelite + kyanite is stable at con-ditions 380∘ndash475∘C and pressure gt2 kbar (Wise and Loh [20]andVisser et al [9])The assemblage kyanite + lazulite on theother hand has a wide thermal and baric stability (gt400∘Cand gt2 kbar Schmid-Beurmann et al [21] andMorteani et al[22]) Stability of florencite at high temperature (up to 550∘C)is reported from the eastern Alps (Nagy et al [6]) and fromAfrican carbonatites (Mckie [23]) Briefly the assemblagekyanite + augelite + lazulite + florencite appears to form attemperature and pressure that exceeded 400∘C and 2 kbarThis is in a good agreement with the calculated 119875-119879 valuesof 490 plusmn 40∘C and sim6 plusmn 1 kbar from the adjoining chloritoidgarnet bearing schist (Sengupta [15])
Origin of florencite in kyanite-quartz rock requires advec-tive transport of LREE and P presumably by infiltrationof aqueous fluids Singhbhum shear zone is characterizedby repeated infiltrations of aqueous fluids that resulted inmineralization ofCu-Fe-U-P and tourmalinization (reviewedin Sengupta et al [13] and Sarkar and Gupta [12]) In thisstudy we document phosphate REE and Mg-metasomatismwhich developed end member lazulite (very low content ofscorzalite) in kyanite-rich rock Several studies have demon-strated that florencite develops in hydrothermally altered(sensu lato) rock in which themetasomatic fluids are oxidizedand have acidic pH (Visser et al [9] Nagy et al [6] Gaboreau
et al [3] Hikov et al [4] and Georgieva and Velinova [18]) Inview of this we envisage that infiltration of acidic fluid froman extraneous source to be responsible for the developmentof florencite Absence ofmuscovitization of kyanite in kyanitequartz rock of this particular studied area and extensivetourmalinization of the adjoining rocks (Sengupta et al [13])supports that acidic metasomatic fluids infiltrated the rocksof the area Studies have shown that acidic fluids can dissolvea large amount of PO
4
minus3 and LREE as these chemical speciesform the ligand (REE (PO
4)∘
aq) (Ayers and Watson [24]cf Jones et al [25]) This fluid upon interacting with per-aluminous host rock stabilized florencite (Nagy et al [6])
4 Conclusion
(1) Florencite a REE-Al phosphate has been reportedfrom a metamorphosed kyanite-rich rock from theSinghbhum shear zone of the east Indian Shield
(2) Petrology of the florencite-bearing mineral associa-tion suggests metamorphic growth of florencite in the119875-119879 range of sim6 plusmn 1 kbar and 490∘plusmn 40∘C This is thefirst report of florencite from Precambrian rocks ofIndia
(3) Florencite was formed due to interaction of acidicaqueous fluids charged with PO4minus and REE and alu-minous country rock during regional metamorphismand ductile shearing in the Singhbhum shear zone
Conflict of Interests
The authors declare that there is no conflict of interestsregarding the publication of this paper
8 International Journal of Mineralogy
Acknowledgments
Maitrayee Chakraborty and Sayan Biswas acknowledge theresearch grants sanctioned by the CSIR New Delhi andUGC New Delhi respectively Nandini Sengupta acknowl-edges the financial assistance from project WOS-A DST(Department of Science and Technology New Delhi) PulakSengupta acknowledges the financial assistance from theCAS Department of Geological Sciences and UPE-II Jadav-pur University They thank Mr Priyadarshi Chowdhuryand Dr A Gupta for their assistance during the fieldworkThey also thank two anonymous reviewers for their helpfulcomments that improved the clarity of the paper
References
[1] P Bayliss U Kolitsch EHNickel andA Pring ldquoAlunite super-group recommended nomenclaturerdquo Mineralogical Magazinevol 74 no 5 pp 919ndash927 2010
[2] H G Dill ldquoThe geology of Aluminium Phosphates and sulfatesof the alunite supergouprdquo Earth-Science Reviews vol 53 pp 35ndash93 2001
[3] S Gaboreau D Beaufort P Vieillard P Patrier and P Brune-ton ldquoAluminum phosphate-sulfate minerals associated withProterozoic unconformity-type uranium deposits in the EastAlligator River Uranium Field Northern Territories AustraliardquoCanadian Mineralogist vol 43 no 2 pp 813ndash827 2005
[4] AHikovC Lerouge andNVelinova ldquoGeochemistry of alunitegroupminerals in hydrothermally altered rocks from the Asarelporphyry copper deposit Central Srednogorierdquo Review of theBulgarian Geological Society vol 71 no 1ndash3 pp 133ndash148 2010
[5] S A Repina ldquoFractionation of REE in the xenotime andflorencite paragenetic association fromAu-REEmineral occur-rences of the Nether-Polar Uralsrdquo Geochemistry Internationalvol 49 no 9 pp 868ndash887 2011
[6] G Nagy E Draganits A Demeny G Panto and P ArkaildquoGenesis and transformations of monazite florencite and rhab-dophane duringmedium grademetamorphism examples fromthe Sopron Hills Eastern Alpsrdquo Chemical Geology vol 191 no1ndash3 pp 25ndash46 2002
[7] I A Izbrodin G S Ripp and A G Doroshkevich ldquoAluminiumphosphate and phosphate-sulphate minerals in kyanite schistsof the Ichetuyskoye area West Transbaikalia Russia crystalchemistry and evolutionrdquoMineralogy and Petrology vol 101 no1 pp 81ndash96 2011
[8] E Janots F Negro F Brunet B Goffe M Engi and M LBouybaouene ldquoEvolution of the REE mineralogy in HP-LTmetapelites of the Sebtide complex Rif Morocco monazitestability and geochronologyrdquo Lithos vol 87 no 3-4 pp 214ndash234 2006
[9] D Visser R O Felius andMMoree ldquoAugelite and cerian cran-dallite in dumortierite quartzites Vaca Morta quarry Veredarange Macaubas Bahia Brazilrdquo Mineralogical Magazine vol61 no 4 pp 607ndash609 1997
[10] J A Dunn and A K Dey ldquoGeology and petrology of EasternSinghbhum and surrounding areasrdquo Memoirs of the GeologicalSurvey of India vol 69 no 2 1942
[11] A K Saha ldquoCrustal evolution of Singhbhum North OrissaEastern IndiardquoGeological Society of IndiaMemoir vol 27 article341 1994
[12] S C Sarkar and A Gupta Crustal Evolution andMetallogeny inIndia vol 741 Cambridge University Press 2012
[13] N Sengupta P Sengupta and H K Sachan ldquoAluminous andalkali-deficient tourmaline from the Singhbhum Shear ZoneEast Indian shield insight for polyphase boron infiltrationduring regional metamorphismrdquo American Mineralogist vol96 no 5-6 pp 752ndash767 2011
[14] D Mukhopadhyay and G K Deb ldquoStructural and texturaldevelopment in Singhbhum shear zone eastern Indiardquo Proceed-ings of the Indian Academy of Sciences vol 104 no 3 pp 385ndash405 1995
[15] N Sengupta ldquoStability of chloritoid + biotite-bearing assem-blages in some metapelites from the Palaeoproterozoic Singhb-hum Shear Zone eastern India and their implicationsrdquo Geolog-ical Society LondonmdashSpecial Publications vol 365 pp 91ndash1162012
[16] R Kretz ldquoSymbols for rock-forming mineralsrdquo American Min-eralogist vol 68 no 1-2 pp 277ndash279 1983
[17] J L Pouchou and F Pichoir ldquoA new model for quantitativeX-ray microanalysismdashpart-I application to the analysis ofhomogeneous samplesrdquo La Recherche Aerospatiale no 3 pp167ndash192 1984
[18] S Georgieva and N Velinova ldquoFlorencite-(Ce La Nd) fromthe advanced argillic alterations in the Chelopech high-sulphidation epithermal Cu-Au deposit Bulgariardquo in Proceed-ings of the National Conference with International Participation(GEOSCIENCES rsquo12) Bulgarian Geological Society 2012
[19] A G Doroshkevich S G Viladkar G S Ripp and M V Burt-seva ldquoHydrothermal REE mineralization in the Amba Dongarcarbonatite complex Gujarat Indiardquo Canadian Mineralogistvol 47 no 5 pp 1105ndash1116 2009
[20] W S Wise and S E Loh ldquoEquilibria and origin of minerals inthe system Al
2
O-AlPO4
-H2
Ordquo American Mineralogist vol 61pp 409ndash413 1976
[21] P Schmid-Beurmann G Morteani and L Cemic ldquoExper-imental determination of the upper stability of scorzaliteFeAl2
[OHPO4
]2
and the occurrence of minerals with a com-position intermediate between scorzalite and lazulite(ss) upto the conditions of the amphibolite faciesrdquo Mineralogy andPetrology vol 61 no 1ndash4 pp 211ndash222 1998
[22] G Morteani D Ackermand and H A Horn ldquoAluminum-phosphates and borosilicates in muscovite-kyanite metaquar-tzites near Diamantina (Minas Gerais Brazil) petrogeneticimplicationsrdquo Periodico diMineralogia vol 70 pp 111ndash129 2001
[23] D Mckie ldquoGoyazite and florencite from two African carbon-atitesrdquoMineralogical Magazine vol 33 pp 281ndash297 1962
[24] J C Ayers and E B Watson ldquoSolubility of apatite mon-azite zircon and rutile in supercritical aqueous fluids withimplications for subduction zone geochemistryrdquo PhilosophicalTransactionsmdashRoyal Society of London A vol 335 no 1638 pp365ndash375 1991
[25] A P Jones F Wall and C T Williams Eds Rare EarthMinerals Chemistry Origin and Ore Deposits vol 357 of TheMineralogical Society Series 7 Chapman and Hall 1996
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
ClimatologyJournal of
EcologyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
EarthquakesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom
Applied ampEnvironmentalSoil Science
Volume 2014
Mining
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal of
Geophysics
OceanographyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of Computational Environmental SciencesHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofPetroleum Engineering
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Geochemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Atmospheric SciencesInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
OceanographyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MineralogyInternational Journal of
Meteorology
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Paleontology JournalHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom
Volume 2014
Geological ResearchJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Geology Advances in
8 International Journal of Mineralogy
Acknowledgments
Maitrayee Chakraborty and Sayan Biswas acknowledge theresearch grants sanctioned by the CSIR New Delhi andUGC New Delhi respectively Nandini Sengupta acknowl-edges the financial assistance from project WOS-A DST(Department of Science and Technology New Delhi) PulakSengupta acknowledges the financial assistance from theCAS Department of Geological Sciences and UPE-II Jadav-pur University They thank Mr Priyadarshi Chowdhuryand Dr A Gupta for their assistance during the fieldworkThey also thank two anonymous reviewers for their helpfulcomments that improved the clarity of the paper
References
[1] P Bayliss U Kolitsch EHNickel andA Pring ldquoAlunite super-group recommended nomenclaturerdquo Mineralogical Magazinevol 74 no 5 pp 919ndash927 2010
[2] H G Dill ldquoThe geology of Aluminium Phosphates and sulfatesof the alunite supergouprdquo Earth-Science Reviews vol 53 pp 35ndash93 2001
[3] S Gaboreau D Beaufort P Vieillard P Patrier and P Brune-ton ldquoAluminum phosphate-sulfate minerals associated withProterozoic unconformity-type uranium deposits in the EastAlligator River Uranium Field Northern Territories AustraliardquoCanadian Mineralogist vol 43 no 2 pp 813ndash827 2005
[4] AHikovC Lerouge andNVelinova ldquoGeochemistry of alunitegroupminerals in hydrothermally altered rocks from the Asarelporphyry copper deposit Central Srednogorierdquo Review of theBulgarian Geological Society vol 71 no 1ndash3 pp 133ndash148 2010
[5] S A Repina ldquoFractionation of REE in the xenotime andflorencite paragenetic association fromAu-REEmineral occur-rences of the Nether-Polar Uralsrdquo Geochemistry Internationalvol 49 no 9 pp 868ndash887 2011
[6] G Nagy E Draganits A Demeny G Panto and P ArkaildquoGenesis and transformations of monazite florencite and rhab-dophane duringmedium grademetamorphism examples fromthe Sopron Hills Eastern Alpsrdquo Chemical Geology vol 191 no1ndash3 pp 25ndash46 2002
[7] I A Izbrodin G S Ripp and A G Doroshkevich ldquoAluminiumphosphate and phosphate-sulphate minerals in kyanite schistsof the Ichetuyskoye area West Transbaikalia Russia crystalchemistry and evolutionrdquoMineralogy and Petrology vol 101 no1 pp 81ndash96 2011
[8] E Janots F Negro F Brunet B Goffe M Engi and M LBouybaouene ldquoEvolution of the REE mineralogy in HP-LTmetapelites of the Sebtide complex Rif Morocco monazitestability and geochronologyrdquo Lithos vol 87 no 3-4 pp 214ndash234 2006
[9] D Visser R O Felius andMMoree ldquoAugelite and cerian cran-dallite in dumortierite quartzites Vaca Morta quarry Veredarange Macaubas Bahia Brazilrdquo Mineralogical Magazine vol61 no 4 pp 607ndash609 1997
[10] J A Dunn and A K Dey ldquoGeology and petrology of EasternSinghbhum and surrounding areasrdquo Memoirs of the GeologicalSurvey of India vol 69 no 2 1942
[11] A K Saha ldquoCrustal evolution of Singhbhum North OrissaEastern IndiardquoGeological Society of IndiaMemoir vol 27 article341 1994
[12] S C Sarkar and A Gupta Crustal Evolution andMetallogeny inIndia vol 741 Cambridge University Press 2012
[13] N Sengupta P Sengupta and H K Sachan ldquoAluminous andalkali-deficient tourmaline from the Singhbhum Shear ZoneEast Indian shield insight for polyphase boron infiltrationduring regional metamorphismrdquo American Mineralogist vol96 no 5-6 pp 752ndash767 2011
[14] D Mukhopadhyay and G K Deb ldquoStructural and texturaldevelopment in Singhbhum shear zone eastern Indiardquo Proceed-ings of the Indian Academy of Sciences vol 104 no 3 pp 385ndash405 1995
[15] N Sengupta ldquoStability of chloritoid + biotite-bearing assem-blages in some metapelites from the Palaeoproterozoic Singhb-hum Shear Zone eastern India and their implicationsrdquo Geolog-ical Society LondonmdashSpecial Publications vol 365 pp 91ndash1162012
[16] R Kretz ldquoSymbols for rock-forming mineralsrdquo American Min-eralogist vol 68 no 1-2 pp 277ndash279 1983
[17] J L Pouchou and F Pichoir ldquoA new model for quantitativeX-ray microanalysismdashpart-I application to the analysis ofhomogeneous samplesrdquo La Recherche Aerospatiale no 3 pp167ndash192 1984
[18] S Georgieva and N Velinova ldquoFlorencite-(Ce La Nd) fromthe advanced argillic alterations in the Chelopech high-sulphidation epithermal Cu-Au deposit Bulgariardquo in Proceed-ings of the National Conference with International Participation(GEOSCIENCES rsquo12) Bulgarian Geological Society 2012
[19] A G Doroshkevich S G Viladkar G S Ripp and M V Burt-seva ldquoHydrothermal REE mineralization in the Amba Dongarcarbonatite complex Gujarat Indiardquo Canadian Mineralogistvol 47 no 5 pp 1105ndash1116 2009
[20] W S Wise and S E Loh ldquoEquilibria and origin of minerals inthe system Al
2
O-AlPO4
-H2
Ordquo American Mineralogist vol 61pp 409ndash413 1976
[21] P Schmid-Beurmann G Morteani and L Cemic ldquoExper-imental determination of the upper stability of scorzaliteFeAl2
[OHPO4
]2
and the occurrence of minerals with a com-position intermediate between scorzalite and lazulite(ss) upto the conditions of the amphibolite faciesrdquo Mineralogy andPetrology vol 61 no 1ndash4 pp 211ndash222 1998
[22] G Morteani D Ackermand and H A Horn ldquoAluminum-phosphates and borosilicates in muscovite-kyanite metaquar-tzites near Diamantina (Minas Gerais Brazil) petrogeneticimplicationsrdquo Periodico diMineralogia vol 70 pp 111ndash129 2001
[23] D Mckie ldquoGoyazite and florencite from two African carbon-atitesrdquoMineralogical Magazine vol 33 pp 281ndash297 1962
[24] J C Ayers and E B Watson ldquoSolubility of apatite mon-azite zircon and rutile in supercritical aqueous fluids withimplications for subduction zone geochemistryrdquo PhilosophicalTransactionsmdashRoyal Society of London A vol 335 no 1638 pp365ndash375 1991
[25] A P Jones F Wall and C T Williams Eds Rare EarthMinerals Chemistry Origin and Ore Deposits vol 357 of TheMineralogical Society Series 7 Chapman and Hall 1996
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
ClimatologyJournal of
EcologyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
EarthquakesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom
Applied ampEnvironmentalSoil Science
Volume 2014
Mining
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal of
Geophysics
OceanographyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of Computational Environmental SciencesHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofPetroleum Engineering
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Geochemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Atmospheric SciencesInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
OceanographyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MineralogyInternational Journal of
Meteorology
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Paleontology JournalHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom
Volume 2014
Geological ResearchJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Geology Advances in
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
ClimatologyJournal of
EcologyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
EarthquakesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom
Applied ampEnvironmentalSoil Science
Volume 2014
Mining
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal of
Geophysics
OceanographyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of Computational Environmental SciencesHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofPetroleum Engineering
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Geochemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Atmospheric SciencesInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
OceanographyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MineralogyInternational Journal of
Meteorology
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Paleontology JournalHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom
Volume 2014
Geological ResearchJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Geology Advances in
