ir.amu.ac.inir.amu.ac.in/12117/1/T10531.pdf · DEPARTMENT OF GEOLOGY ALIGARH MUSLIM UNIVERSITY,...

ABSTRACTTHESIS

SUBMITTED FOR THE AWARD OF THE DEGREE OF

Doctor of PhilosophyIN

GEOLOGY

By

MOHD. SHAIF

UNDER THE SUPERVISION OF

PROF. F. N. SIDDIQUIE

2018

GEOCHEMICAL STUDIES ON THE MANGANESEORES OF BANSWARA DISTT.

(RAJASTHAN) INDIA

ABSTRACT

DEPARTMENT OF GEOLOGYALIGARH MUSLIM UNIVERSITY

ALIGARH (INDIA)

DEPARTMENT OF GEOLOGYALIGARH MUSLIM UNIVERSITY, ALIGARH

Mob. : +91-9997189875Ph. Office: +91-571-2700615

Telex: 564-230-AMU-INFax: 91-571-2700528, 2802382

E-mail: [email protected]

CertificateThis is to certify that the work presented in the Ph.D. thesis entitled,

submitted by , has been carried out and completed under my

supervision. The work is an original contribution to be existing knowledge of the

subject and has not been submitted earlier.

He is allowed to submit the work for the award of Ph.D. degree in the Department of

Geology, Aligarh Muslim University, Aligarh.

Mr. Mohd. Shaif

“Geochemical

studies on the manganese ores of Banswara Distt. (Rajasthan) India

PROF. F. N. SiddiquieSupervisor

Dr. F. N. SiddiquieProfessorB.Sc. (Hons.), M.Sc. (Geology), M.Phil., Ph.D.F.I.A.S, F.G.S.I., M.I.S.A.GRecipient of Aligarh Shiksha Ratan Puraskar-2014

ACKNOWLEDGEMENTS

In the name of Allah, the most Beneficent and the Merciful

First and foremost all praises to the lord of the worlds, the Beneficent, the

Merciful. Surely, He is ever aware of seeing his servants. I am paying all my thanks

to Almighty Allah who enabled me to complete this work successfully.

I express my deepest appreciations and sincere gratitude to my supervisor,

Prof. Farhat Nasim Siddiquie, Deptt. of Geology, Aligarh Muslim University,

Aligarh for his effective guidance, encouragement, and unstinted support

throughout my research work. I am highly thankful to Prof. (Dr.) Syed Ahmad Ali,

Chairman, Deptt. of Geology, A.M.U., Aligarh, for providing me the necessary

facilities for my research work.

I also acknowledged the altruistic support of Mr. Trilok Shankar Sharma

(Sr. Geologist), Mr. Syed Irshad Ali (Sr. Geologist), Department of Mines and

Geology, Banswara District & Udaipur District, Rajasthan respectively, Retd.

Prof. N. K. Chauhan, Department of Geology, MLSU, Udaipur, Rajasthan and

also Mr. Khalid, Mr. Nadeem, Mr. Shahid, Mr. Iqbal, Mr. Kanti and Mr. Avdesh

for providing me help during my field and mine visit.

I express my special and sincere gratitude to Dr. (Prof.) Subir

Mukhopadhyay, Ex H.O.D., Department of Geological Sciences, University of

Jadavpur, Kolkata and his staff members for the assistance and cooperation in

XRD, Ore microscopic studies and rock petrographic studies.

My sincere and special thanks to Dr. Rasik Ravindra (Director) and Dr.

Javed Beg (Director Logistic), Dr. Thamban Meloth (Scientist E), Ms. Lathika

(Scientist B), and his staff members at National Centre for Antarctic and Ocean

Research (NCAOR), Head land Sada, Goa for their special help in geochemical

analysis of my samples.

My sincere thanks to Syed Imam Mujtaba (Sr. Geologist), Mr. Sadiq

(Geologist) and staff at Geological Survey of India, Faridabad for their help in XRD

and geochemical analysis.

My special thanks and regards to Mr. Lovelesh Soni, Mr. Ansari, Dr. Ausaf

Raza, Mr. Bulbul Mondal, Mr. Ahmad, Mr. Zeeshan and Mr. Apritam and Mr.

Sanjay Verma, Geologists for assistance and cooperation during my research work

visit to Head Office, GSI, Western Region, Jaipur (Rajasthan) and CHQ (Kolkata).

My special thanks to NGRI, Hyderabad scientists and staff for their special

help in geochemical analysis of my samples.

Special thanks to all other teaching and non-teaching members of Deptt. of

Geology, A.M.U., Aligarh and also University administration peoples for their help

and encouragement from time to time.

I am always indebted to Sagarian Peoples, Prof. R. K. Trevedi, Prof. P. K.

Kathal, Prof. Shakir Adil, Dr. Mashkoor Khan (Bhaijaan), Dr. Nasir and my

batchmates for constantly encouraging and motivating me in my chores.

The financial assistance received from the University Grant Commission as

Maulana Azad National Fellowship (MANF) is sincerely acknowledged.

I am also thankful to my seniors, Dr. Sajjad Hussain Bhat, Dr. Talat Jawed,

Dr. Kh. Burhamuddin, Dr. Shamshad, Dr. Wasim, Dr. Sadiq, Dr. Tauheed, my

colleagues, Dr. Adnan, Mr. Shamsuddin, Mr. Shoeb, Mr. Azharuddin, Mr. Shovi

Khan, Mr. Siraj, Mr. Saad, Mr. Mashkoor, Mr. Aleem, Mr. Khatib, Mr. Salman,

Mr. Javed, Mr. Iftekhar, Mr. Ramiz, Mr. Meradul, Mr. Salman(Hydro), Mr. Juned

Alam, Mr. Rajiullah Khan, Mr. Masood Ahmed and Mr. Gyas Ahmad Khan

(Admin. Dean Office Faculty of Science, AMU) for their help, cooperation,

encouragement and many fruitful discussions during the course of this research

work.

I am sincerely thankful to my friends and colleagues Mr. Furkan, Mr.

Danish, Mr. Burhan, Mr. Faraz, Mrs. Nazia, Mr. Rizwan, Mr. Kashif, Mr. Faizy,

Mr. Azam, Mr. Naved, Mr. Javed Umar, Mr. Sohail, Mr. Asif, Mr. Istifa and Co.

and Mr. Mohd Fahad (AMUSU-Secretary) and Mr. Shoaib (Akhtar Printing

Works) for directly and indirectly assisting me.

Finally, I would be failing in my duty if I do not place at record the help and

encouragement which I got from my parents, my family and my wife, those have

made big sacrifices for me and stood firmly by my side during the most difficult

moments, and never allowed me to give up. Without their prayers, advice and even

admonishments this accomplishment would have been impossible.

ABSTRACT

The manganese deposits are extensively dispersed both in time and space, in

which majority of manganese (>70 %) wealth lies in Precambrian time. India is a

major continental manganese ore producer in the world and also accounting 6th place

in respect of manganese production in the world. The major stratiform manganese ore

deposits of India belong to late Archaean to early Proterozoic, confined in to several

groups of Precambrian Superacrustal rocks (Roy, 1981) and manganese deposits of

Rajasthan belongs to Aravalli Supergroup. In India, Madhya Pradesh is the largest and

Rajasthan is the smallest producer of manganese ores among all the Indian states. The

manganese deposits belong to Aravalli Supergroup classified as meta-sedimentary

type (Roy, 1968). On the basis of occurrence and distribution, Geological survey of

India referred these deposits as the extension or equivalent to the deposits of Madhya

Pradesh that comes under syngenetic gonditic type deposits. The present study area is

situated in Banswara district, which lies in southern most part of Rajasthan state of

India. The manganese ore deposit of Banswara district mainly occur in a linear belt,

which is stretching about 20 km in NE-SW direction except Talwara village (small

producing locality). The manganese belt situated in a sequence from Gararia to

Ratimauri village in between 23˚12'-23˚20'N to 74˚15'-74˚25'E (Toposheet no. 46 I/7)

and Talwara manganese at 230 33' - 740 19' (Toposheet no. 46I/6). The major

manganese ore deposit sites are Kalakhunta, Ghatia, Gararia, and Tambesara in which

active mining is going on, in Kalakhunta and Ghatia only. The manganese ores and its

associated rocks of Banswara district occurred in Kalinjara formation of Lunavada

group which is the younger group of Aravalli Supergrup of Paleo-Proterozoic age.

The current research work is carried out only to investigate the geochemistry of

manganese ores, but due to lack of complete geoscientific research work and literature

in the study area, the present author also focused on host rocks geochemistry and

detail petrography, occurrence of manganese ores, tectonics in relation of ore

deposits, lithological and structural controls as well as field characters of the ore

deposits and optical studies to evaluate various parameters like the genetic assessment

of the present manganese ore deposits, the parameters which controlled the chemical

composition of Banswara manganese ores during changes in physical and chemical

environments from their formation to metamorphism and finally textural and

mineralogical reconstitution through supergene processes. The geochemical studies of

the present manganese ore deposits of Banswara, is an important piece of research

work to serve the economic geologist entrepreneurs and industrialists for opting the

low to medium grade manganese ores of the study area.

The textures, structures and prevailing mineral assemblages suggest that low

grade regional metamorphism (greenschist to lower amphibolite facies) has played an

important role in metamorphism of these pelitic-psammitic and calcareous sediments

which turn into the prominent manganese comprising rocks of the study area and

finally metamorphosed to present day rock types viz, phyllite, schist and quartzite.

These metasediments occur as inter-banded with present manganese ores and enriched

in silica, alumina and iron contents, structurally the study area is very much disturbed

due to presence of complex structural pattern, which is in support that the area has

passed away with severe tectonism and deformational episodes. This concluded that

the manganiferous beds and associated rocks suffered greatly by intense

deformational phases resulting into co-folded ores deposits of the study area. The

main structural control of ores in the area is foliation plane, shear zone, fissure plane

and weak zone of phyllite etc. The present lithology, structural features and their

relation in form of strict conformity of manganese horizon with bedding of phyllites

and quartzites, sharp contact with overlying and underlying rocks, uniformity in

quality of ores, absence of evidences related to wide spread replacement suggested the

primary syngenetic origin for these deposits.

The manganese deposits of Banswara district occurred as interbedded in a

repetitive sequence or co-folded nature with pelitic and psammitic rocks throughout

the belt. The both primary and secondary manganese ores occurred in manganese ores

of Banswara district, in which chief primary and abundant mineral is braunite with

minor occurrence of bixbyite, pyroxmangite, hollandite and spessartine while

secondary ores are pyrolusite, cryptomelane, psilomelane, coronadite, and wad. The

mineragraphic and XRD studies reveal that braunite, pyrolusite, cryptomelane and

spessartine are common minerals in manganese deposits. The common texture in

present manganese ores are colloform, banded, vein replacement and relict types. The

mineralogy and textures of both, manganese ores and host rocks indicate progressive

and retrogressive type of metamorphism in the study area. The preponderance of

braunite with characteristic banded texture, bedding and conformable relations with

the enclosing rocks, textural and mineralogical studies of other ore minerals

assemblages supported that the ore body formed by regional metamorphism of

syngenetic manganiferous sediments, however hydrothermal manganese bearing

solution also played an important role in the enrichment of manganese in the study

area at later stage.

The major, trace and rare earth elements study of manganese ores and host

rocks is very much helpful to delineate composition, genesis, depositional

environment and tectonic conditions which suggest that the Banswara manganese ores

deposit and their associated metasediments are clearly a metamorphosed and

metasedimentary sequence of manganese ores and its associated host rocks. And also

indicate that the manganese ores of Banswara district evolved through number of

phases from co-precipitation and sedimentation to digenesis followed by low grade

metamorphism, colloidal replacement and finally to supergene enrichment. The

average concentration of manganese in present Mn ores suggests low to medium

grade ore which is enriched in silica, alumina and iron contents. The manganese ores

also consist higher concentration of Ba which indicates that they are affected by

volcanic source and sedimentation (Oksuz, 2011). The manganese ores of study area

is abnormally enriched in Co, V, Cu, Ni, Zn, Zr, Sr, Pb, and Ba. These elements

concentration signify sedimentary to metasedimentary nature of the manganese

deposits. The higher concentration of these trace elements also suggests involvement

of secondary processes and supergene enrichment that confirmed from ore

mineralogical and geochemical studies. The strong sympathetic relation between Si-

Al and Ti-Al with high amounts of Si, Al and Ti in the Banswara manganese ores belt

may be due to the admixture of terrigenous material during precipitation which is

supported by SiO2 vs Al2O3 and Si vs Al binary plot showed hydrothermal-

hydrogenous origin for the manganese ores of present study area and this may be due

to weathering involvement. A number of manganese samples of the study area

interpreted through various diagnostic binary, ternary and discrimination diagram that

reveal hydrothermal source for the present manganese ores deposited in shallow shelf

environment. This marine hydrothermal solution was enriched in manganese and

which was carried out in solution through upwelling of anoxic deep oceanic water and

were delivered to the shelf zone during favorable conditions of their precipitation and

deposition. Later activities like deformation and low grade metamorphism

(greenschist facies) which effected locally and resulted in textural, structural and

mineralogical reconstitution in the present manganese ores and host rocks of the study

area. The rare earth elements data of Banswara manganese deposits show lanthanum

enrichment, la/Ce ratio and strong Eu anomalies which indicate both basinal

hydrothermal fluids and terrigenous materials as source for the manganese deposits, in

which major contribution from the former one. While the positive Eu and Ce anomaly

also suggest reducing environment conditions for the deposition of present manganese

ore deposits of Banswara district.

The bulk geochemistry, petrography, lithological and structural characteristics

of host rocks clearly evident metapelites and calc-silicate composition in protolith of

the host rocks. The geochemical interpretation reveals that the host rocks were most

probably deposited in passive continental margin environment. And these tectonic

setting supported by various binary and discrimination plots like Fe2O3+MgO vs

A12O3/SiO2, Fe2O3+MgO vs A12O3/(CaO+Na2O). The passive continental margin

setting also supported by binary and ternary plots of K2O/Na2O vs SiO2, Sc-Th-Zr/10

and La-Th-Sc, for the studied samples respectively. The sedimentary to

metasedimentary field and felsic to intermediate source for these metasediments in

close affinity with UCC and felsic compositional field also favored shallow shelf

environment condition for the manganese ores of Banswara manganese ores belt,

Banswara district, Rajasthan.

CONTENTS

List of Figures i-xx

List of Tables xxi-xxiii

List of Abbreviations xxiv

Chapter 1

INTRODUCTION 1-28

1.1 General Statement 1

1.2 Worldwide Manganese Mineralization and its Framework 4

1.3

Manganese Framework And Mineralization In Indian Sub-

Continent

8

1.4 Manganese Ore Deposits of India 11

1.5 Location of the Study Area 14

1.6 Topography and Drainage 15

1.7

1.8

Climatic condition

Fauna and Flora

16

16

1.9 Research Methodology 17

1.9.1 Field Investigation & Sampling 17

1.9.2 Laboratory Work 18

1.9.3 Powdering 18

1.9.4 X-Ray Diffraction (XRD) 18

1.9.5 X-Ray Fluorescence (XRF) 18

1.9.6 Loss on Ignition 19

1.9.7 Preparation of Solution B for Trace Elements

Geochemistry

20

1.9.8 Ore Microscopy and Scanning Electron Microscopy 21

1.9.9 Petrography

1.9.10 Data Plotting And Softwares

21

22

1.10 Historical Background of the Banswara Manganese Ores Belt 22

1.11 Purpose of the study 23

1.12 Literature Review 25

Chapter 2

GEOLOGY AND STRUCTURE 29-54

2.1

2.2

2.3

2.4

Introduction

Regional Geology of Banswara District

2.2.1 Mangalwar Complex (Bhilwara Supergroup)

2.2.2 Debari Group

2.2.3 Udaipur Group

2.2.4 Intrusives

2.2.4.1 Granite

2.2.4.2 Granite Gneiss

2.2.4.3 Amphibolite

2.2.4.4 Quartz Vein

2.2.5 Lunavada Group

2.2.5.1 Kalinjara Formation

2.2.6 Infratrappean

2.2.7 Deccan Trap

Regional Structures of Lunavada rocks

Geological Setting of the Study Area

2.4.1 Gararia-Sivnia Section

2.4.2 Kalakhunta-Ghatia Section

2.4.3 Sagwa-Itala Section

2.4.4 Tambesara-Kheria Section

2.4.5 Rupakhera-Ratimauri Section

2.4.6 Talwara Area

29

33

33

34

34

34

35

35

35

35

35

36

37

38

38

38

42

43

44

44

44

45

2.5

2.6

Structural Setting in The Study Area

Description of Manganese Bearing Rocks

2.6.1 Phyllite

2.6.2 Schist

2.6.3 Quartzite

2.6.4 Limestone

45

46

46

47

47

48

Chapter 3

PETROGRAPHIC STUDIES OF HOST ROCKS 55-70

3.1 Introduction 55

3.2

Petrography

3.2.1 Phyllite

3.2.2 Schist

3.2.3 Limestone

3.2.4 Quartzite

55

55

60

64

66

3.3 Modal Analysis 69

Chapter 4

BANSWARA MANGANESE ORES 71-90


4.2 Occurrence and Distribution of Manganese ores 71

4.2.1 Stratified/Primary/Metamorphosed/Syngenetic/Meta-sedimentary

Ores

73

4.2.2 Secondary/Hydrothermal/Supergene Ores 73

4.2.3 Gararia – Sivnia Section 74

4.2.4 Kalakhunta – Ghatia Section

4.2.5 Itala – Sagwa Section

75

76

4.2.6 Tambesara – Kheria Section 81

4.3

4.2.7 Rupakhera – Ratimauri Section

4.2.8 Talwara Section

Mineralogy of Manganese ores

4.3.1 Braunite

4.3.2 Pyrolusite

4.3.3 Hollandite

4.3.4 Cryptomelane

4.3.5 Psilomelane

4.3.6 Wad

4.3.7 Ochre

81

81

82

82

82

83

83

84

84

84

Chapter 5

MINERAGRAPHIC STUDIES OF MANGANESE ORES 91-122


5.2 Mineralogy of the Manganese Ores 92

5.2.1 Braunite 92

5.2.2 Bixbyite 94

5.2.3 Pyroxmangite 95

5.2.4 Spessartine 95

5.2.5 Pyrolusite

5.2.6 Hollandite

5.2.7 Cryptomelane

5.2.8 Psilomelane

5.2.9 Coronadite

5.2.10 Hematite

96

98

99

100

101

102

5.3 Textures and Microstructures 104

5.3.1 Replacement Texture 104

5.3.2 Banded Texture 105

5.3.3 Colloform Texture 105

5.3.4 Veined Texture 109

5.3.5 Granular Texture 109

5.3.6 Spherulitic Texture 109

5.4

5.3.7 Relict Texture

5.3.8 Brecciated Texture

5.3.9 Crystallographic Texture

5.3.10 Mutual Boundary Relation

5.3.11 Open space filling Texture

X-Ray Diffraction Studies

109

109

110

110

110

111

5.5

5.6

Scanning Electron Microscopic (SEM-EDX) Studies

Proposed mineral paragenesis of the manganese ores

115

119

Chapter 6

GEOCHEMISTRY OF MANGANESE ORES 123-186


6.2 Major Oxides in Manganese Ores 138

6.2.1 Silica (SiO2) 139

6.2.2 Alumina (Al2O3) 141

6.2.3 Titanium Oxide (TiO2) 145

6.2.4 Iron Oxide (Fe2O3) 145

6.2.5 Manganese Oxide (MnO) 146

6.2.6 Magnesium Oxide (MgO) 150

6.2.7 Calcium Oxide (CaO) 151

6.2.8 Sodium Oxide (Na₂O) 151

6.2.9 Potassium Oxide (K2O) 152

6.2.10 Phosphorus (P2O5) 153

6.3 Geochemistry of Trace Elements 156

6.3.1 Cobalt (Co) 160

6.3.2 Copper (Cu) 160

6.3.3 Nickel (Ni) 161

6.3.4 Zinc (Zn) 163

6.3.5 Vanadium (V) 163

6.3.6 Chromium (Cr) 164

6.3.7 Lead (Pb) 164

6.3.8 Strontium (Sr) 166

6.3.9 Molybdenum (Mo)

6.3.10 Barium (Ba)

166

167

6.4

Rare Earth Elements

6.4.1 Post Archean Australian Shale Normalized Rare Earth

Elements

167

175

6.5 Characteristics and Proposed Possible Genetic Consideration of

Manganese Deposits

176

Chapter 7

GEOCHEMISTRY OF HOST ROCKS 187-240

7.1

7.2

Introduction

Major Elements

187

187

7.2.1 Silica (SiO2) 187

7.2.2 Alumina (Al2O3) 188

7.2.3 Titanium Oxide (TiO2) 197

7.2.4 Iron Oxide (Fe2O3) 197

7.2.5 Manganese Oxide (MnO) 198

7.2.6 Magnesium Oxide (MgO) 198

7.2.7 Calcium Oxide (CaO) 198

7.2.8 Sodium Oxide (Na2O) 199

7.2.9 Potassium Oxide (K2O) 199

7.2.10 Phosphorous Oxide (P2O5) 202

7.3 Distribution of Trace Elements 202

7.3.1 Large Ion Lithophile Elements (LILE) 203

7.3.1.1 Lead (Pb) 203

7.3.1.2 Rubidium (Rb) 205

7.3.1.3 Hafnium (Hf) 207

7.3.1.4 Lanthanum (La) 207

7.3.1.5 Thorium (Th) 207

7.3.2 High Field Strength Elements (HFSE) 208

7.3.2.1 Uranium (U) 208

7.3.2.2 Niobium (Nb) 209

7.3.2.3 Scandium (Sc) 209

7.3.2.4 Zirconium (Zr) 209

7.3.2.5 Strontium (Sr) 210

7.3.2.6 Yttrium (Y) 210

7.3.3 Transition Elements 212

7.3.3.1 Copper (Cu) 212

7.3.3.2 Nickel (Ni) 212

7.3.3.3 Vanadium (V) 213

7.3.3.4 Chromium (Cr) 213

7.3.3.5 Cobalt (Co) 214

7.3.3.6 Zinc (Zn) 214

7.4 Rare Earth Elements 216

7.5 Comparison with Post Archean Australian Shale (PAAS) and

Upper Continental Crust (UCC)

219

7.6 Source Rock Characteristic and Tectonic Setting 232

Chapter 8 241-250

SUMMARY AND CONCLUSIONS

References 251-285

i

List of Figures

Figure No. Title Page No

1.1 Different applications of manganese ores (Source: Minerals Year

Book, I.B.M. 2015).

2

1.2 Major land based manganese ore producers of the world (Mineral

Commodity Summary, U.S.G.S., 2011).

6

1.3 Bar diagram showing manganese resources of the world by

principal countries (Minerals Year book, I.B.M., 2015).

6

1.4 Histogram showing world's manganese production by principal

countries (Source: Minerals Year Book, I.B.M., 2015).

7

1.5 Map showing manganese ore deposits in India. 9

1.6 Pie diagram showing state wise resources (%) of manganese ores

in India (Source: I.B.M., Market Survey on Manganese Ores,

2014).

10

1.7 Bar diagram showing state wise production (%) of manganese

ores in India (Source: I.B.M., Minerals Year Book, 2015).

10

1.8 Bar diagram showing year wise production of manganese ores

(000' tonnes) in Banswara district, Rajasthan (Source: I.B.M.,

Minerals Year Book, 2012, 2013, 2014 and 2015).

13

1.9 Accessibility and location map of Banswara manganese ores belt,

Banswara district, Rajasthan (www.mapsofindia.com).

15

1.10 Flowchart showing accepted research methodology. 19

2.1 Simplified geological map of Banswara Manganese belt,

Banswara district, Rajasthan (after G.S.I., 2005).

30

2.2 Geological map of study area (Source: DRM, GSI, 1983

Database).

43

2.3A Hand specimen showing secondary folds in thin beds of

manganese ores at Kalakhunta mine.

48

2.3B Field photograph showing ptygmatic folding in interbedded

phyllites and manganiferous beds at Ghatia mine.

48

2.3C Field photograph showing isoclinal folds in manganiferous beds

at Kalakhunta mine.

49

http://www.maps/

ii

2.3D Field photograph showing well preserved alternate beds of

manganese ores and phyllite in Tambesara village.

49

2.3E Field photograph showing manganese ores association with host

rocks just 3 ft' below the earth surface.

49

2.3F Hand specimen of Phyllite showing crenulations at Kalakhunta

mine.

50

2.3G Field photograph showing intrusion of calcite and quartz veins in

phyllite near Itala village.

50

2.3H Field photograph showing 2 sets of joint in manganiferous chert. 50

2.3I Field photograph showing large solution holes in limestone beds

at Talwara village.

51

2.3J Field photograph showing quartzitic intercalation in dolomite

section near Sagwa.

51

2.3K Field photograph showing antiform structure in manganese ores

and their host rocks (phyllite and quartzite) Kalakhunta Mine.

51

2.4 A hand specimen showing dendritic pattern and foliations in

manganiferous Phyllite.

52

2.5 A hand specimen showing Mn-ore (Black) and foliations in

manganiferous Phyllite.

52

2.6 A hand specimen showing folding effect and Mn ore along

foliation planes in phyllite at Ghatia section.

52

2.7 A hand specimen showing porphyroblast of garnet and quartzitic

intercalation in siliceous phyllite near Kalakhunta-Ghatia section.

53

2.8 A hand specimen showing dendritic pattern and patches of

manganese ore in Mn-bearing phyllite at Tambesara section.

53

2.9 A hand specimen of manganiferous schist in Kalakhunta section. 53

2.10 A hand specimen of manganese bearing interbedded phyllite and

quartzite.

54

2.11 A hand specimen of greyish colour manganiferous dolomitic

limestone in Talwara section.

54

3.1 Photomicrograph showing abundant quartz with deposition of

manganese ores in scattered form in siliceous phyllite.

58

iii

3.2 Photomicrograph showing micaceous minerals aligned perfectly

along the foliation in manganiferous phyllite.

58

3.3 Photomicrograph showing schistosity and microfolding of ores in

manganiferous phyllite.

58

3.4 Photomicrograph showing mineral boundary relationship between

lapidoblasts of biotite (Bt) with other minerals in chlorite-biotite

phyllite.

58

3.5 Photomicrograph showing biotite (Bt) alteration into chlorite

(Chl) in muscovite phyllite.

58

3.6 2θ positions of muscovite, chlorite, quartz and braunite in

siliceous phyllite.

59

3.7 2θ positions of muscovite, chlorite, quartz, albite and hematite in


59

3.8 2θ positions of muscovite, chlorite, biotite and quartz in chlorite-

biotite phyllite.

59

3.9-3.10 Photomicrograph showing clusters of perfectly rhombohedral

shaped garnet (Gt) and microfolded bands of manganese ore in

garnetiferous mica schist.

62

3.11 Photomicrograph showing perfect schistosity and quartz

intercalation in quartz mica schist.

62

3.12 Photomicrograph showing deposition of Mn-ore minerals along

the mineral boundaries of uniformly oriented muscovite (Mus)

and chlorite (Chl).

62

3.13 Photomicrograph showing quartz grain layer defining foliation in

muscovite-chlorite schist.

62

3.14 2θ positions of muscovite, chlorite, quartz, albite and garnet in

garnetiferous mica schist.

63

3.15 2θ positions of muscovite, chlorite, orthoclase and quartz in

quartz mica schist.

63

3.16 2θ positions of muscovite, quartz, fluroapatite and dravite in

muscovite-chlorite schist.

63

3.17 Photomicrograph showing mosaic structure with sub graphic 65

iv

intergrowth of quartz in manganese bearing dolomitic limestone.

3.18 Photomicrograph showing dark colour impure variety of

limestone having tremolite, quartz and biotite.

65

3.19 2θ positions of calcite, dolomite and quartz, in manganese bearing

dolomitic limestone.

65

3.20 Photomicrograph showing encrustation of manganese ores with

impurities of iron in quartzite.

67

3.21 Photomicrograph showing granoblastic texture with lamellar

twinned porphyroblast of plagioclase in quartzite.

67

3.22 Photomicrograph showing straight grain boundaries and

sericitization at places with the encrustation of manganese ores in

quartzite.

68

3.23 Photomicrograph showing serrated/sutured grain boundaries in

quartzite.

68

3.24 2θ positions of quartz, muscovite, calcite and albite in manganese

bearing quartzite.

68

3.25 2θ positions of quartz, muscovite, calcite and microcline in

manganese bearing quartzite.

68

4.1 A sketch of section at Kalakhunta mine showing intensely folded

manganese ore beds with quartzite and phyllite.

76

4.2 A sketch of section at Tambesara showing highly folded

manganiferous quartzites and phyllites (after Roy, 1957).

76

4.3 A sketch of section at Talwara locality showing Mn ores as

irregular lenses and pockets in a limestone ridge (after Roy,

1957).

77

4.4 The working open cast manganese mine at Kalakhunta mining

area, Banswara district, Rajasthan.

77

4.5 An active open cast manganese mine at Kalakhunta mining area,


77

4.6 The over burden rehabilitation through tree plantation at

Kalakhunta mine, Banswara district, Rajasthan.

78

4.7 The highly folded manganese ore beds associated with 78

v

interbedded phyllites and quartzites at Kalakhunta mine,


4.8 The folded manganese ore beds at Ghatia section, Banswara

district, Rajasthan.

78

4.9 The highly folded manganese ore beds in association of host rocks

near Kalakhunta section at Banswara-Dohad road, Banswara


79

4.10 The manganese ores old working near Itala, Banswara district,

Rajasthan.

79

4.11 The manganese ores in association with highly folded,

interbedded phyllites and quartzites at Tambesara section,


79

4.12 The manganese bearing host rocks contain folded bands of

manganese ores in Sivnia section, Banswara district, Rajasthan.

80

4.13 The manganese ores pockets in weathered schist (near pen) at

Kalakhunta section, Banswara district, Rajasthan.

80

4.14 The manganese ores associated with highly weathered limestone

at Talwara village, Banswara district, Rajasthan.

80

4.15 A hand specimen of perfectly banded braunite (steel grey) in

Ghatia section, Banswara district, Rajasthan.

85

4.16 A hand specimen of braunite showing bands of pyrolusite in Itala

section, Banswara district, Rajasthan.

85

4.17 A hand specimen showing perfect band of braunite (steel grey)

and manganiferous quartzite in Tambesara section, Banswara


85

4.18 A hand specimen showing alternate folded bands of pyrolusite

and lithomarge (ochre) in Kalakhunta mine, Banswara district,

Rajasthan.

86

4.19 A hand specimen of thick banded pyrolusite in Ghatia section,


86

4.20 A hand specimen showing soft and friable manganese ore wad

(lower part of the specimen) with band of reddish grey jasperoid

86

vi

quartzite and manganiferous quartzite in Kalakhunta mine,


4.21 A hand specimen showing intensely folded bands of braunite

(steel grey), with pyrolusite, jasperoid quartzite and quartz vein in

Kalakhunta Mine, Banswara district, Rajasthan.

87

4.22 A hand specimen of Pyrolusite showing granular texture contain

thin vein of braunite (pointing arrow) in Kalakhunta Mine,


87

4.23 A hand specimen of braunite (steel grey) showing secondary ores

pyrolusite, cryptomelane, psilomelane and gangue (jasperoid

quartzite) in Tambesara section, Banswara district, Rajasthan.

87

4.24 A hand specimen of pyrolusite showing ferruginous manganese,

hollandite and intruded quartz veins in Tambesara section,


88

4.25 A hand specimen of secondary ore pyrolusite (brownish black)

showing lithomarge in form of Ochre (Yellow) in Talwara


88

4.26 A hand specimen of primary ore braunite contain mica flakes in

Sivnia section, Banswara district, Rajasthan.

88

4.27 A hand specimen showing braunite (dark grey), manganiferous

quartzite and secondary pyrolusite in Tambesara section,


89

4.28 A hand specimen showing hollandite (mammilary aggregates),

coronadite, psilomelane and lithomarge in form of ochre (yellow)

in Sivnia section, Banswara district, Rajasthan.

89

4.29 A hand specimen of pyrolusite showing thin veins of quartz in

Gararia section, Banswara district, Rajasthan.

89

4.30 A hand specimen of braunite showing secondary pyrolusite,

jasperoid quartzite and orthoclase vein (flesh color) in Itala


90

4.31 A hand specimen of pyrolusite (brownish black) showing fibrous

coronadite (steel grey), jasperoid quartzite and cryptomelane in

90

vii


5.1 Photomicrograph of manganese ore showing massive braunite. 93

5.2 Photomicrograph of manganese ore showing folding pattern by

braunite along with gangue.

93

5.3 Photomicrograph of manganese ore showing second generation

braunite which is least affected by metamorphic condition.

93

5.4-5.5 Photomicrographs of manganese ore showing bixbyite

replacement by braunite II.

94

5.6 Photomicrograph of manganese ore showing Mn-pyroxene with

braunite and hematite.

95

5.7 Photomicrograph of manganese ore showing rhombohedral

shaped spessartine with pyrolusite.

96

5.8 Photomicrograph of manganese ore showing alteration of braunite

into pyrolusite.

97

5.9 Photomicrograph of manganese ore showing acicular alteration

growth of pyrolusite along the pre-existing braunite: a common

feature of supergene alteration.

97

5.10 Photomicrograph showing pyrolusite formed by supergene

alteration from braunite as established by the diffused grain

boundary where relict braunite is also present.

97

5.11 Photomicrograph showing completely altered/recrystallised

pyrolusite embedded in matrix of cryptomelane/psilomelane.

97

5.12 Photomicrograph showing presence of both neo-crystallised as

well as recrystallised pyrolusite. In the upper to middle part it

shows alteration while right side neo-crystallised pyrolusite shows

different orientation.

97

5.13 Photomicrograph showing growth of pyrolusite from structurally

pre-deformed stretched braunite.

98

5.14 Photomicrograph showing typical grain completion supergene

alteration from braunite to pyrolusite establishing fO2/oxidation

potentiality of the supergene fluid.

98

5.15 Photomicrograph of manganese ore showing fine grained 99

viii

hollandite replacing massive braunite.

5.16 Photomicrograph of manganese ore showing presence of anhedral

grain of hollandite in braunite.

99

5.17 Photomicrograph of manganese ore showing alteration of braunite

to cryptomelane.

100

5.18 Photomicrograph of manganese ore showing fine grained

psilomelane.

101

5.19 Photomicrograph of manganese ore showing fine grained

psilomelane and braunite.

101

5.20 Photomicrograph of manganese ore showing radiated needles of

coronadite, cryptomelane (white) and hollandite.

101

5.21 Photomicrograph of manganese ore showing acicular needles of

coronadite along the boundaries of ferruginous manganese and

braunite.

102

5.22 Photomicrograph of manganese ore showing original minute

specks of primary hematite with massive braunite.

103

5.23 Photomicrograph of manganese ore showing pyrolusite with

hematite II as a product of replacement.

103

5.24 Photomicrograph of manganese ore showing braunite replacement

by pyrolusite, hematite and gangue.

103

5.25 Photomicrograph showing replacement of massive braunite by

pyrolusite.

106

5.26 Photomicrograph showing braunite is replaced by cryptomelane. 106

5.27 Photomicrograph showing thick banded braunite where it is filled

with gangue.

106

5.28 Photomicrograph showing banded braunite where boundary is not

clear due to replacement by cryptomelane.

106

5.29 Photomicrograph showing partially developed colloform bands of

pyrolusite and cryptomelane.

106

5.30 Photomicrograph showing partially developed colloform bands

between pyrolusite and cryptomelane.

107

5.31 Photomicrograph showing colloform texture between braunite, 107

ix


5.32 Photomicrograph showing vein of braunite in pyrolusite and

cryptomelane.

107

5.33 Photomicrograph showing vein of pyrolusite in braunite and

cryptomelane.

107

5.34 Photomicrograph showing vein of pyrolusite filled in braunite. 107

5.35 Photomicrograph showing anhedral to subhedral grains of

braunite and fine grained psilomelane.

108

5.36 Photomicrograph showing fine grained granular psilomelane with

euhedral grain of braunite in centre.

108

5.37 Photomicrograph showing granular texture by psilomelane and

braunite.

108

5.38 Photomicrograph showing spherulitic texture by braunite grains

with occurrence of fine grained ferruginous manganese.

108

5.39 Photomicrograph of manganese ore showing honey comb

structure and crustification.

110

5.40 Photomicrograph showing intergrowth of cryptomelane in

pyrolusite.

110

5.41 Photomicrograph showing angular to subangular braunite grains

embedded in gangue material.

110

5.42-5.43 Photomicrographs showing relics of primary braunite in

pyrolusite.

111

5.44 Photomicrograph showing mutual boundary relation between

braunite and bixbyite.

111

5.45 Showing 2θ position of braunite, albite and quartz, Ghatia village,


112

5.46 Showing 2θ position of pyrolusite, spessartine, hematite and

quartz, Ghatia village, Banswara district, Rajasthan.

112

5.47 Showing 2θ position of braunite, pyroxmangite, bixbyite,

rhodochrosite and quartz, Kalakhunta mine, Banswara district,

Rajasthan.

112

5.48 Showing 2θ position of braunite, hollandite, albite and quartz, 113

x


5.49 Showing 2θ position of braunite, quartz and manganesio-

hornblende, Kalakhunta mine, Banswara district, Rajasthan.

113

5.50 Showing 2θ position of braunite, bixbyite, hollandite, quartz and

orthoclase, Tambesara section, Banswara district, Rajasthan.

113

5.51 Showing 2θ position of cryptomelane and braunite, Kalakhunta

mine, Banswara district, Rajasthan.

114

5.52 Showing 2θ position of pyrolusite, spessartine and quartz,

Tambesara section, Banswara district, Rajasthan.

114

5.53 Showing 2θ position of braunite, spessartine and quartz,


114

5.54 Showing 2θ position of braunite, coronadite and quartz,


115

5.55 Showing 2θ position of braunite and albite, Rupakhera section,


115

5.56 SEM image showing carbonate replacement in the primary

braunite bearing ore, Tambesara section, Banswara district,

Rajasthan.

116

5.57 EDX data showing peaks of different elements at spectrum I,


116

5.58 SEM image showing fissure replacement in secondary manganese

ore, Kalakhunta mine, Banswara district, Rajasthan.

117

5.59 EDX data showing peaks of different elements at spectrum II,


117

5.60 SEM image showing honey Comb like structure by pyrolusite

bearing ore, Kalakhunta mine, Banswara district, Rajasthan.

118

5.61 SEM image showing replacement between primary (braunite) and

secondary (pyrolusite) manganese ores, Ghatia section, Banswara


118

5.62 SEM image showing euhedral crystal of calcite present as an

impurities in braunite, Tambesara section, Banswara district,

Rajasthan.

118

xi

5.63 SEM image showing globules of hollandite in primary ore

braunite, Tambesara section, Banswara district, Rajasthan.

118

6.1 Variation diagram showing the weight percent of major oxides of

manganese ores in Sivnia and Gararia localities, Banswara

district, Rajasthan, India.

135

6.2 Variation diagram showing the weight percent of major oxides

of manganese ores in Kalakhunta and Ghatia localities, Banswara


135


of manganese ores in Itala village, Banswara district, Rajasthan,

India.

136


of manganese ores in Tambesara village, Banswara district,

Rajasthan, India.

136


of manganese ores in Ratimauri village, Banswara district,

Rajasthan, India.

136


of manganese ores near Timamahudi, Banswara district,

Rajasthan, India.

137

6.7 Variation diagram showing the average weight percent of major

oxides of manganese ores, Banswara district, Rajasthan, India.

137

6.8 Relationship of SiO2 with other oxides (Al2O3, TiO2, K2O and

P2O5) of different localities of Banswara manganese ores,

Banswara district, Rajasthan, India.

140

6.9 Relationship between SiO2 and selected trace elements (Pb, Ni

and Ba) of different localities of Banswara manganese ores,


141

6.10 The ternary plot of Fe-Mn-Si (after Dasgupta and

Manickavasagam, 1981) showing the composition of manganese

ore samples of different localities of Banswara manganese ores,


142

xii

6.11 Ternary diagram of Al-Mn-Fe (wt%) (after Bonatti et al., 1972)

showing the manganese ore samples of different localities of

Banswara manganese ores, Banswara district, Rajasthan, India.

143

6.12 Relationship of Al2O3 with K2O of different localities of


143

6.13 Relationship of TiO2 with Al2O3 of different localities of

Banswara manganese ores, Banswara district, Rajasthan, India

143

6.14 Relationship between Al2O3 and selected trace elements (Ni, Cu,

Pb and Ba) of different localities of Banswara manganese ores,


144

6.15 Relationship between TiO2 and selected trace elements (Zn, V

and Cu) of different localities of Banswara manganese ores,


144

6.16 Relationship of Fe2O3 with other oxides (SiO2, Al2O3, TiO2,

MnO, MgO, CaO, Na2O, K2O and P2O5) of different localities

of Banswara manganese ores, Banswara district, Rajasthan, India.

147

6.17 Relationship of Fe2O3 with selected trace elements (Co, Ba, Ni,

Sr, Zr, Zn, Pb and Mo) of different localities of Banswara

manganese ores, Banswara district, Rajasthan, India.

148

6.18 Relationship of MnO with other oxides (SiO2, Al2O3, TiO2,

MnO, MgO, CaO, Na2O, K2O and P2O5) of different localities


149

6.19 Relationship of MnO with selected trace elements (Ba, Ni and

Pb) of different localities of Banswara manganese ores,


150

6.20 Relationship of MgO with selected trace elements (Co, Zr, Sr,

and Zn) of different localities of Banswara manganese ores,


154

6.21 Relationship of CaO with selected trace elements (Co, Pb and

Zn) of different localities of Banswara manganese ores,


154

6.22 Relationship of K2O with selected trace elements (Pb, Sr, Ni and 155

xiii

Mo) of different localities of Banswara manganese ores,


6.23 Relationship of P2O5 with selected trace elements (Ba, Zn, V and

Cu) of different localities of Banswara manganese ores,


155

6.24 Variation diagram for selected trace elements of Sivnia and

Gararia localities of Banswara manganese ores, Banswara


158

6.25 Variation diagram for selected trace elements of Kalakhunta

village of Banswara manganese ores, Banswara district,

Rajasthan, India.

158

6.26 Variation diagram for selected trace elements of Ghatia and

Itala localities of Banswara manganese ores, Banswara district,

Rajasthan, India.

158

6.27 Variation diagram for selected trace elements of Tambesara

block/village of Banswara manganese ores, Banswara district,

Rajasthan, India.

159

6.28 Variation diagram for selected trace elements of Ratimauri

village of Banswara manganese ores, Banswara district,

Rajasthan, India.

159

6.29 Variation diagram for selected trace elements of Timamahudi

block/locality of Banswara manganese ores, Banswara district,

Rajasthan, India.

159

6.30 Relationship of Cu with V in manganese ore samples of

different localities of Banswara manganese ores, Banswara


162

6.31 Relationship of Ni with selected trace elements (Pb and V) in

manganese ore samples of different localities of Banswara


162

6.32 Relationship of Co with selected trace elements (Pb and Zn) in



162

xiv

6.33 Relationship of Cr-Zr in manganese ore samples of different

localities of Banswara manganese ores, Banswara district,

Rajasthan, India.

165

6.34 Relationship of Cr-Zr and Sr-Zr in manganese ore samples of



165

6.35 Chondrite normalized (after Taylor and McLennan, 1985) rare

earth elements (REE) diagram for manganese ore samples of



170

6.36 Post Archean Australian Shale (PAAS) normalized rare earth

elements (REE) diagram for manganese ore samples of different


Rajasthan, India.

171

6.37 Relation between light and heavy rare earth elements

(HREE/LREE) in the manganese ore samples of different


Rajasthan, India.

174

6.38 Relation between light rare earth elements (LREE) and

Al2O3 in the manganese ore samples of different localities of

Banswara manganese ores, Banswara district, Rajasthan, India

174

6.39 Mg vs Na show the manganese ore samples of different

localities of Banswara manganese ores falling in the field of

fresh and shallow water field, Banswara district, Rajasthan,

India.

182

6.40 CaO-Na2O-MgO ternary plot (after Dasgupta et. al., 1999)

shows marine field for the manganese ore samples of different


Rajasthan, India.

182

6.41 Ba vs P2O5 (after Maynard, 2010) shows manganese ore

samples of different localities of Banswara manganese ores,

Banswara district, Rajasthan, India clustered near the euxinic

183

xv

basin and oxygen minimum zone.

6.42 Plot of Fe-Si*2-Mn ternary diagram (after Toth, 1980), showing

the manganese ore samples of different localities of Banswara

manganese ores, Banswara district, Rajasthan, India are

concentrated near the hydrothermal field.

183

6.43 Si vs Al weight percent plot (after Choi and Hariya, 1992)

shows the hydrogenous-hydrothermal origin for the manganese

ores of different localities of Banswara manganese ores,


184

6.44 SiO2 vs Al2O3 plot (after Wonder et al., 1988) shows the

hydrothermal origin for the manganese ores of different


Rajasthan, India.

184

6.45 Cu+Ni vs Cu+Pb+V+Zn discrimination diagram (after

Nicholson, 1992b) shows the manganese ore samples of


district, Rajasthan, India clustered in hydrothermal field.

185

6.46 Co/Zn vs Co+Ni+Cu bivariate diagram (after Toth, 1980) shows

the hydrothermal origin for the manganese ores of different


Rajasthan, India.

185

6.47 Zn-Ni-Co ternary diagram (after Choi and Hariya, 1992) shows

the manganese ores of different localities of Banswara

manganese ores, Banswara district, Rajasthan, India from

hydrothermal origin.

186

6.48 Mn-Fe-(Ni + Co + Cu) X10 ternary discrimination diagram (after

Bonatti et al., 1972; Crerar et al., 1982) showing hydrothermal

origin for manganese deposits of different localities of


186

7.1 Bar diagram showing average weight percent of major oxides of

host rocks Manganiferous phyllite (MNP), Phyllite (PHY), Schist

(SCH), Quartzite (QTZ) and Limestone (LST), of manganese

193

xvi

ores, Banswara district, Rajasthan.

7.2 Bar diagram showing weight percent of SiO2, Al2O3, and Fe2O3 in




194

7.3 Scatter diagrams between SiO2 and other oxides of host rocks

Manganiferous phyllite (MNP), Phyllite (PHY), Schist (SCH),

Quartzite (QTZ) and Limestone (LST), of manganese ores,


195

7.4 Variation diagram showing total average weight percent of major

oxides in Manganiferous phyllite (MNP), Phyllite (PHY), Schist



196

7.5 Bar diagrams showing weight percent of MgO, CaO, Na2O and

K2O in host rocks Manganiferous phyllite (MNP), Phyllite (PHY),

Schist (SCH), Quartzite (QTZ) and Limestone (LST), of

manganese ores, Banswara district, Rajasthan.

200

7.6 Bar diagrams showing weight percent of MnO, TiO2 and P2O5 in




201

7.7 Bar diagram showing the concentration of selected trace elements

in schist rock samples, Banswara district, Rajasthan.

204


in phyllite rock samples, Banswara district, Rajasthan.

204


in manganiferous phyllite rock samples, Banswara district,

Rajasthan.

204


in quartzite rock samples, Banswara district, Rajasthan.

205


in limestone rock samples, Banswara district, Rajasthan.

205

xvii

7.12 Bar diagram showing variation in Rb-La-Hf-Pb-Th (Large ion

lithophile elements) in host rocks Manganiferous phyllite (MNP),

Phyllite (PHY), Schist (SCH), Quartzite (QTZ) and Limestone

(LST), of manganese ores, Banswara district, Rajasthan.

206

7.13 Bar diagram showing variation in Sc-Sr-Y-Zr-Nb-U (High Field

Strength Elements) in host rocks Manganiferous phyllite (MNP),

Phyllite (PHY), Schist (SCH), Quartzite (QTZ) and Limestone


211

7.14 Bar diagram showing variation in V-Cr-Co-Ni-Cu-Zn (Transition

Elements) in host rocks Manganiferous phyllite (MNP), Phyllite

(PHY), Schist (SCH), Quartzite (QTZ) and Limestone (LST), of


215

7.15 Correlation between LREE and HREE of host rocks


Quartzite (QTZ) and Limestone (LST), of manganese ores,


220

7.16 Chondrite normalized REE pattern (Taylor McLennan, 1985) of




223

7.17 PAAS normalized REE pattern (Taylor and McLennan, 1985) of




224

7.18 Chondrite normalized REE pattern (Taylor and McLennan, 1985)

of schist rock samples, Banswara district, Rajasthan.

225


of manganiferous phyllite rock samples, Banswara district,

Rajasthan.

225


of phyllite rock samples, Banswara district, Rajasthan.

225

7.21 Chondrite normalized REE pattern (Taylor and McLennan, 1985) 226

xviii

of quartzite rock samples, Banswara district, Rajasthan.


of limestone rock samples, Banswara district, Rajasthan.

226


schist rock samples, Banswara district, Rajasthan.

226


phyllite rock samples, Banswara district, Rajasthan.

227


manganiferous phyllite rock samples, Banswara district,

Rajasthan.

227


limestone rock samples, Banswara district, Rajasthan.

227


quartzite rock samples, Banswara district, Rajasthan.

228

7.28 UCC normalized diagram (Taylor and McLennan, 1985) of host

rocks (Manganiferous phyllite-MNP, Phyllite-PHY, Schist-SCH,

Quartzite-QTZ, Limestone-LST), of manganese ores, Banswara


229

7.29 UCC normalized REE pattern (Taylor and McLennan, 1985) of

schist rock samples, Banswara district, Rajasthan.

230


manganiferous phyllite rock samples, Banswara district,

Rajasthan.

230


phyllite rock samples, Banswara district, Rajasthan.

230


quartzite rock samples, Banswara district, Rajasthan.

231



231

7.34 A-C-F ternary plot (after Eskola, 1915) shows the pelitic field for

Schist (SCH), Manganiferous phyllite (MNP), Phyllite (PHY),

Quartzite (QTZ) and calcareous field for limestone (LST) rocks,

234

xix


7.35 The ternary plot of Ca-Fe+MgO-Al2O3 (after Wronkiewicz and

Condie, 1989) shows the pelitic rock fields for schist (SCH),

manganiferous phyllite (MNP), phyllite (PHY), quartzite (QTZ)

and calcareous protolith for limestone (LST) rock samples,


234

7.36 The binary plot of K2O/Al2O3 vs Na2O3/Al2O3 (after MacDonald

and Kastura, 1964) shows the samples are lying in the

sedimentary and metasedimentary field for the host rocks


Quartzite (QTZ) and Limestone (LST), of Banswara manganese


235

7.37 The binary plot Fe2O3/K2O vs SiO2/Al2O3 (after Roddaz et al.,

2006), shows the shale-arkose sequence field for the host rocks


Quartzite (QTZ) and Limestone (LST), of Banswara manganese


235

7.38 The ternary plot of MgO-FeO-(Na2O+K2O) (after Kuno, 1968)

shows all the host rock Manganiferous phyllite(MNP), Phyllite

(PHY), Schist (SCH), Quartzite (QTZ) and Limestone (LST),

samples fall in the calc-alkaline field, Banswara manganese ores,


236

7.39 The binary plot of Zr vs TiO2 (after Hayashi et al., 1997) shows

felsic rock composition for the host rocks Manganiferous phyllite

(MNP), Phyllite (PHY), Schist (SCH), Quartzite (QTZ) and

Limestone (LST), of Banswara manganese ores, Banswara


236

7.40

The binary plot of K2O/Na2O vs SiO2 (after Roser and Korsch,

1986) shows PCM type tectonic setting for the host rocks of

Banswara manganese ores, Banswara district, Rajasthan.

237

7.41 Binary plot of Fe2O3+MgO vs Al2O3/SiO2 (after Bhatia, 1983)

shows the active and passive continental margin type tectonic

237

xx

setting for the host rocks of Banswara manganese ores, Banswara


7.42 The binary plot of Fe2O3+MgO vs Al2O3/CaO+Na2O (after

Bhatia, 1983) shows the ACM and PCM type tectonic setting for

the host rocks of Banswara manganese ores, Banswara district,

Rajasthan.

238

7.43 Zr/Sc versus Th/Sc plot (after McLennan et al., 1993) showing

UCC (Upper continental crust) and felsic rock affinity for the host

rocks of Banswara manganese ores, Banswara district, Rajasthan.

238

7.44 La-Th-Sc discrimination diagram (after Bhatia and Crook, 1986)

showing PCM type tectonic setting for the host rocks of Banswara


239

7.45 Sc-Th-Zr/10 discrimination diagram (after Bhatia and Crook,

1986) shows the PCM type tectonic setting for the host rocks of


240

xxi

List of Tables

Table No. Title Page No.

1.1 World manganese ore reserves by principal countries (Source:

Minerals Year Book, I.B.M., 2015).

5

1.2 World production of manganese ore by principal countries

(Source: Minerals Year Book, I.B.M., 2015).

7

1.3 State wise resources of manganese ores in India (Source:

I.B.M., Market Survey on Manganese Ores, 2014).

8

1.4 State wise production of manganese ores in India (Source:

I.B.M., Minerals Year Book, 2015).

11

1.5 District wise resources of manganese ores in Rajasthan

(Source: I.B.M., Minerals Year Book, 2015).

13

1.6 Production of manganese ores in Banswara district from 2010-

2015 (Source: I.B.M., Minerals Year Book, 2012, 2013, 2014

and 2015).

14

1.7 Latitude - Longitude and Toposheet information of different

mines and blocks of Banswara manganese ores belt, Banswara

district (Rajasthan).

14

2.1 Generalized Geological Succession of Banswara district,

Rajasthan (Hydrogeological Atlas of Rajasthan, Banswara

district, 2013).

33

2.2 Lithostratigraphic succession of Lunavada group (After Gupta

et.al., 1980 and 1992).

36

2.3 Stratigraphic succession of Banswara district, Rajasthan

(Source, DRM, GSI, 1983 Database).

39

2.4 Stratigraphic sequence of the study area (After Mukherjee and

Kapoor, 1960 and Sinha, 1980).

40

3.1 Mineral assemblages in phyllite rocks of the study area. 57

3.2 Mineral assemblages in schist rocks of the study area. 61

3.3 Mineral assemblages in limestone rocks of the study area. 64

3.4 Mineral assemblages in quartzite rocks of the study area. 67

xxii

3.5 Mineral percentage in host rocks of the study area. 69

5.1 EDX data of spectrum I in manganese ore of Tambesara


116

5.2 EDX data of spectrum II in manganese ore of Kalakhunta


117

5.3 The suggested possible paragenesis of manganese ores of

Banswara manganese belt.

121

5.4 Mineral paragenesis of manganese deposits from different

metamorphic zones of Madhya Pradesh - Maharashtra

manganese belt (After Roy, 1963).

122

6.1 The major oxides geochemical data of manganese ore samples

of different localities of Banswara district, Rajasthan, India.

126

6.2 The comparative average values of major oxides in wt% from

different types of manganese ores of the world.

128

6.3 The trace elements geochemical data of manganese ore

samples of different localities of Banswara district, Rajasthan,

India.

129

6.4 The comparative average values of trace elements in wt% from

different types of manganese ores of the world.

131

6.5 Correlation between the major oxides of various manganese

ore samples of different localities of Banswara district,

Rajasthan, India.

132

6.6 Correlation between the selected trace elements of various



132

6.7 The rare earth elements (REE) geochemical data of manganese

ore samples of different localities of Banswara district,

Rajasthan, India.

133

7.1 The analyzed geochemical data (Major oxides) of host rocks of


189

7.2 The analyzed geochemical data (Trace Elements) of host rocks

of manganese ores, Banswara district, Rajasthan.

190

xxiii

7.3 The correlation coefficient between trace elements of host

rocks of manganese ores, Banswara district, Rajasthan.

191

7.4 The correlation coefficient between trace elements and major

oxides of host rocks of manganese ores, Banswara district,

Rajasthan.

192

7.5 The geochemical data (Rare earth elements) of host rocks of


221

7.6 The geochemical data for Chondrite normalized Rare earth

elements (Taylor and McLennan, 1985) of host rocks of


222

xxiv

List of Abbreviations

Abbreviation Full Form

ACM Active continental margin

AMB Aravalli Mountain Belt

CIA Continental Island Arc

CPL Crossed Polar light

DRM District Resource Map

EDX Energy Dispersive X-Ray

Ga Giga annum

GSI Geological Survey of India

HREE Heavy Rare Earth Elements

IBM Indian Bureau of Mines

ICP-MS Inductively Coupled Plasma Mass Spectrometer

LREE Light Rare Earth elements

Myr Million years

Ma Mega annum

MSL Mean Sea Level

MT Million tones

OIA Oceanic Island Arc

PCM Passive continental Margin

PPL Plane Polarized Light

ppm Parts Per Million

REE Rare Earth Elements

SEM Scanning Electron Microscopy

UNFC United Nation Frame Work Classification

U.S.G.S United State Geological Survey

Wt% Weight percentage

XRF X-ray Fluorescence Spectrometry

µm Micrometer

∑REE Sum of Rare Earth Elements

* Anomaly

1

CHAPTER-1

INTRODUCTION

1.1 General Statement

Minerals have significant role in our everyday life. These become useful for

human beings only after proper investigation and development. The manganese has a

high seek of key importance and using worldwide. Manganese is one of the primary

metal for ferroalloy industries and still no substitute is present for it. About 90 to 95%

of its use in metallurgy of steel. It is standout as an important metal on which nation

economy rest.

Manganese is one of the significant mineral deposits occurring in India. The

nation’s development and industrial progress is much basis on this metal. In this

modern period, the consumption of manganese has increased all over the globe. The

domestic requirement and use of manganese metal has expanded pointedly because of

manganese based alloys production increased. According to U.S.G.S. Mineral

Commodity Report (2016), India is accounting sixth place in manganese production

in the world and has a solid position about her manganese assets are concerned.

Indian ocean has enough resources of manganese nodules. But now a days the review

of mineral created in India involves concern, because the grade of manganese ores has

gone lower and lower in current years.

Manganese metal is essential in iron and steel metallurgy where it is uses in

both form as remover of oxygen, sulfur and phosphorus. The oxygen, sulfur and

phosphorus always restrict good production of steel therefore it is needy to consider

physical and chemical properties of minerals before its extreme use. Manganese

strengthens the quality, durability, hardness and workability of steel. It is a significant

ingredient for manufacturing steel with its low cost-effectiveness, high melting point

12460C and boiling point 20610C with no significant substitute. These manganese

ores are extensively exploiting in direct steel industry in alloy making and for the

sweetening the low-grade phosphorus rich ores, glass industry, medicines, paints,

weapons and automobile industry (Fig. 1.1).

2

Fig. 1.1 Different applications of manganese ores (Source: I.B.M. Minerals Year

Book, 2015).

However the manganese metal shows contrast from different minerals in its

use. Because of the virtue of corrosion resistance, manganese plays a vital role in

aluminum alloys. Manganese dioxide (MnO2) worked as a depolarizer in making dry

cell batteries. It ought to be free from metallic content like copper, nickel, cobalt,

arsenic, lead and antimony, which are electronegative to zinc (container). In

chemicals, high-grade manganese ores are using for potassium permanganate. KMnO4

chiefly used to wash wound, treat burn affect, waste water treatment and in several

3

others. Manganese phosphate is using removal of rust and prevention of corrosion in

steel. Pyrolusite is using to confer glaze to the ceramics and to make colored blocks. It

also use as driers for oils, varnishes and paints. Manganese sulfide is using as a part to

make salts and in calico printing. Manganese chloride uses in cotton material as a

bronze dye. Manganese salts are using in photography, leather and matchbox

ventures. Manganese has also positive and negative roles in life of human well-being.

Although its quantity in human body is essential to survive but higher concentration

leads to poisonous. Manganese severely affects mainly the respiration system with

other bad impacts of health such as increasing sugar level, coagulation and swelling of

bronchi. Manganese (symbol Mn) is a chemical element of Group 7 (VIIb) in the

periodic table with atomic no. 25 and atomic wt. 54.938. The earth’s crust constitutes

average abundance about l percent of manganese and holds 12th most prolific

elements in crust. It is the fourth broadly devoured metal after Fe, Al and Cu.

Manganese is silver gray metal having specific gravity around 7.2, very hard and

splintery in nature. It is always found in combination with Fe and other minerals and

never accessible in native state. Continental weathering, hydrothermal solution and

sedimentary processes played a major role for the formation of these manganese ores

(Roy, 1981). Manganese ores formed as oxides, silicates and carbonates according to

its origin. According to geochemical classification the manganese comes under the

siderophile (iron loving) elements (Goldschmidt, 1937). This high-density metal has

tendency to sink in the core because of its easily dissolving nature with iron either

solid solution or liquid state. In the upper lithosphere, manganese is oxyphile with

biophile tendency (Rankama and Sahama, 1950). In igneous rocks manganese wealth

has been given as 0.0086% (Clarke and Washington, 1924), 0.0980% (Hevsy et al.,

1934) and 0.1% (Rankama and Sahama, 1950). Mn+2 easily substitute with iron and

magnesium in minerals (Ure and Berrow, 1982). The ionic radius of manganese in

divalent state (67 pm) is comparable with iron and magnesium (61 and 72

respectively) and concentrate with it in early phase of magmatic crystallization

(Rankama and Sahama, 1950; Goldschmidt, 1954). In sedimentary rocks, sandstone

consist minimum abundance of manganese 0.026- 0.05% (Wedepohl, 1969) and

oceanic pelagic red clay consist maximum 0.856% (Ronov and Yaroshevsky, 1972).

The typical average concentration of manganese content in shield metamorphic rocks

is about 0.08% and supported with value 0.076% provided by (Beus, 1976). In pelitic

metamorphic rocks the Mn content recorded around 0.13% (Menhart, 1969). The

4

continents, marine floors and lacustrine floors are fully enriched with manganese ore

deposits. The formation of different types of manganese ore deposits lies upon

continents and can be correlated with the generalized pattern of the crustal evolution

(Stanton 1972; Strakhov, 1969). In the beginning period of basic volcanism,

manganese minerals bodies related to greenstones and jasper prevailed and later

pyroclastic rocks were formed in close affinity of Mn concentration during evolution

of eugeosyncline. The most visible development of manganese ore deposits in

geological past is found on floor without volcanism or volcanic rocks (Roy, 1981).

The investigation of ocean deposits in light of plate tectonic solved the complete

geochemical cycle of manganese and thus a connecting bridge between the deposits

on the continents and those occurring on ocean floors has been established (Jenkyn,

1977).

1.2 Worldwide Manganese Mineralization and its Framework

The manganese deposits present on continent through geological time from

early Precambrian to recent vanished both on land and ocean (Roy, 1981). The

distribution of manganese deposits started through geological record is quite variable

and likely began during the late Archean (Roy 1997, 2000 and 2006). In early 800 ma

of earth geological record, no manganese deposits was formed. This scarcity reflect

inadequacy of oxygen in the atmosphere and hydrosphere (Roy, 1997). During the

late Archean, only a few deposits of manganese ores were formed most likely relating

to expansion of oxygen oases in the otherwise reducing hydrosphere (Nicholson and

Eley, 1997) and these deposits are limited. The earth’s main manganese ore deposits

are of Proterozoic age and have been grouped as Paleo-Proterozoic, Neo-Proterozoic

and Cenozoic (Roy, 2000). The largest volume of Paleo-Proterozoic manganese

deposits are in Kalahari region of South Africa while as the largest Neo-Proterozoic

deposit is in Brazil with many smaller deposits occurring in China and India (Bhat,

2013). The extensive manganese ore mineralization was in Cenozoic which followed

by the Precambrian, the Paleozoic and the Mesozoic in that order (De Villiers, 1971).

The major continental manganese ore producers of the world are South Africa, Brazil,

India, Gabon, China, Morocco and Australia (Fig.1.2). The manganese deposits are

extensively dispersed both in time and space, in which majority of manganese (>70%)

wealth lies in Precambrian time (Roy, 1960, 1965, 1966, 1968, 1969, 1970, 1981,

5

1984, 1988, 1992 and 1997; Nicholson, 1992; Nicholson and Eley, 1997). Manganese

ores of various genetic environments such as hydrothermal-volcanogenic,

sedimentary/meta-sedimentary, hydrogenous (marine, shelf, fresh water, lacustrine),

volcanic and karst hosted reported so far by many geologists (Bhat, 2013). These

diverse genetic environments caused because of the typical processes of land-ocean-

atmosphere system over geological time having clear contrast in occurrence, origin,

mineralogy and geochemistry of manganese ore deposits (Nicholson and Eley, 1997;

Mynard, 2010). The Proterozoic time was the most impressive event of sedimentary

manganese ore deposition. These prominent ore deposits are found in South Africa,

Brazil, Namibia, Botswana, Zaire, India, Gabon, China, Morocco, Canada, Finland,

Australia and Russia (Gross, 1986; Roy, 1990). Terrestrial manganese resources are

large but roughly distributed with a total world reserve of around 620 million tons

(I.B.M. Minerals Year Book, 2015) (Table 1.1, Fig. 1.3).

Table 1.1 World manganese ore reserves by principal countries (Source: I.B.M.

Minerals Year Book, 2015).

Countries Reserve in 000' Tonnes of

metal content

% of Total

Australia 91000 14.6774194

Brazil 50000 8.06451613

China 44000 7.09677419

Gabon 22000 3.5483871

India* 52000 8.38709677

Mexico 5000 0.80645161

Kazakhstan 5000 0.80645161

South Africa 200000 32.2580645

Ukraine 140000 22.5806452

Other countries 11000 1.77419355

Total 620000 100

* India's total UNFC resources of manganese ores as on 1.4.2013 are estimated at 475

million tonnes.

6

Fig. 1.2 Major land based manganese ore producers of the world (Mineral Commodity

Summary, U.S.G.S., 2011).

Fig. 1.3 Bar diagram showing manganese resources of the world by principal

countries (I.B.M. Minerals Year Book, 2015).

7

The total world production of manganese ores is about 54.7 million tonnes in 2014 as

compare to 53.3 million tonnes in 2013 and 47.7 million tonnes in 2012 (Table 1.2).

China was the leading producer for the last few years, 2013-2015 (Report I.B.M.

Minerals Year Book, 2010, 2015) (Fig.1.4).

Table 1.2. World production of manganese ores by principal countries (Source:

I.B.M. Minerals Year Book, 2015).

Country Production (in 000' Tonnes).

2012 2013 2014

Australia 7179 7426 7587

Brazil 2796 2833 2498

China 14500 15500 16000

Gabon 3363 4091 4000

Ghana 1491 1998 1353

India* 2342 2588 2166

Kazakhstan 2975 2852 2609

Malaysia 1100 1125 835

South Africa 8943 10952 13857

Ukraine 1234 1525 1526

Other

countries

1936 2392 2229

Total 47859 53282 54660

* India's production of manganese ores in 2012-13, 2013-14 and 2014-15 was 2.34

million tonnes, 2.63 million tonnes and 2.34 million tonnes, respectively.

Fig. 1.4 Histogram showing world’s manganese production by principal countries

(Source: I.B.M. Minerals Year Book, 2015).

8

1.3 Manganese Framework and Mineralization in Indian Sub-

Continent

India is an independent country about its manganese deposits and one of the

principal producer of manganese ores in world. The country is holding 6th position in

production and reserve of its manganese assets. Majority of manganese ore deposits

are found throughout the peninsular region of India. The overall assets of manganese

ores in the nation as on 1.04.2013 are put at 475 million tonnes according to UNFC

framework. Out of these, 95.87 million tonnes are classified as reserve and the rest

379.31 million tonnes are in the remaining resource category (I.B.M. Minerals Year

Book, 2015). Indian manganese ores are very much preferred because of its hard and

lumpy form and vulnerable to easy reduction. The Indian manganese ore deposits

mainly vanished in ten states, those are Andhra Pradesh, Bihar, Goa, Gujarat,

Karnataka, Madhya Pradesh, Maharashtra, Orissa, West Bengal and Rajasthan (Fig.

1.5). Largest resources of manganese ore to a tune of 190 million tonnes are in the

state of Odisha (Table 1.3). The Odisha state is at the top in the total resources of the

country is 44.20 percent followed by other states (Fig. 1.6). The state wise production

of manganese ores in year 2014-2015 in India has been given in (Table 1.4, Fig. 1.7).

The major deposits in country confined during Precambrian time, are stratiform type.

The Precambrian manganese ore deposits of Africa, Asia and South America consist

stratiform manganese formations and believed to be of either sedimentary origin

(Roy, 1965 and 1968) or volcanogenic sedimentary origin (Gross, 1983).

Table 1.3 State wise resources of manganese ores in India (Source: I.B.M., Market

Survey on Manganese Ores, 2014).

State Resources

(Million tonnes) %

Odisha 190 44.2

Karnataka 96.2 22.37

Madhya Pradesh 55.72 12.96

Maharashtra 34.15 7.94

Andhra Pradesh 17.6 4.09

Others 36.271 8.44

Total 429.941 100

9

Fig. 1.5 Map showing manganese ore deposits in India. 1. Banswara district,

Rajasthan. 2. Madhya Pradesh and Maharashtra manganese ore deposits. 3.

Panchmahal district deposits, Gujarat. 4. Jhabua district deposits, Madhya

Pradesh. 5. Srikakulam district deposits, Andhra Pradesh. 6. Bonai-

Keonjhar deposits, Odisha. 7. Kalahandi-Koraput deposits, Odisha. 8.

Sandur-Bellary, Karnataka. 9. Shimoga deposits, Karnataka. 10. North-

Kanara deposits, Karnataka. 11. Gangpur-Bamra deposits, Odisha. 12.

Goa deposits.

10

Fig. 1.6 Pie diagram showing state wise resources (%) of manganese ores in India

(Source: I.B.M., Market Survey on Manganese Ores, 2014).

Fig. 1.7 Bar diagram showing state wise production (%) of manganese ores in India

(Source: I.B.M., Minerals Year Book, 2015).

11

Table 1.4 State wise production of manganese ores in India (Source: I.B.M., Minerals

Year Book, 2015).

State Production in tonnes Production in %

Andhra Pradesh 253675 10.81603

Goa ---- -------

Jharkhand 4449 0.189694

Karnataka 194123 8.276892

Madhya Pradesh 883784 37.68222

Maharashtra 669813 28.55906

Odisha 326117 13.90477

Rajasthan 5965 0.254332

Telangana 7435 0.317009

The major stratiform manganese ore deposits of India belongs to late Archean

to early Proterozoic confined into following groups of Precambrian Superacrustal

rocks (Roy, 1981). Precambrian Iron Ore Group (Jharkhand and Orissa deposits are

mostly lateritoid type), Dharwar Supergroup (Karnataka and Goa deposits are mostly

lateritoid type) (Fermor, 1909), Khondalite Group (Andhra Pradesh and Odisha),

Aravalli Supergroup (Rajasthan), Champaner Group (Gujarat), Sausar Group

(Madhya Pradesh and Maharashtra), Gangpur Group (Odisha) and Penganga Group

(Deposits associated with carbonate formation (Roy, 1981). The ore bearing

formations of Karnataka, Goa, Jharkhand and Orissa are mostly of lateritoid type

(Fermor, 1909) and free from metamorphic affect where as manganese deposits of

Madhya Pradesh and Maharashtra shows higher grade of metamorphism (Varies from

greenschist facies to upper amphibolite facies). The Manganese ore deposits and

associated rocks of Banswara district, Rajasthan shows low grade regional

metamorphism (greenschist facies to lower amphibolite facies) (Shaif et al., 2017)

while manganese ore bodies and other associated rocks belonging to Andhra Pradesh

and Odisha are metamorphosed up to granulite facies (Siddiquie, 1986, 2003 and

2004; Siddiquie and Raza, 2008; Siddiquie and Bhat, 2010).

1.4 Manganese Ore Deposits of India

On the basis of occurrence and distribution Geological survey of India referred

it in to four major groups.

a. Syngenetic Gonditic Deposits (Archean) - These deposits are extensively

found in Madhya Pradesh, Maharashtra, Gujarat and Rajasthan states and

12

associated with gondites (quartz-spessartite-rhodonite).

b. Syngenetic Reef Deposits - These deposits are mainly found in

Visakhapatnam, Srikakulam, Adilabad and Hyderabad districts of Andhra

Pradesh and Koraput and Balangir districts of Odisha associated with highly

metamorphosed Kodurite series (feldspar-spandite-apatite).

c. Replacement Deposits - These deposits are occurring in Singhbhum, Odisha,

Karnataka and Goa.

d. Lateritoid and Supergene Enrichment Deposits - These deposits associated

with most of the above deposits.

In all deposits, the gonditic deposits are of much important because of large

concentration of key minerals (Braunite, psilomelane followed by minor

cryptomelane and pyrolusite). According to Roy (1981) these deposits are formed in

cratonic shelf environment. Except above classification of manganese ore deposits of

India, Fermor (1909) also categorized three different types based on geological

investigation: manganese ore deposits of metamorphic origin associated with the

Gondite series found in M.P., Maharashtra and also present in parts of Karnataka,

Andhra Pradesh and Odisha. The manganese ore deposits associated with Kodurite

series of Visakhapatnam, Srikakulam (Andhra Pradesh). The lateritoid manganese

deposits with Dharwar group in Singhbhum, Sandur, Mysore etc. The manganese ores

in the present study area are exclusively associated with the Aravalli phyllite, schist,

quartzite and limestone exposed in many villages of the Banswara district (Roy, 1957;

Mukherjee and Kapoor, 1960; Rasul and Khan, 1963 and Sinha, 1980). However the

manganese ore deposits are dominantly associated with phyllite in the study area. The

present manganese ores and their host rock association can be easily compared with

the gonditic ores of Madhya Pradesh and Maharashtra region. Regional

metamorphism has played an important role in metamorphism of these pelitic-

psammitic and calcareous sediments which are the prominent Mn comprising rocks of

the study area and finally metamorphosed to present-day rock types viz: phyllite,

schist and quartzite. The phyllite and schist rocks mineral assemblages falling in

greenschist to lower amphibolite facies and formed by prograde metamorphism of

Aravalli metasediments (Shaif et al., 2017). Manganese ores consist mainly of

braunite, pyrolusite, psilomelane, cryptomelane and wad in the study area.

13

Rajasthan state is enriched with 5.80 million tonnes (Table 1.5) of total

assets of manganese mineral in which Banswara region consist 91.4 percent of total

assets and remaining 8.6 percent are contributed by Udaipur district. The total

resources of state 1.78 million tons are in the reserved class and rest 4.03 million

tonnes are remaining resources. The five year data of manganese production in

present study area has given (Table 1.6).

Table 1.5 District wise resources of manganese ores in Rajasthan (Source: I.B.M.,

Minerals Year Book, 2015).

SI.

No.

District Reserve(00

0' tonnes)

Remaining

Resources(000'

tonnes)

Total

Resources(000'

tonnes)

Important

Deposits/Min

es

1 Banswara 1780 3520 5300 Gararia,

Kalakhunta,

Ghatia,

Tambesara

2 Udaipur - 510 510 Umaira,

Chotisar

Fig. 1.8 Bar diagram showing year wise production of manganese ores (000' tonnes)

in Banswara district, Rajasthan (Source: I.B.M., Minerals Year Book, 2012,

2013, 2014 and 2015).

14

Table 1.6 Production of manganese ores in Banswara district from 2010-2015

(Source: I.B.M., Minerals Year Book, 2012, 2013, 2014 and 2015).

Manganese ores production in 2010 - 2015.

Year 2010-11 2011-12 2012-13 2013-14 2014-15

Mn Ores

in 000'

tonnes. 16638 7483 4987 5401 5965

1.5 Location of the Study Area

The study area is situated in Banswara district, which lies in southern - most

part of Rajasthan state of India. The district lies between 23° 11' N to 23° 56' N

latitude and 73° 58' E to 74° 49' E longitudes. The district is well connected with

Pratapgarh and Udaipur district in North, in east by Ratlam district of M.P, on the

west by Dungarpur district and in south by Jhabua district of Madhya Pradesh. The

district also adjoining the Panchmahal district of Gujarat state on the south west side

(Fig. 1.9). There is no railway station in Banswara district but in east the nearest

railway station is Ratlam Junction. Ratlam is major railway junction for Delhi,

Mumbai, Ahmadabad and Bhopal. In north the major railway junction is Udaipur (city

of lakes) and well-connected by air, rail and road to go anywhere in country.

The study area in Banswara district lies between (23˚15' - 23˚20' N to 74˚15' -

74˚25' E) and falls under toposheet number 45 I/7 except Talwara village. The

deposits occur in a belt which is varying from place to place between Gararia to

Ratimauri villages. The various mines and blocks located between different latitude

and longitude are present in (Table 1.7).

Table 1.7 Latitude - Longitude and toposheet information of different mines and

blocks of Banswara manganese ores belt, Banswara district (Rajasthan).

Mine/Block Latitude Longitude Toposheet No.

Sivnia-Gararia 230 20' - 230 19' 740 16' - 740 17' 46I/7

Kalakhunta-Ghatia 230 19' 740 17' 46I/7

Itala-Sagwa 230 17' 740 18' 46I/7

Tambesara 230 16' 740 20' 46I/7

Ratimauri 230 12' 740 24' 46I/7

Talwara 230 33' 740 19' 46I/6

15

Fig. 1.9 Accessibility and location map of Banswara manganese ores belt, Banswara

district, Rajasthan (www.mapsofindia.com).

1.6 Topography and Drainage

Topographically study area having rugged terrain undulated by medium ridges

in central part of the study area, in NNE-SSW direction. The region shows diverse

topographical features varying from place to place. The eastern part of the area

comprises abundant flat topped hills of Deccan trap. The average elevation is 750m

above MSL with a gentle slope towards NNW in the northern part and NW in the

southern part. In the east and south-east the area ends into flat topped trap hills with

an average elevation of 1300m above MSL. Black soil (northern, southern, central

http://www.maps/

16

and eastern parts) and red soil (western portion) are found chiefly in the district. The

drainage of the study area falls with the Mahi river originating from the Amjera hills.

The regional drainage system empties into the Mahi river originating from Amjera

hills near Dhar in Madhya Pradesh. The main tributaries of the Mahi river are, Chap,

Erav, Anas, Haran and Kagdi. Major part of the surface run off passes through the

Haran river, which flows from SE to NW direction. Chap and Sonal streams drains

the northern parts of the district. A large number of gullies and nalas join these

streams from all sides locally. Scores of lakes are seen in the study area. A large dam

namely Mahi Bajaj Sagar dam has been constructed on the Mahi river, some 16 km

away from Banswara town. The right and left main canals and their distributaries

irrigate 60,149 hectare crop lands of the district.

1.7 Climatic Condition

The normal annual rainfall of the area is about 82.59 cm. The monsoon range

in Banswara district starts from July and till to last week of September. The area has a

moderate, humid climate with an annual rainfall of 40 inches on an average. As

Geiger (1954, 1961) and Köppen (1884) classification scheme, this climate fall in the

class of Aw (Tropical wet and dry climate). The normal yearly temperature in

Banswara is 26.7 °C with tropical climate. During summer the rainfall is much more

in the district as compare to winters. The average annual rainfall is 990 mm. The

driest month is February with 0 mm of rainfall. In July, the precipitation reaches its

peak with an average of 352 mm. The difference in precipitation level between the

driest and wettest months is around 352mm. May is the warmest and January is the

coldest month of the year. The maximum temperature in the area is 450C to 460C and

minimum up to 100C to 200C. The annual temperature variation is about 14.5 °C.

1.8 Fauna and Flora

The Banswara district is famous because of Bamboo forest of the area. Forest

account around 20% of the total region with dominance of Teaks. Most of the forest is

not thick and barren ground are regular. The major crops in the area include maize,

wheat, cotton, gram, sugarcane, black gram, barley, jowar, groundnuts, fenugreek

seeds, bajra and green gram etc. In the district wild creatures such as squirrels, snakes,

ronj, lizards, chinkara and four horned antelope are in profusion. The birds like fowl,

17

black drongo, green bee-eater, shrike bulbul, woodpecker, jungle crow, parrot and

fowl can be easily seen in the city. The various plants are using by tribal communities

of Banswara district for medicinal purposes such as Chirmu Ratti (Abrus

precatorius l. papilionaceae), Khair Kath (Acacia catechu mimosaceae) etc. Apart

from the that the district also comprises important resources include graphite,

soapstone, dolomite, rock phosphate, limestone and many varieties of marbles in

Banswara district. Gold has also been found around Jagpura - Bhukia area of the

district. These resources play vital role in the development of district economy.

1.9 Research Methodology

1.9.1 Field Investigation and Sampling

Usually fieldwork is very important in geosciences field to explore the earth.

In Banswara district various manganese ore deposits are present at different localities.

All sections and mines areas are situated in a sequence from Gararia to Ratimauri

village in Banswara manganese ores belt. The Kalakhunta and Ghatia are active sites

where manganese mining is going on by open cast method. A small deposit in

Talwara village is abandoned in past. The major ore deposit sites are Kalakhunta,

Ghatia, Gararia and Tambesara. Except above deposits the other manganese hosted

blocks are as Itala, Sagwa, Loharia, Kheria, Rupakhera and Ratimauri. The present

worker done field work in all section and mines at Banswara district. The exposed

lithologies such as phyllites are the member of dominant host rock in the study area

with other associated lithology like; Mn bearing quartzite and schist. Abundance of

folding is seen and the foliation planes are the major controls for concentrating

manganese in the present deformed and tectonically shuffled area.

The author gave more attention during collection of primary and secondary

manganese ores and collected around 80 samples of hosts and ores. Systematic

sampling was done from fresh outcrops after scraping out the surface for few

centimeters to avoid weathering. The collected samples were packed in the cotton bag

and covered by zip lock. Because of poor exposure of host and ores the author could

not do sampling in specific grid pattern so he has only followed the trend of

manganese ores belt for collection of ore samples.

18

1.9.2 Laboratory Work

The research work related to laboratory is summarized by the help of

flowchart (Fig. 1.10) which includes preparation of powder (Host rocks and Ores),

polished ore blocks, thin sections (Host rocks), preparation of pellets (Host rocks and

Ores). The laboratory work done in various national laboratories and departments of

different institutes.

1.9.3 Powdering

Rock samples were reduced to smaller sizes (~ 2 mm) rock chips using agate

mortar. The chips were further powdered to -200 mesh size for maintaining the

homogeneity and true representativeness of the sample. The selected samples were

powdered in pulverizer machine for the specific analyses such as X-ray diffraction, X-

ray fluorescence, Loss on Ignition and ICP-MS studies. The techniques needed

powdering of samples up to -200 mesh size for analysis work. The powdering

machine consist Tungsten carbide bowls and every time these bowls washed with

distilled water and acetone respectively before powdering new sample. The powdered

samples should be kept in a labeled polythene bags for future convenience.

1.9.4 X-Ray Diffraction (XRD)

This technique is using worldwide to identify unknown crystalline material.

The X-ray diffraction technique is very much helpful to confirm the mineral present

in the rocks and ores. The analysis done in Department of Geological Sciences,

Jadavpur University, Kolkata by Xpert-Pro Philips, Indian Institute of technology,

Kanpur and Head office, Geological Survey of India, Faridabad. The data obtained in

the form of peaks on 2θ position with d-spacing. This technique was used on

operating current 40kV-30mA. The confirmed minerals through X-ray diffraction

technique are well matched with minerals identified through microscopic studies,

present in both manganese ores and in host rocks.

1.9.5 X-Ray Fluorescence (XRF)

This technique is using for acquiring major oxides data in ores and host rock.

The powdered samples up to -200 mesh size used for making solid pellets and

analyzed under PW-2404 PAN-analytical XRF spectrometer. The accuracy and

19

precision of analyzed data for standard is 5-6 %. Numbers of international standards

namely USGS standard, British chemical standard and synthetic manganese standard

used at SAIF, IIT, Bombay for geochemical analysis. The ores and host samples

analysis of study area were carried out by Wave Length Dispersive XRF Instrument

(Siemens SRS 3000). The Lucas-Tooth and Pyne (1964) procedure was used for

analysis.

Fig. 1.10 Flowchart showing accepted research methodology.

1.9.6 Loss on Ignition (LOI)

LOI value defines the volatile material present in powdered samples. LOI was

resolved gravimetrically at a temperature of 10000C. The samples analyzed in

geochemical laboratory in Department of Geology, A.M.U., Aligarh. U.P. (India).

The 2 gm of each samples transferred into a fire resistant cups and kept it furnace for

about 2 hours. The total weight loss in sample refers that the sample is free from

volatile contents which may be water or organic materials.

20

Calculation of LOI:

• First weigh the empty silica crucible (Wl) and then add 2 gm of sample in it

and again weigh the silica crucible (W2) and note down both reading.

• After finishing of LOI procedure, shift the crucible to desiccators and weigh

them the silica crucible and weigh (W3).

• Now calculate LOI by formula = W2-W3

• Finally calculate the percentage.

1.9.7 Preparation of Solution B for Trace Elements Geochemistry

For Inductively Coupled Plasma Mass Spectrometry technique, -200 mesh size

powder of samples is needed for preparation of solution. This solution of each sample

used to detect the concentration of trace and rare earth elements. The analysis for

detection of trace and rare earth elements done by using open-acid digestion

technique. The acid ratio requirement of digestion are HCL:HF (10:5) ml for

manganese ores and HF:HNO3:HCLO4 (7:3:1) ml.

The procedure accepted for digestion are as follows:

1. Clean the vessels and lids with 1:5 nitric acid and leave it to one hour.

2. Name the lids with sample codes.

3. Weigh .050 gm of samples and transferred in to clean dried vessels.

4. Add 7:3:1 (HF:HNO3:HCLO4) ml mixture to each vessels and place the lid.

5. Now leave overnight.

6. Place the vessels on hot plate or in Q-block at 80°C for the first hour, later

increase the temperature up to 180°C with lid till a clean white jelly paste

occurs.

7. Add 5 ml of 7:3:1 (HF:HNO3:HCLO4) ml again and complete it to dryness.

8. Now add 1 ml of HCL when hot and add one drop of HCLO4 with a clean

glass rod.

9. Add 20 ml 1:1 HNO3 to each vessel and with lid keep it at 80°C for one hour.

10. Now add 5 ml Rh (l ppm) to each vessels. And make solution up to 250 ml,

then take 5 ml ( from 250 ml) and make it to 50 ml.

11. This 50 ml solution is final liquid for ICP-MS technique.

21

For analysis, first ICP-MS instrument calibrated with the known inorganic

ventures. During preparation of solution of ores and host rocks, it also recommended

to make solution of known standards (Rocks and Ores) simultaneously. The known

standards used for reference during analysis. Various standards of ores and rocks used

which are USGS A-l, P-1, Nod P-1, JMN-1 for manganese ores and JSL-1, JDO-l for

host rocks respectively.

1.9.8 Ore Microscopy and Scanning Electron Microscopy

Ore microscopic studies done on polished ore blocks of manganese ores to

study the minerals present in it. The identification of minerals done under reflected

light using advance version ore microscope (Leica Qwin Color-RGB: 1991-2002,

Taiwan Module) in Department of Geological Sciences, Jadavpur University,

Kolkata. The initial preparation of polished ore blocks done in section cutting lab in

Department of Geology, A.M.U., Aligarh. U.P. (India) by using various grade

carborandum powder. The final preparation of polished blocks such as mounting,

rubbing on different grade emery papers, following different grade of diamond paste

done, in accordance of (Margolis and Glasby, 1973; Mukhopadhyay and Banerjee,

1990). The hifin liquid were continuously used to break the bond between the metals.

Then finally prepared blocks studied under microscope with the help of air and oil

immersion lenses. Electron microscopy examinations were made on both Au and

Ccovered specimens (JEOL JFC-560 Auto Fine Coater), (JEOL JEC-1600, Auto

Carbon coater), in National Centre of Antarctic and Oceanic Research, Goa by using

(JEOL JSM 6300) scanning electron microscope. This SEM is combined with a X-

beam vitality dispersive spectrometer. Analytical EDX settings were 20 kV beam

voltage and check time of 60 seconds (crests).

1.9.9 Petrography

The host rock petrography done in Department of Geology, A.M.U., Aligarh,

U.P. (India) and Department of Geological Sciences, Jadavpur University, Kolkata.

To prepare thin sections like, breaking of chips, mounting with canada balsam on

glass slide and grinding by using different grade of carborandum powder, has done by

following standard petrographic method. The grinding of samples repeated several

time till it achieved 0.03 mm thickness. The host rock samples of phyllite, schist,

22

quartzite and limestone prepared for petrographic studies viz. mineral identification,

textural and fabric studies. The studies of these features also provided hints about P-T

condition in the area. The petrographic studies were done under transmitted light with

the help of advanced petrological microscope in petrological lab of respective

departments. Over these thin sections the modal analysis carried out by the following

methods of Gazzi (1966) and Dickinson (1970).

1.9.10 Data Plotting and Software

The whole research data of host rocks and manganese ores obtained from

XRD, XRF, 1CP-MS, LOI and SEM techniques has been plotted with the help of

various software, such as M.S. Excel, Tri Draw, Sigma Plot and Origin. The other

software also used are M.S. Office, Coral Draw and Adobe Photoshop etc.

1.10 Historical Background of the Banswara Manganese Ores Belt

The manganese ore deposits of Banswara district mainly occur in a belt and

stretching about 20 km in NE-SW direction. The width of the belt is varying from

place to place in the area between Gararia to Ratimauri. The major deposits are

located at Kalakhunta, Ghatia and Tambesara. The Manganese resources of the

district are not extensive in comparison to other states of India such as Madhya

Pradesh, Maharashtra and Odisha etc. Banswara district holds total 5.3 million tonnes

of manganese resources only (I.B.M. Minerals Year Book, 2015). Mallet (1887)

referred manganese ore (Psilomelane) with limonite in Mewar near Udaipur district

(Cited by Roy, 1957). Later discovery of manganese ores were mentioned by Fermor

(1909) in Aravalli of Banswara district at Itala, Sagwa, Ghatia, Kalakhunta, Sivnia,

Gararia villages. Heron (1935) referred information of Mallet and Fermor and

confirmed occurrence of manganese ores during his field visit in the region. A

resurvey of the area was carried out by Gupta and Mukherjee (1938) and the

observations were incorporated in "The Geology of Gujarat and Southern Rajputana".

Crookshank (1946) during his short visit to the area examined some manganese ore

deposits. Roy (1957) assessed the manganese ores potential of the belt and also

explored the manganese ores in Udaipur and Banswara. The deposits are recognized

in the area correlated with Gondites of Maharashtra and Madhya Pradesh or

equivalent and extension of the above mentioned deposits. The ore bodies consist of

23

pyrolusite, psilomelane and braunite with some wad. The common gangue minerals

are quartz, ochre, calcite and siderite. Various worker worked over manganese ores

potentialities in the area such as Mukherjee and Kapoor (1960), Rasul and Khan

(1963), Sinha (1980), Babel (1985), Sukhwal and Dixit (2000), Joshi and Jangid

(2008, 2009). The systematic geological mapping in Banswara district done by

different workers like Iqballudin and Negi (1971), Garg (1973), Gadhadharan (1978),

Roy (1985). The geology of the region worked by Gupta (1934), Gupta and

Mukherjee (1938), Heron (1953), Gupta et al., (1980, 1992, 1995a, 1997), Roy and

Jhakhar (2002), Roy and Purohit (2015). In 1950-51, the Department of Mines and

Geology, Government of Rajasthan started some prospecting operations by sinking 27

shallow pits in Tambesara in Banswara district and is known to have demonstrated the

presence of workable manganese ores there. The region was leased out to several

persons for detailed search of mineral deposits. The leaseholders in Tambesara area

were Messars-Mewar Minerals Co., Messars Hariram Dinanath, Messars Panchmahal

Mining and Industries, Messars Sitaram Sodhani, Messars Pandva Shah and Co.,

Messars United Mining Industries, Messars S.G. Bihani, Messars Phoolchand Bihani.

In Talwara localities the leaseholders were Messars Daulatram Nandlal, Messars

Moolchand Suganchand, Messars Sitaram Sodhani.

1.11 Purpose of the study

Manganese metallogenesis in the present study area has never been studied in a

complete scientific and modern technological approach. The manganese ore genesis

on earth since Precambrian has been a long and outstanding debate among the

geologists and economists. Previous workers like Fermor (1909), Mahadevan and Rao

(1956), Krishna Rao (1956a, 1963a, 1963b 1964), Dasgupta (1965), Krishna Rao and

Raju (1966), Krishna Rao and Venkataramaraju (1966), Rao (1981, 2000), Siddiquie

(1986, 2000, 2001, 2003, 2004), Siddiquie and Raza (1990a and 2008), Dasgupta et

al. (1993), Mukhopadhyay et al. (2005), Siddiquie and Bhat (2008, 2010), Bhat

(2013) have made logical conclusions about the Indian manganese ores, however no

experimental and philosophical work has been done so far on the manganese ores of

Banswara district, Rajasthan. Also there is no combined ore mineralogical and

geochemical data in the background of global tectonics, paleoclimate, regional and

local host geology has been interpreted for the genetic assessment of the present

24

manganese ore deposits. The present manganese ores have not attracted much

attention of the companies and the government because of the dominance of the low-

grade ores in the study area, however, the geo-scientific aspects of these ores are

interesting for present studies. A very rare mineralogical and geochemical data of

these manganese ore deposits of Banswara district, Rajasthan make it a real challenge

in the present work to carry out the research based studies to reveal the genesis, paleo-

climate and tectonic setting of these ores on the basis of field investigation, ore

mineralogy, micro-textures, major, trace, REE and isotopic data which also helpful to

describe the present deposits to any particular genetic environment. The studies are

expected to stress on the development of various mineral phases in the light of

available literature on the sedimentary, metamorphic and supergene manganese ore

minerals world over. The major and trace element studies are expected to reveal the

paleo-environmental and genetic conditions of these ores in accordance with Bonatti

et al. (1972), Choi and Hariya (1992) etc.

To develop the mineralogical phases in the original geochemical system

during the initiation of these ore minerals needs a careful examination of the ore

mineral assemblages, bulk ore geochemistry, trace elements, REE and Isotopic

studies. The research work aims at a critical assessment of the parameters that

controlled the formation, chemical composition and mineral phases of these

manganese ores through changes in physical and chemical environments. The major

and trace elements and their inter-elemental relationships are expected to reveal the

contribution of different elements from their sources in the geochemical system. The

incorporation of the selected trace elements in the present manganese ores are also

expected to reveal the different stages of the evolution of the manganese ores. The

geochemical studies of the present manganese ore deposits of Banswara district, is an

important piece of research work to serve the economic geologist entrepreneurs and

industrialists for opting the low grade manganese ores of the study area, as an

alternate mineral resource to cope up with the stress on the existing high-grade

oceanic manganese from PMN (Polymetallic Nodules) and other ores. The source

material of the deposits is also possible to be traced with the help of modern

geochemical techniques. The geochemical study of the manganese ores and the host

rocks has a regional importance in inferring the regional geological history and

tectonics on which correlation with that of the adjacent landmasses like Antarctica

25

will be useful in clearing the doubts in facies mapping, tectonic setup and paleo-

environmental and paleo-tectonic reconstruction of the region. The author is expected

to study the ores with reference to regional tectonic, lithological and structural

controls as well as field characters of the ore deposits, hand specimen features, optical

studies and geochemical studies of these ores in a carefully scientific manner to draw

some possible parallelism and frame their formation in the light of previous studies of

the manganese ores world over.

1.12 Literature Review

As earlier mentioned that Manganese metallogenesis in the present area has

never been studied in a complete scientific and modern technological approach

therefore author also reviewed literature related to manganese ores of important

deposits of India (Madhya Pradesh, Maharashtra and other manganese deposits). Only

a few worker of Geological Survey of India such as Mallet (1887), Fermor (1909),

Heron (1935), Gupta and Mukherjee (1938), Dunn (1942), Roy (1957), Mukherjee

and Kapoor (1960), Rasul and Khan (1963), Sinha (1980), Babel (1985), Sukhwal and

Dixit (2000), Joshi and Jangid (2008, 2009) worked on manganese ores potentialities

of the area and provide his conclusions on occurrence of manganese in the area. In all

the worker only Roy (1957) done a detailed work on description (Occurrence, reserve,

production and mining) of some deposits with few elemental composition. The

deposit was first discover by Mallet (1887) in Udaipur district (Cited by Roy, 1957)

then Fermor (1909) referred the discovery of manganese in various localities of

Banswara district. Gupta (1934) and Gupta and Mukherjee (1938) worked on the

regional geology of district which comprise Deccan traps, Aravalli and Pre-Aravalli

banded gneissic complex. In which Aravalli are constituted a basal quartzitic

formation, calcareous facies and argillaceous series. He mentioned various manganese

ore deposits occurred in Panchmahal state, Jhabua state, Chota Udaipur and Narukot

state (Rewa Khanta States Agency). These deposits occurred in association with

metamorphosed Aravalli schist and quartzite of the area. But he did not mentioned

Banswara manganese ores in his work. Roy (1957) confirmed that manganiferous

beds are confined to the argillaceous and calcareous facies. These manganiferous beds

comprise phyllite, quartzite, schist and limestone, etc., and generally strike between

N-S and NNW-SSE with fairly steep or vertical dips, marked a series of highly folded

26

argillaceous and calcareous suite of rocks (Dunn,1942; Roy, 1957; Mukherjee and

Kapoor,1960; Sinha,1980). The ore occurs as thin beds, lenticels and stringers,

interbedded with the associated phyllite and quartzite (Mukherjee and Kapoor,1960).

These manganese ores bands occurred in the present study area was separated from

each other by a zone of calcareous rocks containing thin bands of chert and quartzite.

According to Roy (1957), chemically the manganese ores are low in iron and high in

silica and generally within the limit of phosphorous and alumina content. Barium

concentration is very high in the manganese ores and not considered as objectionable

for the manufacture for the manganese ores. The average concentration of Mn content

in the study area with specific localities are; Tambesara (40-45%), Kalakhunta and

Sivnia (38-40%), Talwara (44%). According to Roy (1957) ore bodies occurring as

bedded deposits or as irregular veins in Banswara manganese belt while the

manganese ore deposits of Talwara clearly suggested solution effects in the

ferruginous limestone. This probably shows local leaching and infiltration of ground

water (Rasul and Khan, 1963; Sinha, 1980). According to Roy (1957) the ore bodies

do not show any characteristic suite of minerals of the gondite, i.e., spessartite,

rhodonite, etc., or of the Kodurite group, i.e., quartz-orthoclase rock, potash feldspar,

spandite and manganese pyroxenite. Apart from simple oxide with its hydrated

derivatives and some silicates (Braunite and wad), no other manganese silicates and

other manganese compounds, associated with the gonditic types derived from high-

grade metamorphism of manganiferous sediments, are present. This represents the

absence of marked thermal or regional metamorphism in the manganiferous belts in

the Aravalli of Udaipur and Banswara (Roy, 1957).The mammillary or colloform

varieties of ore indicate that the ore solutions have probably originated from colloidal

solutions and the meteoric waters must have played an important role in concentrating

the manganese-ore deposits. As such, highly inclined or folded beds and strata on a

hill or hill slope would be mostly effected by them thus favoring concentration at

greater depths and resulting in better grade and deeper ore bodies. In case of gently

inclined beds there would be a concentration of relatively large spreads of low-grade

ore within a shallow depth. This aspect has been clearly elucidated by Spencer (1948)

in the manganese-ore deposits in Keonjhar, Odisha. Roy (1957) expressed that if the

view of concentration of manganese ores by meteoric waters is accepted, the deposits

are likely to continue at greater depths, judging from their mode of occurrence.

Another view about origin of manganese deposits in this area that they are derived

27

from metasomatic replacement of the phyllite and quartzite by manganese bearing

meteoric solution mentioned in (I.B.M. Minerals Year Book, 2015). Some author and

agencies have different view of the origin of deposits, Dunn (1942) proposed the

deposits and associated rocks are identical with gondites of Madhya Pradesh and are

similar to those of Jhabua district which are also in a lower grade of metamorphic

rocks. Rasul and Khan (1963) expressed that the nature of manganese ores in Talwara

village, their mode of occurrence and structural relation to the host rocks undoubtedly

suggest that the ores are of epigenetic origin. The manganese bearing solution

introduced by meteoric water deposited them largely in solution cavities and pockets

after circulating through the crushed zone, fissures and joints in the limestone and

therefore these deposits are different in origin from those occurring in Sausar series in

the Nagpur and Bhandara district (Hayden, 1921). G.S.I. also classified the

manganese ore deposits of study area as syngenetic gonditic type and described that

the deposits are equivalent and extensions of Madhya Pradesh-Maharashtra

manganese deposits. Gupta and Mukherjee (1938) proposed geology of the study area

in his work ("The Geology of Gujarat and Southern Rajputana") and proposed general

stratigraphy of the area. The rocks of the study area belongs to Lunavada group of

Aravalli Supergroup of Paleo-Proterozoic age and manganese occurrence belongs to

Kalinjara formation of Lunavada group (Mukherjee and Kapoor, 1960; Gadhadharan,

1978; Sinha, 1980).The manganese associated rocks are phyllite, quartzite, schist and

limestone. The rocks of the study area were subjected to low-grade regional

metamorphism during which P-T conditions crossed the biotite isograd (Garg, 1973;

Gadhadharan, 1978; Roy, 1985). The ore bodies of the study area are structurally

controlled and the area is tectonically very much disturbed. Folds of various

generation could be easily identified. Bedding is well preserved in conglomerate,

quartzite, sandstone and manganese bearing horizons and the other planar structures

are schistosity and crenulations cleavage (Sinha, 1980). No faults of any great

magnitude have been encountered in the area except some dip and slip faults with

small displacement in west of Banswara-Dohad main road (Mukherjee and Kapoor,

1960). As mineralization of manganese bands took place along the foliation planes of

phyllite seems to indicate that the mineralization occurred along the shear zone and

such zones provide channels for circulation of meteoric solution.

28

The manganese ore deposits of the present study area has very much

resemblance in respect of mineralogy of manganese ores deposits of Jhabua district,

Madhya Pradesh and Panchmahal district, Gujarat and because of lack of complete

scientific literature about the Banswara manganese deposits, the author deeply

reviewed the literature published on manganese ores of other important deposits by

various authors such as geology, mineralogy and genesis of manganese ore deposits

of Jhabua district by Nayak (1961, 1966 and 1969), Geology of the manganese ore

deposits of Bilaspur district, Madhya Pradesh by Sinha (1963), the manganese ores of

Gujarat states by (Rasul, 1964). The author also reviewed the thesis of Iqballuddin

(1984) and Mamtani (1998) related to the present study area directly or indirectly and

the literature provided significant assistance in present research work. The other

important manganese ores literature of world reviewed by author viz. (Fermor, 1906,

1908, 1917, 1922, 1926, 1932, 1936, 1938; Roy, 1958, 1959, 1960, 1961, 1962, 1963,

1964a, 1964b, 1965, 1966, 1968,1969, 1970, 1981, 1984, 1988, 1990, 1992, 1997,

2000; Roy, 1973, 1976; Siddiquie, 1986, 1988, 2000, 2003, 2004; Siddiquie and Raza,

2008; Siddiquie and Bhat, 2008, 2010; Siddiquie and Shaif, 2015; Siddiquie et al.,

2015a, 2015b, 2015c). In respect of geochemistry the author reviewed literature

published by Goldschmidt (1937, 1954), Rankama and Sahama (1950), Wager and

Mitchell (1951), Mookherjee (1961), Vinogradov (1962), Krauskopf (1967), Piper

(1974), Halbach (1975), Toth (1980), Hallbach et al. (1981), Zantop (1981), Taylor

and Mclenan (1981, 1985, 1995), Klinkhammer et al. (1983), Glasby et al. (1987),

Peters (1988), Wonder et al. (1988), Wronkiewicz and Condie (1989), Flohar and

Huebner (1992), Nicholson (1992a), Varentsov (1995), Wilde et al. (1996), Hayashi

et al. (1997), Usui and Someya (1997), Nicholson and Eley (1997), Koc et al. (2000),

Xie et al. (2006), Mishra et al. (2007), Fu et al. (2010a, 2010b), Oksuz (2011), and

several other important published materials to do a systematic and good scientific

work on Banswara manganese ore deposits.

29

CHAPTER-2

GEOLOGICAL SETTING

2.1 Introduction

The Indian shield reveals an immense geological and metallogenic history of

Precambrian times. Among these the Banswara district host a number of non metallic

and metallic minerals deposits which were actively mined in past and presently also,

and mining in progress by government or private organizations. Among these the

most productive belt is Banswara manganese belt (Fig. 2.1) situated in the southern

most part of Rajasthan state. The manganese deposits of study area occurred in

argillaceous and calcareous series belongs to Lunavada Group of Aravalli

Supergroup. The Precambrian sedimentary basins of Peninsular India were evolved

on four major Archaean cratonic nuclei i.e. Dharwar, Bastar, Singhbhum and

Aravalli-Bundelkhand (Mazumdar and Eriksson, 2015). In all of these cratonic nuclie,

the northern Indian block which is represented by Aravalli craton in west, has its own

importance. The basic stratigraphic framework of Precambrian geology in the

Aravalli terrain and adjoining areas covering Rajasthan and Gujarat were first

developed by Heron (1917a, b, 1923, 1936), Coulson (1933), Gupta (1934), Gupta

and Mukherjee (1938). Blanford (1869) was the first who investigate the geology of

western India and classified rocks of Aravalli mountain range under Vindhyan series,

Bijawar series, Champaner series and metamorphic gneiss. The western part of the

Indian shield which is covering Rajasthan and Gujarat is represented by the

interesting geological assemblage with profusion of mineral deposits.

The Precambrian stratigraphy of southern Rajasthan and northeastern Gujarat

can be assigned to the Bhilwara (>2500 Ma), Aravalli (2500 Ma to 2000 Ma) and

Delhi (2000Ma to 700Ma) geological cycles on the basis of environment of deposition

and tectonothermal magmatic events (Gupta et al., 1980 and 1997). In Rajasthan state

the oldest rocks belongs to 3.3-2.5Ga Banded Gneissic Complex (Heron, 1953) over

which successive metasedimentary and metavolcanic succesions were deposited. The

excellent work of Heron (1953) in Precambrians of Aravalli mountain belt remained

the basis of all stratigraphic and structural revisions till date.

30

Fig. 2.1 Simplified geological map of Banswara Manganese belt, Banswara district,

Rajasthan (after G.S.I., 2005).

The Aravalli Supergroup (Focus of current study) is exposed in the southern

and southern-eastern parts of the Aravalli craton and represent a volcano-sedimentary

accumulation in shelf-like environment (Roy, 1988). There is a confliction in

stratigraphic succession of Aravalli Supergroup from the beginning and changed from

time to time by the workers. A series of modifications in Heron (1953) stratigraphy

31

"who explained Precambrians of Aravalli mountain belt", from beginning to present is

still continue between different authors. Apart from confliction, the two major

research group Roy (1988) and Gupta et al. (1997) broadly recognize three major

events in the development of Aravalli basin (Fareeduddin et al., 2012; Mukherjee et

al., 2016) (i) outpouring of mafic/ultramafic lavas during the initial development of

the Aravalli basin (Delwara volcanic rocks in the Debari Group) (ii) extensive

development of platformal sedimentary sequences during the main basin formation

event (Jaisamand, Berwas-Mukandpura, and Jhamarkotra-Jagpura Formations of

Debari Group) and (iii) deepening of the Aravalli basin and development of deep sea

sedimentary facies towards the west (Jharol Group). In the modified classification

Roy (1988), Roy and Kroner (1996) include the Mewar Gneissic Complex as a true

basement over which metasediments of Aravallis and Delhi system deposited

successively (Table 2.2), According to Crawford (1970), Naha and Halyburton

(1974), Sen (1983), Naha and Roy (1983), Choudhary et al. (1984), Sinha-Roy

(1984), Roy et al. (1984), Roy (1985) and Roy et al. (1988), the rocks of Aravalli

Supergroup (Paleo-Proterozoic) and Delhi Supergroup (Meso-Proterozoic) deposited

due to rifting of BGC. The Aravalli Supergroup has been divided into lower, middle

and upper groups by Roy et al. (2005) or as Delwara (lower Aravalli Supergroup),

Debari (middle Aravalli Supergroup) and Jharol (upper Aravalli Supergroup) by

Sinha-Roy et al. (1998). The Aravalli Supergroup shows two contrasting lithofacies in

which one belongs to shale – sand carbonate assemblages of shore shelf (lower and

middle Aravalli Supergroup) facies and other is carbonate free of deep sea facies

(upper Aravalli Supergroup) (Roy and Paliwal, 1981, Roy and Jhakhar, 2002).

Roy (1988) classified Aravalli Supergroup of rocks in to three contiguous

sectors where they are occurred in terrain: North-Eastern Bhilwara sector, Central

Udaipur sector and Southern Lunavada sector. The present study area lies in the

Lunavada sector. According to Roy and Jhakhar (2002) in the Lunavada sector most

of the workers like Gupta (1934), Gupta and Mukherjee (1938) and Gupta et al.

(1980) seem to agree on the extent and distribution of lithostratigraphic units;

although confusions prevail in regard to the interpretation of geology, primarily due to

the extremely complex deformation pattern that characterize the region. The southern

Lunavada sector is the continuation of the central Udaipur sector without having any

stratigraphic-tectonic break and different lithologies, which occur in the Udaipur

32

sector, also continue into the Lunavada sector (Roy and Jhakhar, 2002). Roy (1988)

interpreted carbonaceous phyllite and manganese bearing dolomite in Jhamarkotra

formation (Resulted due to rapid changes in facies) in the lithostratigraphic column of

Aravalli Supergroup (Roy and Jhakhar, 2002). The rocks of supracrustals have

undergone three main phases of folding (Naha and Halyburton, 1974), in which first

phase showing easterly and westerly plunge first generation reclined or inclined folds,

second phase of folding belongs to steeply inclined axial planes with complex

geometry from isoclinal to open folds. And the earlier folds complexly refolded with

EW or WNW-ESE striking sub vertical axial plane during last phase of folding

(Fareeduddin et. al., 2012). The Aravallis have gone polyphase deformation and

recrystallised under regional metamorphism of greenschist facies that reached up to

amphibolite facies (Sharma, 1988).

The Precambrian stratigraphic succession of AMB is further modified by

Gupta et al. (1992) and presented a modified classification of Aravalli Supergroup

(Lower Proterozoic) of south-western Rajasthan and north-eastern Gujarat. The author

followed this stratigraphic succession in the present work. According to Gupta et al.

(1997) in the eastern side Aravallis is bounded by Bhilwara Supergroup while in west

overlain by Delhi system and southern-eastern part covered by Deccan Trap and

Alluvium. According to Gupta et al. (1997) classification, the base of the Aravalli

Supergroup belongs to Debari group, followed by Udaipur, Bari lake, Jharol,

Intrusive, Lunavada and Champaner groups respectively.

Apart from above theory, lots of pioneer worker did classic work on Aravallis

of Rajasthan viz, Heron (1917a, 1936, 1953), Fermor (1930, 1936), Gupta (1934),

Gupta and Mookherjee (1938), Poddar (1966, 1965), Naha et al. (1969), Raja Rao et

al. (1971), Roy et al. (1971, 1980, 1981, 1984, 1985, 1988, 2005), Roy (1973, 1976,

1978, 1985, 1988, 1990, 1991, 2000a), Naha and Hallyburton (1974b, 1977), Raja

Rao (1976), Sychanthavong et al. (1977, 1981), Gupta et al. (1980, 1995a, 1995b,

1997), Hacket (1881, 1889), Naha and Roy (1983), Sarkar (1983), Sen (1983), Sinha

and Roy (1984b), Powar and Patwardhan (1984), Mohanty and Naha (1986), Nagori

(1988), Sharma (1988), Sharma et al. (1988), Sinha Roy et al. (1992), Raza and Khan

(1993a, 1993b), Golani et al. (1999), Golani and Pandit (1999), Mamtani (1999a,

1999b, 2000), Raza et al. (2001), and Roy and Purohit (2015) instead of this, a very

few workers worked in detail in southern Rajasthan.

33

2.2 Regional Geology of Banswara District

The regional geology of Banswara district comprises Deccan traps, Aravallis

and Pre-Aravalli banded gneissic complex presented in (Table 2.1) (Gupta, 1934;

Sukhwal and Dixit 2000; Joshi and Jangid, 2008; Joshi and Jangid, 2009) and the

manganiferous beds hosted in Aravallis only. The oldest rocks belonging to the

Mangalwar complex (Table 2.3). These rocks overlain by the rocks of Aravalli

Supergroup (Lower Proterozoic), which have been grouped under Debari, Udaipur

and Lunavada groups in decreasing order of antiquity. The Debari group is

represented by quartzite, dolomite, meta-volcanics, schist etc., followed by Udaipur

group which represented by phyllite, quartzite, meta-conglomerate and dolomite etc.

The overlying Lunavada group of rocks exposed in south-western part of the

Banswara district, represented by phyllite, mica schist, meta-subgreywacke, quartzite

and manganiferous phyllite, etc. The above mentioned Archaen-lower Proterozoic

rocks, in the eastern part of the district are overlain by Deccan traps (Cretaceous to

Eocene) which are considered to have erupted from several fissures in earth crust's

about 65 million year ago (Source: DRM, GSI, 1983 Database). Infratrappean Bagh

formation comprising limestone, sandstone and conglomerate occurred in SW of Ram

ka Munna.

Table 2.1 Generalized Geological Succession of Banswara district, Rajasthan

(Hydrogeological Atlas of Rajasthan, Banswara district, 2013).

Age Lithology

Recent to sub Recent Kankar, soil, conglomerates.

Upper Cretaceous to Paleocene extrusive Deccan trap/basalt.

Post Aravalli Intrusive Granite, pegmatites, quartz veins,

amphibolite

Aravalli Supergroup

Phyllite, greywacke, schist, meta-volcanic,

dolomite, marble, limestone, gneisses,

quartzite.

Pre Aravalli's (Bhilwara Supergroup) Schist and gneisses (B.G.C.)

2.2.1 Mangalwar Complex (Bhilwara Supergroup)

The oldest Archaean rocks in Banswara district belonging to Mangalwar

complex of Bhilwara Supergroup exposed along the bank of Mahi river in the north of

Banswara district and chiefly composed migmatite, composite gneiss, schist etc. The

34

gneiss in the study area belongs to a highly metamorphosed and injected facies of

Aravalli schist and the interfoliar injection of granite and pegmatite intrusives in this

schist which is responsible for the formation of these gneisses granite.

2.2.2 Debari Group

The Debari group is represented by quartzite, dolomite, marble, basic

metavolcanics, quartz-chlorite schist and garnetiferous biotite schist etc., in the

Jagpura, Bhukia, Dagal, Jharkha, Khamera, Ghatol and Bhongra villages of Banswara

district. The basic metavolcanic rocks are hard, massive and layered in nature while

the schistose rocks are soft and foliated in this area.

2.2.3 Udaipur Group

Lithologically, the Udaipur Group comprises a thick pile of phyllite,

metagreywacke, feldspathic mica schist and migmatite with intercalatory bands of

greywacke, conglomeratic quartzite, dolomite, gritty dolomite, dolomitic marble,

oligomictic conglomerate, phosphatic and stromatolitic dolomite, chert and amphibole

schists with three different types of phyllite viz.: carbonaceous, manganiferous and

ferruginous. While the important rock types of Udaipur group which found in

Banswara district are para-gneisses, para-amphibolites, feldspathised schist, mica

schist, marble, quartzite, phyllite, dolomite and conglomerate. These lithological units

occurring in the Banswara region presumably the continuation of central Udaipur

sector (Roy and Jhakhar, 2002). The phyllite and schist are highly foliated and having

easily crumbled under the attack of weathering agencies and are very prone to lie

buried under the debris derived from their own disintegration (Gupta and Mukherjee,

1938). The dominant areas where the Udaipur group of rocks occurred are

Bhamanpara, Ghariala, Motagaon, Loharia, Tomatia and Talwara villages.

2.2.4 Intrusives

An intergenous assemblage of metasediments and intrusives comprising

gneisses, schist, quartzite, dolomitic marble, amphibolite, pegmatite and granite

showing intimate association and intermixture were examined in the area around

Banswara district. Gneisses generally form low lying valleys in the area and at places

near traps they form high hills.

35

2.2.4.1 Granite

The intrusions of granite in gneiss, amphibolite and calc-silicates rocks are

seen at many places in the district. They are emplaced during different phases of

igneous activity and occurred as very small bodies which are not mappable. Some

exposure also seen near Ghatol area which are lying in region of thick forest. The

primary structures are totally invisible and this may be due to the intense deformation.

2.2.4.2 Granite Gneiss

Gneiss and granite outcrops occupying major area near Gagri, Nal, Padla,

Samaipura villages of Banswara district. They generally form low lying valleys in the

area. Granite, which is coarse grained is found near Garnawat. In Nawagaon area

appearance of composite gneiss with dark brown biotite rich bands have been noticed.

2.2.4.3 Amphibolite

Amphibolite occurs at number of places in the area, varying in length from 1

m to about 300 m. It occurs as isolated outcrops forming low hummocks and short

strike ridges. The size of the outcrop perhaps reflect the size of the amphibolite

bodies. At places amphibolite has been observed in the well sections in the granite

terrain. Prominent outcrops have been observed near Surapura, Gargi and south of

Banswara near Jagmeri mal. The amphibolite is dark green with medium to coarse

grained texture and generally massive but at places foliated.

2.2.4.4 Quartz Vein

Quartz veins, milky white to bluish white in color, traverses in all the rock

types. They are generally parallel to the foliation of the host rocks.

2.2.5 Lunavada Group

The rocks of Lunavada group dominantly scattered in SW side of the

Banswara district. The rocks are frequently found in Garhi, Talwara, Anjana,

Shergarh, Ram Ka Munna, Sallopat, Dungra, Wagidora, Kalinjara, Gararia, Sivnia,

Kalakhunta, Ghatia, Sagwa, Itala, Tambesara, Pali Bari and Ratimauri areas. The

Lunavada group has been subdivided by Gupta et al. (l997) into the Kalinjara, the

36

Wagidora, the Bhawanpura, the Chandanwara, the Bhukia and the Kadana formations

presented in (Table 2.2). An assemblage of molasses-like sediments deposited in a

widespread basin in the northern parts of Gujarat and southern Rajasthan has been

designated as the Lunavada Group by Gupta et al. (1997). The predominant rock

types of the Lunavada Group are phyllite, metasubgreywacke, quartz chlorite schist

and quartzite with subordinate dolomitic limestone, polymictic conglomerate,

manganiferous phyllite and phosphatic algal dolomite. The rocks have been affected

by at least two phases of deformation and were metamorphosed under greenschist

facies conditions.

2.2.5.1 Kalinjara Formation

The formation has been named due to the nearby Kalinjara town. The rocks of

the formation occurred along Haran river, Banswara-Jhalod road, Kalinjara, Sallopat

and near Anas Railway Station in the south etc. The formation comprises dominantly

of an intimate association of phyllite, feldspathic mica schist with subordinate meta-

subgreywacke and hosting the manganese deposits of study area. Besides this

quartzite, dolomite and petromictic conglomerate, manganiferous phyllite is also

present within the Kalinjara Formation.

Table 2.2 Lithostratigraphic succession of Lunavada group. (After Gupta et al., 1980;

1992)

Formation Lithology

Bhukia Meta-protoquartzite

Chandanwara Meta-subgreywacke

Bhawanpura Quartz-chlorite-sericite Schist

Nahahi Quartzite and Garnetiferous-quartz-sericite-biotite schist

Wardia Garnetiferous quartz-sericite-biotite schist with intercalations of

para-amphibolite, amphibole quartzite and injections of pegmatite

Wagidora Meta-subgreywacke and Quartz-biotite-sericite schist

Kalinjara Meta-subgreywacke, Manganiferous phyllites, Meta-semipelite,

Petromictic conglomerate and Quartz-biotite-sericite schist

Unconformity

Udaipur Group

37

The metasedimentary rocks of the formation i.e. phyllite, mica schist and

meta-subgreywackes are mostly occurred as a sub crop beneath the soil cover and

altered into phyllite and garnetiferous schist in the northern side of the area. The

quartzite occurs as intercalatory bands within phyllite and quartzite while schist are

common in the Kalinjara formation. Near Sallopat locality in Banswara district the

rocks developed in association with the dolomite and impure calcareous

metasediments with brown to grey color. Dolomite is present in the east of Banswara

manganese belt and south-east of Kalinjara with several other localities in the district.

The dolomite occurs in both form as an intercalation and as isolated outcrop. The

dolomitic limestone is pinkish in color near Chinch with medium to coarse grained

texture. In south-eastern side the outcrop covered by traps. Near Marh and Narpura,

outcrop of dolomite with intercalation of chert and carbonaceous phyllite is occurred.

In Sallopat the dolomite is mostly stromatolitic and occasionally phosphatic. Barman

(1974) recorded Baicalia, B. prima. Collonella discreta, Kussiella kussiensis, Minjaria

calocotata as stromatolite biota. Prominent development of conglomerate horizon is

seen in the area between Kalinjara and Kushalgarh and it is also well exposed in

Makri, Borbhator, Wagidora, Padla, Masa, Andeshwar, Chotipali, near Haran river,

striking NNW-SSE and Kalinjara etc., in the district. The petromict conglomerate

with some oligomictic conglomerate outcrop is also present as lenticular bands within

the Kalinjara Formation.

2.2.6 Infratrappean

The infratrappean formations exposed in the district which are protruding

from below the Deccan traps near Ram ka Munna and Dungra. Generally they are thin

and in lenticular bodies where they are forming highly uneven eroded horizontal

cover for ancient metamorphics. The thickness also varying place to place. The

Lameta and Bagh formation only found in the Banswara district. The Bagh formation

comprising limestone, sandstone and conglomerate which are occurring in the SW of

Ram ka Munna, and the Lameta occurring around the Kushalgarh-Banswara frontier.

In southwards of Dungra, the Lameta beds overlying the Aravallis which are

composed of impure massive limestone with a thickness about 10ft. The limestone

comprising pebbles of quartz and chalcedony.

38

2.2.7 Deccan Trap

The Deccan Traps (Cretaceous to Eocene) covering an area of about 10,435 sq

km in south-east Rajasthan and a large part of Banswara district. They occurred in

south-southeast of Chittorgarh-Banswara sector and constitute flat topped plateaus

and isolated hills. In Chittorgarh-Banswara sector they are striking in N-S with a

scarp on the west and overlying Aravalli Supergroup. In the west of Kushalgarh

perfect columnar traps have developed and near Bohen the flows showing some

layering. Unfossiliferous infratrappean (clay) is present around Kushalgarh and

Barodia while infratrappean (limestone) bed is reported from Ram ka Munna in

Banswara district. No sign of major deformation is recorded although, columnar

joints, sheet joints, vesicles and amygdules are common.

2.3 Regional Structures of Lunavada rocks

According to Gupta et al. (1997) the rocks of Lunavada group occurred in

Banswara district corresponding to AF3 and AF4 deformation episodes without

earlier deformational episodes. The axial traces of F2 overturned synform and

antiform folds also lies near Talwara localities. The deformation related to AF3 is

dominant in eastern part of the area (Kalinjara) and with NW-SE trend, which also

determines the spatial disposition of manganese belt of Banswara district. And AF4

deformation episode is dominant in the central part near Anas river with an E-W axis.

Major faulting is very rare in the district except minor structural disturbances near

Ram Ka Munna. A major antiform between Kushalgarh and Wasla described by

Mukherjee and Kapoor (1960) which is tightly folded with conglomerate at the core.

Near Kushalgarh another fold is overturned to the E and axial plane dipping in WSW

direction. The entire belt of the Aravalli Supergroup in the Udaipur and Lunavada

sectors is characterized by a low to very low grade of metamorphism (Roy, 1988;

Sharma, 1988).

2.4 Geological Setting of the Study Area

The geological map of study area is presented in (Fig. 2.2). The manganese

belt starts from 150 m west of Haran river and extends in a ESE direction for about 5

km where it takes a swing in SE direction between Kalakhunta and Bhakhri and

continuous in SE direction from Timamaudi to Ratimauri. A part of the belt may be

39

concealed under soil and Deccan trap between Bhakhri and Timamahudi, Rangi to

Rupakhera and farther about 2 km SE of Ratimauri village. Geologically the area

comprises Lunavada group of rocks and Deccan traps. The earlier workers and

Geological Survey of India reported that the manganiferous phyllite which hosted

chiefly the manganese ores of Banswara district occurred in Kalinjara formation of

Lunavada group. And this Lunavada group is one of the younger group of Aravalli

Supergroup (Gupta et al., 1980, 1992 and 1995).

Table 2.3 Stratigraphic succession of Banswara district, Rajasthan (Source, DRM, GSI,

1983 Database).

Age Supergroup Group/Formation Lithology

Cretaceous

to Eocene Deccan Traps

Aa, Pahoehoe, simple and

compound basaltic flows

Cretaceous Bagh Formation Limestone, nodular limestone,

sandstone, conglomerate

Lower

Proterozoic

Aravalli

Supergroup

Lunavada Group

Meta-subgreywacke, mica schist

Meta-subgreywacke, quartzite

Quartz chlorite schist, quartzite

Meta-subgreywacke, mica schist,

quartzite

Phyllite, meta-subgreywacke, mica

schist, quartzite, dolomite, meta-

conglomerate, manganiferous

phyllite

Intrusive Granite, granite gneiss

Udaipur Group

Para-gneiss, Feldspathised

schist,para-amphibolite,

mica schist, marble,

quartzite

Phyllite, mica schist,

Feldspathised mica schist,

quartzite, dolomite, conglomerate

Debari Group

Quartz chlorite schist,

garnetiferous biotite schist,

quartzite, dolomite

Phyllite, carbonaceous phyllite,

mica schist, quartzite, dolomite

Basic Metavolcanic, marble,

quartzite

Quartzite

Archean Bhilwara

Supergroup

Mangalwar

Complex

Migmatite, Composite gneiss,

Feldspathised schist

40

The manganiferous beds consist Aravalli phyllites, quartzites, schists and

limestone etc., indicating a series of highly folded argillaceous and calcareous suit of

rocks (Roy, 1957). They generally strike N-S and NNW-SSE with fairly steep or

vertical dips. And these Precambrian metasediments belongs to Aravalli Supergroup of

Paleo-Proterozoic age.

Table 2.4 Stratigraphic sequence of the study area (After Mukherjee and Kapoor, 1960;

Sinha, 1980)

6. Alluvium

5. Deccan trap

4. Granite, pegmatite and vein quartz

3. Ultrabasic rock

2. Aravalli system

Unconformity

1. Granite gneiss with minor bands of amphibolites and pyroxene granulite.

Aravalli Further Subdivisions

III. Metamorphosed argillaceous

suite of rocks with arenaceous

intercalations :

(vi) Mica schist and phyllite

(v) Thinly interbedded phyllite and quartzite,

ferruginous phyllite containing bedded

manganese ores.

(iv) Mica schist and phyllite

(iii) Quartzite and conglomerate

(ii) Mica schist

(i) Coarse gritty schist containing lenses of

conglomerate and quartzite, black

schist(Manganiferous) and minor lenses of

diopside tremolite schist and hornblende schist.

II. Crystalline limestone : Pure and impure facies with a thin epidote rich

Band.

I. Conglomerate : Orthoquartzite and polymictite.

The manganiferous beds and associated rocks suffered greatly by intense

deformation phases resulting in to co-folded ores deposits. The rocks in the study area

have undergone from greenschist to lower amphibolite facies of metamorphism

(Sharma et al., 1988 and Mamtani, 1998). Various prominent structures like

ptygmatic folding, lineation and joint sets etc., are present in the study area and they

41

are controlling the manganese mineralization too. The earlier worker like Mukherjee

and Kapoor (1960), Sinha (1980) provide tentative stratigraphy of the area and later

G.S.I. proposed a complete stratigraphic succession of the study area, that discussed

in (Table 2.3). According to Mukherjee and Kapoor (1960) the study area comprises

granite gneiss with minor bands of amphibolite and pyroxene granulite as a basement

over which Aravalli metasediments and post Aravalli intrusives and younger

creatceous flows resting (Table 2.4). These Aravalli metasediments and basement

rocks is separated from an unconformity. The manganese belt at many places may be

hidden under soil and Deccan trap in between Bakhri, Kheria, Rupakhera and farther

1.5 km southeast of Ratimauri. The Aravalli metasediments further divided as

conglomerate in base, followed by crystalline limestone and finally metamorphosed

argillaceous suit of rocks with arenaceous intercalations (Mukherjee and Kapoor,

1960).

The manganese bearing lithounits are interbedded with micaceous schist and

phyllite, and these form the top most metamorphosed Aravalli argillites (Sinha, 1980).

The conglomerate and quartzite band running almost parallel to the manganese belt

for about 15 km to 0.5 km in NE of the manganese-bearing horizon. The schist is well

developed in the area and also associated with manganese ores belt of Banswara

district. The pelitic rocks with which the manganese ores of Banswara are spatially

and genetically associated have been mapped as manganiferous phyllite by Gupta et

al. (1997). The manganese ores associated rocks covering a length of about 20 km

with varying width (1-12 m) from Gararia to Ratimauri localities in Banswara district.

The thickness of stratified manganese ores also varying place to place with highly

folded minor thin bands ( 1 - 2 mm) to thick bands of around 8-10 cm. The ores are

interbedded in a repetitive sequence with pelitic and psammitic rocks throughout the

belt (Mukherjee and Kapoor, 1960; Sinha, 1980; Gupta et al., 1997). The thin layers

of chert are also closely associated with the repetitive sequence. The manganese ores

associated with the rocks referred as strata bound and is characterized by high content

of silica, low sulphur and phosphorous (Roy,1957 and Gupta et al., 1997).

On the basis of field evidence, Sinha (1980) proposed a revised stratigraphic

sequence. According to him base is not seen around the study area and followed by

coarse gritty schist intercalated with lenses of conglomerate and black schist. He

42

described a disconformity which separate mica-schist and phyllite to manganese

bearing horizon. And also an unconformity which separates manganese bearing

horizon to younger strata in the succession. The manganese ores in the area are

occurring in thin or thick beds, lenticles and stringers, interbedded with phyllite and

quartzite. They are occurred in pinching and swelling veins too. The ores occurs in

two closely spaced respective horizons in association of phyllite and separated from

each other by a zone of calcareous rocks contain thin bands of quartzite and chert. The

most persistent horizon containing thin bands of manganese, generally two inches to

less than one inch thick, is interbedded with phyllites and quartzites running all along

the mineralized zone between Gararia and Ratimauri localities.

The other horizon confined near Bakhri, Tambesara, Kheria and Rupakhera

where it is associated with ferruginous phyllites. The different sections of manganese

belt are as follows:



2.4.3 Sagwa-Itala Section



2.4.6 Talwara Area


Geologically area includes Lunavada group of Aravalli Supergroup and

Deccan traps of Cretaceous age. The section exposed between Haran river in the west

and Banswara-Dohad main road in the east. The ores are associated with phyllite in

bedded form and also occurring as thin bands within folded sequence of thinly

interbedded phyllites and quartzites (Fig. 2.3A, D) (Joshi and Jangid, 2009).The

mineralization took place along the shear zone and foliation plane. The general trend

of rocks is N240-310 with dipping 600-640 SW. The manganiferous phyllite in the area

is grayish black in color with metallic nature. The ore bodies just 2 to 5 meter below

from the earth surface.

43

Fig. 2.2 Geological map of study area (Source: DRM, G.S.I., 1983 Database).


The section extending from the main Banswara-Dohad road up to Sagwa to

the SE. The ore zone forms a series of WNW-ESE striking low mounds and ridges

rising up to 40-50 ft above the country rocks. This zone has been tightly folded along

with the associated phyllite and quartzite. The beds dip upwards SW at the angle of

600. It is covered by soil burden up to 5-7ft. Geologically area includes Lunavada

group of Aravalli Supergroup and Deccan traps of Cretaceous age. The ores are

tightly folded along with associated phyllite and quartzite in bedded form (Sinha,

1980). The mineralization took place here along the foliation plane of phyllite. The

manganiferous phyllite is dipping 330-610 SW. This manganiferous phyllite in the

area in range of various shades like pink and grayish white color (Fig. 2.5, 2.6).

44

2.4.3 Sagwa-Itala-Bhakri Section

The section lies around Itala-Bhakri villages in Kushalgarh tehsil of Banswara

district. The area comprises manganiferous phyllite, phyllite, dolomite and quartzites

of Lunvada group. The general dip of the rocks varies from 450 to 600 towards SW.

The ore horizon resting over phyllites and consist a wide zone of ferruginous gritty

rocks which is overlain by deep brown phyllite. The phyllite outcrop is intruded by

calcite veins and quartz veins which are common features in this area (Fig. 2.3G). The

quartzitic intercalations are also common in dolomite near Itala locality in the district

(Fig. 2.3J).There is a well developed barren zone of calcareous rock with thin bends

of chert and quartzite, veinlets of calcite and siderite are quite common in the

southern area, and this part ore horizon also comprises the interbedded phyllite and

quartzite.

2.4.4 Tambesara- Kheria Section

The Tambesara and Kheria villages comes under tehsil Kushalgarh, district

Banswara. And geologically the area belongs to Lunavada groups of Aravalli

Supergroup. It is represented by phyllite, manganiferous phyllite, meta-subgreywacke,

mica schist and dolomite etc. The manganese ores associated with black color

phyllite. The area is also occupied by traps of Cretaceous age. The ores in Tambesara

locality are just 3-4 feet below from the earth surface (Fig. 2.3E) at many places and

indicate the most producing zone in Banswara manganese belt. The area is

tectonically very much disturbed showing complex geometry. The folds developed

here such as antiforms and synforms. The rocks formation generally striking in NW-

SE direction and dipping in SW direction. In Kheria the ores are associated with

ferruginous phyllite. In past various bands of high grade ores already mined. There is

a possibility of high grade manganese horizons at greater depth in this continuous

manganese belt.

2.4.5 Section between Rupakhera and Ratimauri

The low grade manganese ores are associated with brown color interbedded

phyllite and quartzite. Chert intercalation is common in Mn-bearing horizon. The

folded beds are dipping at high angle toward S590W. A small manganiferous chert

beds occurred around Rupakhera in which two sets of joints are present (Fig. 2.3H).

45

2.4.6 Talwara Block

The block referred as small manganese producing locality in Talwara village

of district Banswara. The manganese mining in area is abandoned in past due to small

scattered quarries and the grades were not promising at all. Geologically area

comprises Lunavada group of Aravalli Supergroup and the manganese ores are

associated with Aravalli limestone of southern Rajasthan. The limestone overlain by

phyllite, slates and underlain by quartzite and conglomerate in the study area, where

the phyllite occurring as low lying mounds and quartzite along the ridges top which is

close to Talwara village. The ores here occurred in form of scattered masses

occupying fissures, solution cavities in Aravalli limestone (Fig. 2.3I).The limestone is

crystalline and grayish black in color (Fig. 2.11). These limestones are dolomitic in

composition without structurally related to manganese ores (Rasul and Khan, 1963).

And it may be due to manganese deposition in solution cavities, fissures and joints.

2.5 Structural Setting in the Study Area

The study area is composed of complex structural pattern, such as various

types of folds, minor faults, several linear and planar features, which in support that

the area has passed away with severe deformational episodes and metamorphism. The

prevailed structures are clearly marked during field and petrographic studies. The

manganese ore deposits of the area are cofolded with the host rocks throughout the

manganese belt (Fig. 2.3A, B, C, K). The field disposition and their relation with the

country rocks reveal a major structural control on the ore deposition (Straczek and

Krishnaswamy, 1956). The main structural control of ores in the area are foliation

plane, shear zone, weak zone of phyllite and folding during tectonism and

metamorphism. Foliation plane may be the main zones for ore concentration of

manganese during supergene enrichment. The general strike of the manganiferous

beds follows the regional strike of its associated rocks. The manganese minerals are

found to occur parallel or sub-parallel along the foliation plane as well as schistosity.

The minerals are also found along joints and fractures across the strike and dip of

bedding. Structurally the area passed away from severe tectonism reported by

Mukherjee and Kapoor (1960), Sinha (1980), Roy (1985), Gupta et al. (1997).The

Regional trend of the fold axis is NW-SE, plunging at low angle towards south east.

Ptygmatic folding, antiform and synform are common in the area with secondary

46

folds generation in the interbedded phyllite and quartzite (Fig. 2.3A, B, K). According

to Gupta et al. (1997) folds presents in the study area corresponding to AF5, AF4 and

AF5 type deformational episodes (Gupta et al., 1997). The folds corresponding to AF5

are also presented in Banswara manganese belt (Gupta et al., 1997). Various open,

tight and isoclinal folds are present and associated with phyllite, quartzite and

manganiferous beds from Kalakhunta to Tambesara area where they are gently to

steeply inclined and moderately plunging. Except these folds numerous synform and

antiforms are bounded with the host rocks and with manganese ores present in the

study area. The ptygmatic folding is common in exposed interbedded phyllites and

quartzite associated with manganese ores in the active mining area like Kalakhunta,

Ghatia etc., with lots of open and tight folds. No major faulting recorded in past or

present except some dip and slip fault of minor displacement in the massive quartzite

running along the southern bank of the Haran river, west of the Banswara-Dohad

main road. In the area the bedding (Fig. 2.3D) is well preserved with manganese

bearing horizons and its associated rocks. The bedding also preserved well in Talwara

manganese locality in limestone. The other planar structures are schistosity and

crenulation cleavages well recorded in the study area (Fig. 2.3F). The cross-

crenulations well exemplified in the manganese ores quarries. At some places bedding

is also parallel to the schistosity on limbs, whereas it makes high angle near hinge of

fold. The joint sets which are commonly observed in the study area are parallel to the

dip, parallel to the strike of the foliation and oblique as well as horizontal.

2.6 Description of Manganese Bearing Rocks

2.6.1 Phyllite

The rocks of the argillaceous composition are represented by phyllites

(Gadhadharan, 1978). It is the dominant rock type in Aravalli and associated well

throughout the manganese ores belt. The phyllites are varying in different shades of

color from grayish black, brown and steel grey. The rock is fine grained with shinning

surface and consist garnet crystals at some places. The phyllitic rocks are marked by

pronounced foliation. The manganese ores also associated along the foliation plane,

scattered form, in thin veins and bands. Intrusion of quartz vein and quartizitic

intercalation are common in phyllite. The dendritic pattern (Fig. 2.4, 2.8) formed by

surface water are prominent feature noticed megascopically in phyllite samples of the

47

study area. The common phyllites recognized in the study area microscopically

belong to siliceous phyllite (Fig. 2.7), manganiferous phyllite, chlorite-biotite phyllite

and muscovite phyllite (Shaif et al., 2017).

2.6.2 Schist

Generally the rocks are soft and easily weathered and most of the occurrence

under their own debris. The outcrops are usually of a crumbling and decaying nature

and yielding sandy masses. The rocks are highly foliated and foliation plane being

invariably marked manganese ore deposition (Fig. 2.9). Various forms are noticed and

well associated with manganese deposits in the study area which are garnetiferous

mica schist, quartz mica schist and muscovite-chlorite schist. Mineral assemblages

observed in schist are typical of greenschist to lower amphibolite facies (Shaif et al.,

2017). Both schist and phyllite covering more than 70 % of the belt in which only top

portion is mineralized. Schist occurs in both footwall and hanging wall side of

manganese deposits. The intercalation of quartzite is very common in schistose rocks

in the study area. Near the base the schists are generally calcareous with occasional

lenses of quartzite and conglomerate. Under thin section garnet crystals frequently

occurring in the form of clusters.

2.6.3 Quartzite

The quartzite outcrop extends from Gararia to Ratimauri throughout the

manganese belt. The quartzite are interbedded with the manganiferous phyllite (Fig.

2.10). The interbedded phyllite and quartzite outcrops with manganese horizons are

common in the study area. The quartzite are compact and crystallized with white,

grey, brown and pale pink appearance. The different rock samples are composed

predominantly of quartz with subordinate mica, feldspar, opaque ore minerals and

impurities of hematite (Iqballuddin and Negi, 1971). Sericitization and calcareous

materials also noticed in some thin sections. Thin intercalatory bands of quartzite are

very common throughout the manganese bearing horizons. Apart from manganese

belt some of the quartzite outcrops are very thick and attaining a thickness of about

several hundred feet in other parts of district.

48

2.6.4 Limestone

Calcareous rocks are frequently found in Aravalli Supergroup while the

manganese bearing limestone in the study area is mainly lying in Talwara localities.

Besides this, numerous limestone deposits present in Banswara district. The

manganese hosted limestone in Talwara belong to Aravallis and mostly dolomitic in

composition with various shades of pink and grey (Fig. 2.11). The rocks are

crystalline and having fine to coarse grained texture. The limestone beds are thick

and showing conformity with phyllites and quartzites. The impure varieties

commonly having siliceous and ferruginous veins and stringers. The red color variety

of limestone rich in hematite and limonite and sometimes its highly ferruginous in

nature. The manganese occurrence in limestone in the Talwara area happened through

meteoric water action and deposited in pockets, fissure, solution cavities and joints

(Rasul and Khan, 1963).

Fig. 2.3(A) Hand specimen showing secondary folds in thin beds of manganese ores

at Kalakhunta mine.

Fig. 2.3(B) Field photograph showing ptygmatic folding in interbedded phyllites and

manganiferous beds at Ghatia mine.

49

Fig. 2.3(C) Field photograph showing isoclinal folds in manganiferous beds at

Kalakhunta mine.

Fig. 2.3(D) Field photograph showing well preserved alternate beds of manganese

ores and phyllite in Tambesara village.

Fig. 2.3(E) Field photograph showing manganese ores association with host rocks just

3 ft' below from the earth surface.

50

Fig. 2.3(F) Hand specimen of Phyllite showing crenulations at Kalakhunta mine.

Fig. 2.3(G) Field photograph showing intrusion of calcite and quartz veins in phyllite

near Itala village.

Fig. 2.3(H) Field photograph showing 2 sets of joint in manganiferous chert.

51

Fig. 2.3(I) Field photograph showing large solution holes in limestone beds at

Talwara village.

Fig. 2.3 (J) Field photograph showing quartzitic intercalation in dolomite near Sagwa.

Fig. 2.3 (K) Field photograph showing antiform structure in manganese ores and their

host rocks (phyllite and quartzite) Kalakhunta Mine.

52

Fig. 2.4 A hand specimen showing dendritic pattern and foliations in Manganiferous

Phyllite.

Fig. 2.5 A hand specimen showing Mn-ore (Black) and foliations in Manganiferous

Phyllite.

Fig. 2.6 A hand specimen showing folding effect and Mn ore along foliation planes in

Phyllite at Ghatia section.

53

Fig. 2.7 A hand specimen showing porphyroblast of garnet and quartzitic

intercalation in siliceous phyllite near Kalakhunta-Ghatia section.

Fig. 2.8 A hand specimen showing dendritic pattern and patches of manganese ore in

Mn-bearing Phyllite at Tambesara section.

Fig. 2.9 A hand specimen of Manganiferous schist in Kalakhunta section.

54

Fig. 2.10 A hand specimen of manganese bearing interbedded phyllite and quartzite.

Fig. 2.11 A hand specimen of grayish color manganiferous dolomitic limestone in

Talwara section.

The numerous other litho-units are present in the other parts of Banswara

district i.e. coarse gritty schist, mica schist, phyllite, conglomerate (oligomictic and

polymictic type), crystalline limestone, dolomite, intrusives (quartz vein, granite and

pegmatite dykes), ultrabasic rock (thin bands of calc-tremolite schist), Deccan traps,

granite gneiss and alluvium.

55

CHAPTER-3

PETROGRAPHY OF HOST ROCKS

3.1 Introduction

Petrography deals with the systematic study of mineral constituents in thin

sections and complete description of textural relationship among different mineral

components. The petrographic study is a vital tool for providing detailed and relevant

information of mineralogical composition, metamorphism, and paragenetic history of

rocks to understand their origin. These details always helpful to resolve

palaeoclimate, geo-tectonic setting and depositional environment of meta-sediments.

The comprehensive analysis of minerals by optical microscope in thin sections viz.

micro texture and structure are critical in understanding the origin of rocks. In this

work author made an attempt to explain detailed petrographic and X-ray diffraction

studies of host rocks associated with Banswara manganese ores belt, with an aim to

understand mineralogical assemblages, textures, microstructures and possible P-T

conditions of the study area. The modal analysis of host rocks also carried out. The

host rocks of Banswara manganese ores belongs to the Lunavada Group of Aravalli

Supergroup. On the basis of mineralogical assemblages following is the list of various

host rocks types viz.: phyllite, schist, quartzite and limestone etc., and their subtypes.

3.2 Petrography

The megascopic and petrographic examination of the manganese associated rocks of

the study area is given here.

3.2.1 Phyllite

3.2.2 Schist

3.2.3 Quartzite

3.2.4 Limestone

3.2.1 Phyllite

Phyllite is a type of foliated metamorphic rock and formed from slate through

regional metamorphism under low grade metamorphic condition. The phyllite is the

56

dominant rock types of Banswara manganese ores belt. The rocks of the argillaceous

composition are represented by phyllites (Gadhadharan, 1978). Megascopically, the

manganese associated phyllite rock of study area is fine-grained, light grey in color

with various hardness and fissility. They are characterized by well developed

cleavages, schistosity and pronounced foliations. On the other hand, manganiferous

fine-grained phyllite with various shades of gray, brown and black with metallic

nature has also been reported and occurred in the study area. The manganese ores is

associated with phyllite mostly in interbedded form. Dendritic pattern and

crenulations are the prominent features seen by naked eye. Tectonically, phyllite beds

are co-folded with manganese ores. Pronounced foliations, schistosity and folding are

indicating various phases of deformation in phyllites.

Various samples of phyllite have taken for petrographic studies and reveal

almost similar mineralogical assemblages with the occurrence of manganese ores. On

behalf of minerals identification and minerals percentage in every samples of phyllite

rock, the four varieties have occurred in the study area. The identified siliceous

phyllite, which is a common rock type in Lunavada and Kadana areas is composed of

fine-grained muscovite and chlorite as abundant minerals with enough amount of

quartz. The garnet, hematite, feldspar and opaque are accessory minerals in this rock

type. At some places, chlorite grains are coalesced with each other indicating

deformational history of the study area. The quartz grains are xenoblastic and show

undulose extinction with the encrustation of manganese ores. Garnet crystals are in

perfect rhombohedral shaped with several encrustations of opaque ore minerals (Fig.

3.1). Another variety belongs to manganiferous phyllite, which is the dominant rock

type in the study area from the point of view of manganese ores. This rock shows the

dominance of muscovite flakes along with chlorite grains. Quartz layers are

sandwiched between muscovite and opaque minerals layer (Fig. 3.2). All rock

forming minerals with manganese ores throughout the thin section are parallel to

pronounced foliation plane (Fig. 3.2). Another sample is fine to medium grained exhibit

schistose structure (Fig. 3.3). It is mainly composed lapidoblasts of muscovite, biotite

and coarse grained quartz. Muscovite flakes uniformly cleaved with perfect preferred

orientation and form the schistosity. The rock showing well developed cleavage

defined by preferred orientation of micaceous and opaque minerals, and folding effect

in manganese ores also noticed.

57

The another variety is defined as chlorite-biotite phyllite which is rich in

perfect lapidoblastic biotite grains set in the fine-grained micaceous matrix (Fig. 3.4).

Biotite shows strong pleochroism (brown to yellow) with high relief. In plane

polarized light biotite displays perfect cleavage in one direction. The mineral

boundary relation of biotite with other minerals (Fig. 3.4) suggests that the biotite

grains are possibly formed at the later stage. Here chlorite is characterized by light

greenish color with weak birefringence. The rock is also composed of xenoblastic

medium grained quartz and uniformly cleaved muscovite flakes. The accessory

minerals are feldspar, tourmaline and opaque ore minerals. The thin section of

muscovite phyllite is composed of fine to medium grained texture, essentially

composed of muscovite and chlorite as dominant mineral with quartz, biotite, garnet,

feldspar and opaque as accessory minerals. The chlorite mineral clearly showing its

diagnostic green to brownish color with low relief in plane polarized light. Most of

the chlorite grains occurs in lens-shaped form. The biotite alteration in chlorite clearly

noticed in the lower part of thin section (Fig. 3.5). The minute garnet crystals

occurring in perfect rhombohedral shape and the fractures in garnet filled with

manganese ores and opaques. In all rock samples, Mn ores bands consistently

associated with phyllite along the foliation planes indicating that the mineralization

may be occurred along shear zones. Manganese ores also found as encrustation or in

inclusion in various minerals. The mineralogical assemblages suggest that the phyllite

formed under greenschist to lower amphibolite facies of metamorphism. Petrographic

studies revealing mineral assemblages of different phyllite samples are listed in

(Table 3.1) while 2θ position of different minerals has given in (Fig. 3.6-3.8).

Table 3.1. Mineral assemblages in phyllite rocks of the study area.

Type of

sediments

Metamorphic

equivalent

Mineral assemblages

Pelites Siliceous phyllite Muscovite + chlorite + quartz + garnet +

opaque

Pelites Manganiferous

phyllite

Muscovite + chlorite + quartz ± biotite +

opaque

Pelites Muscovite phyllite Muscovite + chlorite + quartz ± biotite +

garnet + opaque

Pelites Chlorite-biotite

phyllite

Chlorite + biotite + muscovite + quartz +

opaque

58

Fig. 3.1 Photomicrograph showing abundant quartz with deposition of manganese

ores in scattered form in siliceous phyllite.

Fig. 3.2 Photomicrograph showing micaceous minerals aligned perfectly along the

foliation in manganiferous phyllite.

Fig. 3.3 Photomicrograph showing schistosity and microfolding of ores in


Fig. 3.4 Photomicrograph showing mineral boundary relationship between

lapidoblasts of biotite (Bt) with other minerals in chlorite-biotite phyllite.

Fig. 3.5 Photomicrograph showing biotite (Bt) alteration into chlorite (Chl) in

muscovite phyllite.

59

Fig. 3.6 2θ positions of muscovite, chlorite, quartz and braunite in siliceous phyllite.

Fig. 3.7 2θ positions of muscovite, chlorite, quartz, albite and hematite in


Fig. 3.8 2θ positions of muscovite, chlorite, biotite and quartz, in chlorite-biotite

phyllite.

60

3.2.2 Schist

The mica schist and phyllite are predominant rocks in the study area and form

about 70% of the rocks of Banswara manganese belt, where only the top portion of

this formation having mineralization of manganese ores (Mukherjee and Kapoor,

1960). Megascopically, the schist rocks are fine to medium grained and highly

foliated. The color of schist varies between shades of gray, brown and reddish brown

with black and brown stains. The brown and black stains may be due to

decomposition of ferruginous contents or due to the presence of manganese

mineralization. The schist at places highly intercalated with quartzite band. Good

foliations and crenulations are common features noticed in schist rocks. The

manganese ores found in the form of thin layer, lenses and pockets clearly noticed by

naked eye. The schist rocks are highly foliated and marked by parallel orientation of

several disconnected lamellar or lapidoblastic micaceous constituents. Under the thin

section, schist samples are medium to coarse grained and composed of quartz,

muscovite, chlorite, biotite, garnet, alkali feldspar, plagioclase, fluroapatite and

opaques ore minerals. At some places, biotite occurs as large porphyroblast with

rugged termination (Iqballuddin and Negi, 1971). Quartz grain occurs in both coarser

and finer form. Garnet occurs as porphyroblast in clusters and forming the perfect

porphyroblastic type of texture. Schistose texture well defined by muscovite, chlorite

and biotite flakes. Mineral assemblages observed in schist are typical of greenschist to

lower amphibolite facies. Petrographic studies reveal that manganese ores deposited

along the foliation planes and sometime along the mineral boundaries. The manganese

ores also occurred as encrustation and in inclusions with embedded form in various

minerals.

Petrographic and modal analysis studies of schist rock reveals that the

garnetiferous-mica schist, quartz-mica schist and muscovite-chlorite schist are

occurred in association of Banswara manganese belt. The garnetiferous-mica schist is

medium grained, showing clusters of garnet crystals and consists mainly of muscovite

as a dominant mineral with quartz, biotite, chlorite, feldspar and opaque (including

manganese ore) as accessory minerals. The microfolded manganese ores bands also

present in groundmass here (Fig. 3.9). The encrustation of opaque and manganese ore

minerals over quartz, garnet and other minerals are common. Garnet is generally

61

abundant constituents of this group of rocks with perfect rhombohedral shape (Fig.

3.10) and also found in embedded form within quartz grains at various places. Quartz

grains appears as xenoblastic and encrusted by minute garnet and secondary quartz

itself. The Quartz-mica schist is composed of medium to coarse-grained quartz,

muscovite as essential minerals. The muscovite shows well developed schistose

texture. The lamellae of muscovite shows moderate relief with perfect one set

cleavage. Under cross polars muscovite shows high birefringence. The xenoblastic

quartz grains are arranged parallel to muscovite and biotite lapidoblasts and showing

typical undulose extinction. The concentration of micaceous minerals is also noticed

around garnet crystals (Fig. 3.11).

The muscovite-chlorite schist is composed of dominant mineral as muscovite

and chlorite. The muscovite and chlorite flakes uniformly oriented with the deposition

of dark color minerals (opaque ore minerals) along their boundaries (Fig. 3.12). The

rock having well developed schistose texture due to parallel orientation of lamellar or

flaky minerals (Fig. 3.11-3.13). Perfect elongated crystals of chlorite mineral are

showing moderate relief. Under cross polars chlorite grain shows low birefringence

with first order interference color. Muscovite occurs as lapidoblasts with basal

cleavage. Quartz is usually xenoblastic and highly fractured. The garnet crystals are

rounded in shape and partially filled with opaque (including manganese ore) minerals.

In another rock section, quartz grains arrange themselves parallel to foliation plane

and sandwiched from both sides by micaceous minerals (Fig. 3.13). The mineral

dravite and fluroapatite also noticed in thin section. Petrographic studies revealing

mineral assemblages of different samples are listed in (Table 3.2) and 2θ position of

different minerals has given in (Fig. 3.14-3.16).

Table 3.2 Mineral assemblages in schist rocks of the study area.

Type of

sediments Metamorphic equivalent Mineral assemblages

Pelites Garnetiferous-mica schist Garnet + muscovite + chlorite ± biotite +

quartz + opaque.

Pelites Quartz-mica schist

Quartz + muscovite + chlorite ± biotite +

garnet + opaque

Pelites Muscovite-chlorite schist

Muscovite + chlorite ± biotite + quartz +

opaque

62

Fig. 3.9-3.10 Photomicrograph showing clusters of perfectly rhombohedral shaped

garnet (Gt) and microfolded bands of manganese ore in garnetiferous

mica schist.

Fig. 3.11 Photomicrograph showing perfect schistosity and quartz intercalation in

quartz mica schist.

Fig. 3.12 Photomicrograph showing deposition of Mn ore minerals along the mineral

boundaries of uniformly oriented muscovite (Mus) and chlorite (Chl) in

muscovite chlorite schist.

Fig. 3.13 Photomicrograph showing quartz grain layer defining foliation in muscovite

chlorite schist.

63

Fig. 3.14 2θ positions of muscovite, chlorite, quartz, albite and garnet in garnetiferous

mica schist.

Fig. 3.15 2θ positions of muscovite, chlorite, orthoclase and quartz in quartz mica

schist.

Fig. 3.16 2θ positions of muscovite, quartz, fluroapatite and dravite in muscovite

chlorite schist.

64

3.2.3 Limestone

The limestone samples were collected from Talwara village. Besides these

deposits, there are numerous minor occurrences of limestone between Kalinjara and

Pali Chhoti localities in Banswara district. The limestone is thickly bedded and

crystalline. The bedding of limestone is in conformity with phyllites and quartzites.

Various irregular joints, fissures, cavernous pockets are characteristic features of

limestone in Talwara village in which manganese ores deposited. The manganese ores

are distributed very irregularly in the limestone. The manganese ores also occurred in

scattered form in limestone rock. The petrographic studies reveal that mostly

limestone are dolomitic in composition but some ferruginous varieties are also noticed

at places (Rasul and Khan, 1963). Dolomitic limestone is composed of calcite,

dolomite and some magnetite (Table 3.3). The rock is medium to coarse grained and

shows mosaic structure (Fig. 3.17) (Rasul and Khan,1963). Minor amount of quartz,

tremolite, and minute flakes of biotite occur in impure varieties (Fig. 3.18). The

ferruginous variety of limestone contains disseminations of hematite and limonite.

The other impurities are in form of chert, flint and iron bearing minerals like hematite.

Due to impurities, the color of limestone changes from white to red brick and grayish.

Manganese ores replacing limestone constituents around minerals boundaries.

Table 3.3 Mineral assemblages in limestone rock of the study area.

Type of sediments Rock type Mineral assemblages

Calcareous

Limestone

Calcite + dolomite + magnetite + quartz

+ chert + opaque.

Calcareous

Limestone

Calcite + dolomite + quartz + hematite +

opaque.

Calcareous

Limestone

Calcite + dolomite + tremolite + biotite

+ quartz + opaque.

According to Rasul and Khan (1963) the dolomitic limestone were probably

formed due to low grade metamorphism, equivalent to albite-epidote-amphibolite

facies (Henrich, 1956), of a sedimentary limestone having some original impurities,

from which the accessory minerals such as tremolite, hornblende, biotite and quartz,

etc., were derived (Middlemiss, 1915). Fermor (1909) has also expressed similar

views regarding origin of manganiferous crystalline limestone of the Sausar series.

65

The two-theta position of various minerals has given in (Fig. 3.19). Texturally, the

rock is medium to coarse grained and showing all the mineral grains are

approximately equal in size which referred mosaic structure. Mostly crystals showing

polysynthetic type of twinning.

Fig. 3.17 Photomicrograph showing mosaic structure with sub graphic intergrowth of

quartz in manganese bearing dolomitic limestone.

Fig. 3.18 Photomicrograph showing dark color impure variety of limestone having

tremolite, quartz and biotite.

Fig. 3.19 2θ positions of calcite, dolomite and quartz in manganese bearing

dolomitic limestone.

66

3.2.4 Quartzite

The quartzite outcrop extends over miles within the area from Gararia to

Ratimauri village with roughly NW-SE direction and contains thin bands of

manganese ores. The manganese bearing quartzite and phyllite is associated in

interbedded form with manganiferous beds in the study area while according to Roy

(1957) quartzites are disposed conformably with the phyllite and are at times

brecciated and later re-cemented by secondary chert and manganese in the study area.

The various samples of quartzite rocks collected at different places in the study area

from Gararia to Ratimauri villages and near Talwara localities of Banswara district.

The manganese ores also found as encrustation, in inclusions and in embedded forms

in quartzite assemblages. The different rock samples are composed predominantly of

quartz with subordinate mica, feldspar, opaque ore minerals and impurities of

hematite. Sericitization and calcareous materials also noticed in some thin sections

(Fig. 3.22). The quartz grains are xenoblastic to sub-idioblastic type. According to

Harker (1939) the rounded to subrounded shape of quartzite fragments might be due

to mutual attrition during brecciation. The petrographic study reveals that quartz

grains are medium to coarse grained, low in relief and birefringence. The rock type

showing granoblastic texture in few sections (Fig. 3.21). Apart from this Feldspar

minerals (orthoclase and plagioclase) showing polysynthetic and lamellar twinning

respectively (Fig. 3.20) while microcline showing a peculiar cross hatched twinning

in thin section (Fig. 3.23). Manganese ore is occasionally associated with orthoclase

as small inclusions observed by Siddiquie (2010). The quartz inclusion in larger

grains of quartz shows optical homogeneity (Garg, 1973). In Talwara, mostly

fragments of quartzite rock shows undulatory extinction and contain fractured filled

with sericite. Quartz grains also show straight grain boundaries with sharp extinction.

According to Urai et al. (1986) and Passchier and Throw (1996) the presence

of serrated/sutured grain boundaries indicates that the rock underwent grain boundary

migration recrystallization (GBMR). Granoblastic texture and its subtype is reported

from quartzite thin sections of study area. The quartz grains showing straight, sutured

and serrated grain boundaries in Fig. 3.21 and 3.23. The other thin section also

showing granoblastic amoeboid texture (Fig. 3.20) where grains have irregular

outlines, while granoblastic interlobate texture represented by (Fig. 3.22), where all

the minerals have somewhat irregular outline.

67

The mineral assemblages and two theta position of different samples of

quartzite rock is given in (Table 3.4) and (Fig. 3.24, 3.25) respectively.

Table 3.4 Mineral assemblages in quartzite rocks of the study area.

Type of Sediments

Metamorphic

equivalent

Mineral assemblages

Psammite

Quartzite

Quartz + plagioclase + orthoclase +

sericite + calcite + opaque.

Psammite

Quartzite

Quartz + orthoclase + sericite + calcite +

opaque.

Psammite

Quartzite

Quartz + plagioclase + orthoclase +

hematite + muscovite + opaque.

Psammite

Quartzite

Quartz + microcline + muscovite +

opaque.

Fig. 3.20 Photomicrograph showing encrustation of manganese ores with impurities

of iron in quartzite.

Fig. 3.21 Photomicrograph showing granoblastic texture with lamellar twinned

porphyroblast of plagioclase in quartzite.

68

Fig. 3.22 Photomicrograph showing straight grain boundaries and sericitization at

places with the encrustation of manganese ores in quartzite.

Fig. 3.23 Photomicrograph showing serrated/sutured grain boundaries in quartzite.

Fig. 3.24 2θ positions of quartz, muscovite, calcite and albite in manganese bearing

quartzite.

Fig. 3.25 2θ positions of quartz, muscovite, calcite and microcline in manganese

bearing quartzite.

69

3.3 Modal analysis

Petrographic studies and modal analysis (Table 3.5) suggest that the different

rock types in the study area are; Siliceous phyllite, Manganiferous phyllite, Muscovite

phyllite, Chlorite-biotite phyllite, Garnetiferous-mica schist, Quartz-mica schist,

Muscovite-chlorite schist, Limestone and Quartzite. In the light of above fact, it

appears that low grade regional metamorphism has played an important role in

metamorphism of pelitic-psammitic and calcareous sediments which turn into the

prominent manganese comprising rocks of the study area and finally metamorphosed

to present day rock types viz, phyllite, schist and quartzite.

Table 3.5. Mineral percentage in host rocks of the study area.

MBM(Mn-bearing minerals), (P-Phyllite), (SP-Siliceous phyllite), (CP-Chlorite phyllite), (MP-

Muscovite phyllite), (GMS-Garnetiferous mica schist), (QMS-Quartz mica schist), (MCS-

Muscovite chlorite schist), (Lst-Limestone), (Qtz-Quartzite).

MBM P SP CP MP GMS QMS MCS Lst Qtz

Qtz 22 39 24 21 23 39 21 5 80

Mus 31 31 12 44 34 28 41 1 2

Bio 3 4 29 6 3 5 2 1 1

Chl 14 7 22 19 7 7 20 × 1

Feld 2 2 1 2/0 3 4 1 × 4

Gt 3 2 3 3 21 4 4 × ×

Op 20 15 9 5 8 11 9 9 8

Mg 2 × × × × × × 3 ×

Hem 3 × × × × × × 2 2

Fa/Epi × × × × 1 1 2 × ×

Ca × × × × × × × 56 2

Do × × × × × × × 22 ×

Total 100 100 100 100 100 100 100 100 100

71

CHAPTER-4

BANSWARA MANGANESE ORES


The manganese ores deposits of world show a vast range of distribution over

continents and on the bottom of oceans, both in time and in space. The deposits

occurred on land belongs to different ages from early Precambrian to Recent time.

The Indian province is one of the richest among manganese ores deposits of world

and holding the oldest metasedimentary manganese deposits belongs to Iron ore group

(3200-2950 Ma) (Roy, 1981). The manganese ore deposits of Aravalli Supergroup

belongs to (1500-900 Ma) in age (Roy, 1981).

The manganese ores of the study area occurred in a narrow but fairly

persistent linear belt from Gararia to Ratimauri localities in the study area. These

manganiferous beds with associated rocks generally strike N-S and NNW-SSE

direction with fairly steep and vertical to subvertical dips and indicating a highly

folded argillaceous and calcareous series of rocks (Roy, 1957). Instead of this a small

manganese producing localities belongs to Talwara village, which is now abandoned

and manganese ores occurred in scattered form. The manganese belt passing through

Sivnia, Kalakhunta, Ghatia, Sagwa, Itala, Bhakhri, Timamahudi, Tambesara, Kheria,

Rupakhera and Wagaicha villages. The belt at various places covered by soil and

Deccan traps (Cretaceous age). The belt is divided in various sections and blocks such

as Gararia-Sivnia section, Kalakhunta-Ghatia section, Itala-Sagwa section, Tambesara

block and Rupakhera-Ratimauri section. These section and blocks reveals the

occurrence, distribution and grade of manganese ores.

4.2 Occurrence and Distribution of Manganese ores

The manganese deposits of India were originally discovered and studied by

Fermor (1909) and divided into following groups; i) Deposits interbedded with

Archean rocks ii) Deposits associated with lateritic character. The metasedimentnary

deposits of India (Sausar Group, Aravalli Supergroup, Gangpur Group, and

Khondalite Group) are representative of this type mentioned by Roy (1968).

According to Roy (1957) the manganese oxides replaced the country rock at varying

72

degree and after complete replacement the ore bodies look like sedimentary origin. He

also illustrated that the relict of country rocks noticed in the field as well as

megascopic and microscopic studies favored the process of partial replacement and

concluded that the deposits formed due to the alteration and replacement of associated

rocks by manganese bearing solution. The solution might be of hydrothermal origin or

might have concentrated from sedimentary rocks themselves by the action of meteoric

water. While Mukherjee and Kapoor (1960) illustrated that the strict conformity of

thin manganese bands with bedding of phyllites and quartzites, sharp contact with

overlying and underlying rocks, uniformity in quality of ores, absence of evidences

related to wide spread replacement suggest the syngenetic origin for these deposits.

He concluded that the manganese ores deposited principally as a chemical precipitates

under fluctuating sedimentary conditions which allowed alternate deposition of clastic

and non-clastic sediments. Sinha (1980) has supported Mukherjee and Kapoor (1960)

views regarding the origin of manganese deposits. The present author has similar

views regarding the occurrence of manganese ores in the study area and followed the

statements of Mukherjee and Kapoor (1960) and Sinha (1980) except that after

formation of principal deposits, various secondary processes (role of meteoric and

ground water, hydrothermal manganese bearing solution) acted on the deposits and

resulting in to secondary manganese ores. The author referred such deposits as

syngenetic or syn-hydrothermal metamorphosed type deposits. The deposits of

Banswara manganese belt associated with Archean rocks as interbedded form except

Talwara deposits (Babel, 1985). Geological survey of India referred these deposits, as

the extension or equivalent to deposits of Madhya Pradesh classified as syngenetic

gonditic deposits. Microscopic studies of associated rocks also suggest that they could

be compared with manganese bearing rocks of Jhabua, Madhya Pradesh and

considerable similarities to the Dharwar of M.P. The host rocks are less

metamorphosed in comparison of Sausar group of Madhya Pradesh. The occurrence

of manganese ores in the study area reveal that the primary manganese ores are

occurred conformably with metasediments of Aravalli Supergroup. The primary

manganese ores are syngenetic and stratified low grade metamorphosed bedded

deposits. The deposits of study area also having varying shapes and sizes and also

occurred as irregular veins, pockets, stringers and lenticular bodies in form of

secondary manganese ores due to irregular supergene and replacement bodies. The

classification regarding the mode of occurrence of present manganese deposits in

73

Banswara manganese belt except Talwara suggested on the basis of field studies

(structural and lithological) in relation with the mineralogical studies are as follows:

4.2.1 Sratified/Primary/Metamorphosed/Syngenetic/Metasedimentary

Ores

The co-folded manganese ores occurred in bedded, laminated and tabular form

belongs to this category with principal mineral assemblages of braunite with minor

occurrences of bixbyite, pyroxmangite, hollandite and spessartine.

4.2.2 Secondary/Hydrothermal(Colloidal)/Supergene Ores

The secondary manganese ores occurred along foliation planes, fractures,

lenses, pockets, veins and in the form of thin bands. The secondary manganese ores

resulted due to both colloidal derivatives and irregular supergene enrichment are viz.,

pyrolusite, psilomelane, cryptomelane, pyrochroite, coronadite and wad. The

manganese bearing hydrothermal solution replaced country rocks as a large measure

and local enrichment of manganese took place in the study area also.

The manganese deposits are co-folded (Fig. 4.1, 4.2, 4.7, 4.8, 4.9) with the

associated rocks like; phyllite, schist and quartzite throughout the belt. The quartzite

layers consist manganese ores and having a wavy and saw-teeth like contact with

phyllite (Sinha, 1980). The study area is very much tectonically disturbed and

manganese beds are occupied in the antiforms, synforms and other folds (Fig. 4.7,

4.8). According to Mamtani et al. (2000), the Lunavada group of rocks reveals three

episodes of deformation Dl, D2 and D3, and an important constituent of the southern

parts of AMB and is known to have undergone polyphase deformation during the

Meso-Proterozoic. The identified manganese ore mineral assemblages and its

association with present rock types also indicating the rocks of the area have

undergone greenschist facies to lower amphibolite metamorphism on regional scale.

The manganese associated with interbedded phyllites and quartzites have been

buckled up in the direction of regional folds as well as other folds in the study area.

The folded manganiferous beds are in the form of thick bands (up to several cm) to

minute thin bands (Fig. 4.1, 4.2). The ores of Talwara village, which abandoned in

past represent the deposition in caverns and cavities resulting from solution effects in

ferruginous limestone which indicates local leaching and infiltration of meteoric

74

waters (Fig 4.3). Presently the limestone outcrops associated with manganese ores

have been weathered and transformed into powdery form with lots of ochres (Fig.

4.14). The ores were hard, colloform and cavernous without much alteration and

undoubtedly suggest epigenetic origin for Talwara manganese ores (Rasul and Khan,

1963). These deposits have been totally different in occurrences in comparison of

Banswara manganese belt. The Talwara manganese deposits associated with

limestone is also totally different from those occurring in metamorphosed crystalline

limestone of Sausar series in the district of Nagpur and Bhandara (Hayden, 1921).

According to Mukherjee and Kapoor (1960) the manganese ores belt occurred in two

horizons in which most persistent horizon running all along the mineralized zone from

Gararia to Ratimauri village. While the other one is confined to small areas near Itala-

Sagwa and Tambesara-Kheria section. Sinha (1980), who worked over manganese

investigation in Banswara manganese belt provided very much similar views

regarding occurrence of deposits except that there may be at least three manganese

sub zones throughout the belt in which one is persistent up to half of total strike length

of belt and other two sharing 25% of total strike length of belt. The description of

sections, blocks, active mines and manganese ores are based on behalf of field visit

and literature reviews which are as follows:

4.2.3 Gararia - Sivnia Section

The section is named after Gararia and Sivnia localities of Banswara district

where manganese deposits exposed. In Gararia, the manganiferous phyllite exposed in

N68°W to N78°W. The manganese ores associated with these grayish black rocks in

bedded form. There are few old working in the form of trenches and pits are present.

The manganese horizon lies at top of high ridge in east of Haran river and

mineralization takes place along shear zone and also along the foliation planes in

phyllites. The ore zone is striking WNW-ESE. The chocolate brown soil covering as

overburden around 2 to 4 meter. The ores are well associated with folded interbedded

phyllite and quartzite. The manganiferous phyllite covering an area of about 1km in

length and varying in width up to 40 m, reported by Joshi and Jangid (2009). The

sporadic nature of manganese ores associated with yellow ochre noticed at various

places in this section. In Sivnia, the manganese ores are associated with highly folded

interbedded phyllite and quartzite (23° 18' : 74° 16' ) (Fig. 4.12). The outcrops

75

forming low ridges and generally striking WNW-ESE. The quartzite band are thin and

has minor amounts of manganese mineralization. The samples have taken for studies

belongs to soft and crystalline varieties. The number of pits and holes are present. Roy

(1957) reported that the approximate width of mineralization is around 300 ft or more.

The old workings have explored up to 18ft (Mukherjee and Kapoor, 1980). Sinha

(1980) reported that the mining of manganese ores was done for a strike length of

about 200 m.


The Kalakhunta mine is located at latitude 23°19' N and longitude 74°19' E

and is about 35 km far from Banswara district. This open cast mine is under working

(Fig. 4.4, 4.5, 4.6). The deposits occurred in association with manganiferous phyllite,

schist (Fig. 4.13), interbedded phyllite and quartzite. These tightly folded rocks

striking in WNW-ESE direction, forming low ridges rising up to 50 ft above the plain.

The interbedded ore zone is covered by brown soil which is 4-6 ft thick (Fig. 4.1).

The maximum width of mineralization is about 300ft. The ores occurred here in

bedded form as well as pockets, stringers, veins or in sporadic form. The thickness of

manganese ores beds varying from 2 cm to 10 cm and highly co-folded with

interbedded phyllite and quartzite. The ores also occurred with red and yellow color

ochre. The beds show varying strike and dip direction, striking N230-280 with dipping

560-640SW. The various synforms, antiforms, ptygmatic folding, isoclinal folds and

buckling of strata are common. The length of mining area is around 250 meter with

varying width of 30-40 ft. The mining area is very close to Banswara-Dohad road and

road side cutting clearly indicating that the deposits go ahead to Sagwa in SE

direction (Fig. 4.9). Earlier 1 km mining is done in past (Sinha, 1980). While Roy

(1957), Mukherjee and Kapoor (1960) reported that the ore to rock proportion is

around 1:20 by volume in Kalakhunta area while 1:30 by volume in whole

Kalakhunta-Ghatia section respectively. The manganese ores belongs to both hard,

crystalline, soft and powdery nature (Fig. 4.18, 4.20, 4.21, 4.22, 4.31). The manganese

ore deposits of Ghatia also occurred in similar nature like Kalakhunta manganese

deposits (Fig. 4.15, 4.19). The manganese associated rocks are highly folded with

buckling of strata and generally striking in WNW-ESE with varying dip (vertical to

sub-vertical).

76

4.2.5 Itala-Sagwa Section

The section belongs to ltala (23° l7' to 74° 19') and Sagwa (23° 18' to 74° 17')

where manganiferous phyllites and quartzites striking NW-SE direction and generally

dipping in 50°-60° SW. The ores are occurred here in thin bands around 2-3 inches

thick. The ores also found in veins and pockets (Fig. 4.10). The interbedded phyllite

and quartzite are intruded by calcite and quartz vein. The manganiferous belts extend

up to Bhakhri and covered by Deccan traps. The ore/rock ratio is around 1:20 to 1:30

reported by Sinha (1980).

Fig. 4.1 A sketch of section at Kalakhunta mine showing intensely folded manganese

ore beds in quartzite and phyllite.

Fig. 4.2 A sketch of section at Tambesara showing highly folded manganiferous

quartzites and phyllites after (Roy, 1957).

77

Fig. 4.3 A sketch of section at Talwara locality showing Mn ores as irregular lenses

and pockets in a limestone ridge (after Roy,1957).

Fig. 4.4 The working open cast manganese mine at Kalakhunta mining area,


Fig. 4.5 An active open cast manganese mine at Kalakhunta mining area, Banswara


78

Fig. 4.6 The over burden rehabilitation through tree plantation at Kalakhunta mine,


Fig. 4.7 The highly folded manganese ore beds associated with interbedded phyllites

and quartzites at Kalakhuta mine, Banswara district, Rajasthan.

Fig. 4.8 The folded manganese ore beds at Ghatia section, Banswara district,

Rajasthan.

79

Fig. 4.9 The highly folded manganese ore beds in association of host rocks near

Kalakhunta section at Banswara-Dohad road, Banswara district, Rajasthan.

Fig. 4.10 The manganese ores old working near Itala, Banswara district, Rajasthan.

Fig. 4.11 The manganese ores in association with highly folded, interbedded phyllites

and quartzites at Tambesara section, Banswara district, Rajasthan.

80

Fig. 4.12 The manganese bearing host rocks contain folded bands of manganese ores

in Sivnia section, Banswara district, Rajasthan.

Fig. 4.13 The manganese ores pockets in weathered schist (near pen) at Kalakhunta


Fig. 4.14 The manganese ores associated with highly weathered limestone at Talwara

village, Banswara district, Rajasthan.

81


The section is named after Tambesara (23° l5'-740 21') and Kheria (23°15-

74°19') villages of Banswara district. The Tambesara ore deposits are rich in

manganese content and belongs to high grade zone throughout the manganese belt.

The associated Aravalli phyllites and quartzites striking in NNW-SSE direction. The

manganese ores also associated with gritty schist here. The numerous synform and

antiform showing by phyllite and quartzite outcrop in the manganese belt (Fig. 4.2).

The belt is around 2.5 km long and 600 m wide and is covered by Deccan traps in

west and in east it is passing into a series of conglomerate-quartzite forming ridge

(Roy, 1957). The both low and high grade zone occurred in the section. The ores are

associated here in thick bands and also found in the form of small veins and pockets

(Fig. 4.17, 4.23, 4.24, 4.27). The total width of mineralization zone in Tambesara is

600 ft and in Kheria is around 100 ft reported by Sinha (1980). The ores at places just

3 ft below from the soil cover (Fig. 4.11). The ore zone is dipping with an angle of

41° to 59° SW. The ore zone also covered with huge overburden at places. The huge

manganese ores extracted already in past.


The section exposed in Rupakhera (23° l3'-74° 22') and in Ratimauri (23° 22'

to 74° 23'). The rocks here mainly included a series of highly folded interbedded

phyllite and quartzite with thin bands of chert in southern side and striking NW-SE

and NNW-SSE with SW dips. The phyllites are highly puckered and contorted in this

area. The manganese ores are highly siliceous in this section and it may be due the

impurities of chert. The ores are exposed in trenches and nalas. The small

manganiferous chert outcrop showing two sets of joint near Rupakhera locality.

4.2.8 Talwara

The manganese ores of Talwara villages (230 34'-74° 22') occurred in small

deposits in the study area and here the manganese ores are associated with calcareous

facies of Aravalli rocks. The country rock is generally striking in NW-SE and NNW-

SSE direction. The deposits occurred in sporadic form along the bedding planes,

solution cavities, joints, fissures and irregular pockets and lenses (Fig. 4.3). The

presence of yellow ochre in secondary ores clearly suggest that the ores must be

82

associated with ferruginous materials (Fig. 4.25). The old workings which were

extensively mined present near Kanji Katoria. A small trench of manganese over

200ft long near Tripura Sundari temple is surrounded from all side by marble

deposits. The manganese bearing limestone extensively weathered and large features

like solution holes are present in Talwara locality.

4.3 Mineralogy of Manganese ores

The manganese ores of study area which were collected from Gararia, Sivnia,

Kalakhunta, Ghatia, Itala, Tambesara, and Rupakhera localities are visually examined

and found that the ores are largely composed of braunite, pyrolusite, psilomelane-

cryptomelane and wad as important minerals. The braunite is found chiefly in most of

the samples. Quartz veins, jasperoid quartzite with some iron ores viz.: limonite,

hematite and ochre are the common gangue minerals found in manganese ores of the

study area. The megascopic descriptions of collected manganese ores are as follows:

4.3.1 Braunite

Braunite is found in hard and compact form throughout the belt. The color is

varying from metallic steel gray, brownish gray and grayish black with black streak. It

is also occurred in the forms of bands, fine to coarse granular form with association of

various ores and gangue minerals such as pyrolusite, hollandite, coronadite, wad,

jasperoid quartzite, pinkish orthoclase (Fig. 4.15, 4.30) and ochre. The crystalline

variety is noticed in Kalakhunta, Ghatia and Tambesara areas. The braunite is fine to

coarse grained with sub-metallic lustre. The fine grained variety also associated with

manganiferous mica (Fig. 4.26). The hardness of braunite is 6 or more than 6 with

specific gravity is around 4.5-4.7. The braunite is recorded chiefly in Kalakhunta,

Ghatia, Gararia, Itala and Tambesara areas. The folding effect is noticed in few

samples of braunite ores in the study area.

4.3.2 Pyrolusite

The mineral pyrolusite is essentially consist manganese dioxide. It is black to

grayish in color and occurred in various forms like granular, earthy or fibrous. It is

also occurs in non crystalline to very finely crystalline form. The hardness of

pyrolusite is varying between 1-1.6 with specific gravity is around 4.7-4.8. In the

study area it is banded, soft and friable in nature (Fig. 4.16, 4.18, 4.19, 4.25, 4.29).

83

The color is varying in different shades from dark grayish black to brownish black

with dark black streak. In study area pyrolusite occurred in the form of granular,

finely crystalline and soft dull black form which soil the finger. The folded bands

clearly marked in the samples from most of the places. The pyrolusite occurred in

association of braunite, cryptomelane, coranadite with ochre, quartz vein and feldspar

as gangue minerals. In Talwara, pyrolusite has minor occurrence and soft in form due

to which it is easily crumbles (Rasul and Khan, 1963). It is associated with gangue

like ochre and ferruginous materials in Talwara area. No crystalline variety has seen

in study area.

4.3.3 Hollandite

The mineral is first reported from Kajlidongri mine in Jhabua district, Madhya

Pradesh by Fermor (1906). It is the end member product of mineral coronadite group

and belongs to barium manganese oxide. The ore is silver grey in color with metallic

lustre. The ore is hard with lumpy form and other variety consist fine to medium

prismatic crystals (Fig. 4.28). The hardness is between 4-6. The specific gravity is

around 4.84. It is a low temperature mineral and crystallized in monoclinic system. It

is mainly associated with braunite and cryptomelane. In study area it is found in

Kalakhunta, Ghatia, Gararia, Itala, Tambesara and Rupakhera sections.

4.3.4 Cryptomelane

The Cryptomelane is occurred Gararia-Sivnia, Kalakhunta-Ghatia and

Tambesara section in the study area. It is a potassium manganese oxide ore mineral.

Cryptomelane occurred commonly in oxidized deposits or by replacement. In the

study area it is mainly associated with braunite and also unevenly distributed in the

ores (Fig. 4.23). It is gray to bluish grey in color and having brownish streak. The

cryptomelane occurred as a alteration product of primary ores may be due to

oxidation or weathering or through manganese bearing hydrothermal solution of later

stage. The hardness varies from 6-6.5 with specific gravity 4.1-4.2. Cryptomelane has

choncoidal fracture. Near Talwara, it is occurred in botryoidal form. The color of

cryptomelane is varying from grey to black in Talwara area. It is very soily and

powdery in feel and form.

84

4.3.5 Psilomelane

Psilomelane mineral is referred as hydrated manganese oxides with barium. It

is mainly crystallized in monoclinic system. The ore mineral is formed due to

supergene alteration of primary minerals in the study area. It is found in Kalakhunta,

Ghatia, Gararia and Tambesara sections. It is occurred in pisolitic form with

association of pyrolusite and gangue minerals (Fig. 4.23, 4.28). The mineral having

uneven fracture with metallic lustre. The color is varying from iron black to steel gray

and also having brownish black streak. The hardness varies between 5-6 and specific

gravity is in range of 3.6-4.6. The both psilomelane and cryptomelane are differ in

chemical composition and XRD pattern. The chemical formulae of both minerals

(Ba,H2O)2Mn5O10 and K(Mn4+,Mn2+)8O16 suggested by Hewett and Fleischer (1963).

4.3.6 Wad

In India, wad mineral first reported from Karnataka by Fermor (1909) while

Rasul (1964) discovered it from Shivrajpur manganese deposits of Gujarat state,

Siddiquie (1986, 2004) and Siddiquie and Bhat (2008) reported from Gharbham

block, Vizianagram district, Andhra Pradesh. The wad ore is fine grained, black and

very soft earthy manganese substances and in the typical form of cauliflower (Fig.

4.20). It is mainly hydroxide rich manganese oxides. The wad ore present throughout

the manganese belt and also in Talwara deposits. It is dark gray to black in color and

easily soiled the finger. It must be considered as a mixture of secondary ores.

4.3.7 Ochre

The ochre occurred in association with manganese ores throughout the

manganese belt in the study area. The ochre is yellowish brown in color. And clearly

seen in association with mixture of iron and ferruginous materials in Kalakhunta and

Sivnia mine and also in rest of the part of manganese belt (Fig. 4.18-4.28).

85

Fig. 4.15 A hand specimen of perfectly banded braunite (steel grey) in Ghatia section,


Fig. 4.16 A hand specimen of braunite showing bands of pyrolusite in Itala section,


Fig. 4.17 A hand specimen showing perfect band of braunite (steel grey) and

manganiferous quartzite in Tambesara section.

86

Fig. 4.18 A hand specimen showing alternate folded bands of pyrolusite and

lithomarge (ochre) in Kalakhunta mine, Banswara district, Rajasthan.

Fig. 4.19 A hand specimen of thick banded pyrolusite in Ghatia section, Banswara


Fig. 4.20 A hand specimen showing soft and friable manganese ore wad (lower part of

the specimen) with band of reddish gray jasperoid quartzite and

manganiferous quartzite in Kalakhunta mine, Banswara district, Rajasthan.

87

Fig. 4.21 A hand specimen showing intensely folded bands of braunite (steel grey),

with pyrolusite, jasperoid quartzite and quartz vein in Kalakhunta Mine,


Fig. 4.22 A hand specimen of Pyrolusite showing granular texture contain thin vein of

braunite (pointing arrow) in Kalakhunta Mine, Banswara district,

Rajasthan.

Fig. 4.23 A hand specimen of braunite (steel grey) showing secondary ores pyrolusite,

cryptomelane, psilomelane and gangue (jasperoid quartzite) in Tambesara


88

Fig. 4.24 A hand specimen of pyrolusite showing ferruginous manganese, hollandite

and intruded quartz veins in Tambesara section, Banswara district,

Rajasthan.

Fig. 4.25 A hand specimen of secondary ore pyrolusite (brownish black) showing

lithomarge in the form of ochre (Yellow) in Talwara section, Banswara


Fig. 4.26 A hand specimen of primary ore braunite contain mica flakes in Sivnia


89

Fig. 4.27 A hand specimen showing braunite (dark grey), manganiferous quartzite

and secondary pyrolusite in Tambesara section, Banswara district,

Rajasthan.

Fig. 4.28 A hand specimen showing hollandite (mammilary aggregates), coronadite,

psilomelane and lithomarge in the form of ochre (yellow) in Sivnia section,


Fig. 4.29 A hand specimen of pyrolusite showing thin veins of quartz in Gararia


90

Fig. 4.30 A hand specimen of Braunite showing secondary pyrolusite, jasperoid

quartzite and orthoclase vein (flesh color) in Itala section, Banswara


Fig. 4.31 A hand specimen of pyrolusite (brownish black) showing fibrous coronadite

(steel grey), jasperoid quartzite and cryptomelane in Kalakhunta mine,


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CHAPTER-5

MINERAGRAPHIC STUDIES OF MANGANESE ORES


Mineralogical studies of ores is an important tool to establish various

mineralogical assemblages in due course of time at different P-T path. Although it is

also disclose paragenetic sequence of ore minerals and their depositional history. It

plays key role during genetic interpretation of the manganese ores (Calendar and

Bower, 1976; Nicholson, 1992). The ore microscopic studies consist identification of

minerals, texture, their forms, nature of occurrence, depositional history and genesis.

Earlier Roy (1957), Mukherjee and Kapoor (1960) and Sinha (1980) reported

braunite, pyrolusite, psilomelane and wad megascopically in Banswara manganese

belt. While Rasul and Khan (1963) reported pyrolusite and cryptomelane in Talwara

manganese ores, Banswara district, Rajasthan. The Banswara manganese ores has

been occurred in narrow linear belt except Talwara locality. The manganese ores of

different sections of belt show a small variation in ore mineralogy of primary and

secondary manganese ores throughout the manganese belt. The different form of

manganese ores like massive, crystalline, botryoidal, mammilated, pisolitic, boxwork,

granular, soft-powdery and cavernous are noticed at places in study area. No detailed

optical studies of these manganese ores done in past. The deposits show very much

similarities in occurrence with manganese deposits of Jhabua, Madhya Pradesh and to

the Dharwars of Madhya Pradesh. Because of this authors reviewed excellent work

done by pioneer workers like Fermor (1906, 1908, 1909, 1917), Dunn (1936), Mason

(1943, 1944, 1947), Roy (1958, 1960, 1961, 1962, 1963, 1966, 1968, 1981), Muan

(1959a, b), Nayak (1959, 1961, 1964, 1966, 1969, 1973), Rasul (1964), Ramdohar

(1969), Kleyyenstuber (1984), Nicholson (1986, 1992a, 1992), Acharaya et al.

(1994b, 1997), Jawed and Siddiquie (2014), Siddiquie et al. (2015 a, b, c) to conclude

ores mineralogical studies in the study area.

The various fresh and unweathered manganese ores samples collected from

the mines of the study area. A number of samples belongs to mixture of various ore

minerals in different ratio. On the basis of their mode of occurrence, the manganese

ores classified as massive type, mixture of massive and replacement type and

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supergene type in the study area. The detailed ore microscopic studies of manganese

ores in the study area by using number of techniques also provided physico-chemical

properties of the chief ore minerals.

The collected samples from different sections throughout the manganese belt

examined for optical and X-ray diffraction technique to identify various types of

mineral assemblages and micro textures. The detail optical studies of manganese ores

of study area reveals that the primary manganese ores are braunite which is present

almost in every manganese ores polished block with minor occurrence of Mn-Fe

oxide, Mn silicate and Mn carbonate together which look like gonditic assemblages

and spotted in few polished blocks. Mineralogical and textural studies revealing that

the primary ores are formed by regional metamorphism of syngenetic manganiferous

sediments in the study area. Mukherjee and Kapoor (1960) and later Sinha (1980)

illustrated syngenetic origin for these deposits. These manganiferous sediments were

metamorphosed at low temperature. The primary ores are concordant with the country

rocks and occurred as bedded deposits. The secondary manganese ores identified in

polished blocks are pyrolusite, psilomelane, cryptomelane, pyrochroite, coronadite

and wad. These secondary ores are the product of both colloidal hydrothermal

solution and supergene enrichment. The secondary ores mainly occupied in joints,

fissures, pockets, stringers, thin veins and as minor bands. The second generation of

braunite is also recorded. The gangue minerals which are chiefly found in Banswara

manganese ores belt are quartz, orthoclase, jasperoid quartzite, limonite, hematite,

ochre and calcite etc.

5.2 Mineralogy of the Manganese Ores

5.2.1 Braunite 3(MnFe)2O3MnSiO3

The general formula of Braunite is 3(MnFe)2O3MnSiO3 and categorized as a

lower oxide high temperature and pressure mineral (Roy, 1963). Braunite is rather a

silicate but conventionally called as lower oxides of Mn (Bhat, 2013). It is a silicate

mineral generally consist di and tri valent manganese and crystallized in tetragonal

system. Braunite is a dominant mineral which occurred throughout the manganese

belt of the study area. The mineral megascopically represented crystalline, massive

and banded forms in the study area (Fig. 5.1). Siddiquie (2004), Siddiquie and Bhat

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(2008) reported massive and banded form of braunite in mineralogical studies of

Vizianagram manganese ores. The mineral found alone as well as in association with

other manganese minerals like bixbyite, pyroxmangite, rhodochrosite, spessartine,

pyrolusite, cryptomelane, psilomelane and coronadite (Nayak, 1966, 1976; Siddiquie

and Bhat, 2008; Bhat, 2013; Sarkar, 2013; Burhamuddin, 2015; Jawed, 2015). The

association of braunite with manganese silicates viz; pyroxmangite which represent

metamorphic origin (Jawed and Siddiquie, 2014). Braunite generally transform into

secondary ores and also replaced by pyrolusite, cryptomelane, psilomelane etc. The

common gangue occurring as hematite and silica. Braunite is showing massive and

fine to coarse granular form. It is usually exhibit dark gray in color with brownish or

pinkish tint. But second generation braunite show grayish white color (Fig. 5.3).

Pleochroism and reflectivity of braunite is weak. Under cross nicols it is weakly

anisotropic. While twinning is absent and provides weak pinkish internal reflection.

Some manganese minerals showing fold patterns in few polished ore blocks at some

places (Fig. 5.2).

Fig. 5.1 Photomicrograph of manganese ore showing massive braunite.

Fig. 5.2 Photomicrograph of manganese ore showing folding pattern by braunite

along with gangue.

Fig. 5.3 Photomicrograph of manganese ore showing second generation braunite

which is least affected by metamorphic conditions.

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Under microscope braunite also coarse grained with euhedral to subhedral grains

shape (Fig. 5.41). It is also showing anhedral shape due to replacement and alteration.

Two sets of cleavage are present. Various other minerals occurred interstitially in

braunite like pyrolusite, cryptomelane, hollandite, coronadite and gangue. While

second generation braunite is mostly free from these minerals (Fig. 5.3). The coarse

grained recrystallized braunite also reported in Kajlidongri manganese deposits by

Nayak (1976). Braunite also associated with quartz vein (Fig. 5.32). Braunite II is the

only one of its kind in the world believed to be formed due to hydrothermal activity

(Bhat, 2013).

5.2.2 Bixbyite (Mn, Fe)2O3

The general formula of Bixbyite is (Mn, Fe)2O3 and crystallized in isometric

system. Bixbyite is characteristically formed in high temperature metamorphic zone

(Jawed and Siddiquie, 2014). In study area the mineral bixbyite is found as minor

occurrence and mainly associated with braunite in few polished blocks (Fig. 5.4, 5.5).

Depending on the bulk composition (availability of silica and iron etc.), Temp and O2

fugacity, braunite and bixbyite may form together in metamorphosed manganese

oxide ore body (Muan, 1959 a, b). It is not identified megascopically in samples.

Bixbyite mineral occurred as fine grain with rounded to subrounded shape. It is non

pleochroic with slightly higher reflectivity in comparison to braunite.

Fig. 5.4-5.5 Photomicrographs of manganese ore showing bixbyite replacement by

braunite II.

Under cross nicols it is isotropic and internal reflection is absent. The bixbyite

is formed by the sediments those were rich in Mn-hydroxide, silica and Fe-oxide,

which reacted with iron oxide to form bixbyite (Krishna Rao, 1963b). The iron oxide

95

(hematite) as inclusions in other minerals also identified in some ore sections while

similar properties also reported by Siddiquie (2004) and Siddiquie and Bhat (2008) in

Vizianagram manganese ores. The bixbyite and braunite may be derived from high

temperature hydrothermal solution (Roy, 1968).

5.2.3 Pyroxmangite (MnSiO3)

The general formula of pyroxmangite is MnSiO3 and it is crystallized in

triclinic system. The pyroxmangite is high pressure and low temperature mineral. It is

the dimorph of rhodonite (Mn, Fe, Mg, Ca)SiO3. In study area the pyroxmangite

mineral is found in minor occurrence and mainly associated with braunite (Fig. 5.6). It

is basically occurs in regionally metamorphosed deposits rich in manganese. It is not

identified megascopically. Pyroxmangite mineral occurred with prismatic shape and

showing pinkish color (PPL). It has smooth mineral grain boundaries and rimmed by

quartz mineral at places. Pyroxmangite is weakly pleochroic with high reflectivity.

One set of cleavage is common. Under cross nicols it is anisotropic with reddish

internal reflection. Pyroxmangite shows lamellar twinning also. The pyroxmangite

mineral themselves contain number of inclusions of rhodochrosite and quartz. The

mineral is not only formed between the reaction of quartz and rhodochrosite but also

due to a number of other processes (Bhat, 2013).

Fig. 5.6 Photomicrograph of manganese ore showing Mn-pyroxene with braunite and

hematite.

5.2.4 Spessartine Mn3Al2(SiO4)3

Spessartine mineral is crystallized in isometric system with chemical

composition Mn3Al2(SiO4)3. In study area, it is mainly associated with braunite and

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pyrolusite (Fig. 5.7). It is not identified megascopically in samples. It is basically

occurs in low grade metamorphic rocks like phyllite. Spessartine mineral occurred as

porphyroblast or in clusters in manganese ores of study area. The mineral under

microscope shows pale pink to brownish color. It is weakly pleochroic with low

reflectivity. Under cross nicols it is isotropic without internal reflection or show weak

anisotropism. The relief of mineral is high.

Fig. 5.7 Photomicrograph of manganese ore showing rhombohedral shaped

spessartine with pyrolusite.

5.2.5 Pyrolusite MnO2

It is an important secondary manganese ores with general formula MnO2. It is

formed at the expanse of primary manganese minerals by the processes of alteration

or replacement. It is a manganese dioxide mineral and crystallized in tetragonal

system. Pyrolusite is also a dominant secondary mineral which occurred throughout

the manganese belt of the study area. The mineral megascopically represented as

crystalline or non crystalline varieties in the study area. It is found in association with

other manganese minerals like braunite, spessartine, cryptomelane, coronadite and

wad. The mineral generally is a product of primary ore (braunite) alteration, colloidal

solution and supergene enrichment (Fig. 5.8, 5.13). Pyrolusite is commonly a

secondary alteration product of MnO2 and MnSiO3 (Siddiquie, 2004). The common

gangues with pyrolusite are hematite, silica and ochre. Colloform and replacement

texture are common in pyrolusite which is also reported in manganese ores of Kandri,

Mansar, Beladongri and Satak mines in Nagpur district (Jawed and Siddiquie, 2014).

The pyrolusite is considered to be of colloidal derivation and of supergene origin (Fig.

5.11, 5.14).

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Fig. 5.8 Photomicrograph of manganese ore showing alteration of braunite into

pyrolusite.

Fig. 5.9 Photomicrograph of manganese ore showing acicular alteration growth of

pyrolusite along the pre-existing braunite: a common feature of supergene

alteration.

Fig. 5.10 Photomicrograph showing pyrolusite formed by supergene alteration from

braunite as established by the diffused grain boundary where relict braunite

is also present.

Fig. 5.11 Photomicrograph showing completely altered/recrystallised pyrolusite

embedded in matrix of cryptomelane/psilomelane.

Fig. 5.12 Photomicrograph showing presence of both neo-crystallised as well as

recrystallised pyrolusite. In the upper to middle part it shows alteration

while right side neo-crystallised pyrolusite shows different orientation.

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Under microscope it is medium to coarse grained with euhedral to

prismatic crystals. It is usually exhibit grey to yellowish color. The mineral is weakly

pleochroic with moderate reflectivity. Under cross nicols it is showing strong

anisotropism. While twinning is absent and provides weak yellowish internal

reflection. The number of minerals occurred as inclusion in pyrolusite like

cryptomelane, coronadite and gangue. In Talwara manganese deposits the mineral

pyrolusite showing grayish white color and occurred in granular form. The mineral is

weakly pleochroic with high reflectivity. Under cross nicols mineral is strongly

anisotropic.

Fig. 5.13 Photomicrograph showing growth of pyrolusite from structurally pre-

deformed stretched braunite.

Fig. 5.14 Photomicrograph showing typical grain completion supergene alteration

from braunite to pyrolusite establishing fo2/oxidation potentiality of the

supergene fluid.

5.2.6 Hollandite Ba(Mn4+6Mn3+

2O16)

Chemical composition of Hollandite is Ba(Mn4+6Mn3+

2O16) and crystallized in

tetragonal. It is first described by Fermor (1909) in manganese deposits of India. It is

basically formed from low temperature manganese oxides. Optically hollandite is fine

grained (Fig. 5.15). Under microscope, It is showing white to grayish white color with

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yellowish tint. It is weakly pleochroic with low to moderate reflectivity. Under cross

nicols it is showing strong anisotropism. The distinct prismatic cleavage is present. In

cleavage direction mineral showing strong white color. Some grains showing lamellar

twinning. The mineral is occurring along the margin of quartz grain at many places

(Fig. 5.16).

Fig. 5.15 Photomicrograph of manganese ore showing fine grained hollandite

replacing massive braunite.

Fig. 5.16 Photomicrograph of manganese ore showing presence of anhedral grain of

hollandite in braunite.

5.2.7 Cryptomelane K(Mn4+,Mn2+)8O16

The mineral is very similar to psilomelane in physical properties but differ in

chemical properties and XRD patterns (Ramsdell, 1942). Chemically it is

K(Mn4+,Mn2+)8O16 and crystallized in tetragonal system. It is commonly occurred

with oxidized manganese deposits as replacement product. It is mostly occur in

association with both pyrolusite and braunite in the study area. It is found as fine to

medium grained granular or botryoidal masses. Cryptomelane is one of the major

constituent of Banswara manganese ores. It is occurred in both way as alteration of

primary minerals, replacement and supergene origin (Fig. 5.17). Optically it is

showing white to grayish white color with weak pleochroism. The reflectivity is high

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with feebly anisotropic. Colloform texture is common in cryptomelane. In manganese

deposits of Talwara, cryptomelane exhibit white to grayish white color with weak

pleochroism. The mineral showing moderate reflectivity. Under cross nicols it is

showing strong anisotropism.

Fig. 5.17 Photomicrograph of manganese ore showing alteration of braunite to

cryptomelane.

5.2.8 Psilomelane Ba(Mn2+)(Mn4+)8O16(OH)4

The mineral is assigned as a group of compact black manganese oxide having

general composition Ba(Mn2+)(Mn4+)8O16(OH)4 or as (Ba,H2O)2Mn5O10. It is

crystallized in monoclinic system. Psilomelane mineral consist BaO as an essential

component with or without a small percentage of potassium oxide (Fleishcer, 1960).

According to Richmond and Fleischer (1942) psilomelane mineral is a hard, compact

and amorphous variety of manganese oxides. The mineral is occurred in association

with pyrolusite and braunite (Fig. 5.18). It is fine grained with grayish white in color

and showing weak pleochroism (Fig. 5.19). The fined grained psilomelane also

reported by Siddiquie (2004) in Vizianagram manganese ores. Under cross nicols, it is

strongly anisotropic. It is showing colloform texture and zoning very commonly. The

mineral psilomelane also contains BaO as one of the essential constituents with little

or no K2O (Fliescher, 1960).

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Fig. 5.18 Photomicrograph of manganese ore showing fine grained psilomelane.

Fig. 5.19 Photomicrograph of manganese ore showing fine grained psilomelane and

braunite.

5.2.9 Coronadite Pb(Mn4+6 Mn3+

2)O16

It is a Pb-Mn hydrous oxide of manganese having chemical composition is

Pb(Mn4+6 Mn3+

2)O16. It belongs to tetravalent manganese oxide rich mineral and

usually associated with supergene manganese ores (Hewett, 1971 and Frenzel, 1980)

and crystallized in monoclinic system. Originally it is discovered by Lindgreen and

Hillebrand (1904). The mineral is also formed through lateritization reported by

Bricker (1965) and coronadite formed by epigenetic solution also reported by Ehrlich

et al. (2004). Under microscope it is fine grained having fibrous or radiated form and

exhibit dark grey to white color (Fig. 5.20, 5.21). It is strongly pleochroic with

submetallic lustre. Under cross nicols it is strongly anisotropic. In study area it is

associated with braunite. The coronadite mineral in association of cryptomelane,

limonite, quartz and kaolinite also reported in other deposits (Orcel, 1942).

Fig. 5.20 Photomicrograph of manganese ore showing radiated needles of coronadite,

with cryptomelane (white) and hollandite.

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Fig. 5.21 Photomicrograph of manganese ore showing acicular needles of coronadite

along the boundaries of ferruginous manganese and braunite.

5.2.10 Hematite

It is a mineral form of iron (III) oxide (Fe2O3) and crystallized in trigonal

system. In study area it is occurred as an original constituent and also as a

replacement product in few polished blocks (Fig. 5.24). Under microscope it is

exhibiting reddish brown color with weak pleochroism. Cleavage and twinning are

absent. Under cross nicols it is feebly anisotropic with reddish internal reflection. It is

also associated with braunite and secondary ores in study area (Fig. 5.22). The

mineral is formed in high temperature and pressure, and also depict about high grade

metamorphic conditions manganese ores of Kandri, Mansar, Beladongri and Satak

mines in Nagpur district (Jawed and Siddiquie, 2014). Nayak (1976) reported three

ways of hematite mineral occurrence in Kajlidongri manganese deposits of Jhabua

district, Madhya Pradesh;

i) As an original constituent of manganese ores.

ii) As a secondary mineral (II) crystallized from the Fe2O3 released during

conversion of bixbyite to braunite (Fig. 5.23).

iii) As micaceous hematite associated with quartz veins.

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Fig. 5.22 Photomicrograph of manganese ore showing original minute specks of

primary hematite with massive braunite.

Fig. 5.23 Photomicrograph of manganese ore showing pyrolusite with hematite II as a

product of replacement.

Fig. 5.24 Photomicrograph of manganese ore showing braunite replacement by

pyrolusite, hematite and gangue.

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5.3 Textures and Microstructures

The manganese ores of the study area characterized by distinct texture because

of the presence of different mineral association. A number of textures identified in the

manganese ores of study area are as follows:

5.3.1 Replacement Texture

5.3.2 Banded Texture

5.3.3 Colloform Texture

5.3.4 Veined Texture

5.3.5 Granular Texture

5.3.6 Spherulitic Texture



5.3.9 Crystallographic Intergrowth

5.3.10 Mutual Boundary relation

5.3.11 Open Space Filling Texture

5.3.1 Replacement Texture

A vast replacement took place in the manganese ores and the associated

country rocks of the study area. Replacement relations are of major importance here

as Roy (1957) referred that the manganese ores of the study area formed by

replacement process. The replacement texture noticed in various ore assemblages and

out of which braunite mineral is dominantly replaced by the other ore minerals. The

various assemblages in which replacement texture formed are Braunite-Pyrolusite,

Braunite-Cryptomelane (Fig. 5.25, 5.26), Braunite-Psilomelane, Pyrolusite-

Coronadite, Braunite-Hollandite, Pyrolusite-Cryptomelane, and Pyrolusite-

Psilomelane. The replacement texture formed along the grain boundaries, periphery of

mineral grain, fractures, cleavages and fissures. These paths also served ways for

circulation of mineralizing fluids. Due to replacement, the grain boundary of braunite

is almost wiped out while at places the original braunite granules are seen within the

mass of other ore minerals like cryptomelane, pyrolusite etc. Braunite is replaced at

many places in irregular form by pyrolusite and cryptomelane. The fractures in

braunite serve as planes of structural weakness and provided ways for replacement by

psilomelane and hollandite. Hollandite and psilomelane also occurred as interstitial

105

spaces in braunite. Pyrolusite replaced along walls of fractures by cryptomelane, and

psilomelane. Vein replacement also very common where pyrolusite occurred as veins

and transecting braunite. These pyrolusite veins wall are thin and thick at places,

irregular and crenulated. Rim replacement where pyrolusite replaced by braunite.

Partial replacement of pyrolusite by braunite observed at places. Replacement texture

is more common in manganese ores of Talwara village.

5.3.2 Banded Texture

The banded texture is formed in hard, massive and compact manganese ores.

The texture is associated with braunite. Braunite layers show distinct crystal outline

alternate with gangue. The bands intersected innumerably and filled by other

secondary manganese ores and gangue. Banding is seen very wide at places (Fig.

5.27). The bands are curved and tighten at places in some polished blocks. The

primary bands of braunite also replaced superficially with cryptomelane (Fig. 5.28).

At various places in other polished section the braunite crystal outline is not distinct

due to replacement by cryptomelane and other manganese ores. This type of ore

indicating that they are the remnant of primary metamorphosed ore and largely

replaced and altered by the secondary ores of later origin.

5.3.3 Colloform Texture

This type of texture mainly associated with cryptomelane, pyrolusite and

gangue. The texture is very much pronounced in manganese ores of Talwara where it

is associated mainly with cryptomelane and pyrolusite. In manganese deposits of

Banswara the texture consist irregular concentric layers, where at some places circular

layer is smooth and simple (Fig. 5.30). The texture showing a small nucleus of

braunite or gangue surrounded with concentric layers of cryptomelane and pyrolusite

at places (Fig. 5.31). The colloform bands of cryptomelane and pyrolusite also

partially developed in few polished ore blocks (Fig. 5.29). The successive concentric

bands of cryptomelane are common in manganese ores of Talwara.

106

Fig. 5.25 Photomicrograph showing replacement of massive braunite by pyrolusite.

Fig. 5.26 Photomicrograph showing braunite is replaced by cryptomelane.

Fig. 5.27 Photomicrograph showing thick banded braunite where it is filled with

gangue.

Fig. 5.28 Photomicrograph showing banded braunite where boundary is not clear due

to replacement by cryptomelane.

Fig. 5.29 Photomicrograph showing partially developed colloform bands of pyrolusite

and cryptomelane.

107

Fig. 5.30 Photomicrograph showing partially developed colloform bands between


Fig. 5.31 Photomicrograph showing colloform texture between braunite, pyrolusite

and cryptomelane.

Fig. 5.32 Photomicrograph showing vein of braunite in pyrolusite and cryptomelane.

Fig. 5.33 Photomicrograph showing vein of pyrolusite in braunite and cryptomelane.

Fig. 5.34 Photomicrograph showing veins of pyrolusite filled in braunite.

108

Fig. 5.35 Photomicrograph showing anhedral to subhedral grains of braunite and fine

grained psilomelane.

Fig. 5.36 Photomicrograph showing fine grained granular psilomelane with euhedral

grain of braunite in centre.

Fig. 5.37 Photomicrograph showing granular texture by psilomelane and braunite.

Fig. 5.38 Photomicrograph showing spherulitic texture by braunite grains with

occurrence of fine grained ferruginous manganese.

109

5.3.4 Veined Texture

In the study area manganese minerals observed in form of veins. The braunite

occurred as irregular vein and replaced by pyrolusite and cryptomelane along vein

walls (Fig. 5.36). The secondary ores pyrolusite also occurred in veins and cut across

the crystalline and massive braunite (Fig. 5.33, 5.34)

5.3.5 Granular Texture

This type of texture is very much prominent in the study area. It is mainly

associated with all ore minerals, occurred in the form of fine to coarse grains.

Braunite is showing coarse grained anhedral to euhedral grains with pyrolusite and

psilomelane (Fig. 5.35, 5.36). The pyrolusite, cryptomelane and hollandite occurred as

intergranular masses in coarse grained braunite (Fig. 5.37). Hollandite and pyrolusite

also showing granular texture but it is not fully developed.

5.3.6 Spherulitic Texture

In few polished blocks of study area spherulites consist mainly braunite. The

inner portion on higher magnification made up of cryptocrystalline hollandite and

coronadite minerals (Fig. 5.38).


This type of texture represent between hard and soft ores. A subhedral grain of

hard braunite remained as relics in fine grained groundmass of secondary pyrolusite

(Fig. 5.43). The microfractures and intergranular spaces in braunite and pyrolusite are

filled with secondary ores and gangue. In another polished blocks a large subhedral

crystal of braunite present as a remnant in fine grained groundmass of pyrolusite (Fig.

5.42).


In few polished section braunite occurred in angular to subangular shape (Fig.

5.41). The grains are cemented with pyrolusite, cryptomelane and gangue. While the

intergranular spaces filled with pyrolusite, cryptomelane and gangue.

110

5.3.9 Crystallographic Texture

Such texture is observed in pyrolusite and cryptomelane in study area. The

cryptomelane occurred along specific crystallographic direction in pyrolusite and

showing intergrowth relation (Fig. 5.40).

5.3.10 Mutual Boundary relation

This type of relation is mainly shown by braunite and bixbyite in the study

area. The braunite and bixbyite showing sharp contact along their boundaries without

any replacement (Fig. 5.44).

5.3.11 Open space filling Texture

This type of texture mainly showing by secondary manganese ores like

pyrolusite, cryptomelane and psilomelane (Fig. 5.39). The open spaces like

microfractures and fissures filled with these manganese minerals.

Fig. 5.39 Photomicrograph of manganese ore showing honeycomb structure and

crustification.

Fig. 5.40 Photomicrograph showing intergrowth of cryptomelane in pyrolusite.

Fig. 5.41 Photomicrograph showing angular to subangular braunite grains embedded

in gangue material.

111

Fig. 5.42-5.43 Photomicrographs showing relics of primary braunite in pyrolusite.

Fig. 5.44 Photomicrograph showing mutual boundary relation between braunite and

bixbyite.

5.4 X-Ray Diffraction Studies

A number of samples of manganese ores of study area were analyzed by using

X-ray diffraction technique for the confirmation of manganese ore minerals. The

dominant manganese ore minerals occurred in the study area as earlier mentioned are;

braunite, pyrolusite, cryptomelane, coronadite and wad. The other manganese ore

minerals which found in association and in minor occurrence are bixbyite,

pyroxmangite and rhodochrosite. The manganese minerals identified by the XRD

technique using d-spacing and intensity of 2 theta position. The technique confirmed

the presence of manganese minerals are braunite, pyrolusite, cryptomelane, coronadite

and spessartine. Some associated other minerals of minor occurrence also recorded on

the XRD spectrum. The gangue minerals which identified in XRD spectrum are

quartz, orthoclase, albite, calcite and hematite. The identified minerals confirmed by

XRD technique represented in (Fig. 5.45-5.55).

112

Fig. 5.45 Showing 2θ position of braunite, albite and quartz, Ghatia village, Banswara


Fig. 5.46 Showing 2θ position of pyrolusite, spessartine, hematite and quartz, Ghatia

village, Banswara district, Rajasthan.

Fig. 5.47 Showing 2θ position of braunite, pyroxmangite, bixbyite, rhodochrosite and

quartz, Kalakhunta mine, Banswara district, Rajasthan.

113

Fig. 5.48 Showing 2θ position of braunite, hollandite, albite and quartz, Kalakhunta


Fig. 5.49 Showing 2θ position of braunite, quartz and manganesio-hornblende


Fig. 5.50 Showing 2θ position of braunite, bixbyite, hollandite, quartz and orthoclase,


114

Fig. 5.51 Showing 2θ position of cryptomelane and braunite, Kalakhunta mine,


Fig. 5.52 Showing 2θ position of pyrolusite, spessartine and quartz, Tambesara


Fig. 5.53 Showing 2θ position of braunite, spessartine and quartz, Tambesara section,


115

Fig. 5.54 Showing 2θ position of braunite, coronadite and quartz, Kalakhunta mine,


Fig. 5.55 Showing 2θ position of braunite and albite, Rupakhera section, Banswara


5.5 Scanning Electron Microscopic Studies

The few manganese samples coated with carbon were used to reveal micro

textures, and mineralogical studies were conducted by scanning electron microscope

(SEM). The SEM analysis with the help of EDX microanalyzer is very much helpful

to identify important micro textures and structures, reveal sequential phases in the

paragenesis of the manganese ores belongs to sedimentary, metamorphosed and

supergene phases (Bhat, 2013). The scanning electron microscopic images and EDX

data are attached in (Fig. 5.56-5.63) and the description are as follows: The EDX

graph revealing that the silica percentage is very high (43.17 wt %) where as Mg, Al,

K, Ca present in negligible amount with iron percentage is around (4.87-5.87 wt%)

(Table 5.2). In another SEM image white patches of carbonate present in various

forms observed as an impurity in manganese ores of study area (Fig. 5.56, 5.57, 5.62)

116

and confirmed by EDX graph revealing high percentage of CaCO3 around (89.40%)

(Table 5.l). The textures and structures like replacement (fissure replacement),

honeycomb structure etc., also confirmed by SEM images (Fig. 5.58, 5.60, 5.61, 5.62

and 5.63).

Fig. 5.56 SEM image showing carbonate replacement in the primary braunite bearing

manganese ores, Tambesara section, Banswara district, Rajasthan.

Fig. 5.57 EDX data showing peaks of different elements at spectrum I, Tambesara


Table 5.1 EDX data of spectrum I in manganese ore of Tambesara section, Banswara


Oxide(In Wt%) Spectrum I

SiO2 2.14

Al2O3 1.61

TiO2 -

Fe2O3 2.41

MnO 3.20

MgO 0.65

CaO 89.40

Na2O .01

K2O .26

P2O5 -

Total 99.68

117

Fig. 5.58 SEM image showing fissure replacement in secondary manganese ore,


Fig. 5.59 EDX data showing peaks of different elements at spectrum II, Kalakhunta


Table 5.2 EDX data of spectrum II in manganese ore of Kalakhunta mine, Banswara


Oxide (In wt%) Spectrum II

SiO2 43.17

Al2O3 2.43

TiO2 .01

Fe2O3 5.87

MnO 47.37

MgO 0.38

Cao .22

Na2O .01

K2O .01

P2O5 -

Total 99.47

118

Fig. 5.60 SEM image showing honeycomb like structure showing by pyrolusite

bearing manganese ore, Kalakhunta mine, Banswara district, Rajasthan.

Fig. 5.61 SEM image showing replacement between primary (braunite) and secondary

(pyrolusite) manganese ores, Ghatia section, Banswara district, Rajasthan.

Fig. 5.62 SEM image showing euhedral crystal of calcite present as an impurities in

braunite, Tambesara section, Banswara district, Rajasthan.

Fig. 5.63 SEM image showing globules of hollandite in primary ore braunite,


119

5.6 Proposed mineral paragenesis of the manganese ores

The paragenetic sequence of manganese minerals is determined by the

appearance and textural relationship of ore minerals. The mineragraphic and XRD

studies reveal that braunite is abundant mineral in study area with gonditic

assemblages (Orthoclase-Pyroxmangite-Spessartine). The presence of these minerals

reveal that the primary manganese ores of study area similar to gonditic type. As the

minerals braunite is recorded almost in all polished blocks of study area as well as

through XRD spectrum. So on behalf of mineragraphic and textural relation studies, it

is concluded that the braunite minerals was the earliest mineral crystallized in the

study area. The original manganiferous sediments were metamorphosed under low

grade metamorphism with the formation of braunite first followed by bixbyite, while

bixbyite mineral presence is in minor amount in the study area. These bixbyite

mineral formed at the peak of metamorphism. The braunite and bixbyite formation

largely controlled by Fe and Si concentration in original manganiferous sediments

(Nayak, 1976). In the study of the Fe2O3-Mn2O3 system by Mason (1944), it has been

shown that bixbyite can accommodate up to 60% Fe2O3 in its structure and that this

entry of iron is a function of temperature. The Fe3O4-Mn3O4 system has been studied

by Mason (1943), Van Hook and Keith (1958).

According to Mason (1943) the braunite would preferentially be formed in Si-

rich environment in comparison of bixbyite which would form in silica poor

condition. There is no presence of minerals like jacobsite and hausmannite in ore

mineralogical assemblages of the study area which indicates that the stability field of

mineral bixbyite was not much exceeded. Nayak (1976) provided similar views about

the stability of bixbyite in Kajlidongri manganese deposits of Jhabua district, Madhya

Pradesh. The geochemical data also confirmed that the iron content in manganese ores

was not sufficient for the formation of these two minerals. The bixbyite formed in the

study area by the reaction between braunite and originally present hematite in

manganiferous sediments. According to Schneiderhohn (1931) the formation of

bixbyite by the reaction is as follows;

Mn. MnO3 + Fe2O3 (Mn.Fe) MnO3

Braunite Hematite Bixbyite

120

The second generation of braunite also recorded which possibly formed by

transformation of bixbyite in an undeformed manner with decreasing metamorphic

conditions. The formation of second generation braunite during retrogressive

metamorphism suggested by Dunn (1936). The braunite also occurred in form of

bands, alternate with gangue and as a porphyroblast in fine grained ground mass of

pyrolusite and braunite. The bands also intersect by pyrolusite veins and intergranular

space filled with secondary manganese or gangue as well.

The cryptomelane and pyrolusite are recrystallized as secondary alteration

product of primary and colloidal manganese. The successive bands of pyrolusite and

cryptomelane are present in polished ores blocks and presence of successive layering

of cryptomelane and pyrolusite indicating simultaneous deposition. While in few

polished blocks, both first and second generation pyrolusite present with totally

different orientation. Apart from these ore minerals the hollandite ore mineral

occurring with first generation braunite and replacing it. The acicular alteration

growth of pyrolusite is the common feature of supergene enrichment presented in

prevailing ore mineral assemblages of the study area. While on other side colloform

texture indicates derivation of manganese ore minerals from colloidal aqueous

hydrothermal solution.

Due to dominance of braunite with characteristic banded texture, bedding and

conformable relations with the enclosing rocks, textural and mineralogical studies of

other ore minerals assemblages of the study area suggested that the ore body formed

by regional metamorphism of syngenetic manganiferous sediments, however

hydrothermal manganese bearing solution also play an important role in the

enrichment of manganese ores in the study area at later stage. The various ore

minerals found in the study area are differently classified which are as follows:

i) Primary ores- Braunite-Bixbyite-Pyroxmangite-Hollandite-Mn Garnet-Hematite

ii) Secondary ores- Pyrolusite-Cryptomelane-Psilomelane-Coronadite-Hematite

The suggested ore minerals paragenesis (Table 5.3) of Banswara manganese

ores can be compared to paragenesis of manganese deposits of different metamorphic

zones of Madhya Pradesh-Maharashtra manganese belt (Table 5.4). The ore mineral

assemblages of study area very much similar to manganese deposits of different areas

121

of Madhya Pradesh-Maharashtra manganese belt which are as follows: The low

temperature gel formation (Metamorphic zones) of Dongri Buzurg area of Bhandara

district (Pyrolusite-cryptomelane-manganite-coronadite), Chlorite zone of Shivrajpur,

Panch Mahal district, Gujrat (Braunite-pyrolusite-cryptomelane) and Biotite zone in

Kajlidongri, Jhabua district, Madhya Pradesh, where represented mineral assemblages

(Braunite-Bixbyite-Hollandite)-(Pyrolusite-cryptomelane-hematite). In relation to ore

mineral assemblages the country rocks also played an important role in the formation

of these phases during low greenschist facies to lower amphibolite facies of

metamorphism which is also confirmed by the presence of clusters of minute size

garnets in phyllite and schist rocks

Table 5.3 The suggested possible paragenesis of manganese ores of Banswara

manganese belt.

Minerals Time

Braunite --------------------------------

Bixbyite -----

Pyroxmangite -----

Hematite --------- -------

Pyrolusite --------- --------

Cryptomelane ------ --------

Hollandite ------

Coronadite -------

Primary Colloidal Supergene

122

Table 5.4 Mineral paragenesis of manganese ore deposits from different metamorphic

zones of Madhya Pradesh - Maharashtra manganese belt (After Roy, 1963).

Zone of

Metamorphism

Area Manganese oxide mineral assemblages

Low temperature

‘gel’ formation Dongri Buzurg

Pyrolusite-cryptomelane-manganite-

coronadite

Chlorite zone Shivrajpur, Gujarat Braunite-(pyrolusite-cryptomelane)

Biotite zone Kajlidongri, Jhabua

District, M.P.

Braunite-bixbyite-hollandite-

(pyrolusite-cryptomelane-hematite)

Almandine zone

Bharweli-Ukwa area,

Balaghat District, M.P.

Braunite-bixbyite-hollandite-manganite-

(pyrolusite-cryptomelane)

Dongri Buzurg (west)-

Kurmura area, Bhandara

District, Maharashtra.

Braunite-hollandite-manganite-


Staurolite-

Kyanite zone

Chikla-Sitasaongi

area, Bhandara District,

Maharashtra



Braunite-vredenburgite-hollandite-

(pyrolusite- cryptomelane)

Braunite-bixbyite-jacobsite-hollandite-


Sillimanite zone

Gowahari-Wadhona

area, Chhindwara

District, Madhya Pradesh



Braunite-bixbyite-vredenburgite-jacobsite-

hausmannite-(pyrolusite-cryptomelane)

Ramdongri- Gumgaon

area, Nagpur District,

Maharashtra

Braunite-vredenburgite-bixbyite-

hausmannite-(pyrolusite-cryptomelane)

Braunite-bixbyite-jacobsite-hausmannite-

manganite-(pyrolusite-cryptomelane)

Braunite-vredenburgite-hollandite-

hausmannite- (pyrolusite-cryptomelane)

Tirodi-Sitapathore area,

Balaghat District, Madhya

Pradesh.



Braunite-hausmannite-jacobsite-


Braunite-bixbyite-vredenburgite-


123

CHAPTER-6

GEOCHEMISTRY OF MANGANESE ORES


Manganese is the third most abundant transition metal in Earth’s crust and has

the largest number of oxidation states of 3d row elements (Armstrong, 2008), and so

consequently the manganese cycle both (modern and ancient) involves multiple redox

conversions (Johnson et al., 2016). It is an important strategic metallic element and lies

under VIIth group of periodic table. Geochemically manganese occurs as strong

lithophile element. It is not siderophile at all but show some chalcophile characters

(Roy, 1981). According to Rankama and Sahama (1950) it is oxyphile in upper

lithosphere and also shows a biophile tendency. Manganese is the 12th most abundant

element in the earth’s crust with an atomic weight around 54.93 and is represented in

nature by its single isotope (55Mn). It has +2, +3 and +4 valance states and out of which

only +2 valance state is the most stable for oxidation. Manganese metal is widespread

in nature and occurring in all rocks and soils (Krauskopf and Bird, 1995) and serves as

a useful tool to explore the genetic environment and the paleo-environmental

conditions.

The average abundance of manganese in the earth crust calculated by various

workers in past which is very close to 1000 ppm (1000 ppm, Goldschmidt, 1954 and

950 ppm, Krauskopf, 1967) while average abundance values of Ronov and

Yaroshevsky (1972) is 1060 ppm which is slightly higher than the Goldschmidt (1954)

and Krauskopf (1967) values. The abundance of manganese content in different rock

types always varies according to mineralogical composition and also due to behavior of

different elements such as Mn, V, Ni, Fe, Co, Cu, Ba, Sr, Zn, Mo, La, Yb, Zr, Ir, Pb and

P present in it. Elements that are present in the earth’s crust are also present in the

manganese ores distinctly as three types (Bhat, 2013) (i) Elements enriched in Mn ores

related to their normal crustal abundances include Mn, Fe, Co, Ni, Cu, Zn, Sr, Y, Zr,

Mo, Ag, Cd, Ba, La, Yb, B, P, V, W, Ir, Hg, Pb and Bi (ii) Elements which are neither

significantly enriched nor depleted, Na, Mg, Ca, Pb, Ti, Ga, and Au. (iii) Elements

which are somewhat depleted Al, Si, Sc, K and Cr. According to Rankama and Sahama

(1950) and Goldschmidt (1954) that the manganese tends to concentrate in the latest

124

phases of magmatic crystallization with reference to iron and magnesium due to its

larger ionic radius in the divalent state. And therefore Roy (1981) explained that the

enrichment of manganese in rock forming minerals as well as specific manganese

minerals is recorded in pegmatite (Mn-Phosphates, spessartite, helvite, manganiferous

columbite and tantalite, etc.) and also in the post magmatic pneumatolytic and

hydrothermal deposits (rhodochrosite, wolframite, different Mn-oxides and

Mn-silicates).

No independent manganese minerals are found in the main stage of magmatic

crystallization and therefore the available manganese is fixed in the ferromagnesian

phases (Roy, 1981). The average abundance of manganese content and Mn/Fe ratio has

been calculated in igneous and sedimentary rocks by various workers. The average

abundance of manganese content in igneous rocks have been calculated around 0.980%

(Hevsy el al., 1934), 0.086% (Clarke and Washington, 1924) and 0.01% (Rankama and

Sahama, 1950) and the average Mn/Fe ratio in the earth crust is equivalent to crustal

average and is about 0.017%. Vinogradov (1962) reported the world average

concentration of manganese and Mn/Fe ratio for different igneous rocks such as .15%

Mn, .015 Mn/Fe (Ultrabasic rocks), .2 % Mn, .023 Mn/Fe (basic rocks), .12 % Mn, .20

Mn/Fe (Intermediate rocks). Manganese ores are basically precipitates of hydrous

manganese, abundant in hydrosphere especially oceans, shallow marine environments

and temperate lakes (Bhat, 2013). Beus (1976) calculated an average .056 %

manganese content for sedimentary rocks in general. The average Mn/Fe ratio of

sedimentary rocks has been calculated as 0.0166-0.025 and its ratio is highest in

limestone as 0.08% Mn (Stanton, 1972). The average abundance of manganese among

sedimentary rocks has been calculated by different workers and reveal that the

minimum concentration in sandstone is .026-.05 % (Wedepohl, 1969) and .001 - .01 %

(Turkenian and Wedephol, 1961) while the maximum concentration lies in oceanic

pelagic red clay is .856% (Ronov and Yaroshevsky, 1972), .67% (Green, 1972) and

.177% (Rankama and Sahama, 1950). The average manganese content of shale is

calculated as 0.085% (Krauskoff, 1967 and Beus, 1976), 0.07% (Wedepohl, 1969).

The average manganese content of shield metamorphic rocks is calculated as .08%

(Ronov and Yaroshevsky, 1972) and these values agrees well with the average values

calculated by Beus (1976) as .076%. Manhert (1969) found 0.057-0.13% of manganese

in pelitic metamorphic rocks. Beus (1972) has been recorded .12 % in amphibolites.

125

The average abundance of manganese content and Mn/Fe ratio (less than .1) is

generally low in all type of rocks on land and on the ocean bottom. According to Crerar

et al. (1978) that Mn is the most abundant soluble inorganic component in natural

waters. Unlike iron, manganese does not readily form sulfides, but is only insoluble in

its oxidized forms (Van Cappellen et al., 1998; Maynard, 2010). Thus, the presence of

significant manganese deposition in the sedimentary record should reflect the history

of manganese oxidation.

Different workers like Shatskiy (1964), Strakhov (1967 and 1969) and Stanton

(1972) stated that the formation of different types manganese ore deposits now resting

on continents can be broadly correlated with the general pattern of the crustal

evolution. The most conspicuous development of manganese deposits in geological

history, however, is found on platforms which are mostly devoid of volcanic rock

association (Roy, 1981). While in initial stages of basic volcanism, manganese ore

bodies associated with greenstones and jasper predominated. The geosynclinal studies

reveal that, with the development of eugeosyncline, Mn ore concentration were formed

in association with pyroclastic volcanic rocks (basalt, andesite, dacite) and stratiform

iron and base metal sulphide and barite deposits on the seafloor (Burhamuddin, 2015).

In more advanced stages of geosynclinal development, manganese deposits are also

formed substantially in the mio-geosynclinal domain. Instead of the fine efforts of

pioneer workers, among whom Fermor (1909) stand out conspicuously, while others

are as Shatisky (1964), Varentsov (1964), Hewett (1966), Strakhov (1967, 1969), Dorr

(1973) and Dorr et al. (1973) on broad spectrum of geology of the manganese, started

an integrated and cogent approach on many aspects of the subject. The geochemical

studies of manganese ores is very much helpful to delineate the nature of depositional

environment and their evolution, the rate of the deposition of manganese ores and

physico-chemical conditions involved in it.

126

Table 6.1 The major oxides geochemical data of manganese ore samples of different localities of Banswara district, Rajasthan, India

Oxides(wt%) Banswara Manganese Ores

S1 S2 G1 G2 K1 K2 K3 K4 GH1 GH2 IT-1 IT-2

SiO2 32.82 43.5 58.77 55.08 29.75 46.44 28.44 12.58 36.21 50.9 28.72 21.84

Al2O3 2.67 2.91 2.66 2.66 2.8 2.96 2.98 2.58 3.02 4.41 1.17 2.51

TiO2 0.11 0.31 0.08 0.06 0.26 0.22 0.39 0.7 0.12 0.45 0.04 0.06

Fe2O3 2.66 2.93 1.95 1.18 3.98 2.7 4.3 3.22 4.02 3 4.01 3.05

MnO 55.02 42.78 30.99 34.39 54.27 40.35 53.66 76.75 46.41 35.21 62.09 68.93

MgO 0.41 0.73 0.51 0.49 0.62 0.69 0.83 0.79 0.71 0.94 0.51 0.62

CaO 1.26 0.97 0.8 0.99 1.24 0.84 1.29 1.58 1.49 1.55 1.48 1.01

Na2O 0.08 0.11 0.08 0.07 0.09 0.09 0.05 0.06 0.11 0.13 0.03 0.07

K2O 0.89 0.63 1.22 0.94 0.05 1.52 0.86 0.14 0.94 0.35 1.13 0.58

P2O5 0.61 0.63 0.59 0.61 0.64 0.64 0.74 0.42 0.76 0.98 0.63 0.43

LOI 2.52 4.55 3.01 4.13 6.48 3.29 6.91 1.99 5.55 2.69 0.93 1.01

Total 99.05 100.05 100.66 100.6 100.18 99.74 100.45 100.81 99.34 100.61 100.74 100.11

MnO/Fe2O3 20.68 14.6 15.89 29.14 13.64 14.94 12.48 23.84 11.54 11.74 15.48 22.6

SiO2/Al2O3 12.29 14.95 22.09 20.71 10.63 15.69 9.54 4.88 11.99 11.54 24.55 8.7

SiO2/TiO2 298.36 140.32 734.63 918 114.42 211.09 72.92 17.97 301.75 113.11 718 364

Cao/MgO 3.07 1.33 1.57 2.02 2 1.22 1.55 2 2.1 1.65 2.9 1.63

Na2O/K2O 0.09 0.17 0.07 0.07 1.8 0.06 0.06 0.43 0.12 0.37 0.03 0.12

127

Oxides(wt%)

Banswara Manganese Ores

RT1 RT2 RT3 TM1 TM2 TM3 TM4 TM5 TM6 T1 T2 T3 Average

SiO2 22.9 35.59 37.65 30.97 44.76 28.44 35.71 45.17 15.57 24.59 20.2 25.99 33.86

Al2O3 3.08 3.49 4.13 2.5 2.7 1.33 2.74 2.75 3.16 3.12 2.67 3.15 2.84

TiO2 0.13 0.42 0.17 0.06 0.06 0.11 0.06 0.09 0.16 0.13 0.11 0.16 0.19

Fe2O3 3.34 3.45 4.27 3.36 2.05 2.95 2.11 5.2 2.85 3.23 4.53 3.41 3.24

MnO 59.6 52.24 45.99 56.97 41.3 61.87 49.47 42.18 53.47 57.5 63.03 54.22 51.61

MgO 0.69 0.72 0.85 0.14 1.2 0.7 0.9 0.88 1.1 1.01 0.94 0.97 0.75

CaO 1.83 1.22 2.17 0.5 3.52 0.86 3.06 1.83 8.82 3.8 3.43 4.31 2.08

Na2O 0.11 0.12 0.11 0.07 0.08 0.08 0.08 0.1 0.11 0.08 0.08 0.11 0.09

K2O 7.47 1.82 3.59 0.4 0.68 0.9 0.16 0.37 6.46 5.23 1.81 5.14 1.8

P2O5 0.48 0.78 1.04 0.47 0.49 0.47 0.48 0.61 0.48 0.48 0.89 0.52 0.62

LOI 0.84 0.42 0.96 4.6 2.89 2.06 5.13 1.23 7.64 1.06 3.2 2.23 3.14

Total 100.47 100.27 100.93 100.04 99.73 99.77 99.9 100.41 99.82 100.23 100.89 100.21 100.21

MnO/Fe2O3 17.84 15.14 10.77 16.96 20.15 20.97 23.45 8.11 18.76 17.8 13.91 15.9 16.93

SiO2/Al2O3 7.44 10.2 9.12 12.39 16.58 21.38 13.03 16.43 4.93 7.88 7.57 8.25 12.61

SiO2/TiO2 176.15 84.74 221.47 516.17 746 258.55 595.17 501.89 97.31 189.15 183.64 162.44 322.39

Cao/MgO 2.65 1.69 2.55 3.57 2.93 1.23 3.4 2.08 8.02 3.76 3.65 4.44 2.63

Na2O/K2O 0.01 0.07 0.03 0.18 0.12 0.09 0.5 0.27 0.02 0.02 0.04 0.02 0.2

S-Sivnia, G-Gararria, K-Kalakhunta, Gh-Ghatia, It-Itala, Rt-Ratimauri, Tm-Tambesara, T-Timamahudi

128

Table 6.2 The comparative average values of major oxides in wt% from different types of manganese ores of the world.

Oxides(wt%) 1 2 3 4 5 6 7 8 9 10 11

SiO2 43.69 58.16 9.41 43.69 58.16 13.68 10.65 13.43 28.15 2.02 33.86

TiO2 0.32 0.04 0.84 0.32 0.04 0.1 0.22 0.1 0.3 0.04 0.19

Al2O3 0.73 0.55 12.53 0.73 0.55 2.49 2.85 2.95 9.65 0.27 2.84

Fe2O3 2.96 0.92 20.33 2.96 0.92 3.72 2.46 14.33 3.15 2.3 3.24

MnO 45.88 32.5 33.78 45.88 32.5 63.78 33.39 40.33 31.48 48.52 51.61

MgO 0.6 0.19 0.59 0.6 0.19 1.99 1.27 12.72 0.61 1.58 0.75

CaO 1.28 4.15 6.43 1.28 4.15 4.05 18.96 6.82 1.51 0.97 2.08

Na2O 0.29 0.04 0.07 0.29 0.04 0.24 0.39 0.06 1.71 0.64 0.09

K2O 0.22 0.1 0.88 0.22 0.1 0.05 0.56 0.19 2.13 0.22 1.8

P2O5 0.25 0.1 3.73 0.25 0.1 0.18 0.31 0.08 5.31 0.04 0.62

1. Banffshire, Arudily, (Hydrothermal deposit) (Nicholson, 1986).

2. Wakasa, Japan (Hydrothermal) (Choi and Hariya, 1992).

3. Hydrothermal-Hydrogenous manganese ores, Hazara, Pakistan (Shah and Moon, 2004).

4. Hydrothermal manganese ores, Wajiristan ophiolite complex, Pakistan (Shah and Khan, 1999).

5. Islay, Argyllshire (Sedimentary Fresh Water) (Nicholson, 1988).

6. Ulukent, Turkey (Sedimentary) (Ozturk, 1993).

7. Binkilic, Turkey (Sedimentary digenetic) (Gultekin, 1998).

8. Kasimaga, Turkey (Volcano-sedimentary) (Koc et al., 2000).

9. Garbham, Andhra Pradesh, India (Meta-sedimentary) (Siddiquie and Bhat, 2010; Siddiquie et al., 2015a).

10. Indian Ocean, India (Marine manganese nodules) (Mohapatra et al., 1987).

11. Study area.

129

Table 6.3 The trace elements geochemical data of manganese ore samples of different localities of Banswara district, Rajasthan, India.

Elements

(ppm) Banswara Manganese Ores

S1 S2 G1 G2 K1 K2 K3 K4 GH1 GH2 I1 I2

Sc 10.58 12.07 7.63 6.09 13.84 13.15 21.40 12.81 11.14 11.51 8.87 7.96

V 39.50 22.40 56.24 97.75 41.92 42.14 63.40 36.98 81.73 93.27 60.49 57.76

Cr 30.26 32.14 28.94 28.83 32.56 34.56 33.79 33.32 24.41 23.47 14.89 12.19

Co 88.76 117.92 242.73 103.66 123.92 121.25 131.26 119.60 93.50 99.07 118.81 116.14

Ni 269.20 260.18 285.57 392.61 715.10 702.23 530.16 363.72 505.10 447.69 232.12 226.15

Cu 623.16 537.85 275.76 743.24 995.45 948.36 806.76 676.60 535.34 398.22 466.03 501.05

Zn 694.73 519.94 642.82 852.55 2305.71 2435.26 1170.42 691.65 1293.35 1105.68 348.38 331.07

Ga 14.93 14.47 8.56 15.89 18.81 19.54 20.20 17.91 16.68 17.86 20.54 18.59

Rb 13.67 16.23 7.44 13.65 9.95 8.75 20.38 5.15 20.84 18.63 11.67 9.95

Sr 554.46 519.55 621.12 722.61 794.21 724.25 807.57 680.33 1106.73 780.01 990.55 891.65

Y 47.82 62.03 38.70 25.95 82.00 81.25 134.82 78.92 70.76 70.70 25.71 26.35

Zr 140.80 135.47 210.75 180.92 163.53 169.25 229.53 154.60 287.60 472.80 40.63 38.59

Nb 2.70 5.43 2.03 2.67 9.03 8.25 5.76 7.66 3.78 4.62 3.55 2.95

Cs 1.38 4.63 0.32 0.84 0.95 0.89 2.27 0.83 0.95 1.49 0.68 0.75

Mo 6.89 4.49 36.86 33.69 17.42 7.48 36.36 24.95 1.03 2.63 5.98 7.24

Ba 7440.65 24633.56 3160.61 8810.29 21090.70 20884.25 22477.24 20696.89 5972.81 8411.76 7429.58 8012.57

Hf 2.82 2.85 2.77 3.55 3.34 3.89 4.84 3.19 4.57 3.93 0.81 0.92

Ta 1.65 2.58 0.81 0.71 0.96 1.05 1.73 1.06 0.35 0.64 0.56 0.49

Pb 144.53 133.10 76.81 99.77 172.58 189.12 269.70 121.56 129.27 93.07 21.70 19.99

Th 3.88 7.46 3.41 1.34 6.46 7.56 14.57 5.22 3.37 7.36 3.34 2.96

U 2.76 2.69 6.05 2.18 2.93 3.21 5.20 2.63 28.14 24.32 2.45 2.57

Co/Ni 0.33 0.45 0.85 0.26 0.17 0.17 0.25 0.33 0.19 0.22 0.51 0.51

Co/Zn 0.13 0.23 0.38 0.12 0.05 0.05 0.11 0.17 0.07 0.09 0.34 0.35

Ni/Cu 0.43 0.48 1.04 0.53 0.72 0.74 0.66 0.54 0.94 1.12 0.50 0.45

Cu/Co 7.02 4.56 1.14 7.17 8.03 7.82 6.15 5.66 5.73 4.02 3.92 4.31

Cu/Cr 20.60 16.73 9.53 25.78 30.57 27.44 23.88 20.30 21.93 16.97 31.30 41.10

130

Elements

(ppm) Banswara Manganese Ores


S 8.89 7.86 9.98 12.79 11.95 9.47 11.68 12.57 12.77 8.37 4.69 8.53 10.69

V 57.76 95.73 54.42 224.85 217.25 30.87 51.99 907.91 444.17 75.75 205.84 28.81 128.71

Cr 18.63 29.07 25.14 17.84 16.65 20.09 50.81 27.31 31.11 23.90 26.51 35.52 27.16

Co 64.70 90.93 102.70 98.23 101.25 112.78 115.12 138.02 144.47 69.87 91.16 107.71 113.07

Ni 140.89 320.57 306.11 159.07 165.68 195.56 178.15 389.64 231.23 293.68 237.23 360.08 329.49

Cu 62.28 540.66 654.54 336.56 341.29 426.27 407.25 618.35 356.97 260.13 459.67 638.63 525.43

Zn 305.85 854.88 809.21 275.00 276.58 331.68 438.79 847.35 412.73 580.89 646.64 771.26 789.27

Ga 12.53 13.10 17.00 23.05 22.03 21.66 20.49 17.70 21.05 9.52 17.55 18.45 17.42

Rb 12.75 9.33 8.99 87.08 85.62 15.36 23.53 49.72 83.65 7.82 8.81 9.79 23.28

Sr 501.50 799.66 732.49 1716.16 1638.25 480.01 590.79 1360.65 2174.21 489.63 553.70 689.66 871.66

Y 58.60 35.86 92.17 55.21 58.35 39.08 54.57 68.21 64.97 35.27 29.88 43.96 57.55

Zr 185.82 268.54 243.12 72.24 75.09 64.56 56.81 209.90 103.81 276.23 113.38 150.76 168.53

Nb 5.32 2.91 2.34 5.11 4.95 4.89 6.32 5.11 5.88 2.09 1.24 3.96 4.52

Cs 0.70 0.55 1.32 9.46 7.68 1.09 7.24 5.01 8.27 0.35 0.29 0.88 2.45

Mo 16.76 10.68 4.85 24.95 61.13 59.58 44.82 10.55 9.56 5.66 8.00 7.75 18.72

Ba 6345.18 5334.77 5179.11 15996.38 16589.98 21154.78 23189.96 21860.09 22752.41 2097.29 5057.64 20003.20 13524.24

Hf 1.79 4.14 4.09 1.45 1.58 1.43 1.60 4.16 2.26 3.00 2.17 2.87 2.83

Ta 0.54 0.77 1.48 1.11 0.95 0.61 0.84 0.88 0.64 1.24 0.12 1.34 0.96

Pb 33.42 95.21 105.17 69.66 72.58 43.80 89.84 125.87 45.28 103.02 187.52 129.84 107.18

Th 4.08 2.73 5.73 9.74 10.32 5.77 7.91 8.16 11.33 6.22 1.71 4.54 6.05

U 16.91 8.44 10.68 6.96 5.86 1.75 2.87 4.28 3.96 16.10 13.49 2.57 7.46

Co/Ni 0.46 0.28 0.34 0.62 0.61 0.58 0.65 0.35 0.62 0.24 0.38 0.30 0.40

Co/Zn 0.21 0.11 0.13 0.36 0.37 0.34 0.26 0.16 0.35 0.12 0.14 0.14 0.20

Ni/Cu 2.26 0.59 0.47 0.47 0.49 0.46 0.44 0.63 0.65 1.13 0.52 0.56 0.70

Cu/Co 0.96 5.95 6.37 3.43 3.37 3.78 3.54 4.48 2.47 3.72 5.04 5.93 4.77

Cu/Cr 3.34 18.60 26.03 18.87 20.50 21.22 8.02 22.64 11.47 10.88 17.34 17.98 20.13


131

Table 6.4 The comparative average values of trace elements in wt% from different types of manganese ores of the world.

Traces 1 2 3 4 5 6 7 8 9 10 11 12 13 14.1 14.2 14.3 15

Cr 225 247 10 NR 10 NR NR NR 128 108 83 NR NR NR NR NR 107.21

Co 142 404 2 13 49.5 10 169 45.42 185 358 173 2840 1430 2140 3040 195 4.77

Ni 87 305 28 10 23 5 56 77.08 71 93 45 4800 9770 15200 8600 7420 89.39

Cu 1519 375 50 56 126.8 1400 174 174 169 233 146 2595 7100 11870 4980 3710 31.03

Zn 676 580 26 70 63.5 ‹50 225 NR 101 101 173 NR NR 1690 760 2340 137.36

Pb 3665 2357 112 65 53.5 700 32 18.75 40 156 23 NR NR NR NR NR 16.49

1. Hydrothermal manganese deposit, Banffshire, Arudily (Nicholson, 1986).

2. Hydrothermal-Hydrogenous manganese ores, Hazara, Pakistan (Shah and Moon, 2004).

3. Wakasa, Japan (Hydrothermal) (Choi and Hariya, 1992).

4. Ulukent, Turkey (Sedimentary) (Ozturk, 1993).

5. Kasimaga, Turkey (Volcano-sedimentary) (Koc et al., 2000).

6. San Francisco, USA (Volcanogenic manganese deposits) (Zantop, 1981).

7. Sedimentary manganese deposits, Barbil, India (Ajmal, 1990).

8. Fresh water sedimentary manganese deposits, Barbil, Odisha, India (Ajmal, 1990).

9. Meta-sedimentary manganese deposits, Bhandara district, India (Acharya et al., 1997).

10. Manganese deposits (Metasedimentary), Bhandara, India (Rai et al., 1979).

11. Garbham, Andhra Pradesh, India (Meta-sedimentary) (Siddiquie and Bhat, 2010; Siddiquie et al., 2015a).

12. Marine manganese nodules (Nicholson, 1992).

13. Indian Ocean, India (Marine/hydrothermal) (Mohapatra et al., 1987).

14. (14.1,14.2,14.3) Ferromanganese nodules of Pacific Ocean (Roy, 1992).

15. Guichi, China (Sedimentary) (Xie et al., 2006).

16. Hydrothermal manganese ores, Wajiristan ophiolite complex, Pakistan (Shah and Khan, 1999).

17. Study area

NR- Not reported

132

Table 6.5 Correlation between the major oxides of various manganese ore samples of

different localities of Banswara district, Rajasthan, India.

SiO2 Al2O3 TiO2 Fe2O3 MnO MgO CaO Na2O K2O P2O5

SiO2 1.00

Al2O3 0.21 1.00

TiO2 -0.18 0.38 1.00

Fe2O3 -0.38 0.07 0.14 1.00

MnO -0.92 -0.41 0.19 0.34 1.00

MgO -0.16 0.38 0.18 0.11 -0.06 1.00

CaO -0.41 0.20 -0.12 -0.01 0.09 0.68 1.00

Na2O 0.21 0.73 0.16 0.06 -0.40 0.35 0.24 1.00

K2O -0.39 0.28 -0.15 0.05 0.13 0.34 0.62 0.36 1.00

P2O5 0.32 0.56 0.21 0.40 -0.37 0.11 -0.15 0.36 -0.12 1.00

Table 6.6 Correlation between the selected trace elements of various manganese ore

samples of different localities of Banswara district, Rajasthan, India.

Cu Pb Zn Co Ni Sr Cr V Ba Mo Zr

Cu 1.00

Pb 0.67 1.00

Zn 0.77 0.64 1.00

Co 0.08 0.01 0.08 1.00

Ni 0.81 0.67 0.96 0.13 1.00

Sr -0.13 -0.25 -0.16 0.13 -0.13 1.00

Cr 0.40 0.53 0.36 0.21 0.34 -0.24 1.00

V -0.08 -0.04 -0.11 0.15 -0.07 0.61 -0.07 1.00

Ba 0.38 0.27 0.18 0.18 0.21 0.26 0.48 0.24 1.00

Mo -0.14 -0.11 -0.26 0.25 -0.26 0.05 0.07 -0.07 0.32 1.00

Zr 0.05 0.29 0.38 -0.09 0.45 -0.20 0.07 -0.01 -0.35 -0.37 1.00

133

Table 6.7 The rare earth elements (REE) geochemical data of manganese ore samples of different localities of Banswara district, Rajasthan, India.

Elements(ppm) Banswara Manganese Ores S1 S2 G1 G2 K1 K2 K3 K4 GH1 GH2 I1 I2

La 55.49 55.87 20.24 26.52 89.48 87.75 167.82 84.95 35.82 44.44 39.36 41.25

Ce 115.21 133.23 48.10 45.12 181.74 182.52 228.86 174.84 112.89 124.85 77.56 69.15

Pr 12.77 13.64 4.86 5.70 22.77 23.56 39.30 21.63 8.56 11.03 8.98 9.01

Nd 50.65 59.58 20.41 23.57 91.37 89.25 153.00 87.21 35.97 46.67 37.17 39.28

Sm 10.09 14.39 4.99 4.65 18.61 16.65 30.19 17.90 8.07 10.14 7.45 5.95

Eu 2.53 5.37 1.57 1.82 5.74 6.01 8.10 5.60 2.44 2.92 2.00 1.89

Gd 9.21 13.53 6.57 4.52 17.02 17.24 27.95 16.62 9.43 10.93 6.33 7.01

Tb 1.44 1.97 1.12 0.69 2.60 2.78 4.01 2.55 1.70 1.81 0.87 0.79

Dy 8.53 10.50 6.64 4.07 14.70 15.09 21.78 14.29 11.18 11.31 4.59 3.89

Ho 1.73 1.99 1.30 0.82 2.87 3.11 4.16 2.81 2.41 2.38 0.86 0.77

Er 4.33 4.67 3.25 2.06 6.86 7.08 10.03 6.60 6.17 6.00 2.09 1.95

Tm 0.62 0.62 0.46 0.29 0.89 1.01 1.38 0.87 0.90 0.85 0.29 0.39

Yb 3.85 3.77 2.86 1.75 5.18 6.12 8.45 5.05 5.41 5.28 1.87 1.75

Lu 0.54 0.53 0.40 0.26 0.70 0.95 1.17 0.68 0.75 0.70 0.25 0.37

y 47.82 62.03 38.70 25.95 82.00 81.25 134.82 78.92 70.76 70.70 25.71 26.35

∑REE 324.81 381.68 161.46 147.79 542.52 540.37 841.02 520.51 312.46 350.00 215.40 209.79

∑LREE 246.74 282.07 100.17 107.38 409.71 405.74 627.27 392.12 203.75 240.04 172.54 166.53

∑HREE 30.25 37.58 22.59 14.45 50.81 53.38 78.93 49.47 37.94 39.26 17.15 16.91

∑LREE/∑HREE 8.16 7.51 4.43 7.43 8.06 7.60 7.95 7.93 5.37 6.11 10.06 9.85

Ce/Ce* 4.33 4.83 4.85 3.67 4.03 4.01 2.82 4.08 6.45 5.64 4.12 3.59

Eu/Eu* 0.26 0.38 0.27 0.40 0.32 0.35 0.28 0.32 0.28 0.28 0.29 0.29

(La/Nd)N 1.10 0.94 0.99 1.13 0.98 0.98 1.10 0.97 1.00 0.95 1.06 1.05

(Dy/Yb)N 2.22 2.78 2.32 2.33 2.84 2.47 2.58 2.83 2.07 2.14 2.45 2.22

Ce/La 2.08 2.38 2.38 1.70 2.03 2.08 1.36 2.06 3.15 2.81 1.97 1.68

Y/Ho 27.63 31.15 29.85 31.66 28.56 26.13 32.40 28.10 29.39 29.67 29.74 34.44

La/Lu 102.54 104.52 50.05 103.04 128.10 92.37 143.25 125.42 47.60 63.63 156.37 113.01

La/Yb 14.42 14.81 7.09 15.18 17.26 14.34 19.87 16.81 6.62 8.42 21.04 23.57

134

Elements(ppm)

Banswara Manganese Ores


La 23.63 30.21 37.57 54.93 56.89 42.25 51.98 64.47 63.14 20.45 27.90 44.94 52.81

Ce 93.05 63.47 162.90 149.01 148.35 98.90 124.39 145.97 146.65 48.29 71.57 104.88 118.81

Pr 5.94 7.06 9.39 11.64 11.95 10.38 12.59 13.34 12.95 5.00 6.84 10.86 12.49

Nd 24.88 29.17 40.57 47.36 48.01 43.12 54.91 53.43 51.27 21.16 30.14 45.63 50.99

Sm 6.13 6.08 10.31 11.07 10.08 9.15 13.63 10.90 10.50 5.05 7.09 9.67 10.78

Eu 1.86 1.85 3.12 3.53 3.16 3.41 4.55 4.25 3.98 1.43 2.01 3.81 3.46

Gd 7.26 6.25 13.67 10.91 9.69 8.34 12.37 11.35 10.54 6.22 7.44 9.19 10.82

Tb 1.39 1.00 2.45 1.76 1.95 1.22 1.80 1.93 1.86 1.06 1.10 1.35 1.72

Dy 9.26 5.78 14.47 10.09 10.79 6.41 9.49 11.79 11.35 6.18 6.08 7.18 9.81

Ho 2.01 1.15 2.83 1.97 2.01 1.23 1.81 2.45 2.32 1.23 1.14 1.41 1.95

Er 5.13 2.88 6.84 4.68 5.25 2.85 4.20 5.96 5.56 3.10 2.68 3.35 4.73

Tm 0.73 0.41 0.91 0.63 0.69 0.37 0.56 0.81 0.73 0.44 0.35 0.44 0.65

Yb 4.59 2.59 5.35 3.95 4.11 2.22 3.43 4.82 4.40 2.85 2.05 2.79 3.94

Lu 0.58 0.37 0.73 0.51 0.57 0.31 0.49 0.66 0.56 0.41 0.29 0.39 0.55

y 58.60 35.86 92.17 55.21 58.35 39.08 54.57 68.21 64.97 35.27 29.88 43.96 57.55

∑REE 245.05 194.14 403.28 367.26 371.85 269.24 350.76 400.35 390.76 158.14 196.57 289.84 341.04

∑LREE 155.50 137.85 263.86 277.53 278.44 207.22 262.04 292.37 288.48 101.38 145.55 219.79 249.34

∑HREE 30.95 20.43 47.25 34.51 35.06 22.94 34.15 39.76 37.31 21.49 21.14 26.09 34.16

∑LREE/∑HREE 5.02 6.75 5.58 8.04 7.94 9.03 7.67 7.35 7.73 4.72 6.89 8.42 7.32

Ce/Ce* 7.85 4.34 8.67 5.89 5.69 4.72 4.86 4.98 5.13 4.77 5.18 4.75 4.97

Eu/Eu* 0.28 0.30 0.26 0.32 0.32 0.39 0.35 0.38 0.38 0.25 0.28 0.40 0.32

(La/Nd)N 0.95 1.04 0.93 1.16 1.18 0.98 0.95 1.21 1.23 0.97 0.93 0.98 1.03

(Dy/Yb)N 2.02 2.23 2.70 2.56 2.63 2.89 2.77 2.45 2.58 2.17 2.96 2.57 2.49

Ce/La 3.94 2.10 4.34 2.71 2.61 2.34 2.39 2.26 2.32 2.36 2.57 2.33 2.41

Y/Ho 29.18 31.30 32.56 28.09 29.03 31.82 30.19 27.85 28.06 28.65 26.10 31.14 29.70

La/Lu 40.72 80.93 51.41 107.15 99.81 137.02 106.52 98.21 112.20 50.02 96.67 116.58 96.96

La/Yb 5.15 11.66 7.02 13.91 13.84 19.04 15.16 13.38 14.36 7.18 13.59 16.09 13.74


135

Fig. 6.1 Variation diagram showing the weight percent of major oxides in manganese

ores of Sivnia and Gararia localities, Banswara district, Rajasthan, India.


ores of Kalakhunta and Ghatia localities, Banswara district, Rajasthan, India.

136


ores of Itala village, Banswara district, Rajasthan, India.


ores of Tambesara village, Banswara district, Rajasthan, India.

Fig. 6.5 Variation diagram showing the wt % of major oxides in manganese ores of

Ratimauri village, Banswara district, Rajasthan, India.

137


ores near Timamahudi, Banswara district, Rajasthan, India.

Fig. 6.7 Variation diagram showing the average weight percent of major oxides in

manganese ores of Banswara district, Rajasthan, India.

138

6.2 Major oxides in Manganese ores

A total twenty four manganese ore samples of Banswara manganese ore deposits

were analyzed for major oxides by using X-ray fluorescence instrument to understand

the relationship among these oxides. In the analysis of manganese ores the total ten

major oxides are recognized which are as follows, SiO2, Al2O3, Fe2O3, MnO, K2O, CaO,

P2O5, MgO, Na2O and TiO2. These oxides contribute major amount in manganese ores

of study area. Major oxides are very much important to understand inter-elemental

relationship between different ores. The elemental relationship of different parts of

world volcanogenic sedimentary manganese deposits keenly described by pioneers

workers like Borchert (1970), Bostrom (1973), Bonatti et al. (1972, 1976), Choi and

Hariya (1990). The manganese ores deposited throughout the world in space and time

under different prevailing conditions and for that these deposits are variable in their

form, nature and also in chemical and mineralogical composition. These prevailing

conditions through space and time may be attributed to a number of different factors

which act individually or in a combined form. Most importantly the rates of the

concentration of the elements, the depositional environment of ore, sediment

accumulation, biological productivity, nodules growth, Eh-pH, temperature, pressure,

basin geometry, the adsorptic and crystallo-chemical properties of the authegenic phases

in the ores controlled the concentration of major and trace elements in manganese ores

under different environments. Calvert and Price (1977a) explained that the total

concentration of Mn and Fe contents broadly controlled the nature and amount of minor

element concentration in manganese ores.

In Precambrian period due to high atmospheric carbon dioxides and lower Ph

value of surface water, the manganese ores deposition were extensive throughout the

world and these prevailing conditions made easier formation of manganese deposits and

manganese was shifted from the triad Al-Fe-Mn to pelagic part of the basin. These

manganese ores deposition continuously decrease from past and up to recent

(Precambrian to recent) due to decrease in CO2 and increase in Ph of surface water.

Strakhov (1969) also described that the solution migration and manganese ores

deposition decrease from Precambrian to present owing to decrease of the CO2 in the

atmosphere. Geochemically, Mn is more mobile than Fe and Al in the Al-Fe-Mn triad

from continents and it has the greatest tendency to migrate farthest into the basin of

139

deposition owing to its mobility. Both hydrogenous and digenetic contributions to

nodule genesis are evident in the Pacific in all scales (Calvert et al., 1978). Lynn and

Bonatti (1965), Calvert and Price (1970) adequately outlined the process of digenetic

remobilization leading to enrichment in Mn and depletion of Fe and minor elements in

nodule (B-type of Mero, 1965) in the continental borderland areas of the pacific. Calvert

and Price (1970) suggested that the post depositional migration milieu of rapidly

accumulating biogenous sediment, though Piper and Williamson (1977) and Calvert et

al. (1978) established that abyssal nodules with high Mn/Fe ratio occur in the areas of

slow sedimentation rate. Calvert et al. (1978) further observed that there are two types of

digenetic manganese and iron deposits, one is formed at fast and the other at slow rates

of sediment accumulation and this is reflected in systematic variation in their

composition in a given area. Cronan (1977) pointed out that in pacific, the Mn ores show

a greater increase in manganese content in areas of relatively low sedimentation than in

sectors of rapid biogenic and terrigenous sedimentation rates and as such digenetic

controls on manganese ores composition is of much less importance outside the

continental borderland and the equatorial zones of pacific.

The major oxides in manganese ores of the study area were studied for

quantitative estimation, inter-elemental correlation and genetic interpretation. These

oxides are present in variable concentration in studied manganese ore samples. The

manganese ores of study area occurred in stratiform and meta-sedimentary in nature and

this may be resulted due the process of fractionation and separation during digenesis of

manganese rich sediments and the ore forming elements during secondary processes of

weathering, transportation, deposition, digenesis and metamorphism. The post

magmatic process directly or indirectly affects the quantity and quality of manganese

ores. The analyzed ten major oxides and their interpretations are discussed as follows:

6.2.1 Silica (SiO2)

In the study area primary manganese minerals are the chief source for the significant

silica content. Another source of silica in ores may be attributed to presence of jasperiod

quartzite and quartz which are associated with manganese ores in study area. The

manganiferous quartzite is present below and above the manganese horizons. The

average weight percentage of SiO2 in the manganese ores of the present study area is

33.86 wt% (Table 6.1). SiO2 shows sympathetic relation with Al2O3, Na2O and P2O5

140

while antipathetic relation with Fe2O3, K2O, CaO, MgO, MnO and TiO2 (Table 6.5 and

Fig. 6.8). The positive relation with iron and antipathetic relation with MnO, which

attributed presence of detrital quartz grains in the iron ores rather than the manganese

ores (Saad et al., 1994; Khalifa and Seif, 2014). The antipathetic relation between silica

and magnesia referred that the silica increases with the decrease of magnesia and vice

versa. In case of trace elements, SiO2 shows positive correlation with Cu, Zn, Co and Ni

while negative correlation with Ba, Sr and Rb (Fig. 6.9). The samples of study area lie

near braunite-rhodonite composition field in Fe-Mn-Si ternary plot (Fig. 6.10) by

Dasgupta and Manickavasagam (1981). This confirmed that braunite present as main

minerals due to high content of silica in the study area. According to Kleyenstoeber

(1984), braunite (SiO2-10%) is formed due to sedimentary-digenetic to very low grade

metamorphism while braunite II (SiO2-4%) is formed due to characteristic of

hydrothermal alteration zones.

Fig. 6.8 Relationship of SiO2 with other oxides (Al2O3, TiO2, K2O and P2O5) of different

localities of Banswara manganese ores, Banswara district, Rajasthan, India.

(S-Sivnia, G-Gararia, K-Kalakhunta, Gh-Ghatia, It-Itala, Rt-Ratimauri,

Tm-Tambesara, T-Timamahudi)

141

Fig. 6.9 Relationship between SiO2 and selected trace elements (Pb, Ni and Ba) of

different localities of Banswara manganese ores, Banswara district, Rajasthan,

India. (S- Sivnia, G-Gararia, K-Kalakhunta, Gh-Ghatia, It-Itala, Rt-Ratimauri,


6.2.2 Alumina (Al2O3)

The concentration of Al2O3 is very much important to delineate the composition

of manganese ores. Alumina has been used widely as an important element in

determining the genetic environment of the manganese ores by many workers like Peters

(1988), Choi and Hariya (1992) through various diagrams especially for the sedimentary

manganese ores. The alumina and titania show similar behavior during the

mineralization as referred by Sugisaki (1984), Roy et al. (1990) and for that both can be

used to decipher the origin of mineralization. The calculated average weight percentage

of alumina in the manganese ores of the study area is 2.84 wt% (Table 6.1). The

variation diagrams (Fig. 6.1, 6.2, 6.3, 6.4, 6.5, 6.6 and 6.7) show very much similar

concentration of alumina that indicates more resemblance in mineralogy. Al2O3 shows

sympathetic correlation with TiO2, Fe2O3 K2O, P2O5, Na2O and MgO while antipathetic

correlation with MnO (Table 6.5, Fig. 6.12). The manganese samples of the study area

lies in zone of manganese nodules in triad of Al-Fe-Mn (Fig. 6.11) after Bonatti et al.

(1972). In case of trace elements Al2O3 shows positive correlation with Ni, Zn, Cu and

142

Pb while negative correlation with Ba (Fig. 6.14). The average weight percent of Al2O3

is very near to the Ulukent (Sedimentary), Binklic (Sedimentary- digenetic) and

Kasimaga (Volcano-sedimentary) manganese deposits of Turkey (Table 6.2). Alumina

and titania concentrations in the ores can be used for genetic assessment in the similar

way as iron and magnesia. When Si decrease in manganese ores then it is balanced by

increasing content of alumina, iron and manganese that referred changes in the

physico-chemical conditions associated with increased input of Mn, Al and Fe

(Burhamuddin, 2015). According to Crerar et al. (1982), the Al2O3 incorporation is

enhanced by the base metal cooperation as the Al3+ for Mn4+ with charge neutralization

by bivalent base metal ions.

Fig. 6.10 The ternary plot of Fe-Mn-Si (after Dasgupta and Manickavasagam, 1981)

showing the composition of manganese ore samples of different localities of

Banswara manganese ores, Banswara district, Rajasthan, India. (S-Sivnia,

G-Gararia, K- Kalakhunta, Gh-Ghatia, It-Itala, Rt-Ratimauri, Tm-Tambesara,

T-Timamahudi)

143

Fig. 6.11 Ternary diagram of Al-Mn-Fe (wt%) (after Bonatti et al., 1972) showing the

manganese ore samples of different localities of Banswara manganese ores,


Fig. 6.12 Relationship of Al2O3 with K2O in manganese ore samples of different


Fig. 6.13 Relationship of TiO2 with Al2O3 in manganese ore samples of different


144

Fig. 6.14 Relationship between Al2O3 and selected trace elements (Ni, Cu, Pb and Ba) in


Banswara district, Rajasthan, India. (S-Sivnia, G-Gararia, K-Kalakhunta,

Gh-Ghatia, It-Itala, Rt-Ratimauri, Tm-Tambesara, T-Timamahudi)

Fig. 6.15 Relationship between TiO2 and selected trace elements (Zn, V and Cu) in



Gh-Ghatia, lt-ltala, Rt-Ratimauri, Tm-Tambesara, T-Timamahudi)

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6.2.3 Titanium oxide (TiO2)

The average weight percentage of TiO2 in the manganese ores of the study area

samples is .19 wt % and concentration of TiO2 ranges from 0.04% -.7 wt % (Table 6.1).

The titanium oxide shows positive correlation with Al2O3 (Fig. 6.13), Fe2O3, MnO, P2O5

and Na2O (Table 6.5) while negative correlation with SiO2, CaO and K2O. In case of

trace elements, titanium oxide shows positive correlation with Cu, Ni, Cr, Sc, Zn and Ba

while negative relation with Co, Sr and V (Fig. 6.15). The positive correlation between

Ti-Cu (Fig. 6.15 C) in the manganese ores suggests their co-supply as terrigenous input

and the leaching especially in case of the secondary manganese ores confined to the

meteoric or weathering zone (Bhat, 2013). The chief source of Ti in the manganese ores

of study area due to the presence of ilmenite, Mn-Ti minerals and gangue minerals.

Si-Ti diadochy may be of less importance for the manner of occurrence of Ti and most

of it would replace Al, Fe and Mg in minerals (Rankama and Sahama, 1950).

6.2.4 Iron Oxide (Fe2O3)

The average weight percentage of Fe2O3 in the manganese ores of the study area

is 3.24 wt % and concentration of Fe2O3 ranges from 1.18 % -5.2 wt % (Table 6.1). The

manganese ores of this area are characterized by lower concentration of iron and

showing variation in Fe values. The variable content of Fe in the manganese ores and

host rocks of the study area may be due to repeated reduction and oxidation of iron

within silicates with the help of chemical agents, and could be the possible reason of the

highly variable content of Fe Rozenson and Heller-Kallai (1976a). The lower values of

iron oxide in the manganese ores of the study area may be due to presence of braunite as

a main mineral only and lack of other manganese minerals such as bixbyite,

hausmannite and jacobsite in the study area. Iron oxide shows sympathetic relation with

MnO, TiO2, Al2O3, P2O5, K2O, MgO and Na2O while negative relation with SiO2 and

CaO (Table 6.5, 6.16). The negative relation of iron oxide with silica, and calcium oxide

refers that Fe replaced these elements while positive correlation inferred same source. In

case of trace elements, iron oxide shows positive relation with Cu, Ni, Sc, Zn, V and Ba

and negative relation with Co, Cr, and Rb (Fig. 6.17). The weight percent of iron oxide is

very near to the other hydrothermal, sedimentary and metasedimentary manganese

deposits of the world (Table. 6.2). In manganese ores of the study area no hausmannite

mineral observed which is a common digenetic oxidation product. Nel et al. (1986)

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refers that the digenetic/low temperature hausmannite contains up to 4.5 weight percent

iron oxide. Fe is a characteristic element of the hydrothermal influx and its major portion

in marginal sea sediments occurs in terrigenous clay minerals as chlorites, smectites and

iron rich hydromicas. Apart from this it is also occur in detrital sediments due to the

weathering of iron rich rocks. Therefore in manganese ores of the study area it seems

that the iron may also concentrated by hydrogenous and terrigenous supply from the host

rocks rather than direct hydrothermal influx.

6.2.5 Manganese Oxide (MnO)

The average weight percentage of MnO in the manganese ores of the study area

is 51.61 wt % and concentration of MnO ranges from 30.99-76.75 wt % (Table 6.1). The

ores are characterized by higher contents of manganese except few samples. The higher

values of MnO are recorded in secondary ores and these secondary ores may be

attributed to supergene enrichment. The average Mn/Fe ratio in the manganese ores of

the study area is 18.97. The lower values of Mn/Fe ratio are related to the primary

manganese ores while higher Mn/Fe values attributed to secondary or supergene ores in

study area. Fe and Mn have very similar behavior, Mn has more mobility than Fe

especially in sedimentary environments (Simmonds and Ghasemi, 2007). The Mn-Fe

(Transition elements) are formed through the process of flocculation of iron-manganese

hydroxides in primary manganese ores which suggest the formation of manganiferous

sedimentary protolith for the Mn ores. Canfield et al. (1993) referred that the adsorption

of Mn2+ and Fe2+ into Mn and Fe oxides can significantly reduce the Mn2+ and Fe2+

concentration in sediments due to the reaction of adsorbed species with the oxygen in

oxidized conditions. MnO shows positive relation with Fe2O3, CaO and TiO2, and

negative relation with SiO2, Al2O3, MgO, Na2O and P2O5 (Table 6.5 and Fig. 6.18). The

positive relation between Si and Fe suggest their precipitation in single environment

while negative relation between these suggest their precipitation under different

environment and the fractionation between these two elements takes place during their

formation (Krauskopf, 1957). In case of trace elements, MnO shows positive relation

with Ba and negative relation with Cu, Co, Ni and Zn (Fig. 6.19). The negative relation

of MnO with Si, Al and Cu reflect the clastic contribution of the these elements

excluding Mn itself during the manganese mineralization (Bhat, 2013).

147

Fig. 6.16 Relationship of Fe2O3 with other oxides (SiO2, Al2O3, TiO2, MnO, MgO, CaO,

Na2O, K2O and P2O5) in manganese ore samples of different localities of


G-Gararia, K-Kalakhunta, Gh-Ghatia, It-ltala, Rt- Ratimauri, Tm-Tambesara,

T-Timamahudi)

148

Fig. 6.17 Relationship of Fe2O3 with selected trace elements (Co, Ba, Ni, Sr, Zr, Zn, Pb

and Mo) in manganese ore samples of different localities of Banswara

manganese ores, Banswara district, Rajasthan, India. (S-Sivnia, G-Gararia,

K-Kalakhunta, Gh-Ghatia, It-ltala, Rt- Ratimauri, Tm-Tambesara,

T-Timamahudi)

149

Fig. 6.18 Relationship of MnO with other oxides (SiO2, Al2O3, TiO2, MnO, MgO, CaO,

Na2O, K2O and P2O5) in manganese ore samples of different localities of


G-Gararia, K-Kalakhunta, Gh-Ghatia, It-Itala, Rt-Ratimauri,


150

Fig. 6.19 Relationship of MnO with selected trace elements (Ba, Ni and Pb) of different


6.2.6 Magnesium Oxide (MgO)

The average weight percentage of MgO in the manganese ores of the study area

is .75 wt % and concentration of MgO ranges from 0.14-1.20 wt % (Table 6.1). The

MgO concentration in manganese ores of the study area is in negligible amount. MgO

shows positive relation with Al2O3, CaO, Na2O, Fe2O3, K2O, TiO2 and P2O5 and

negative relation with SiO2 and MnO (Table 6.5). The negative relation with these

oxides suggest replacement of these oxides by MgO. In case of trace elements, MgO

shows positive correlation with V, Cr, Ba, Zr and Sc and negative relation with Cu, Zn

and Ni (Fig. 6.20). The negative relation between Mg and Mn, which possibly suggest

the replacement of bivalent manganese by MgO (Siddiquie, 2004). Magnesium can be

substituted Al in manganese ores (Deer et al., 1963) which is observed in present study.

The Mg is an important element to reveal the depositional environment of manganese

ores. In Na-Mg discrimination diagram the manganese ore samples lies in the zone of

fresh and shallow water depositional environment (Fig. 6.39). This diagram also reveals

whether there is a hydrothermal metal discharge into sedimentation environment (Bhat,

2013). According to Alibert and Mc Culloch (1993), Mn precipitates may also scavenge

MgO and other trace elements in direct proportion to their concentration in sea water.

151

6.2.7 Calcium oxide (CaO)

The average weight percentage of CaO in the manganese ores of the study area is

2.08 wt % and concentration of CaO ranges from 0.5-8.82 wt% (Table 6.1). The

concentration of CaO is high in the manganese ores of study area. The higher weight %

of CaO (6.82 wt%) is reported from the manganese ores (Volcano-sedimentary) deposits

of Kasimaga, Turkey as detailed in (Table 6.2). The source of high CaO in the

manganese ores may be due to gangue minerals (Calcite, tremolite, dolomite or

carbonate rich sediments etc.). The mineralogical studies suggest that the calcium

incorporated by various processes from initial stage to final stage (Precipitation to

supergene enrichment). CaO shows sympathetic relation with K2O and MnO. The

positive relation with MnO and negative relation with Fe2O3 referred early digenesis and

carbonate replacement by manganese minerals (Hausmannite and rhodhochrosite) like

phases (Crerar et al., 1982). The positive relation of Ca and Mn also suggest that Mn is

mainly enriched in the carbonate sediments (Siddiquie, 2004). The antipathetic relation

with SiO2, TiO2, P2O5, and Fe2O3 show that the Ca is replaced these oxides (Table 6.5).

Mn is substituted by Ca in manganese ore minerals referred by Deer et al. (1963). The

limestone also possible source of calcium oxide in the manganese ores of the study area

especially from Talwara manganese ores. According to Nayak (1969) that lime is

probably present as a manganite (psilomelane or hollandite) braunite structure of

Kajlidongri deposits of Jhabua district, M.P., but in few cases CaO replace braunite

structure too. In case of trace elements, CaO shows positive correlation with Ba, Sr, V,

Rb and Cs while negative relation with Cu, Zn, Co and Ni (Fig. 6.21).

6.2.8 Sodium Oxide (Na2O)

The average weight percentage of Na2O is 0.09 wt % and concentration of

sodium oxide ranges from 0.03-0.12 wt % in manganese ores of the study area (Table

6.1). The average Na2O values is near to the manganese deposits of hydrothermal and

volcano-sedimentary origin of Hazara (Pakistan) and Kasimaga (Turkey) respectively

(Table 6.2). Mohapatra et al., (1987) reported average Na2O values in manganese

nodules from Indian ocean is .64 wt %. Na2O shows positive relation with SiO2, Al2O3,

Fe2O3, K2O, TiO2 and P2O5 while negative relation with MnO (Table 6.5). The negative

152

relation suggest that Na2O replaced by MnO in manganese ores of the study area. In case

of trace elements, Na2O shows positive correlation with Zn, Ni, Sr, Rb and Cs while

negative relation with Cr, Co and Zr. According to Siddiquie (2004), Siddiquie and Raza

(2008), most of the manganese mineral phases as they carries of Na and other alkalies

include cryptomelane, psilomelane and hollandite. In Na vs Mg discrimination diagram,

manganese ores fall in fresh and shallow water field in the study area (Fig. 6.39).

Mukherjee (1961) illustrated that the Na concentration is higher than the K2O

cconcentration in gondite while in the study area samples potassium oxide content is

higher in comparison of soda content which depict that the source of these higher values

of K2O due to the presence of feldspar and mica minerals which are the prominent

constituent of host rocks of the study area.

6.2.9 Potassium Oxide (K2O)

The average weight percentage of K2O in the manganese ores of the study area is

1.80 wt % and concentration of K2O ranges from 0.05-7.47 wt % (Table 6.1). Some

manganese ores samples of study area showing higher values of K2O which is clearly

observed in the variation diagrams (Fig.6.1, 6.2, 6.3, 6.4, 6.5, 6.6 and 6.7). The

manganese minerals (Psilomelane, cryptomelane, and hollandite) are responsible for the

presence of K2O in the manganese ores of the study area. The chief source of K2O are

K-feldspar and mica minerals which are the dominant minerals present in the host rocks

of the study area. Siddiquie, 2004 also reported these minerals from Vizianagaram

district, A.P., and are responsible for the rich source of K2O in the manganese ores. K2O

show positive relation with Al, Fe, Mn, Ca and Na while negative relation with Ti, Si

and P. The positive relation between potassium oxide and iron oxide suggest coherence

while negative relation with other oxide shows replacement. The negative relation show

that the K2O increase as Ti, Si and P decrease and vice versa (Table 6.5). In case of trace

elements, K2O shows positive correlation with Sr, V, Rb, Zr and negative relation with

Cu, Zn, Co, Ni, Sc and Ba (Fig. 6.22). According to Novikov (1996), Novikov and

Baturin (1997), Novikov et al. (2006), Novikov and Murdmaa (2007), the exchange

reactions between metal cations (Na+, Mg2+, K+, Ca2+, and Mn2+) in ore minerals of

ferro-manganese rocks and metal cations (Cu2+, Ni2+, Co2+, and others) in solutions yield

cationic forms of these minerals (Cu-Co-Ni-rich species and others). This type of

153

geochemical behavior reported in different manganese deposits of India as Nishikhal

manganese ore from the Eastern Ghats (Mohapatra et al., 2005; 2009) and gonditic

manganese ores of Madhya Pradesh and Maharashtra, India (Mookherjee, 1961)

indicating resemblance in genesis of the manganese ores.

6.2.10 Phosphorous (P2O5)

The average value of P2O5 in the manganese ore samples of the study area is .62

wt % (Table 6.1) and the concentration of phosphorous ranges from .42 wt % - 1.04 wt

%. The average values of phosphorous more or less similar to hydrothermal manganese

deposits of Banffshire, Arudily and Wajiristan, Pakistan and sedimentary diagenetic

manganese deposits of Binklic, Turkey (Table 6.2). According to Summerhayes (1967)

and Glasby and Summerhayes (1975), the association of phosphorites with Mn deposits

has been reported from sea mounts, oceanic plateaus, banks and shallow parts of the

seas. Generally in most of the cases the manganese and iron oxides occur as coatings on

phosphorite nodules. The manganese ores of intermediate and high grade in

Maharashtra-Madhya Pradesh manganese belt are enriched in phosphorous due to

presence of manganese silicate Straczek and Krishnaswamy (1956). According to

Sivaprakash (1980) and Siddiquie (2001), P is mainly leached out from minerals like

apatite to the adjacent rocks by the action of weathering and chemical activity in the

form of alkali phosphates or colloidal calcium phosphate. Phosphorous shows

sympathetic relation with SiO2, Al2O3, Fe2O3, TiO2, Na2O and MgO whereas

antipathetic relation with MnO, K2O and CaO (Table 6.5). According to Halbach (1975)

and Halbach et al. (1981), the manganese ores of lacustrine origin also show a good

correlation between Fe and P. In case of trace elements, P2O5 shows sympathetic relation

with Cu, Ni, Zr and Zn and antipathetic relation with Co, Sr, V, Sc, Rb, Cs and Ba (Fig.

6.23). Calvert and Price (1977a) delineate first time the strong correlation of

phosphorous with iron from shallower parts of pacific and such strong relation in present

study suggest the shallow shelf environment of the present ores. The chief source of

phosphorous in the manganese ores of the study area is due to the presence of apatite and

garnet mineral. Siddiquie (2001 and 2004) also reported high P2O5 content in the

manganese ores of the Garividi, Garbham and Chipurupalle areas of Vizianagaram

district (Andhra Pradesh) due to the presence of apatite and garnet in the host rocks.

154

Mukherjee (1961) referred that the apatite and spessartite are the common constituents

of gonditic deposits where apatite is associated with quartz, orthoclase and garnet or as

collophane in the voids or adsorbed on goethite, cryptomelane, romanechite etc.,

(Acharya et al., 1994a, b).

Fig. 6.20 Relationship of MgO with selected trace elements (Co, Zr, Sr and Zn) in



Fig. 6.21 Relationship of CaO with selected trace elements (Co, Pb and Zn) in



155

Fig. 6.22 Relationship of K2O with selected trace elements (Pb, Sr, Ni and Mo) in




Fig. 6.23 Relationship of P2O5 with selected trace elements (Ba, Zn, V and Cu) of

different localities of Banswara manganese ores, Banswara district,

Rajasthan, India. (S-Sivnia, G-Gararia, K-Kalakhunta, Gh-Ghatia, It-Itala,

Rt-Ratimauri, Tm- Tambesara, T-Timamahudi)

156

6.3 Geochemistry of Trace Elements

Goldschmidt (1937) categorized trace elements as chalcophile, siderophile, and

lithophile on the basis of their chemical affinities determined by the electronic

configuration of their atoms. Washington (1913) discussed trace element distribution in

earth’s crust and also explained mutual relation between trace elements and major

oxides of rocks and ores. The trace elements concentration in the ores and rocks is an

important tool to decipher mineral phases in ores and rocks, their genetic types,

post-magmatic processes and their effects. Therefore they are similar in importance like

major oxides and also very much helpful in delineation of prevailing tectonic conditions,

geochemical environment incorporated during their formation. The trace elements are

very important in the formation of ores and rocks. Due to small occurrence they are

always measure in parts per million (ppm), but they are always important to define

geochemical properties. Due to peculiar properties of trace element their presence

elaborated in terms of its significance and distribution in ores and rocks. Various

researcher explained their views about significance of its distribution and geochemical

pattern like Vogt (1918), Buddington (1933), Bragg (1937). In respect of manganese

ores the concentration of trace elements such as Ni, Cr, Co, Cu, Sr, V, Ba, Zr, Pb, Zn, Li

and Mo are very much important. The concentration of trace elements always varies in

manganese ore deposits formed under different depositional environment. The higher

concentration of Cu, Zn and Pb are considered to be the diagnostics of hydrothermal

manganese deposits (Zantop, 1981; Nicholson, 1988). According to Price (1967), Harris

and Troup (1969), Hallbach (1975) the fresh water manganese deposits are highly

depleted in Ni, Co and Cu like trace elements in compare of marine deposits. Similarly

these element concentration and distribution varies in the manganese deposits formed on

continent, lake, shallow shelf and open ocean. Dixon and While (2002) explained that

the trace elements like Co, Ni and Zn are manganophile elements and consist divalent

properties due to which they have close affinity with Mn oxides and accumulate with

these oxides during weathering. Crerar et al. (1982) and Nicholson (1992) referred that

the concentration of Ba, Cu, As, Mo, Li, Sb, Pb, V, Zn, Sr, and Mn are high in

hydrothermal manganese deposits and Co-Ni-Cu-Sr are enriched in supergene

manganese deposits while supergene terrestrial manganese deposits have high content of

Ba and Mn-Ba association and content of Sn and Sr are related to concentration of Cu

and Ba. Monin et al. (2001) referred that the hydrothermal deposits are more enriched in

157

Ba compared to sea water since they are affected from volcanic activity and

sedimentation. The inter-elemental relationship in trace elements of stratiform

manganese deposits reveal that Cu, Ni, Co, Pb and Zn are adsorbed on precipitating

hydrous Mn oxides and Li, Sc, Nb and Y are contributed by volcano-clastic rocks. On

the basis of geochemical behavior and distribution pattern of trace elements various

discrimination and variation diagram with binary and ternary plots proposed in present

work to decipher prevailing depositional environment and tectonic conditions for the

formation of manganese deposits of the study area. The geochemical behavior of trace

elements depends upon the adsorption and present phase condition of host lattice. The

adsorption capacity of Mn and Fe oxides for some elements such as Cu, Pb, Sr, Ba, Ni,

Co, V and Zn, various discrimination diagrams on the basis of these elements have been

proposed and the above mentioned elements used to discriminate between the different

genetic types of manganese ores (i.e., sedimentary, hydrothermal and hydrogenous).

According to Nicholson (1992a) these elements are frequently occur in hydrothermal

manganese systems.

According to Goldberg (1957) and Krinsley and Bieri (1959) biological activity

also play an important role for the accumulation of trace elements like other processes

such as phase, fractionation and remobilization. Greenslate et al. (1973) and Piper and

Williamson (1977) referred that the marine organism especially siliceous organism have

open and high volume pore structures, which are helpful in remobilization and

accumulation of trace elements along with Mn content in the interstitial water which

form digenetic deposits such as from Indian ocean. In the present study area the trace

elements data showing significant concentration of Co, Ni, Cu, Zn, Pb, Sr, V, Ba, and Zr.

The variation diagram (Fig. 6.24, 6.25, 6.26, 6.27, 6.28 and 6.29) shows similar

concentration for trace elements in the manganese ores of present study area. The trace

elements interpretation of manganese ores in the study area is showing hydrothermal

nature of the present deposit. The trace elements and their interpretation are discussed as

follows:

158

Fig. 6.24 Variation diagram for selected trace elements of Sivnia and Gararia localities


Fig. 6.25 Variation diagram for selected trace elements of Kalakhunta village of


Fig. 6.26 Variation diagram for selected trace elements of Ghatia and ltala localities of


159

Fig. 6.27 Variation diagram for selected trace elements of Tambesara block/village of


Fig. 6.28 Variation diagram for selected trace elements of Ratimauri village of Banswara


Fig. 6.29 Variation diagram for selected trace elements of Timamahudi block/locality of


160

6.3.1 Cobalt (Co)

Co is siderophile element and member of Fe family which is closely related to Ni

in respect of charge and size in periodic table. The ionic radius of cobalt (0.72Å) is close

to that of Fe, Ni and Mg as 64 Å, 69 Å, and 66 Å respectively. The average cobalt

concentration in the manganese ores of the study area is 113.07 ppm and concentration

of cobalt ranges from 64.69-242.73 ppm (Table 6.3). Mukherjee (1961) reported 900

ppm Co in gonditic manganese ores (Table 6.4). The average value of Co is near about to

hydrothermal manganese deposits of Arndily, Banffshire (Table 6.4). Co shows positive

relation with Cu, Ni, Zn, V, Sc and Ba, whereas negative relation with Zr (Table 6.6 and

Fig. 6.32). In case of major oxide Co shows negative relation with SiO2 while positive

relation with rest of the major oxides. The trace element complexes of Ni-Cu-Co are

common in weathered areas. According to Siddiquie et al. (2015a) the slightly bigger

ionic size of cobalt than nickel can restrict its entry into the lattices of the minerals as

compared to Ni2+ and can be accounted as the reason for higher nickel concentration than

cobalt. Butler (1953) explained that Co is less stable in solution rather than Ni. Glasby

and Thijsen (1982), Glasby et al. (1997) and Glasby and Schultz (1999) proposed their

views regarding Co occurrence and its association. He proposed that the uptake of Co,

Cu and Ni is associated with ferromanganese oxides in marine environment. According

to Krishna Rao (1956) and Nayak (1969) reported traces of Co in Indian manganese ores

of psilomelane, braunite and Vredenbergite. Roy (1966) also found traces of Co in

braunite-hollandite manganese ores of Kajlidongri manganese mines, Jhabua district,

Madhya Pradesh.

6.3.2 Copper (Cu)

Cu is a strong chalcophile element and its ionic radius (.71 Å) is similar to ionic

radii of iron and magnesium. The average copper concentration in the manganese ores of

the study area is 525.43 ppm and concentration of Cu ranges from 62.82-995.45 ppm

(Table 6.3). The average value of Cu in the study area is higher than the values reported

from meta-sedimentary manganese deposits (146 ppm) of Gharbham district, Andhra

Pradesh, India (Siddiquie and Raza, 1990a, 2008; Siddiquie, 2004; Siddiquie and Bhat,

2010; Siddiquie et al., 2015a), (169 ppm) meta-sedimentary deposits of Bhandra district,

Maharashtra, India (Acharya et al., 1997), (233 ppm) meta-sedimentary manganese

161

deposits of Bhandara, India (Rai et al., 1979), (126.80 ppm) volcano-sedimentary

deposit of Kasimaga, Turkey (Koc et al., 2000), (375 ppm) hydrothermal-hydrogenous

manganese deposits, Hazara, Pakistan, (Table 6.4). Mukherjee (1961) reported .034 %

copper from gonditic manganese and Hewett et al., 1963 reported .015% to .15% copper

from deep sea Mn-nodules. Nayak (1969) reported .03% to .15% Cu from Kajlidongri

manganese deposits of Jhabua district, Madhya Pradesh. According to Siddiquie (2004)

and Siddiquie and Bhat (2010) that the copper preferentially accumulate in manganese

minerals particularly ferromanganese hydroxides. Cu show positive relation with Zn,

Co, Ni, Cr, Ba and Zr, whereas negative relation with Sr, V and Mo (Table 6.6 and Fig.

6.30). In case of major oxides Cu shows positive relation with Si, Al, Ti, Fe, Mg and P

while negative relation with Ca, Mn, Na and K. The negative relation with Na and other

oxides shows replacement. Wager and Mitchell (1951) referred that during formation of

sulphide minerals Cu replaces Na and Fe from silicates and oxide. According to

Krauskopf (1956) Cu is effectively adsorbed by Mn(OH)4, Fe(OH)3 and clay minerals.

6.3.3 Nickel

The average nickel concentration in the manganese ores of the study area is

329.49 ppm and concentration of Ni ranges from 140.91-715.10 ppm (Table 6.3). The

average value of Ni in the study area is near to the values reported in gonditic manganese

deposits (270 ppm) (Mukherjee, 1961) and hydrothermal-hydrogenous manganese

deposits (375 ppm) Hazara, Pakistan (Table 6.4). Ni is a siderophile element having

ionic radius 0.69Å closer to Fe2+ (0.75 Å) and Mg2+ (66 Å) and can easily substitute any

one of the two (Fe or Mg). Magnesium bearing minerals are good in hosting Ni because

of covalent bond which is stronger in Ni-O bond rather that Mg-O bond (Goldschmidt,

1944). Ni is less mobile rather than Fe and stable in aqueous solution and remain longer

in solution and therefore it is more likely to enriched in magnesium bearing minerals.

Rankama and Sahama (1950) referred that Ni replaces Mg diadochially in mineral

structure of Mg bearing minerals. While Siddiquie (2004), Siddiquie and Raza (2008)

and Siddiquie el al. (2015a) referred that Ni probably entered in the structure of

ferromagnesian minerals during their crystallization. Ni shows positive relation with Cu,

Zn, Co, Cr, Ba and Zr, while negative relation with Sr, V, and Mo (Table 6.6 and Fig.

6.31). In case of major oxide Ni shows positive relation with Si, Al, Ti, Fe, and P while

negative relation with Mn, Mg, Ca and K.

162

Fig. 6.30 Relationship of Cu with V in manganese ore samples of different localities of


G-Gararia, K-Kalakhunta, Gh-Ghatia, It-Itala, Rt-Ratimauri, Tm-Tambesara,

T-Timamahudi)

Fig. 6.31 Relationship of Ni with selected trace elements (Pb and V) in manganese ore

samples of different localities of Banswara manganese ores, Banswara district,

Rajasthan, India. (S-Sivnia, G-Gararia, K-Kalakhunta, Gh-Ghatia, It-Itala,

Rt-Ratimauri, Tm-Tambesara, T-Timamahudi).

Fig. 6.32 Relationship of Co with selected trace elements (Pb and Zn) in manganese ore

samples of different localities of Banswara manganese ores, Banswara district,

Rajasthan, India. (S-Sivnia, G-Gararia, K-Kalakhunta, Gh-Ghatia, It-ltala,

Rt-Ratimauri, Tm-Tambesara, T- Timamahudi)

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6.3.4 Zinc

Zn is a chalcophile element and its ionic radius (.83 Å) is similar to Fe (.83 Å)

and Mg (.78 Å) (Neumann, 1949). Zinc is also an important element to decipher genesis

of the manganese deposits. The average concentration in the manganese ores of the

study area is 789.27 ppm and concentration of Zn ranges from 275.00-2335.26 ppm

(Table 6.3). The average value of Zn in the study area is near to the values reported in

hydrothermal manganese deposits of Ardinally, Banffshire (Nicholson, 1986).

Mukherjee (1961) reported .102 % Zn from gonditic manganese deposits especially in

braunite. In the earth crust the Zn content is reported around 40 ppm reported by Clark

and Washington (1924) while Goldschmidt (1938) referred that the average

concentration in earth crust is 40g/ton which is mainly bound in Fe-Mn minerals of

igneous origin, for example amphiboles, augites and especially biotite. In the study area

the Zn shows positive relation with Cu, Co, Ni, Cr, Sc, Ba and Zr while negative relation

with Sr, V, and Mo (Table 6.6). In case of major oxides Zn shows sympathetic relation

with Si, Al, Fe, Ti, Na, and negative relation with Ca, K, Mg and Mn. The higher

concentration of Zn suggest presence of Mn-Fe garnet in host rocks which are supposed

to be enriched in zinc (Neumann, 1949). A part from that supergene ores also consist

good host for Zn and the higher % of Zn lead to higher amount of Pb (Hewett et al.,

1963). According to Siddiquie (2004) that the Zn-O bond is more covalent than the Fe-O

bond as indicated by electro negativity and ionization potential data. Here the garnet,

biotite could be the possible carrier of zinc in manganese ores of the study area.

6.3.5 Vanadium (V)

V is a lithophile element and stable in trivalent, quadrivalent and quinquevalent

state under different environment while geochemically it is immobile and insoluble. V is

stable in all three state in igneous rocks while in sedimentary rocks it is only stable in

quinquivalent state. The average vanadium concentration in the manganese ores of the

study area is 128.71 ppm and concentration of V ranges from 22.40-907.91 ppm (Table

6.3). The average value of V in the study area is near to the hydrothermal manganese

ores of Wajiristan, Pakistan (144 ppm) (Shah and Khan, 1999), sedimentary manganese

deposits of Guichi, China (167.86 ppm) (Xie, et al., 2006), the metasedimentary deposits

of Garbham, A.P., India (147.5 ppm) (Siddiquie and Bhat, 2010) and

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volcano-sedimentary manganese deposit of Kasimaga, Turkey (106.10 ppm) (Koc et al.,

2000) (Table 6.4). Manheim (1965) reported 440 ppm V in oceanic water and 200 ppm

is reported in hot spring by Hewett et al. (1963) while fresh water originated

ferromanganese rocks show average concentration around 69 ppm by Callander and

Bower (1976). V shows positive relation with Co, Sr, and Ba while negative relation

with Cu, Zn, Ni, Cr and Zr (Table 6.6). In case of major oxides V shows positive relation

with Si, Al, Fe, Na, Ca and K while negative relation with Mn, Ti and P. The vanadium

concentration is too high and ubiquitous in few samples of manganese ores of the study

area. The chief source of V in the study area is due to frequent presence of ilmenite and

magnetite (Jawed, 2015; Burhamuddin, 2015). Among vanadium minerals manganese is

found in vanadates (Siddiquie, 2004).

6.3.6 Chromium (Cr)

Cr is a transition metal with atomic no. 24 and stable in trivalent, pentavalent and

hexavalent state while in silicate and phosphate enriched rocks it is occurred as

pentavalent state. In silicate minerals it occurs as a cation outside the complex

silicon-oxygen framework (Siddiquie, 2004). The average chromium concentration in

the manganese ores of the study area is lower than the other manganese deposit of the

world (Table 6.4), the average value is 27.16 ppm and concentration of Cr ranges from

12.19-50.81 ppm (Table 6.3). Siddiquie and Raza (1990a, 2008), Siddiquie and Bhat

(2008), Siddiquie and Shaif (2015) and Siddiquie et a1. (2015a) also reported low

concentration of Cr in metasedimentary and supergene manganese deposits. The low

value of Cr is also reported by Rai et al. (1979) and Acharya et al. (1997) in

metasedimentary deposits of Bhandara, Maharashtra and Nishikhal manganese deposit,

India. Cr shows positive relation with Cu, Co, Zn, Ni, Sc, Cs, Ba and Zr while negative

relation with Sr and V (Table 6.6 and Fig. 6.33). In case of major oxides Cr shows

positive relation with Si, Al and Ti while negative relation with Fe, Mn, and K. In study

area the probable source of chromium is metasediments rich in mica and clay minerals.

6.3.7 Lead (Pb)

The Pb is a chalcophile element with atomic number 82. The average lead

concentration in the manganese ores of the study area is 107.18 ppm and concentration

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of Pb ranges from 21.70-269.70 ppm (Table 6.3). The average value of Pb in the

manganese ores of the study area is less than or near the metasedimentary manganese

deposits of Bhandara district, Maharashtra (156 ppm) (Rai et al., 1979) while similar to

hydrothermal deposits of Wakasa, Japan (Table 6.4). The higher amount of Pb in the

ores may be attributed to K-feldspar of the gangue minerals (Siddiquie and Bhat, 2010).

Pb shows sympathetic relation with Cu, Zn, Co, Ni, Cr and Ba while antipathetic relation

with Sr, V and Mo (Table 6.6). Siddiquie (2004) and Siddiquie and Bhat (2010) referred

that the positive relation of Pb with Cu and Zn suggests the Cu-Pb-Zn associations in the

manganese ores. In case of major oxides it shows positive relation with Si, Al, Ti, Fe,

Mg and P while negative relation with Mn, Ca, Na and K. Pb shows negative relation

with Ca whereas in accordance to Rankama and Sahama (1950) lead partially replaces

Ca+2 diadochically and is found particularly in such calcium mineral as apatite

(Goldschmidt, 1937b). Lead is partially replaced by calcium due to ionic radius

(Rankama and Sahama, 1950).

Fig. 6.33 Relationship of Cr-Zr in manganese ore samples of different localities of


Fig. 6.34 Relationship of Cr-Zr and Sr-Zr in manganese ore samples of different


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6.3.8 Strontium

Sr is a siderophile element while in upper lithosphere it is strongly oxyphile. In

residual sediments it is occurs as oxysalts. The average strontium concentration in the

manganese ores of the study area is 871.66 ppm and concentration of Sr ranges from

480.014-2174.208 ppm (Table 6.3). The average Sr value is too high in comparison of

earlier reported Sr values from different metasedimentary manganese deposits such as

361.65 ppm, Bhandara, Maharashtra (Rai et al., 1979). The higher values of Sr is

reported from near the surface parts of continental crust (0.25 %) while Harley (1998)

calculated (.030 wt %) for the lower crust and can be ascribed to the metamorphism

associated granitic intrusions. Sr shows positive relation with Co, V, Mo and Ba,

whereas negative relation with Cr, Cu, Zn, Ni and Zr (Table 6.6 and Fig. 6.34B). In case

of major oxides Sr shows positive correlation with Fe, Na, Ca, Mg and K while negative

relation with Si, Ti, Na and P. The identical ionic radii of Sr, K and Ca as 1.27 Å, 1.33 Å

and 1.06 Å suggest mutual replacement between them. Siddiquie and Raza (1990a,

2008) and Siddiquie et al. (2015a) referred that in manganese ores the adsorption of Sr

occur mainly due to presence of manganiferous minerals, which suggested strong

coherence of Sr with manganiferous minerals. Strontium usually occurs in association of

calcium (Rankama and Sahama, 1950). Some strontium could have been due to its

presence in the associated gangue minerals like apatite, pyroxenes and amphiboles

(Siddiquie and Bhat, 2010).

6.3.9 Molybdenum (Mo)

Mo is siderophile element which shows oxyphile behavior and in upper

lithosphere forms stable complex anions with oxygen. The average Mo concentration in

the manganese ores of the study area is 18.72 ppm and concentration of Mo ranges from

1.03-61.13 ppm (Table 6.3). Callender and Bower (1976) reported 20 ppm Mo in fresh

water originated ferromanganese oxides. The molybdenum concentration up to 10 ppm

in manganese ores of Vizianagram, A.P. is reported by Siddiquie (1986), Siddiqui and

Raza (1990) and Siddiquie (2004). In case of trace elements Mo shows positive relation

with Co, Sr, Cr, and Ba, whereas negative relation with Cu, Zn, Ni, V and Zr (Table 6.6 and

Fig. 6.34A).

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6.3.10 Barium (Ba)

Barium is an alkaline earth metal and never found as free element. The average

Ba concentration in manganese ores of the study area is around 13524.24 ppm and

concentration ranges from 2097.29-24633.56 in studied samples (Table 6.3). According

to Nicholson (1992) hydrothermal Mn-oxide deposits characteristically shows

geochemical enrichment of barium along with As-Cu-Li-Sb-Sr-Mo-Pb-V-Zn. Ba

concentrations in hydrothermal solutions are higher than seawater because of the

influence of volcanic activity and sedimentation (Monnin et al., 2001; Oksuz, 2011). Ba

shows sympathetic relation with Ti, Mn, Fe, Mg and Ca while negative relation with Si,

Al, Na, K and P. In case of trace elements it shows positive relation with Cu, Zn, Ni, Co,

Cr and Pb while negative relation with V, Sr and Mo. Ba along with other trace element

content like As, Cu, Li, Pb, Sb, Mo, Sr, V and Zn shows an enrichment tendency in oxide

ores deposited from hydrothermal fluids (Nicholson, 1992). The higher values of Ba and

analyzed geochemical data of manganese ores suggested that the hydrothermal solution

provided a source of large metal along with Ba.

6.4 Rare Earth Elements

The geochemical data of rare earth elements are very much important like major

and trace elements data to delineate different processes involved in ore formation and

also to interpret depositional environment and tectonic setting of the study area. A group

of elements in periodic table from lanthanum (La) to lutetium (Lu) that form a part of the

inner transition group of metals known as Rare earth elements. These chemical elements

occur in traces and found in the earth crust which measured in parts per million. Shanon

(1976) explained that a group of heavy elements from La to Lu (REE) having gradually

decreasing ionic radii with increasing number of atomic number. The REE are highly

electropositive in nature and their compounds are ionic in nature. Various workers like

e.g. Elderfield et al. (1981), Klinkhammer et al. (1983) and Alpin (1984) used these

elements to understand the possible source of it in the deposits and also to decipher the

different processes and environment of deposition. The all REE occurs in the ore

deposits, therefore concentration of these elements are very important to determine the

source of the ores and host rocks. According to Piper (1974), Elderfield (1988) and De

Carlo (1991) the variation in rare earth elements distribution pattern may reflect a

change in redox potential and might be due to the change in sorption properties of solid

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phases (Alpin, 1984; Byrne and Kim, 1990). They are very much important to classify

provenance of sediments Mclennan (1989), chemistry and environment of source.

According to Dymond et al., (1984), De Carlo (1991) and Ozturk and Frakes (1995), the

mobility of rare earth elements can be used to recognize the post depositional processes

(digenesis, weathering etc.). Rare earth elements concentration are higher in

hydrogenous than hydrothermal deposits because their oceanic residence times

(102-103 years) are shorter than the mixing time of the ocean (1600 years)(Goldberg et

al., 1963; Elderfield and Greaves, 1982; Grandjean et al., 1987). Therefore, due to these

peculiar properties REE have been utilize to trace the changes in depositional

environment during the formation of ores.

There are two categories of Rare earth elements which defined on the basis of

their electronic configurations in which one is known as light rare earth elements viz:

Lanthanum (La), Cerium (Ce), Praseodymium (Pr), Samarium (Sm), Neodymium (Nd)

and Europium (Eu) and another is known as heavy rare earth elements viz., Gadolinium

(Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Erbium (Er), Thulium (Tm),

Ytterbium (Yb) and Lutetium (Lu) elements.

The total twenty four samples of manganese ores of study area analyzed for rare

earth elements. The average concentration of REE in the manganese ores is 341.04 ppm

and concentration of REE ranges from 147.79-841.02 ppm (Table 6.7). In sea water the

concentration of REE for hydrogenous deposits is 1400 ppm while for hydrothermal

deposits, it is 40 ppm (Usui and Someya, 1997). Rare earth element data of the

hydrothermal and hydrogenous ferromanganese and manganese deposits differ

considerably and therefore they can provide general information about the genetic

processes involved in the formation of submarine manganese and ferromanganese ores

(Bender et al., 1971; Piper, 1974; Toth, 1980; Ruhlin and Owen, 1986; Wonder et al.,

1988; Hein et al., 1997; Shah and Moon, 2004). The results of geochemical analyses of

manganese ores of the study area show that total REE is decreasing from low to high

grade manganese ores in the study area. The analytical data shows that the manganese

ores of study area are enriched in light rare earth elements (LREE) and in contrast of

LREE the heavy rare earth elements (HREE) showing depleted values (Table 6.7). In

manganese ore deposits of the study area the average concentration of light rare earth

elements (LREE) is 249.34 ppm and the concentration ranges from 100.17-627.27

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ppm (Table 6.7) while the average concentration of heavy rare earth elements (HREE)

is 34.16 ppm and the value of heavy rare earth elements (HREE) ranges from

14.45-78.93 ppm. After plotting the REE data in chondrite normalized Taylor and

Mclennan (1985) light rare earth elements (LREE) show enriched pattern and heavy rare

earth elements (HREE) show near to flat pattern (Fig. 6.35). The enriched LREE and

depleted HREE pattern in manganese ores of the study area suggest that the source is

more felsic than the mafic for the manganese deposits of study area. Chondrite

normalized manganese data shows that REE pattern of the studied manganese ores is of

typical hydrothermal with scarcity of hydrogenous ferromanganese ores. The REE data

yet suggest that the manganese ores studied are not fully sourced from a pure

hydrothermal ones. However, geochemical studies indicate dominant contribution from

the earlier source.

The average ratio between (∑LREE)/∑HREE) is 7.32 (Table 6.7). The ratio of

(∑LREE)/∑HREE) in the study area shows that LREE were enriched before the

formation of manganese deposits which clearly indicate mineralization in association

with hydrothermal solutions (Fernandez and Moro, 1998; Fitzgerald, 2006; Xie et al.,

2006). The correlation coefficient between ∑LREE)/∑HREE(r=0.88) is positive

(Fig.6.37) which suggest that the same mechanism was also responsible for rare earth

elements uptake during the ore formation (Oksuz, 2011).

In the study area La/Lu and La/Yb ratio is used to delineate the degree of

fractionation of LREE and HREE. The average ratio of La/Lu is 96.96 and La/Yb

average ratio is 13.74 which show higher values, suggesting significant fractionation of

LREE and HREE representing stratiform manganese deposits (Mishra et al., 2007). La

and Ce show variation amongst the light rare earth elements (LREE) in the study area

and ranges from 20.24-167.82 ppm and 45.12- 228.86 ppm respectively. According to

Varentsov (1995), La is considered as the most mobile REE and used to measure the

degree of differentiation between LREE and HREE.

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Fig. 6.35 Chondrite normalized (After Taylor and McLennan, 1985) rare earth elements

(REE) diagram for manganese ore samples of different localities of Banswara


171

Fig. 6.36 Post Archaean Australian Shale (PAAS) (After Taylor and McLennan, 1985)

normalized rare earth elements (REE) diagram for manganese ore samples of

different localities of Banswara manganese ores, Banswara district,

Rajasthan, India.

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In rare earth elements Ce and Eu anomaly always plays an important role to

decipher the provenance and origin of the manganese ores and host rocks. Eu occurs in

3+ oxidation states, but it is also reduce to 2+ under certain conditions. The Eu*

calculated by using Sm and Gd concentration of the analyzed manganese ores of the

study area. The average concentration of Sm is 10.78 ppm and the values of Sm ranges

from 4.65-30.19 ppm. While the gadolinium (Gd) which is placed next to europium in

periodic table, consist the average concentration is 10.82 ppm and the values of Gd

ranges from 4.52-27.95 ppm. The Chondrite normalized value of both Sm and Gd value

is used to calculate the europium anomaly. In the study area, the average concentration

of Eu is 3.46 ppm and the values of Eu ranges from 1.43-8.10 ppm. The REE data shows

positive correlation with Al2O3 (Fig. 6.38). According to Taylor and Mclennan (1981,

1985) europium anomalies are primarily due to the preferential incorporation of the

divalent form into plagioclase as a substitute for Sr2+ in reducing magmas. If the

plagioclase crystal accumulates in magma before solidification then the magma will

enriched in europium whereas it is separated before the solidification of magma than the

magma will be depleted in Eu concentration. Therefore the values of gadolinium and

samarium are very important and Eu anomaly is calculated by using the formula as

follows (Taylor and Mclennan, 1995; Fu et al., 2010a, 2010b):

Eu anomaly=Eu/Eu* =EuN/√ (SmN x GdN)

The Eu anomaly values called negative if it is less than one while positive when

the value is greater than one. The europium values is positive and showing enriched

pattern in the manganese ores of the study area. Like Eu anomaly, Ce anomaly

calculation and concentration is very much important. Ce occurs in different oxidation

states and can be oxidized to +4. Elderfield (1988) and Taylor and Mclennan (1995)

referred that the Ce+3 is the more soluble form, whereas in oxic water Ce dioxide and

stable Ce hydroxides precipitates. This indicate the enrichment of Ce in sedimentary

rocks which deposited under oxic environments whereas in anoxic and more reducing

condition show depletion (Wilde et al., 1996).

The Ce anomaly calculated by using La and Pr concentration present in the

manganese ores of the study area. The average concentration of La in the study area is

52.81 ppm and ranges from 20.24 to 167.82 ppm whereas the average concentration of

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Pr is 12.49 and concentration ranges from 5.00 to 39.30 ppm. The both lanthanum and

praseodymium is present in all samples of manganese ores of the study area. The

concentration of Nd is abnormally high in comparison of Pr. The average concentration

of neodymium is around 50.99 ppm in the manganese ores with ranges from 20.41 to

153.00 ppm. In calculation of Ce anomaly the chondrite normalized value of La and Pr

elements are used. The average concentration of cerium in the study area samples is

118.81 ppm and the concentration ranges from 45.12 -228.86 ppm. The Ce anomaly is

used to delineate enrichment or depletion of Ce in the study area and cerium anomaly

calculated by using the formula as follows (Taylor and Mclennan, 1995; Fu et a1.,

2010a, 2010b): The formula for Ce anomaly is given below as,

Ce anomaly = Ce/Ce* =CeN/√ (LaN x PrN)

Hydrogenous ferromanganese deposits are multifold enrichment of rare earth

elements compared to their hydrothermal counterparts, with a distinct positive Ce

anomaly in the former and distinct negative Ce anomaly in the later (Goldberg et al.,

1963; Bender et al., 1971; Bostrom, 1973; Bonatti, 1975; Addy, 1979; Elderfield et al.,

1981; Wonder et al., 1988; Hein et al., 1997; Shah and Moon, 2004). Ce shows slightly

positive values for the manganese ores of the study area and also show a smooth flat

pattern of cerium enrichment. Positive cerium anomaly suggested that the manganese

ores derived from continental source (Bau and Dulski, 1993). The positive Eu and weak

positive Ce anomaly in the manganese ores might be due to the presence of higher

detrital material (El Hasan et al., 2008). The Ce anomaly, however, depends on the

temperature of fluid and proximity to the hydrothermal source, redox conditions and

amount of hydrogenetic contamination (Clauer et al., 1984; Hein et al., 1994, 1997;

Shah and Moon, 2004). The Ce/la ratio in the study area is 2.41 (Table 6.7). The high

Ce/La ratio stands for addition of terrigenous material, e.g. the ratio is 2.3 in average in

the pelagic clays of the pacific ocean (Dubinin and Volkov, 1986). Dubinin and Volkov

(1986) referred that the low ratio of Ce/La suggest that the rare earth elements are

associated with hydrogenous manganese hydroxides which absorbed from sea water and

this ratio increase with the increase of the amount of carbonate, biogenic and terrigenous

components (Xie et al., 2013). The La/Ce ratio for the present manganese ores varies

between 0.23 and 0.73. This ratio is higher from Fe-Mn hyrdogenous crust (~0.25) and

also lower than that of the hydrothermal crust and seawater (~2.8). As earlier mentioned

that the concentration of LREE is far higher than the HREE which also suggest more

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felsic source rather than the mafic source for the study area. In interpretation author

found significant relation of rare earth elements with major oxides. The LREE showing

positive relation with Al2O3 (Fig. 6.38). MnO and other oxides which suggest attribution

of LREE mostly by volcanoclastic influx (Mishra et al., 2007). Whereas the HREE do

not show any significant relation with MnO.

Fig. 6.37 Relationship between light and heavy rare earth elements (HREE/LREE) in

the manganese ore samples of different localities of Banswara manganese

ores, Banswara district, Rajasthan, India. (S-Sivnia, G-Gararia, K-

Kalakhunta, Gh-Ghatia, It-Itala, Rt-Ratimauri, Tm-Tambesara,

T-Timamahudi)

Fig. 6.38 Relationship between light rare earth elements (LREE) and Al2O3 in the




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6.4.1 Post Archean Australian Shale Normalized Rare Earth Elements

The analyzed geochemical rare earth elements data normalized with Post

Archean Australian Shale (PAAS) (Fig. 6.36). The manganese ores of study area is

related to sedimentary and metasedimentary processes the standardization is done is

using PAAS primordial standards. However, the data also normalized with Chondrites

data of Taylor and McLennan (1985) (Fig. 6.35). In the study area the PAAS normalized

data show enrichment pattern of LREE while depletion in HREE elements (Fig. 6.35 and

6.36). In the study area the average Eu (PAAS) value is 3.2 and concentration ranges

from 1.32-7.50 ppm whereas the normalized average Ce value is 1.49 with ranges from

.57-2.88 ppm. All the manganese ore samples show strong positive Eu anomaly with

slightly positive values for Ce (Fig. 6.36). The Eu and Ce anomaly derived by putting

normalized value (PAAS) of Sm, Gd, La and Pr concentration respectively in the

formula which are as follows (Taylor and Mclennan, 1995; Fu et al., 2010a, 2010b):

Eu anomaly=Eu/Eu* =EuN/√(SmN x GdN)


The calculate average values of Eu/Eu* and Ce/Ce* of the ores are 1.50 and 1.15

respectively. The Ce anomaly value reflect oxidation and reduction condition of ancient

sea water, when Ce*>1 (Deficiency of Oxygen) (Xie et. al., 2013) and Ce*<1

(Sedimentary water is oxidative) (Wright and Hosler, 1987). The significant observation

is to find out positive Eu anomaly of the manganese ores in the study area. According to

Wright et al. (1987) and Murray et al. (1991) the Ce anomaly is high in anoxic condition

in compare to oxic ocean water which reflects the redox control of Ce thus Ce anomalies

have been used to understand depositional environment under redox conditions for

present study area manganese ores. The positive Eu anomaly is clearly seen in all

samples of study area and it increasing towards the high grade ores (Fig. 6.35, 6.36 and

Table 6.7) and this positive values of europium shows reducing environmental

conditions due to change in Eu+3 to Eu+2.

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6.5 Characteristics and Proposed possible genetic consideration of

Manganese Deposits

Previous extensive literature of manganese deposits clearly indicate significant

mineral variations, pointedly the redox state of manganese varies in these minerals from

Mn(II) to Mn(III) to Mn(IV) (Okita et al., 1988; Roy, 2006; Maynard, 2010). According

to Maynard (2010) rhodochrosite dominated in sedimentary environments, braunite in

volcanic deposits, and other Mn oxides were found in karstic and supergene

environments. The occurrence of bixbyite and braunite has been reported in different

geological environments varying from greenschist to granulite facies conditions (Roy,

1981; Dasgupta and Manickavasagam, 1981; Abs-Wurmbach et al., 1983; Gutzmer and

Beukes, 1997) as well as sedimentary (Serdyuchenko, 1980; Hou, 1994) and supergene

environments (Ostwald, 1992; Shah and Moon, 2004). The mineralogical studies of

manganese ores of the study area reveal that the dominant minerals are braunite,

pyrolusite, cryptomelane, psilomelane, hollandite, coronadite and manganese garnet

(spessartine) whereas the minerals bixbyite, pyroxmangite and rhodochrosite are present

in minor occurrence in study area. This mineralogical assemblages therefore, concluded

that both mineralogy and texture of the studied manganese ores indicate that the host

rocks of the study area have undergone low greenschist facies metamorphism up to

lower amphibolite facies at least. Holland (1984) explained that in late Archean and

early Precambrian period vigorous hydrothermal activities reported and the solution was

enriched in manganese and iron content.

According to Dorr (1968), Glasby (1988) and Dasgupta et al. (1992) referred that

this above mentioned time, the suspended manganese start to react with oxygen and

formed manganese oxides and it was happened due to the development of oxygen oases

in reducing hydrosphere environment and later these manganese oxides ores are

subjected to strong metamorphism. Roy (2000) explained that manganese was

mineralized under different environments (sedimentary) and tectonic settings

throughout the Precambrian terrain in India. The high Mn+2 concentration in Archean

seawater was directly related to the lack of Mn oxidation before the rise of oxygen,

approximately 2.3 billion years ago (Jhonson et al., 2016). There is a very limited set of

processes and oxidants able to oxidize manganese due to its high redox potential (Tebo

et al., 2004).

177

The manganese bearing host rocks of study area belong to Kalinjara formation of

Lunavada group of Aravalli supergroup of Paleo-Proterozoic age. And that time was

very much important regarding the deposition of manganese, as large scale deposition of

manganese ores took place from Paleo-Proterozoic to Neo-Proterozoic throughout the

world which is only possible due to oxygenation of the atmosphere and stabilization of

the stratified ocean system (Roy, 1997) and this time the dissolved Mn+2 was

concentrated under anoxic deep water which referred the source was hydrothermal or

terrigenous. The geochemical studies of manganese bearing rocks in study area

suggested metasedimentary field of protolith and felsic to intermediate source for the

metasediments, those hosted manganese ores. The composition of host rocks (Phyllite,

schist, quartzite and limestone) is pelitic/calcareous respectively suggested by ACF

ternary plots after Eskola (1915). And for these metasediments the tectonic setting

suggested as active and passive continental margin type after Bhatia (1983), Roser and

Korsch (1986) and Bhatia and Crook (1986).

In the study area various discrimination, binary and ternary plots proposed to

decipher source of manganese sediments, its depositional environment, tectonic settings

and genesis for the present manganese deposits. The Na-Mg discrimination diagram

used to distinguish the relation between oxides deposits of fresh, shallow and marine

environment. After plotting manganese ore samples in the Na-Mg discrimination

diagram, the all samples fall under shallow water zone with a few one's in fresh water

field which suggest shallow shelf environment genesis of the present manganese ores of

study area (Fig. 6.39). To distinguishes the lacustrine and marine field for the

manganese ore samples, the geochemical data plotted in ternary plot (Fig. 6.40) of

CaO-Na2O-MgO after Dasgupta et al. (1999) which reveal that almost all the samples of

manganese ores of the study area falls in marine field. The Cao/(CaO+MgO) ratio is

around .98 for the manganese ores of the study area. This ratio is too high and is possibly

due to the involvement of supergene enrichment in present manganese deposits which is

indicated by the presence of pyrolusite, cryptomelane in the manganese ores associated

with braunite, bixbyite, hematite and quartz (Dasgupta and Manickavasagam, 1981).

On the plotting of Ba Vs P2O5 binary diagram after Maynard (2010), the all

manganese ore samples falls in the oxygen minimum zone and near euxinic basin

deposits which suggest anoxic and oxygen deficient depositional conditions for the

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manganese ore deposits of the study area (Fig. 6.41). This pattern suggest two different

mechanism of Mn transport from deep to shallow water, which suggest oxygen minimum

zone and euxinic basin type mineralization. Due to the high-potential redox chemistry of

Mn, the geologic record of manganese deposits should reflect ancient oxygen availability

and the paleo-environmental chemistry (Maynard, 2010). The transgression and

regression within the ocean, the upwelling of anoxic deep water to an oxic shallow water

regime in the basin margin, the attainment of anoxic and oxic interface and resulted

precipitation of Fe and Mn along the cratonic shelf is well established for many

manganese deposits of the world (see for example Holland, 1973; Drever, 1974; Hallam

and Bradshaw, 1979; Pomerol, 1983; Cannon and Force, 1983; Frakes and Bolton, 1984;

Jenkyn, 1988; Force and Cannon, 1988; Pratt et al., 1991; Roy, 1992; Ostwald and

Bolton, 1992, Shah and Moon, 2004). Considering this mechanism the geochemical data

of manganese ores suggest that the manganese ores or manganese rich sediments were

preeipitated in form of manganese oxides or hydroxides above the anoxic and oxic

interface on cratonic shelf as a consequence of upwelling anoxic deep ocean water with

in the basin. Frakes and Bolton (1984) explained that in the marine transgression period,

manganese is accumulated in the narrow zone and the dissolved manganese is

concentrated in the water column. Calvert and Pederson (1993) referred that water in the

basin margin was buried to a reducing zone below where on dissolution, a very high level

O2 dissolved Mn+2 could be attained. Organic matter, therefore, must have played a

major role in the dissolution of manganese, iron and other metals in the anoxic zone as

the abundance of carbon causes the deficiency of oxygen and hence increases the

dissolution ability of water (Frakes and Bolton, 1984; Prothero and Schwab, 1996).

In the study area, the concentration of SiO2, Al2O3, Fe2O3, MnO, CaO and P2O5

is varying in manganese ore deposits and characterized by high SiO2, and MnO, which

are high from the sedimentary digenetic. The positive relation between SiO2-Al2O3 and

TiO2-Al2O3 with high amounts of SiO2, Al2O3 and TiO2 wt % in the manganese ores of

the study area suggest admixture of terrigenous material during precipitation of

manganese deposits. Volcanogenic sedimentary manganese deposits are highly

siliceous in nature, with Si content up to 40 percent in some deposits (Roy, 1981; Crerar

et al., 1982; Peters, 1988). The high silica content in hydrothermal manganese deposits

is a matter of argument (Khalifa and Seif, 2014). The hydrothermally originated

manganese deposits are commonly occur in close association with the ferruginous silica

179

gel which is formed by submarine effusive process and metal discharge into marine

sediments and so that the hydrothermal deposits are commonly rich in their silica

content (Roy, 1992). The another source of higher silica possibly may be due to the

presence of jasperoid quartzite in the manganese ores of study area. The high SiO2 in

manganese ores due to presence of quartz-feldspathic rocks while alumina concentration

may be due to presence of aluminosilicate minerals. The iron concentration is mostly

depend upon nature and association of manganese ores. In the study area the antipathetic

relation of Mn with Si, Al, Mg, Na and P shows increase of Mn with the reduction of

these oxides. The positive correlation between MnO and Fe2O3 shows that Fe increase

with the increase of Mn. The average ratio of MnO/Fe2O3 is 17.08 which is high and

indicates digenetic hydrothermal deposits (Hein et al., 1994, 1997). The binary and

ternary diagram after Toth (1980) and Choi and Hariya (1992) plotted to distinguish

hydrogenous, hydrothermal and supergene origin for the study area manganese deposits.

In Fe-Si*2-Mn ternary diagram after Toth (1980) the samples falls in hydrothermal field

(Fig. 6.42). And in binary plot between Si vs Al after Choi and Hariya (1992) (Fig. 6.43),

the manganese ore samples fall in hydrogenous field with few samples lying in

hydrothermal field too. The average Si/Al ratio for marine sediments is 3 (Turkenian and

Wedepohl, 1961). The Si/Al ration in present manganese ores is 11.14. The high Si/Al

ratio, of 10 to 20, are also found in some of the hydrothermal manganese rich crusts

(Toth, 1980). The both diagram in majority show hydrothermal field of origin for the

present manganese ores of the study area with some supply of terrigenous material also

in the depositional basin. While the binary plot after Wonder et al. (1988) suggest

hydrothermal field for present manganese ores with a few manganese ore samples also

lies in hydrogenous field (Fig. 6.44). The variation of Al2O3, as function of SiO2

concentration has been used to discriminate between hydrothermal and hydrogenous

deposits (Bonatti et al., 1972). Cu, Co and Ni are known to be strongly enriched in

hydrogenous ferromanganese deposits as compared to those formed by hydrothermal

processes along the mid-oceanic ridges (Bonatti et al., 1972; Toth, 1980). The

geochemical data of trace elements is very important to delineate the genesis of

manganese ores. The elements like Co, Cu, V, Ni, Zn and Ba concentration are used in

respective binary and ternary plots after Bonatti et al. (1972), Toth (1980), Nicholson

(1992) and Choi and Hariya (1992) to reveal the source field for the origin of manganese

ores of the study area. In Cu+Ni vs Cu+Pb+V+Zn discrimination diagram (Fig. 6.45)

180

after Nicholson (1992), all the manganese ore samples are falling in hydrothermal field

and showing hydrothermal origin. On the plotting of Co/Zn vs Co+Ni+Cu binary plot

after Toth (1980) also supported hydrothermal origin (Fig. 6.46) for the manganese ore

deposits of the study area. The relationship of Zn, Ni and Co are also considered to

distinguish the hydrogenous deposits (i.e. deep seated Mn nodules) from submarine

hydrothermal Mn-deposits by Choi and Hariya (1992). The rare earth element data and

the ternary diagram of Zn-Ni-Co after Choi and Hariya (1992) shows hydrothermal

origin for the manganese ore samples of the study area (Fig. 6.47). The ternary plot of

Mn-Fe-(Cu-Ni-Co) X 10 after Bonatti et al. (1972) and Crerar et al. (1982) suggests that

the manganese ore samples show hydrothermal affinity and falling in hydrothermal field

which is shown by diagram (Fig. 6.48). The Mn-Fe-(Cu-Ni-Co) X10 discrimination

diagram used to distinguish hydrothermal, hydrogenous and digenetic deposits (Bonatti

et al., 1972).

In the study area the concentration of Cu, Ni, Co and Zn is very high and also

define that high concentration of trace elements indicate sub-marine hydrothermal

affinity of manganese oxide ores while these elements lower concentration indicate

hydrogenous type deposits. The higher concentration of Ba in the manganese samples of

the study area also indicates that they are affected by volcanic activity and sedimentation

(Oksuz, 2011). Pb and Ba were also present in significant amounts along with Mn and

Fe in dissolved form within the anoxic deep water zone. Upwelling of anoxic water

brought up these metals to anoxic-oxic interface and precipitated them as Fe and Mn

oxides and hydroxides along with fluroapatite and barite. According to the trace

elements Co, Ni, Zn which are present in hydrothermal solution are absorbed by the

manganese oxides/hydroxides during the formation of ore deposits.

The interpretation of the geochemical data of these manganese ores reveal

sympathetic correlation between Co-Ni (r= 0.13), Co-Cu (r= 0.08), Co-Zn (r= 0.08),

Cu-Pb (r= 0.67) (Table 6.6) which suggest the precipitation of manganese ores from the

hydrothermal solutions (Ibrahim et al., 2014). The ratio between Co/Zn and Co/Ni is

very much important to delineate the genesis of the deposits (Fernandez and Moro,

1998). Co, Ni, Cu and Zn elements as well as the Co/Zn ratio is good indicator of

hydrothermal versus normal authegenic source of trace metals. The average ratio of

Co/Zn is 0.20 (Table 6.3) which suggests the hydrothermal origin of the manganese ores

181

of the study area (Toth, 1980). According to Fernandez and Moro (1998), the value of

Co/Ni is used to find out the genesis of manganese ores if the Co/Ni<l in the manganese

ores show sedimentary environment but Co/Ni>l represents a deep marine

environmental condition. The average value of Co/Ni is 0.40 which is less than one and

indicate origin of manganese ores of the study area under sedimentary environment

(Table 6.3).

The manganese ores of Banswara area formed in shallow marine shelf

environment. Later activities like deformation and low grade metamorphism

(greenschist facies) which effected locally and resulted in textural, structural and

mineralogical reconstitution in the present manganese ores and host rocks of the study

area. The rare earth elements data of Banswara manganese deposits show lanthanum

enrichment, la/Ce ratio and strong Eu anomalies which indicate both basinal

hydrothermal fluids and terrigenous materials as source for the manganese deposits, in

which major contribution from the former one. While the positive Eu and Ce anomaly

also suggest reducing environment conditions for the deposition of present manganese

ore deposits of Banswara district.

182

Fig. 6.39 Mg vs Na diagram show the manganese ore samples of different localities of

Banswara manganese ores, falling in the field of fresh and shallow water field,


Gh-Ghatia, I-Itala, Rt-Ratimauri, Tm-Tambesara, T-Timamahudi)

Fig. 6.40 CaO-Na2O-MgO ternary plot (after Dasgupta et. al., 1999) shows marine field

for the manganese ore samples of different localities of Banswara manganese

ores, Banswara district, Rajasthan, India. (S-Sivnia, G-Gararia,

K-Kalakhunta, Gh-Ghatia, It-Itala, Rt-Ratimauri, Tm-Tambesara,

T-Timamahudi)

183

Fig. 6.41 Ba vs P2O5 (after Maynard, 2010) shows manganese ores samples of different

localities of Banswara manganese ores, Banswara district, Rajasthan, India

clustered near the Euxinic basin and oxygen minimum zone. (S-Sivnia,

G-Gararia, K-Kalakhunta, Gh-Ghatia, It-Itala, Rt-Ratimauri, Tm-Tambesara,

T-Timamahudi)

Fig. 6.42 Plot of Fe-Six2-Mn ternary diagram (after Toth, 1980) showing the manganese

ore samples of different localities of Banswara manganese ores, Banswara

district, Rajasthan, India are concentrated near the hydrothermal field.



184

Fig. 6.43 Si vs Al weight percent plot (after Choi and Hariya, 1992) shows the

hydrogenous-hydrothermal origin for the manganese ores of different




Fig. 6.44 SiO2 vs Al2O3 plot (after Wonder et al., 1988) shows the hydrothermal origin

for the manganese ores of different localities of Banswara manganese ores,



185

Fig. 6.45 Cu+Ni vs Cu+Pb+V+Zn discrimination diagram (after Nicholson, 1992)

shows the manganese ore samples of different localities of Banswara

manganese ores, Banswara district, Rajasthan, India clustered in

hydrothermal field. (S-Sivnia, G-Gararia, K-Kalakhunta, Gh-Ghatia, It-Itala,

Rt-Ratimauri, Tm-Tambesara, T-Timamahudi)

Fig. 6.46 Co/Zn vs Co+Ni+Cu bivariate diagram (after Toth, 1980) shows the

hydrothermal origin for the manganese ores of different localities of


G-Gararia, K-Kalakhunta, Gh-Ghatia, It-Itala, Rt-Ratimauri,


186

Fig. 6.47 Zn-Ni-Co ternary diagram (after Choi and Hariya, 1992) shows the manganese

ores of different localities of Banswara manganese ores, Banswara district,

Rajasthan, India from hydrothermal origin. (S-Sivnia, G-Gararia,

K-Kalakhunta, Gh-Ghatia, It-Itala, Rt-Ratimauri, Tm-Tambesara,

T-Timamahudi)

Fig. 6.48 Mn-Fe-(Ni + Co + Cu) X10 ternary discrimination diagram (after Bonatti et al.

1972; Crerar et al. 1982) showing hydrothermal origin for manganese

deposits of different localities of Banswara manganese ores, Banswara

district, Rajasthan, India. (S-Sivnia, G-Gararia, K-Kalakhunta, Gh-Ghatia,

It-Itala, Rt-Ratimauri, Tm-Tambesara, T-Timamahudi)

187

CHAPTER-7

GEOCHEMISTRY OF HOST ROCKS

7.1 INTRODUCTION

The geochemical studies of host rocks were carried out to understand various

aspects of geological history of the area like physico-chemical conditions,

paleo-environment of deposition, tectonic settings of the area, mineralogical

assemblages and their relation with ores etc. The manganese hosted rocks in the study

area are phyllite, schist, quartzite and limestone, in which manganiferous phyllite is the

dominant rock type throughout the Banswara manganese belt. The petrographic studies

refers that regional metamorphism has played an important role in metamorphism of

pelitic-psammitic and calcareous sediments which are the prominent Mn comprising

rocks of the study area and finally metamorphosed to present day rock types viz.

phyllite, schist and quartzite. These host rocks occurred as cofolded and in interbeded

form with manganese horizons in the study area.

In the present work the total fifteen samples of different host rocks were

selected for the detailed study of major oxides (XRF) (Table 7.1), trace (Table 7.2) and

rare earth elements analysis (Table 7.5) (ICP-MS). The detailed description of accepted

methods and techniques explained in earlier chapter (Introduction).

7.2 Major Elements

The fifteen samples of different host rocks which are summarized in Table 7.1,

analyzed through XRF for major elements (SiO2+TiO2+A12O3+Fe2O3+MnO+MgO

+Na2O+K2O+P2O5) to understand the relationships between these different elements.

The major oxides are measured in weight percent.

7.2.1 Silica

The SiO2 percent in host rocks varies from 8.67 wt % to 91.05 wt % with an

average percentage of 57.84 wt% (Table 7.1) (Fig. 7.1). The highest average silica

percentage lies in quartzite samples (90.26 wt%) while the lowest average values in

limestone samples (9.66 wt %). The order of SiO2 variation in host rocks are

quartzite>schist>phyllite>manganiferous phyllite>limestone. In host rocks SiO2 shows

188

positive relation with A12O3, Fe2O3, TiO2, MnO, Na2O, K2O and P2O5 (Table 7.4) (Fig.

7.3A, B, C, D, G, H and I). It shows that the alumina, manganese oxide, sodium oxide,

potassium oxide and phosphorous oxide increases with the increase of silica. The

sympathetic relation of SiO2 with sodium oxide and potassium oxide are due to

presence of K-feldspar and other A1 silicate minerals (Jawed, 2015). The negative

relation show by MgO and CaO with SiO2 (Fig.7.3 E-F) which means that the SiO2

increases with the decrease of magnesium oxide and calcium oxide and vice versa. The

negatively correlated oxides have downward linear trend suggesting non association

with SiO2. The antipathetic relation with these oxides suggest that they are substituted

by SiO2. The higher percentage of SiO2 in host rocks is thought to be due to the

presence of silicates while in quartzite samples show very high SiO2 values refers to

predominance of quartz over feldspar and suggest high stability field of quartz in wide

range of pressure-temperature conditions. The higher values of SiO2 have also been

reported by Krishna Rao (1967) and Siddique (2004) from host rocks of Vizianagram

manganese ores of Andhra Pradesh.

7.2.2 Alumina

The order of variation in A12O3 wt % in host rock samples varies in the order of

phyllite>manganiferous phyllite>schist>quartzite>limestone (Fig. 7.1). The alumina

percent in host rocks varies from .38 wt % to 22.87 wt % with an average percentage of

11.87 wt % (Table 7.1). The highest average A12O3 percentage lies in phyllite samples

(18.55 wt %) while the lowest average values in limestone samples (.4 wt %). In host

rocks A12O3 shows strong positive relation with SiO2, TiO2, Fe2O3, Na2O, K2O and

P2O5 (Table 7.4). It shows that the silica, titanium oxide, iron oxide, sodium oxide,

potassium oxide and phosphorous oxide increases with the increase of alumina and vice

versa. The sympathetic relation of A12O3 with these oxides refers presence of

orthoclase, muscovite, biotite and garnet. In the study area A12O3 shows strong

sympathetic relation with MnO. The negative relation show by CaO with alumina

which means that the calcium oxide increase with the decrease of alumina and vice

versa. According to Rankama and Sahama (1950) Si4+ is replaced by Al3+ in K-

feldspar. The average ratio of SiO2/A12O3 is 9.76 which indicate dominance of silicate

minerals.

189

Table 7.1 The analyzed geochemical data (Major oxides) of host rocks of manganese ores, Banswara district, Rajasthan.

Oxide(wt

%)

Schist Manganiferous Phyllite Phyllite Quartzite Limestone

Average SCH-1 SCH-2 SCH-3 MNP-1 MNP-2 MNP-3 PHY-1 PHY-2 PHY-3 QTZ-1 QTZ-2 QTZ-3 TLS-1 TLS-2 TLS-3

SiO2 76.39 68.51 70.72 59.75 49.33 61.77 58.06 60.53 62.76 89.72 90.01 91.05 10.86 8.67 9.45 57.84

Al2O3 13.89 17.11 14.93 15.66 22.87 16.45 21.05 17.29 17.31 6.69 7.11 6.46 0.41 0.38 0.41 11.87

TiO2 0.38 0.54 0.46 0.61 0.43 0.80 0.78 0.58 0.59 0.05 0.10 0.11 0.02 0.02 0.03 0.37

Fe2O3 2.13 1.73 1.65 3.51 4.47 6.01 9.57 5.37 5.50 0.12 0.11 0.12 0.15 0.26 0.26 2.73

MnO 0.16 0.92 0.79 9.59 1.47 3.93 0.88 0.93 2.05 0.10 0.07 0.07 0.21 0.14 0.14 1.43

MgO 0.51 2.35 0.61 2.63 6.77 0.24 3.27 2.23 1.65 0.06 0.09 0.08 4.44 3.90 4.44 2.22

CaO 0.78 1.32 1.13 0.98 0.41 1.46 0.18 0.18 0.87 1.63 1.92 1.44 49.18 45.14 44.11 10.05

Na2O 2.82 2.93 3.01 0.54 3.45 2.60 2.04 2.27 3.80 0.05 0.07 0.07 0.07 0.06 0.06 1.59

K2O 1.32 2.76 2.24 2.46 6.60 3.69 0.88 3.48 2.91 0.67 0.58 0.44 0.11 0.10 0.10 1.89

P2O5 0.62 0.95 0.70 0.31 0.15 0.45 0.90 0.60 0.10 0.05 0.003 0.003 0.01 0.003 0.003 0.32

LOI 1.78 1.65 1.98 2.67 4.90 2.83 2.28 5.59 1.48 0.81 0.49 0.51 34.92 40.96 41.08 9.60

Total 100.78 100.77 99.97 98.71 100.85 100.23 99.89 99.05 99.02 99.95 100.56 100.34 100.38 99.64 100.08 100.01

SiO2/Al2O3 5.50 4.00 4.74 3.82 2.16 3.76 2.76 3.50 3.63 13.41 12.66 14.09 26.49 22.82 23.05 9.76

Al2O3/TiO2 36.55 31.69 32.46 25.67 53.19 20.56 26.99 29.81 29.34 133.80 73.30 60.94 17.08 19.00 15.19 40.37

K2O/Na2O 0.47 0.94 0.74 4.56 1.91 1.42 0.43 1.53 0.77 13.40 8.34 6.21 1.55 1.67 1.76 3.05

Al2O3/CaO 17.81 12.96 13.21 15.98 55.78 11.27 116.94 96.06 19.90 4.10 3.70 4.48 0.01 0.01 0.01 24.81

Al2O3/MgO 27.24 7.28 24.48 5.95 3.38 68.54 6.44 7.75 10.49 111.50 79.00 80.75 0.09 0.10 0.09 28.87

Fe2O3/MgO 4.18 0.74 2.70 1.33 0.66 25.04 2.93 2.41 3.33 2.00 1.20 1.45 0.03 0.07 0.06 3.21

190

Table 7.2 The analyzed geochemical data (Trace Elements) of host rocks of manganese ores, Banswara district, Rajasthan.

Elements

(ppm)

Schist Manganiferous Phyllite Phyllite Quartzite Limestone


Sc 8.77 11.55 6.01 14.96 13.46 9.09 17.66 13.73 18.53 0.10 0.14 0.13 0.10 0.15 0.17 7.64

V 261.90 40.08 26.04 60.54 63.24 55.29 119.82 96.08 119.58 2.69 2.65 3.58 2.38 4.91 5.34 57.61

Cr 58.43 36.09 42.59 58.00 34.74 37.94 73.96 71.64 74.80 5.99 6.54 6.51 5.29 6.95 7.07 35.10

Co 33.48 33.63 41.12 44.20 12.45 27.55 25.72 16.47 30.75 1.96 2.56 0.24 0.20 0.53 0.51 18.09

Ni 41.63 39.30 33.81 35.61 37.81 56.69 52.56 52.56 43.62 2.85 3.76 2.93 2.19 11.07 12.09 28.57

Cu 33.07 10.71 27.89 31.52 23.33 38.19 56.37 42.39 19.13 1.26 1.45 1.09 0.83 1.98 2.01 19.42

Zn 105.44 61.89 80.71 87.00 72.42 111.90 169.68 108.80 88.71 32.54 30.86 38.34 17.90 41.35 42.98 72.70

Rb 120.50 151.28 67.39 141.27 343.17 146.44 252.30 186.64 297.39 1.31 1.29 1.47 1.23 1.93 2.19 114.39

Sr 197.26 125.17 201.53 176.06 180.73 220.59 286.38 193.48 168.65 105.25 114.50 88.91 72.59 141.32 139.98 160.83

Y 32.84 10.10 11.44 30.13 7.41 17.56 29.17 22.59 24.99 7.79 7.22 8.98 5.24 9.28 10.30 15.67

Zr 103.09 68.55 76.74 108.68 105.69 106.32 161.22 135.02 184.83 0.54 0.66 0.45 0.39 0.59 0.64 70.23

Nb 6.13 10.52 4.70 5.78 12.63 5.73 10.99 15.74 13.09 0.11 0.13 0.07 0.06 0.35 0.24 5.75

Cs 8.99 11.02 5.55 12.54 41.23 11.47 14.61 12.57 16.99 0.03 0.02 0.02 0.01 0.04 0.02 9.01

Ba 1610.22 2537.22 776.21 1079.36 5165.57 1411.54 502.92 368.85 611.57 6.39 7.66 5.30 4.02 12.16 13.19 940.81

La 53.43 35.99 8.10 28.12 29.41 37.83 60.15 43.18 67.43 5.85 5.36 6.97 3.26 11.35 12.32 27.25

Ce 123.59 54.71 47.34 55.88 29.88 60.38 122.98 87.03 140.48 2.95 2.66 3.80 1.78 4.97 5.16 49.57

Nd 49.83 31.08 9.26 23.08 9.83 33.33 52.19 34.50 58.40 4.85 4.51 5.55 2.68 8.45 8.30 22.39

Hf 3.49 1.97 2.60 3.52 3.39 3.38 5.15 4.53 4.88 0.09 0.12 0.08 0.07 0.15 0.11 2.24

Ta 1.55 2.31 2.06 1.85 1.06 1.52 0.94 1.44 1.10 0.07 0.05 0.01 0.01 0.02 0.01 0.93

Pb 15.66 16.26 11.76 14.67 10.28 20.62 28.02 20.41 39.32 1.26 1.21 1.11 0.58 5.15 5.35 12.78

Th 13.63 15.54 11.28 14.98 20.07 15.08 23.46 15.51 31.70 0.08 0.05 0.06 0.03 0.08 0.09 10.78

U 1.56 0.50 1.16 1.32 1.03 2.02 3.39 2.76 3.22 1.21 0.91 1.34 1.40 0.71 1.00 1.57

La/Yb 16.62 49.62 7.51 12.17 52.52 28.01 20.28 20.25 25.18 20.17 16.58 20.85 16.92 24.67 28.77 24.01

La/Sc 6.09 3.12 1.35 1.88 2.18 4.16 3.41 3.14 3.64 58.50 38.77 55.39 32.83 75.67 72.50 24.18

Th/Sc 1.55 1.35 1.88 1.00 1.49 1.66 1.33 1.13 1.71 0.80 0.37 0.45 0.33 0.53 0.56 1.08

Zr/Th 7.56 4.41 6.80 7.26 5.27 7.05 6.87 8.71 5.83 6.75 12.86 7.89 11.72 7.38 6.76 7.54

Sc/Cr 0.15 0.32 0.14 0.26 0.39 0.24 0.24 0.19 0.25 0.02 0.02 0.02 0.02 0.02 0.02 0.15

Ni/Co 1.24 1.17 0.82 0.81 3.04 2.06 2.04 3.19 1.42 1.45 1.47 12.26 11.16 20.89 23.59 5.77

Ti/Zr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.06 0.09 0.14 0.04 0.02 0.03 0.03

Zr/Hf 29.52 34.75 29.53 30.91 31.15 31.44 31.28 29.80 37.90 6.00 5.60 5.80 5.38 3.93 5.79 21.25

191

Table 7.3 The correlation coefficient between trace elements of host rocks of manganese ores, Banswara district, Rajasthan.

Sc V Cr Co Ni Cu Zn Rb Sr Y Zr Nb Cs Ba La Ce Nd Hf Ta Pb Th U

Sc 1.00

V 0.60 1.00

Cr 0.93 0.74 1.00

Co 0.73 0.55 0.77 1.00

Ni 0.87 0.65 0.89 0.76 1.00

Cu 0.78 0.65 0.86 0.67 0.90 1.00

Zn 0.80 0.68 0.87 0.65 0.89 0.97 1.00

Rb 0.92 0.54 0.78 0.52 0.80 0.67 0.69 1.00

Sr 0.71 0.59 0.78 0.62 0.85 0.93 0.95 0.64 1.00

Y 0.72 0.83 0.85 0.68 0.69 0.77 0.80 0.50 0.70 1.00

Zr 0.96 0.69 0.97 0.73 0.91 0.84 0.86 0.89 0.79 0.77 1.00

Nb 0.91 0.55 0.85 0.55 0.85 0.70 0.70 0.91 0.61 0.52 0.89 1.00

Cs 0.74 0.38 0.54 0.38 0.63 0.51 0.48 0.92 0.49 0.25 0.68 0.77 1.00

Ba 0.47 0.27 0.24 0.33 0.45 0.26 0.22 0.67 0.26 0.00 0.37 0.53 0.87 1.00

La 0.87 0.81 0.89 0.59 0.84 0.73 0.82 0.81 0.70 0.80 0.91 0.81 0.55 0.29 1.00

Ce 0.84 0.86 0.94 0.70 0.82 0.77 0.84 0.71 0.72 0.86 0.91 0.75 0.42 0.16 0.95 1.00

Nd 0.80 0.82 0.87 0.63 0.80 0.71 0.81 0.67 0.67 0.84 0.86 0.71 0.36 0.13 0.98 0.97 1.00

Hf 0.95 0.71 0.97 0.73 0.93 0.90 0.90 0.87 0.83 0.79 0.99 0.88 0.68 0.38 0.89 0.90 0.84 1.00

Ta 0.70 0.47 0.71 0.93 0.79 0.64 0.58 0.55 0.55 0.51 0.67 0.65 0.46 0.49 0.53 0.59 0.53 0.69 1.00

Pb 0.89 0.61 0.90 0.66 0.84 0.70 0.79 0.79 0.70 0.72 0.94 0.80 0.49 0.18 0.93 0.92 0.92 0.89 0.57 1.00

Th 0.96 0.62 0.90 0.71 0.86 0.72 0.77 0.94 0.70 0.65 0.97 0.89 0.75 0.48 0.89 0.87 0.83 0.94 0.67 0.93 1.00

U 0.65 0.50 0.74 0.27 0.59 0.68 0.73 0.57 0.61 0.65 0.76 0.59 0.26 -0.18 0.74 0.76 0.75 0.74 0.14 0.78 0.66 1.00

192

Table 7.4 The correlation coefficient between trace elements and major oxides of host rocks of manganese ores, Banswara district, Rajasthan.

Cu Zn Co Ni Sr Cr V Sc Rb Cs Ba Zr Nb Ta U Ce Nd Y SiO2 Al2O3 TiO2 Fe2O3 MnO MgO CaO Na2O K2O P2O5

Cu 1.00

Zn 0.97 1.00

Co 0.67 0.65 1.00

Ni 0.90 0.89 0.76 1.00

Sr 0.93 0.95 0.62 0.85 1.00

Cr 0.86 0.87 0.77 0.89 0.78 1.00

V 0.65 0.68 0.55 0.65 0.59 0.74 1.00

Sc 0.78 0.80 0.73 0.87 0.71 0.93 0.60 1.00

Rb 0.67 0.69 0.52 0.80 0.64 0.78 0.54 0.92 1.00

Cs 0.51 0.48 0.38 0.63 0.49 0.54 0.38 0.74 0.92 1.00

Ba 0.26 0.22 0.33 0.45 0.26 0.24 0.27 0.47 0.67 0.87 1.00

Zr 0.84 0.86 0.73 0.91 0.79 0.97 0.69 0.96 0.89 0.68 0.37 1.00

Nb 0.70 0.70 0.55 0.85 0.61 0.85 0.55 0.91 0.91 0.77 0.53 0.89 1.00

Ta 0.64 0.58 0.93 0.79 0.55 0.71 0.47 0.70 0.55 0.46 0.49 0.67 0.65 1.00

U 0.68 0.73 0.27 0.59 0.61 0.74 0.50 0.65 0.57 0.65 -0.18 0.76 0.59 0.14 1.00

Ce 0.77 0.84 0.70 0.82 0.72 0.94 0.86 0.84 0.71 0.71 0.16 0.91 0.75 0.59 0.76 1.00

Nd 0.71 0.81 0.63 0.80 0.67 0.87 0.82 0.80 0.91 0.36 0.13 0.86 0.71 0.53 0.75 0.97 1.00

Y 0.77 0.80 0.68 0.69 0.70 0.85 0.83 0.72 0.50 0.25 0.00 0.77 0.52 0.51 0.65 0.86 0.84 1.00

SiO2 0.17 0.17 0.29 0.13 0.07 0.21 0.22 0.16 0.10 0.05 0.06 0.18 0.14 0.28 0.11 0.22 0.18 0.19 1.00

Al2O3 0.79 0.77 0.71 0.86 0.72 0.81 0.54 0.89 0.89 0.81 0.65 0.87 0.86 0.76 0.47 0.70 0.64 0.53 0.43 1.00

TiO2 0.88 0.88 0.80 0.95 0.81 0.86 0.51 0.89 0.77 0.59 0.39 0.90 0.78 0.79 0.60 0.77 0.75 0.67 0.08 0.89 1.00

Fe2O3 0.89 0.92 0.51 0.86 0.86 0.82 0.51 0.86 0.82 0.62 0.29 0.89 0.78 0.46 0.81 0.76 0.75 0.65 0.08 0.79 0.88 1.00

MnO 0.37 0.29 0.58 0.37 0.27 0.39 0.08 0.48 0.29 0.29 0.18 0.39 0.20 0.47 0.10 0.20 0.20 0.48 0.04 0.36 0.52 0.33 1.00

MgO -0.01 -0.04 -0.21 0.03 0.04 -0.03 -0.11 0.17 0.34 0.49 0.45 0.05 0.23 -0.12 -0.09 -0.13 -0.14 -0.17 -0.76 0.02 -0.07 0.14 0.02 1.00

CaO -0.52 -0.51 -0.56 -0.53 -0.42 -0.56 -0.41 -0.56 -0.51 -0.44 -0.35 -0.57 -0.53 -0.57 -0.32 -0.50 -0.44 -0.42 -0.88 -0.79 -0.63 -0.46 0.07 0.50 1.00

Na2O 0.60 0.62 0.68 0.82 0.60 0.48 0.60 0.75 0.81 0.72 0.63 0.80 0.82 0.75 0.40 0.73 0.67 0.40 0.22 0.83 0.74 0.61 0.07 0.04 -0.55 1.00

K2O 0.46 0.37 0.43 0.65 0.40 0.48 0.25 0.65 0.80 0.90 0.84 0.61 0.74 0.60 0.14 0.32 0.26 0.14 0.15 0.79 0.62 0.51 0.35 0.28 -0.52 0.75 1.00

P2O5 0.72 0.73 0.72 0.74 0.66 0.65 0.49 0.59 0.42 0.26 0.28 0.58 0.59 0.80 0.28 0.61 0.59 0.49 0.26 0.67 0.73 0.55 0.09 -0.13 -0.48 0.61 0.28 1.00

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Fig. 7.1 Bar diagram showing average weight percent of major oxides of host rocks

Manganiferous phyllite (MNP), Phyllite (PHY), Schist (SCH), Quartzite

(QTZ) and Limestone (LST), of manganese ores, Banswara district, Rajasthan.

194

Fig. 7.2 Bar diagram showing weight percent of SiO2, A12O3, and Fe2O3 in host

rocks Manganiferous phyllite (MNP), Phyllite (PHY), Schist (SCH),

Quartzite (QTZ) and Limestone (LST), of manganese ores, Banswara


195

Fig. 7.3 Scatter diagrams between SiO2 and other oxides of host rocks Manganiferous

phyllite (MNP), Phyllite (PHY), Schist (SCH), Quartzite (QTZ) and Limestone


196

Fig. 7.4 Variation diagram showing total average weight percent of major oxides in


(QTZ) and Limestone (LST), of manganese ores, Banswara district,

Rajasthan.

197

7.2.3 Titanium Oxide

The TiO2 concentration in host rocks ranges from .02 % to .80 wt % with an

average value of .37 wt% (Table 7.1). The highest average TiO2 wt % found in phyllite

(.65 wt %) samples and lowest value in limestone samples (.02 wt %)(Fig. 7.6). It

shows positive relation with A12O3, Fe2O3, MnO, Na2O, K2O, P2O5 and negative

relation with CaO and MgO (Table 7.4). Titanium always tend to concentrate in mafic

minerals instead of felsic one and because of it the concentration always high in mafic

rocks. In TiO2 vs Zr binary plot after Hayashi et al. (1997), the host rock samples falling

in the field of felsic to slight intermediate rocks composition which confirmed the lower

percentage of Ti in these rocks. The highest A12O3/TiO2 values found in order of

quartzite (89.35)>schist (33.56)>manganiferous phyllite (33.14)>phyllite (28.71)>

limestone (17.09). The titanium bearing minerals ilmenite and biotite present in host

rock samples and also confirmed by XRD technique which is the source of

concentration of TiO2 (Siddiquie 2004; Siddiquie and Raza, 2008; Siddiquie and Bhat,

2010 ).

7.2.4 Iron Oxide

The quantitative variation trend of Fe2O3 in the host rock samples ranges from

.12 wt % to 9.57 wt % and the average Fe2O3 value is 2.73 wt % (Table 7.1). The

highest average iron oxide percentage lies in phyllite samples (6.81 wt %) while the

lowest average values in limestone samples (.l wt%) (Fig. 7.2). The order of

quantitative variation in host rock samples from phyllite>manganiferous

phyllite>schist> limestone> quartzite. In host rocks Fe2O3 shows positive relation with

TiO2, A12O3, MgO, MnO, Na2O, K2O and P2O5 (Table 7.4). It shows that the alumina,

titanium oxide, manganese oxide, magnesium oxide, sodium oxide, potassium oxide

and phosphorous oxide increases with the increase of silica. The sympathetic relation of

Fe2O3 with manganese oxide and potassium oxide are due to presence of iron bearing

minerals (Siddiquie 2004; Siddiquie and Raza, 2008) like biotite, garnet and

amphiboles. The negative relation of CaO with Fe2O3 which means that the Fe2O3

increases with the decrease of calcium oxide. The downward linear trend suggested by

these negatively skewed oxides indicate non association with Fe2O3.

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7.2.5 Manganese oxide

The manganese oxide concentration in the host rocks varying from .07 wt% to

9.1 wt % with an average percent of 1.43 wt% (Table 7.1). The highest average

percentage calculated in manganiferous phyllite (5.00 wt %) and lowest concentration

in quartzite samples (.08 wt%) (Fig. 7.6). MnO showing strong sympathetic relation

with all major oxides from SiO2 to P2O5 (Table 7.4) (Fig. 7.3D). According to Siddiquie

(1986), Siddiquie (2004), Siddiquie and Raza (2008) and Siddiquie and Bhat (2010),

the sympathetic relation of MnO with iron oxide and alumina shows the presence of

tourmaline and garnet. Manganiferous phyllite and phyllite are more rich in manganese

oxide concentration in compare of schist, quartzite and limestone as seen in the bar

charts which indicating wt % of MnO in the host rock samples of MNP, PHY, SCH,

QTZ and LST are shown in (Fig. 7.6). The average Si/Mn ratios in the host rocks is

301.57 with separated average ratio of individual host rock as 213.81 (schist), 18.50

(manganiferous phyllite), 13.89 (phyllite), 1161.26 (quartzite) and 60.39 (limestone).

7.2.6 Magnesium Oxide

The MgO concentration in the host rock samples show positive relation with

MnO, CaO and Fe2O3 while negative relation with SiO2 TiO2 and P2O5 (Fig. 7.3E)

(Table 7.4). The higher concentration of magnesium oxide lies in limestone samples

from 4.44 wt % to 3.99 wt% (Fig. 7.1 and 7.4). In other samples the order of

quantitative variation of average MgO wt% from manganiferous phyllite (3.21 wt

%)>phyllite (2.38 wt %)> schist (1.60 wt %)> quartzite (.08 wt%) (Table 7.1) (Fig.

7.1). The higher concentration of magnesium in limestone due to presence of minerals

like dolomite and tremolite while in other samples due to biotite, tourmaline and garnet.

The average alumina/magnesia ratio is 28.87. The high value of magnesium in samples

of study area is due to its felsic rock composition. According to Siddiquie (2004) the

lower values of MgO indicate less mafic components from the source rocks.

7.2.7 Calcium Oxide

The average wt % of Cao in the study area samples is 1.03 wt % except

limestone samples where the average value of calcium oxide is 46.14 wt %. The higher

concentration of CaO belongs to manganese bearing limestone samples of the study

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area (Fig. 7.4). CaO is an important constituent of calcareous rocks. The quantitative

variation trend of CaO in the studied samples from .18 wt% to 49.18 wt % (Table 7.1).

The order of increasing CaO in host rocks are phyllite (.41 wt %)<manganiferous

phyllite (.95 wt %)<schist (1.08 wt %)<quartzite (1.67wt %)< limestone (46.14 wt%)

(Fig. 7.1 and 7.5). CaO shows strong sympathetic relation with MnO and MgO, while

antipathetic relation with SiO2, A12O3, TiO2, Na2O, K2O and P2O5 (Table 7.4). The

higher concentration of CaO in the host rocks especially in limestone due to the

presence of calcite, dolomite, tremolite and epidote (Siddiquie, 2004) while in rest of

samples due to the presence of calcite and dolomite minerals.

7.2.8 Sodium Oxide

In the host rocks of study area the average percent of Na2O is 1.59 wt % with an

order of variation from .05 wt % to 3.8 wt% (Table 7.1). The quantitative analysis

depict that the order of average Na2O wt % variation in host rock samples from

schist>phyllite>manganiferous phyllite>quartzite>limestone (Fig. 7.1 and 7.5). In

phyllite, schist and manganiferous phyllite the average wt % of Na2O is 2.70, 2.92 and

2.20 respectively. The sodium oxide show antipathetic relation with CaO while

sympathetic relation with SiO2, A12O3, TiO2, Fe2O3, MnO, K2O and P2O5 (Table 7.4).

The sympathetic relation of sodium oxide with silica and alumina indicates the

presence of plagioclase feldspar (albite) and tourmaline, these minerals are frequent in

the host rocks of the study area.

7.2.9 Potassium Oxide

The analytical results show that the K2O value in studied samples ranges from

.1 wt % to 6.60 wt % with an average wt % of 1.89 (Table 7.1). The average wt % of

K2O in schist, manganiferous phyllite, phyllite, quartzite and limestone are 2.10 wt %,

4.25 wt %, 2.42 wt %, .56 wt %, .10 wt % respectively (Fig. 7.1). K2O shows positive

relation with all the major oxides except calcium oxide (Table 7.4). The positive

relation with alumina and sodium oxide refers the presence of potassic and sodic

feldspar in the studied host rock samples. In pelitic assemblages the concentration of

K2O is high in comparison of limestone due to the presence of orthoclase and

microcline. The considerable amount of K2O in host rocks suggest their derivation may

be from continental sources (Donaldson and Jackson, 1965).

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Fig. 7.5 Bar diagrams showing weight percent of MgO, CaO, Na2O and K2O in host


Quartzite (QTZ) and Limestone (LST), of manganese ores, Banswara district,

Rajasthan.

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Fig. 7.6 Bar diagrams showing weight percent of MnO, TiO2 and P2O5 in host rocks

Manganiferous phyllite (MNP), Phyllite (PHY), Schist (SCH), Quartzite (QTZ) and

Limestone (LST), of manganese ores, Banswara district, Rajasthan.

202

7.2.10 Phosphorous Oxide

The P2O5 concentration in host rocks ranges from .003 % to .95 wt % with an

average value of .32 wt % (Table 7.1). The highest average phosphorous oxide wt %

found in schist (.76 wt %) samples and lowest value in limestone (.003 wt %) samples

(Fig. 7.1 and 7.4). It shows positive relation with A12O3, Fe2O3, MnO, Na2O, K2O and

P2O5 and negative relation with CaO and MgO (Fig. 7.4 and 7.31). The positive relation

of P2O5 with manganese oxide and alumina indicate the presence of apatite and garnet

in studied samples (Siddiquie, 1986, 2004, 2010; Siddiquie and Shaif, 2015).

7.3 Distribution of Trace Elements

The study of trace element distribution in the rocks is an important tool to

decipher various aspects like its source rock characteristics, mineral phases and

genesis, geochemical environment and tectonic conditions of their formation.

Goldschmidt (1937) categorized trace elements as lithophile, siderophile and

chalcophile by using their chemical affinities which is determined on behalf of

electronic configuration of their atoms. According to Taylor and Mclennan (1985),

Bhatia and Crook (1986), Cullers et al. (1988) and Mclennan et al. (1993) the immobile

elements always provide necessary information to delineate provenance and tectonic

settings of sediments. Because the ratios of relatively immobile trace elements are least

affected by post magmatic processes viz., weathering, metamorphism and alteration.

The concentration of trace elements always vary with the rock types weather it belongs

to mafic, ultramafic, intermediate or felsic composition, e.g. nickel and chromium

always show higher concentration in mafic and ultramafic rocks while zirconium and

rubidium are more liable to concentrate in acidic or felsic rock types. The variation in

mobility of elements depends upon P-T condition and depositional environment

(Jawed, 2015). The variation in mobility up to certain extent also relies on viscosity of

magma etc. The analytical results of the different samples (Table 7.2) showing

variation in the distribution of trace elements and these variation in distribution depends

on compatibility and incompatibility of trace elements with solid and liquid. The

compatible behavior of elements preferentially partitioned into solid phases while

incompatible behavior of elements preferentially partitioned in melt. Washington

(1913) explained distribution of trace elements in earth crust and suggested that the

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major oxides of host and ores are having mutual relationship. The trace elements are

grouped under following categories, which are as follows.

7.3.1 Large Ion Lithophile Elements (LILE)

7.3.2 High Field Strength Elements (HFSE)

7.3.3 Transition Elements

7.3.1 Large Ion Lithophile Elements (LILE)

The term LILE was first used by Gast (1972) to encompass the cations K, Rb,

Sr, Cs, Ba, REE, Th and U. These elements generally refers on the basis of large ionic

radius to ionic charge (or low field strength elements). Gast (1972) also included Li as a

LILE, since it has a large radius to charge ratio, even though it is small (IR = 0.82).

These elements refers as a synonym for incompatible trace elements and generally

present in major silicate minerals like feldspar and mica. These elements are highly

mobile during weathering and hydrothermal alteration, and are convenient for the

studies of partial melting, fractional crystallization, metasomatic alteration, and fluid

component behavior (Akihisa et al., 2015). The large ion lithophile elements are very

much helpful to understand the magmatic evolution process. For example, Rb/K ratio

indicates the grade of magma fractionation (Abbott, 1967 and Shaw, 1968) while

Rb/Ba and Rb/Sr are plagioclase fractionation indicators. The Ba concentration is very

high in the host rocks of the study area with an average value of 940.81 ppm. The LILE

show enrichment pattern in host rock samples except quartzite where these elements

show depleted pattern (Fig. 7.12).

7.3.1.1 Lead

The Pb concentration in host rocks varies from .58 ppm to 39.32 ppm with an

average value of 12.78 ppm (Fig. 7.2). The highest average lead concentration lies in

phyllite samples (29.25 ppm) (Fig. 7.8) while the lowest average values in quartzite

samples (1.19 ppm) (Fig. 7.10). The order of Pb variation in host rocks are phyllite

(29.25ppm)>manganiferous phyllite (15.19ppm)>schist (14.56 ppm)>limestone (3.69

ppm)> quartzite (1.19 ppm). In host rocks Pb shows sympathetic relation with all

elements in the study area (Table 7.3). The analytical result allows recognition of a

good correlation of Pb with La, Ce, Nd, Zr, Cr, Ni, Cu, Zn, Rb, Nb, U, Th, Y and

moderate correlation between Sc, Co and Ba.

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Fig. 7.7 Bar diagram showing the concentration of selected trace elements in schist rock

samples, Banswara district, Rajasthan.

Fig. 7.8 Bar diagram showing the concentration of selected trace elements in phyllite

rock samples, Banswara district, Rajasthan.

Fig. 7.9 Bar diagram showing the concentration of selected trace elements in

manganiferous phyllite rock samples, Banswara district, Rajasthan.

205

Fig. 7.10 Bar diagram showing the concentration of selected trace elements in quartzite


Fig. 7.11 Bar diagram showing the concentration of selected trace elements in


7.3.1.2 Rubidium

The highest concentration of rubidium in the studied rock types were observed

in manganiferous phyllite (343.17 ppm) followed by phyllite (297.390 ppm)> schist

(151.28 ppm)> limestone (2.19 ppm)> quartzite (1.47 ppm) (Fig. 7.7, 7.8, 7.9, 7.10 and

7.11) with an average values of 245.44, 210.30, 113.05, 2.19 and 1.47 ppm respectively

(Table 7.2). Rubidium shows almost a stable distribution as shown in variation

diagrams and bar charts (Fig. 7.11 and 7.12) especially in the phyllite, manganiferous

phyllite and schist samples. In case of major elements, rubidium shows positive

correlation with SiO2, A12O3, MnO, MgO and K2O (Table 7.4). Rb is define as

incompatible elements and for that lead to concentrate in continental crust (Jawed,

2015). However in case of trace elements rubidium shows strong positive correlation

with Cr, Cu, Ni, Zn, Ba, Zr, Nb, Nd, Th and moderate correlation with La, Ce, Nd, Sr,

U, and Pb in the present study (Table 7.3).

206

Fig. 7.12 Bar diagram showing variation in Rb-La-Hf-Pb-Th (Large ion lithophile

elements) in host rocks Manganiferous phyllite (MNP), Phyllite (PHY),

Schist (SCH), Quartzite (QTZ) and Limestone (LST), of manganese ores,


207

7.3.1.3 Hafnium

In the study area, the concentration of hafnium vary from .07 to 5.15 ppm and

the average concentration of Hf is 2.24 ppm (Table 7.2, Fig. 7.12). The Hf average

concentration in phyllite, manganiferous phyllite, schist, quartzite and limestone is

4.85, 3.43, 2.69, .10 and .11 ppm respectively. In study area Hf shows strong

correlation with Cr, Cu, Ni, Zn, Ba, Zr, Nb, Nd, Pb, Th and U (Table 7.3). The positive

relation between Hf and Zr suggest presence of zirconium minerals in the studied rocks.

The value of Zr/Hf ratio in metamorphic rocks is low in the study area and close to

those of the continental crust estimated by Rudnick and Fountain (1995) while

carbonate rocks contain much higher values. According to Vlasov (1966) that the

carbonate rocks contain significant amount of Hf while Hf is negligible in sedimentary

rocks. The highest concentration of hafnium is observed in granite around 4 mg kg-1

(Taylor, 1964).

7.3.1.4 Lanthanum

The concentration of La varies from 3.26-67.42 ppm and the average

concentration of La is 27.25 ppm (Table 7.5). In the study area, the lowest average

concentration (6.06 ppm) of La is observed from quartzite while the highest average

concentration (56.92 ppm) is from phyllite. The order of variation of La is phyllite

(56.92 ppm)>schist (32.50 ppm)>manganiferous phyllite (31.78 ppm)> limestone

(8.98 ppm)>quartzite (6.06 ppm). La shows sympathetic relation with Sc, V, Cr, Co,

Sr, Nb, Ba, Ce , Ni, Cu, Rb, Y, Zr, Nb, Cs, Hf and U. Lanthanum along with the other

trace elements commonly used for the interpretation of the petrogenesis of rocks. In

Th-La-Sc ternary plot (Fig. 7.44) shows studied samples falling in the ACM and PCM

tectonic setting field.

7.3.1.5 Thorium

In the study area, the concentration of Thorium vary from .03 to 31.70 ppm and

the average concentration of thorium is 10.78 ppm (Table 7.2, Fig. 7.12). The Th

average concentration in phyllite, manganiferous phyllite, schist, limestone and

quartzite is 23.55, 16.71, 13.48, .07 and .06 ppm respectively. In the study area, Th

shows strong correlation with Cr, Cu, Ni, Zn, Ba, Zr, Nb, Nd, Pb and U (Table 7.3). The

208

average values of Th/U ratio is 7.39 which are higher than average early Proterozoic

crust and average chemical composition of UCC after Condie (1993) and Taylor and

Mclennan (1985) respectively. According to Taylor and Mclennan (1985) the higher

values suggest contribution of crustal material during formation of these host

sediments. The ternary plot between Th-Sc-Zr/10 (Fig. 7.45) suggesting passive

continental margin setting for the host rocks of study area after (Bhatia and Crook,

1986).

7.3.2 High Field Strength Elements (HFSE)

High field strength elements and REE provides most reliable information about

the provenance history and tectonic conditions of an area because these elements

remain in suite during geological processes like intense metamorphism and chemical

weathering. These elements generally consist high charge and large cations. They do

not posses high ionic charge. These elements fall in the category of incompatible

elements such as U, Sc, Nb, Zr, Sr, Hf, Ta and Y (all elements having z/r>2) and

generally present in minerals of high density such as Zr, Ti etc (Fig. 7.13). The variation

diagram of HFSE in host rocks of the study area are shown in (Fig. 7.13). These High

Field Strength Elements (HFSE), like U, N, Sc, Zr, Sr and Y, Zr shows elevated

concentration in schist, phyllite, manganiferous phyllite and limestone while depletion

in concentration in quartzite rock of the study area.

7.3.2.1 Uranium

The quantitative variation in concentration of U in studied samples vary from .7

to 3.39 ppm and the average concentration of U is 1.57 ppm (Table 7.2, Fig. 7.13). The

uranium average concentration in phyllite, manganiferous phyllite, schist, quartzite and

limestone is 3.12, 1.45, 1.07, 1.15 and 1.04 ppm respectively. In study area U shows

strong positive correlation with Zr, Cr, Cu, Ni, Zn, Nb, Nd, Pb and Th except barium

where it shows negative relation (Table 7.3). Uranium shows positive relation with

SiO2, MnO and Fe2O3 and other major oxides except calcium oxide and magnesium

oxide (Table 7.4). The average values of Th/U ratio is 7.39 which are near about to the

average Th/U values of passive margin (Bhatia and Crook, 1986).

209

7.3.2.2 Niobium

The concentration of Nb varies from .06-15.74 ppm and the average

concentration of Nb is 5.75 ppm (Table 7.2). In the study area, the lowest average

concentration (.10 ppm) of Nb is observed from quartzite while the highest average

concentration (13.27 ppm) is from phyllite. The order of variation of Nb is

phyllite(13.27 ppm)>manganiferous phyllite(8.04 ppm)>schist(7.12 ppm)>limestone

(.21 ppm)>quartzite(.10 ppm). Nb shows antipathetic relation with calcium oxide while

sympathetic relation with rest of major oxides (Table 7.4). In case of trace elements Nb

shows positive relation with Co, Sr, Sc, V, Ni, Cu, Cr, Ba, Ce, Rb, Y, Zr, Cs, Hf and U

(Table 7.3).

7.3.2.3 Scandium

Scandium(Sc) is an important trace element to decipher petrogenesis of rocks.

The various ratios like La/Sc, Th/Sc are used to determine the composition of rocks. In

analyzed samples the concentration of scandium vary from .10 to 18.53 ppm and the

average concentration of scandium is 7.64 ppm (Table 7.2). The Sc average

concentration in phyllite, manganiferous phyllite, schist, limestone and quartzite is

16.64, 12.50, 8.78, .14 and .12 ppm respectively. In study area Sc shows strong

correlation with Cr, Cu, Ni, Zr, Nb, Nd, Pb, La, Th and U. Scandium shows positive

relation with all the major oxides except Ca (Table 7.3, 7.4). The sympathetic relation

with A12O3 confirmed presence of garnet. The average value of La/Sc and Th/Sc is

24.18 and 1.08 respectively. The ternary plots of La-Th-Sc and Th-Sc-Zr/10 after

Bhatia and Crook (1986) shows active continental margin and passive margin type

settings for the host rocks of study area (Fig. 7.44, 7.45).

7.3.2.4 Zirconium

In the study area the average values of Zr is 70.23 ppm in host rocks and the

concentration of Zr ranges from .39 to 184.82 ppm (Table 7.2). The highest average

values of zirconium found in phyllite is 160.35 ppm (Fig. 7.8) and the lowest value in

limestone .54 ppm (Fig. 7.11 and 7.13). The average concentration of Zr are 106.90,

82.79 and .55 in manganiferous phyllite, schist and quartzite respectively. Zr shows

positive relation with Cr, Cu, Ni,Hf, Nb, Rb, Nd, Pb, La, Th, U, SiO2, A12O3 and Fe2O3

210

while negative relation with CaO. Zr is an important element to know the tectonic

setting of the host rocks and also very much useful in geochronology. The average

Zr/Hf ratio in the samples of study area is 21.25 which is very much similar to ACM

and PCM values of Bhatia and Crook (1986).

7.3.2.5 Strontium

The concentration of Sr varies from 72.59-286.38 ppm and the average

concentration of Sr is 160.83 ppm (Table 7.2). In the study area, the lowest average

concentration (102.89 ppm) of Sr is observed from quartzite (Fig. 7.10) while the

highest average concentration (216.17 ppm) is from phyllite (Fig. 7.8). The order of

variation of Sr is phyllite (216.17 ppm)>manganiferous phyllite (l92.46 ppm)>schist

(174.65ppm)>limestone (l17.96 ppm)>quartzite (102.89 ppm). Sr shows sympathetic

relation with Co, Sc, V, Ni, Cu, Cr, Nb, Ba, Ce, Rb, Y, Zr, Nb, Cs, Hf and U. Sr shows

negative relation with calcium oxide while positive relation with rest of the major

oxides. The presence of biotite, zircon, apatite and amphibole minerals support the

enrichment of strontium in studied samples.

7.3.2.6 Yttrium

The quantitative variation in concentration of yttrium in studied samples vary

from 5.24 to 32.84 ppm and the average concentration of Y is 15.67 ppm (Table 7.2 and

Fig. 7.13). The yttrium average concentration in phyllite, manganiferous phyllite,

schist, quartzite and limestone is 25.58, 18.37, 18.13, 8.00 and 8.27 ppm respectively.

In study area Y shows strong positive correlation with Zr, Cr, Cu, Ni, Zn, Nb, Nd, Pb,

Th. Yttrium shows positive relation with SiO2, MnO and Fe2O3 and other major oxides

except magnesium and calcium oxides.

211

Fig. 7.13 Bar diagram showing variation in Sc-Sr-Y-Zr-Nb-U (High Field Strength

Elements) in host rocks Manganiferous phyllite (MNP), Phyllite (PHY),

Schist (SCH), Quartzite (QTZ) and Limestone (LST), of manganese ores,


212

7.3.3 Transition Elements

A series of elements in periodic table that share similar electronic configuration

and hence similar chemical properties are commonly defined as Transition elements.

These elements characterized by small ionic radii and strongly compatible with solid

phase which indicate early stages of crystallization during magmatic evolution and are

therefore referred as “compatible” with mantle phases. Examples include nickel,

cobalt, copper, zinc and scandium. The variation diagram between Co-Ni-Cu-Zn (Fig.

7.14) shows depletion pattern for these elements. In present study, distribution and

variation of transition elements are discussed as follows;

7.3.3.1 Copper

The quantitative ranges of Cu values in the host rocks varies from .83-56.37

ppm and the average value of Cu is 19.42 ppm (Table 7.2 and Fig. 7.14). In the study

area, the lower concentration (.83 ppm) of Cu is observed from limestone (Fig. 7.11),

while the higher concentration (56.37 ppm) is from phyllite (Fig. 7.8). The order of

average values of Cu variation ranges from phyllite (39.30 ppm)>manganiferous

phyllite (31.02 ppm)> schist (23.89 ppm)> limestone (l.61 ppm)>quartzite (1.27 ppm).

Copper shows sympathetic correlation with Sc, V, Cr, Zn, Sr, Y, Zr, Cs, Ba, Hf, Th, U

and Ni. Cu shows positive relation with all major oxides except CaO and MgO where it

shows negative correlation in the studied samples. Manganese and iron hydroxides are

tend to adsorb copper (Krauskops, 1956). The positive correlation of Cu with K2O and

Na2O suggest that there is no replacement. The strong sympathetic relation with

alumina decipher coherence between copper and alumino-silicate minerals.

7.3.3.2 Nickel

Geochemically Ni always associated with metallic iron and belongs to

siderophile element. According to Siddiquie (2004) and Siddiquie et al. (2015a). It has

more tendency of enrichment in ferro-magnesian and magnesian minerals. The

analyzed samples shows variation in Ni values ranges from 2.19-56.79 ppm and the

average concentration of Ni is 28.57 ppm (Table 7.2 and Fig. 7.14). In studied samples,

the lower concentration of Ni (2.19 ppm) is found from limestone (Fig. 7.11), while the

213

higher concentration (56.79 ppm) is from manganiferous phyllite (Fig. 7.9). The trend

of average values of Ni in the samples ranges from phyllite (49.58

ppm)>manganiferous phyllite (43.37 ppm)>schist (38.25 ppm)>limestone (8.45

ppm)>quartzite (3.18 ppm). Nickel shows sympathetic correlation with Sc, V, Cr, Co,

Cu, Zn, Rb, Sr, Y, Zr, Nb, Cs, Ba, La, Ce, Nd, Hf, Pb, Th, and U while Ni shows

antipathetic relation with CaO in the study area samples and shows replacement (Table

7.3 and 7.4). According to Ringwood (1955 and 1956) the replacement process occur

due to electronegativity charges of these elements. The ionic radius of Ni+2 close to Fe+2

and Mg and due to this it can easily substitute any one of the two.

7.3.3.3 Vanadium

Vanadium is an immobile element and stable in igneous rocks under trivalent,

quadrivalent and quinvalent state. While in sedimentary rocks its remain under

quinquivalent state. The quantitative variation in concentration of vanadium in studied

samples vary from 2.38 to 261.90 ppm and the average concentration of vanadium is

57.61 ppm (Table 7.2 and Fig. 7.14). The average concentration of V in phyllite,

manganiferous phyllite, schist, quartzite and limestone is 111.82, 59.69, 109.34, 2.97

and 4.21 ppm respectively. Vanadium shows strong positive correlation with Sc, Cr,

Co, Cu, Zn, Rb, Sr, Y, Zr, Nb, Cs, Ba, La, Ce, Nd, Hf, Pb, Th, and U while in case of

major oxides V shows negative correlation with CaO and MgO. Vanadium shows

positive relation with SiO2, MnO and Fe2O3 and other major oxides except calcium

oxide. The presence of mica minerals with apatite confirms the higher concentration of

vanadium in the study area samples and positive relation with titanium reveal close

coherence with Ti bearing minerals.

7.3.3.4 Chromium

The quantitative variation in concentration of chromium in host rocks vary from

5.29 to 74.80 ppm and the average concentration of Cr is 35.10 ppm (Table 7.2 and Fig.

7.14). The order of chromium average concentration ranges from phyllite>schist>

manganiferous phyllite>limestone > quartzite is 73.46, 45.70, 43.56, 6.44 and 6.35 ppm

respectively. In study area Cr shows strong positive correlation with V, Co, Cu, Zn, Rb,

Sr, Y, Zr, Nb, Cs, Ba, La, Ce, Nd, Hf, Pb, Th, and U. Chromium shows positive relation

214

with SiO2, A12O3, MnO and Fe2O3 and other major oxides except calcium oxide and

magnesium oxide where it shows negative relation. Cr tend to replace Al+4 in all silicate

rocks and exist in octahedral site. In study area the phyllite and schist samples shows

regular distribution while quartzite and limestone samples are very much low in

chromium concentration. The minerals like muscovite, chlorite, phengite, garnet and

epidote are the main source for chromium in host rocks. Siddiquie et al (2015a) also

reported exceptionally high Cr in all the samples, which might have its source in

ferromagnesium minerals.

7.3.3.5 Cobalt

In the study area, the concentration of cobalt vary from .20 to 44.20 ppm and the

average concentration of cobalt is 18.09 ppm (Table 7.2 and Fig. 7.14). The Co average

concentration in phyllite, manganiferous phyllite, schist, limestone and quartzite is

24.31, 28.06, 36.08, .41 and 1.59 ppm respectively. The Ni-Cu-Co shows trace element

complex in weathering area and the weathered rocks of study area supplied the higher

rate of chromium and nickel in host rocks. The higher concentration of Cr and Ni in

comparison of Co is may be due to supply of detritus from moderately to deeply

weathered Archean soil profile of study area. According to Siddiquie (1986) and

Siddiquie and Bhat (2010) the Co and Ni are frequent constituents of silicate rocks. In

study area Co shows strong correlation with Cr, Cu, Ni, Zn, Ba, Zr, Nb, Nd, Pb and U

(Table 7.3). In case of major oxides it shows antipathetic relation with calcium oxide

and magnesium oxide (Table 7.4). This negative relation of Co to Mg is due to similar

ionic radii of Co+2 and Mg+2 which suggest replacement between these two (Rankama

and Sahama, 1950).

7.3.3.6 Zinc

In the study area the average values of Zn is 72.70 ppm and the concentration of

Zn ranges from 17.90 to 169.68 ppm (Table 7.2 and Fig. 7.14). The highest average

values of zinc found in phyllite is 122.40 ppm and the lowest value in quartzite 33.91

ppm. The average concentration of Zn are 90.44, 82.67 and 34.07 in manganiferous

phyllite, schist and limestone respectively. Zn shows positive relation with Cr, Cu, Ni,

215

Zr, Hf, Nb, Rb, Nd, Pb, La, Th, U and negative relation with Sc. In case of major oxide

it shows sympathetic relation with SiO2, A12O3 and Fe2O3, while it shows antipathetic

relation with Cao and MgO. The sympathetic relation with MnO and Fe2O3 suggest

coherence of these elements (Siddiquie, 2004). In the host rocks the possible carrier of

Zn could be garnets, amphiboles and biotite minerals. These minerals as a crarrier of Zn

also reported by Siddiquie and Bhat (2010) in host rocks of Vizianagaram manganese

ores (A.P.).

Fig. 7.14 Bar diagram showing variation in V-Cr-Co-Ni-Cu-Zn (Transition Elements)

in host rocks Manganiferous phyllite (MNP), Phyllite (PHY), Schist (SCH),

Quartzite (QTZ) and Limestone (LST), of manganese ores, Banswara district,

Rajasthan

216

7.4 Rare Earth Elements (REE)

In periodic table, a group of seventeen metallic elements, in which the fifteen

lanthanides, (Lanthanum To Lutetium) with atomic numbers 57 to 71 respectively

together with yttrium (Y, atomic number 39) and scandium (Sc, atomic number 21)

known as rare earth elements (REE). According to Shannon (1976) the REE (La-Lu)

having progressively decreasing ionic radii with increasing atomic number. These

elements possesses similar chemical properties and divided in two categories known as

LREE (Light Rare Earth Elements) and HREE (Heavy Rare Earth Elements). The

LREE includes the lower atomic weight elements from lanthanum(La) to samarium

(Sm), with atomic numbers 57 to 62 respectively while the HREE include, europium

(Eu) to lutetium (Lu), with atomic numbers 63 to 71 respectively, and known as the

heavy rare earth elements (HREE).

The concentration of rare earth elements are higher in hydrogenous deposits in

comparison of hydrothermal deposits and this is because of their short ORT (Oceanic

residence time) (102-103 yrs) than the mixing time of ocean (1600 yrs) (Goldberg et al.

1963; Elderfield and Greaves, 1982 and Grandjean et al., 1987). The geochemical

analysis performed on total fifteen host rock samples of study area and out of these

three representative samples of every rock type (Phyllite, manganiferous phyllite,

schist, quartzite and limestone) analyzed respectively. Due to insoluble properties of

REE, they have wide application. According to Piper (1974), Elderfield (1988) and De

Carlo (1991) few changes in concentration of rare earth element may reflect a change in

redox potential or this is might be due to changes in sorption properties of solid phases

(Alpin, 1984 and Byrne and Kim, 1990). They are very much important to classify

provenance of sediments (Mclennan, 1989), chemistry and environment of source.

According to Dymond et al. (1984), De Carlo (1991) and Ozturk and Frakes (1995), the

mobility of rare earth elements can be used to recognize the post-depositional

processes.

In host rocks of study area the values of REE ranges from 15.71-336.81 ppm

and the average concentration is 133.716 ppm (Table 7.5). In the study area, the lowest

average concentration (26.80 ppm) of REE is observed from quartzite while the highest

average concentration from phyllite. The order of variation of average REE values is

217

phyllite (286.35 ppm)>schist (l80.82 ppm)>manganiferous phyllite (141.22 ppm)>

limestone (33.36 ppm)>quartzite (26.80 ppm). In sea water the concentration of REE

for hydrogenous deposits is 1400 ppm while for hydrothermal deposits, it is 40 ppm

(Usui and Someya, 1997). The analyzed samples of study area show enrichment of

LREE while depletion of HREE. The plots after chondrite normalized (Taylor and

Mclennan, 1985) (Fig. 7.16) of each host sample shows enrichment pattern of LREE

and flat pattern of HREE such as phyllite (Fig. 7.20), manganiferous phyllite (Fig.

7.19), schist (Fig. 7.18), quartzite (Fig. 7.21) and limestone (Fig. 7.22). The average

ratio of LREE/HREE is 3.76 and shows positive correlation (Fig. 7.15) which depict

that the enrichment of LREE took place before the formation process of host rocks of

the study area. The LREE concentration ranges from 8.75 to 291.50 ppm with average

value is 108.71 ppm (Table 7.5).

In rare earths only Ce and possibly Eu show potential variations as a function of

oxidation-reduction conditions found in natural sedimentary/oceanic environments

(Wilde et al., 1996). The use of the cerium anomaly was first proposed by Elderfield

and Greaves (1982) as a consequence of the change in the ionic state of Ce as a function

of oxidation state. In host samples the concentration of Ce* varies from .27 to 2.96 ppm

(Table 7.6). The average value of Ce* is .87 ppm in the studied samples. The order of

quantitative variation of Ce* values from schist (1.67 ppm)>phyllite (1.12

ppm)>manganiferous phyl1ite (.95 ppm)>quartzite (.31 ppm)>limestone (.30 ppm).

The analyzed rock samples of study area shows slightly negative cerium anomaly. In

oxidizing environment the oxidation of Ce+3 to Ce+4 taken place which lead to develop

a positive cerium anomaly (EI-Hasan et al., 2008). In past researchers have observed

that Ce appears to be preferentially mobilized with Mn in nitratic (suboxic,

Mn-reducing) waters (German and Elderfield, 1989, 1990; De Baar, 1991 and German

et al., 1990, 1991). In oxic conditions, Ce is less readily dissolved in seawater, so that

oxic seawater is more depleted with respect to Ce, whereas oxic sediments are more

enhanced with respect to Ce while in anoxic sediments, Ce is depleted and the

sediments show a negative anomaly (Wilde et al, 1996). The Ce anomaly is calculated

by using the formula as (Taylor and Mclennan, 1995; Fu et al, 2010a, b).

The formula used to calculate Ce anomaly is


218

The Eu anomaly is very much useful to delineate petrogenesis and depositional

environment. In the host rocks the calculated chondrite normalized (Taylor and

Mclennan, 1985) Eu* values ranges from .56 to 1.51 ppm with average concentration

of .79 ppm (Table 7.6). The order of quantitative variation of Eu* values from

limestone(.97 ppm)>manganiferous phyllite(.93 ppm)>quartzite(.80 ppm)>schist(.65

ppm)>phyllite(.61 ppm). The value of Eu anomaly is greater than one is considered as

positive while the values less than one is known as negative anomalies. The chondrite

normalized (Taylor and Mclennan, 1985) Sm and Gd values (Table 7.6) used to

calculate Eu anomaly by using the formula which is

Eu anomaly=Eu/Eu* =EuN/√ (SmN x GdN)

The Ce and Eu anomalies are calculated to find out the provenance and origin of

the host rocks and therefore these two elements are very much important during

assessment of REE group of elements. The HREE concentration in host rocks ranges

from 6.96 to 53.50 ppm with average value is 24.85 ppm. The order of HREE average

variation in host rock samples ranges from phyllite (43.34 ppm)>schist (30.03

ppm)>manganiferous phyllite (28.65 ppm)>limestone (l1.42 ppm)>quartzite (10.76

ppm). The HREE values in analyzed samples are very low in comparison of LREE. The

average (La/Yb)N values of studied samples is 24.01 (Table 7.2). This average high

value suggest that heavy rare earth elements may have been retained for its higher

existence by garnet during the formation of source rocks and also shows depletion in

HREE (Gd/Yb)N ratio which in range from 1.57 to 3.88 (Table 7.6).

219

7.5 Comparison with Post Archean Australian Shale(PAAS) and

Upper Continental Crust(UCC)

The analyzed samples of study area normalized with average Post Archean

Australian Shale (PAAS) and Upper Continental Crust (UCC) values (Taylor and

Mclennan, 1985). The PAAS normalized (Taylor and Mclennan, 1985) (Fig. 7.17)

samples show LREE enrichment and HREE depleted pattern for schist (Fig. 7.23),

phyllite (Fig. 7.24), manganiferous phyllite (Fig. 7.25) samples, limestone (Fig. 7.26)

and quartzite (Fig. 7.27) samples. The pattern of LREE and HREE observed in PAAS

normalized spider diagram is very similar to chondrite normalized pattern. The major

and trace elements data of host rocks also normalized with average Upper Continental

Crust (UCC) values (Taylor and Mclennan, 1985) (Fig. 7.28). The normalized data of

host rocks show variable enrichment in MnO, Na2O, P2O5 while depletion of SiO2,

A12O3, TiO2, Fe2O3, CaO, K2O and MgO (Fig. 7.29, 7.30, 7.31, 7.32 and 7.33). In

limestone samples enrichment of CaO is observed (Fig. 7.28). In case of trace elements

UCC normalized diagram shows enrichment in V, Cr, Ni, Co, Rb, Y, La, Pb, Hf and Th

while Sc, Cu, Sr, Zr, Nb, and U depleted pattern in the host rocks of study area. The

large ion lithophile elements such as Sr, K, and Rb are generally mobile during

post-magmatic processes (Seewald and Seyfried, 1990; Verma, 1992; Rollinson, 1993;

Condie and Sinha, 1996). While HFSE, such as Y, Zr, P, Nb, Ti, and Hf, are supposed

to be immobile during the low grade metamorphism and hydrothermal alterations

(Pearce and Cannon 1973; Winchester and Floyd, 1976; Floyd and Winchester, 1978;

Rollinson, 1993 and Jochum and Verma, 1996). The abundance and enrichment of Ba,

Pb, Hf, Th, Rb and La suggest felsic source for the host rocks of the study area.

220

Fig. 7.15 Correlation between LREE and HREE of host rocks Manganiferous phyllite

(MNP), Phyllite (PHY), Schist (SCH), Quartzite (QTZ) and Limestone


221

Table 7.5 The geochemical data (Rare earth elements) of host rocks of manganese ores, Banswara district, Rajasthan.

REE(ppm) Schist Manganiferous Phyllite Phyllite Quartzite Limestone


La 53.43 35.99 8.10 28.12 29.41 37.83 60.15 43.18 67.43 5.85 5.36 6.97 3.26 11.35 12.32 27.25

Ce 123.59 54.71 47.34 55.88 29.88 60.38 122.98 87.03 140.48 2.95 2.66 3.80 1.78 4.97 5.16 49.57

Pr 10.23 6.58 1.73 4.98 2.08 7.09 11.19 7.74 12.39 0.85 0.79 0.95 0.47 1.49 1.52 4.67

Nd 49.83 31.08 9.26 23.08 9.83 33.33 52.19 34.50 58.40 4.85 4.51 5.55 2.68 8.45 8.30 22.39

Sm 9.62 5.68 2.21 4.78 1.98 6.12 9.90 6.04 11.05 0.81 0.70 0.89 0.45 1.29 1.30 4.19

Eu 1.56 0.96 0.50 1.03 0.86 1.06 1.75 1.04 1.61 0.25 0.17 0.22 0.11 0.46 0.44 0.80

Gd 6.93 3.47 2.09 4.92 1.54 4.20 6.78 4.32 6.86 0.79 0.77 0.88 0.48 1.26 1.19 3.10

Tb 0.85 0.47 0.30 0.78 0.18 0.49 0.80 0.59 1.02 0.14 0.11 0.12 0.07 0.19 0.15 0.42

Dy 6.40 2.05 2.30 5.65 1.27 3.24 5.61 4.58 5.25 0.69 0.81 0.96 0.54 1.15 1.20 2.78

Ho 0.80 0.36 0.29 0.62 0.15 0.37 0.67 0.55 1.06 0.22 0.17 0.20 0.11 0.21 0.23 0.40

Er 1.41 0.87 0.49 1.00 0.25 0.61 1.20 0.93 2.81 0.39 0.37 0.44 0.26 0.49 0.52 0.80

Tm 0.50 0.11 0.17 0.35 0.09 0.21 0.44 0.32 0.39 0.04 0.05 0.05 0.03 0.06 0.07 0.19

Yb 3.21 0.73 1.08 2.31 0.56 1.35 2.97 2.13 2.68 0.29 0.32 0.33 0.19 0.46 0.43 1.27

Lu 0.56 0.11 0.19 0.41 0.11 0.25 0.54 0.39 0.39 0.06 0.05 0.05 0.03 0.08 0.06 0.22

Y 32.84 10.10 11.44 30.13 7.41 17.56 29.17 22.59 24.99 7.79 7.22 8.98 5.24 9.28 10.30 15.67

∑ LREE 248.26 135.00 69.13 117.86 74.03 145.80 258.17 179.54 291.35 15.56 14.18 18.39 8.75 28.01 29.04 108.87

∑ HREE 53.50 18.27 18.33 46.16 11.54 28.27 48.16 36.40 45.46 10.41 9.86 12.03 6.96 13.18 14.15 24.85

∑ REE 301.76 153.27 87.46 164.02 85.57 174.07 306.33 215.94 336.81 25.97 24.04 30.41 15.71 41.19 43.19 133.72

222

Table 7.6 The geochemical data for Chondrite normalized Rare earth elements (Taylor and McLennan, 1985) of host rocks of manganese ores,


REE(ppm) Schist Manganiferous Phyllite Phyllite Quartzite Limestone

Average SCH-1 SCH-2 SCH-3 MNP-1 MNP-2 MNP-3 PHY-1 PHY-2 PHY-3 QTZ-1 QTZ-2 QTZ-3 TLST-1 TLST-2 TLS-3

La 145.57 98.06 22.06 76.63 80.13 103.07 163.91 117.67 183.73 15.94 14.60 18.98 8.88 30.93 33.56 74.24766

Ce 129.14 57.16 49.47 58.39 31.22 63.09 128.51 90.94 146.79 3.08 2.78 3.97 1.86 5.19 5.39 51.79974

Pr 74.70 48.06 12.63 36.34 15.16 51.76 81.70 56.53 90.42 6.20 5.76 6.93 3.41 10.88 11.07 34.10312

Nd 70.08 43.71 13.02 32.46 13.82 46.88 73.40 48.52 82.14 6.82 6.34 7.81 3.78 11.88 11.68 31.48977

Sm 41.66 24.58 9.55 20.69 8.56 26.48 42.86 26.14 47.82 3.51 3.01 3.86 1.95 5.58 5.64 18.12515

Eu 17.98 11.07 5.70 11.80 9.92 12.19 20.13 11.91 18.49 2.87 1.91 2.55 1.27 5.29 5.10 9.212233

Gd 22.64 11.35 6.82 16.07 5.03 13.72 22.14 14.11 22.42 2.58 2.52 2.89 1.58 4.12 3.88 10.12462

Tb 14.61 8.09 5.09 13.40 3.09 8.40 13.75 10.13 17.51 2.41 1.81 2.06 1.13 3.28 2.64 7.159407

Dy 16.79 5.38 6.03 14.82 3.33 8.50 14.71 12.02 13.78 1.81 2.13 2.53 1.42 3.02 3.15 7.294317

Ho 9.39 4.26 3.38 7.29 1.72 4.40 7.89 6.44 12.50 2.59 1.95 2.33 1.30 2.47 2.76 4.711049

Er 5.66 3.50 1.95 4.00 0.99 2.43 4.81 3.75 11.30 1.57 1.50 1.79 1.03 1.97 2.08 3.22159

Tm 14.05 3.04 4.79 9.82 2.40 5.78 12.46 9.04 11.06 1.12 1.36 1.50 0.87 1.69 1.94 5.393946

Yb 12.96 2.92 4.34 9.32 2.26 5.44 11.96 8.60 10.80 1.17 1.30 1.35 0.78 1.85 1.73 5.11933

Lu 14.65 2.77 5.12 10.85 2.83 6.53 14.19 10.23 10.22 1.57 1.28 1.22 0.78 2.10 1.62 5.731322

Y 15.42 4.74 5.37 14.14 3.48 8.25 13.69 10.61 11.73 3.66 3.39 4.22 2.46 4.36 4.84 7.356692

Sm/Nd 0.59 0.56 0.73 0.64 0.62 0.56 0.58 0.54 0.58 0.51 0.47 0.49 0.52 0.47 0.48 0.557753

La/Sm 3.49 3.99 2.31 3.70 9.36 3.89 3.82 4.50 3.84 4.55 4.85 4.92 4.57 5.54 5.96 4.620117

Gd/Yb 1.75 3.88 1.57 1.72 2.23 2.52 1.85 1.64 2.08 2.21 1.93 2.14 2.04 2.22 2.25 2.135192

LaxPr 10874.68 4712.69 278.63 2784.35 1214.85 5334.66 13390.38 6651.61 16612.85 98.90 84.12 131.47 30.32 336.35 371.62 4193.832

SmxGd 942.98 279.11 65.15 332.51 43.08 363.17 949.09 368.81 1072.07 9.05 7.58 11.14 3.08 22.99 21.84 299.4445

Ce/Ce* 1.24 0.83 2.96 1.11 0.90 0.86 1.11 1.12 1.14 0.31 0.30 0.35 0.34 0.28 0.28 0.875005

Eu/Eu* 0.59 0.66 0.71 0.65 1.51 0.64 0.65 0.62 0.56 0.96 0.70 0.76 0.73 1.10 1.09 0.795026

223

Fig. 7.16 Chondrite normalized REE pattern (Taylor and McLennan, 1985) of host


Quartzite (QTZ) and Limestone (LST), of manganese ores, Banswara

district, Rajasthan

224

Fig. 7.17 PAAS normalized REE pattern (Taylor and McLennan, 1985) of host rocks



Rajasthan.

225

Fig. 7.18 Chondrite normalized REE pattern (Taylor and McLennan, 1985) of schist


Fig. 7.19 Chondrite normalized REE pattern (Taylor and McLennan, 1985) of


Fig. 7.20 Chondrite normalized REE pattern (Taylor and McLennan, 1985) of phyllite


226

Fig. 7.21 Chondrite normalized REE pattern (Taylor and McLennan, 1985) of quartzite


Fig. 7.22 Chondrite normalized REE pattern (Taylor and McLennan, 1985) of


Fig. 7.23 PAAS normalized REE pattern (Taylor and McLennan, 1985) of schist rock


227

Fig. 7.24 PAAS normalized REE pattern (Taylor and McLennan, 1985) of phyllite


Fig. 7.25 PAAS normalized REE pattern (Taylor and McLennan, 1985) of


Fig. 7.26 PAAS normalized REE pattern (Taylor and McLennan, 1985) of limestone


228

Fig. 7.27 PAAS normalized REE pattern (Taylor and McLennan, 1985) of quartzite


229

Fig. 7.28 UCC normalized diagram (Taylor and McLennan, 1985) of host rocks



Rajasthan.

230

Fig. 7.29 UCC normalized REE pattern (Taylor and McLennan, 1985) of schist rock


Fig. 7.30 UCC normalized REE pattern (Taylor and McLennan, 1985) of


Fig. 7.31 UCC normalized REE pattern (Taylor and McLennan, 1985) of phyllite rock


231

Fig. 7.32 UCC normalized REE pattern (Taylor and McLennan, 1985) of quartzite rock


Fig. 7.33 UCC normalized REE pattern (Taylor and McLennan, 1985) of limestone


232

7.6 Source Rock Characteristics and Tectonic Setting

The major oxide and trace elements data of analyzed host rocks are useful to

delineate the source rock characteristics (Cullers, 2000, 2002; Armstrong Altrin, 2009)

and to know tectonic conditions of depositional environment (Mcdonald and Katsura,

1964; Bhatia, 1983; Bhatia and Crook, 1986; Wronkiewicz and Condie, 1989 and

Armstrong Altrin and Verma, 2005). By using the geochemical data various binary and

ternary plots interpreted to know source rock characteristics and tectonic setting of the

study area. The binary plots of K2O/A12O3 vs Na2O/Al2O3, (Fig. 7.36) after Mcdonald

and Katsura (1964) suggested sedimentary to metasedimentary field for protolith. The

Binary plot of Zr vs TiO2 (Fig. 7.39) after Hayashi et al. (1997) suggest the nature and

composition of source rock in which the host rocks of study area falls in felsic to

intermediate field of composition. The ternary plots of ACF (Fig. 7.34) after Eskola

(1915) suggest pelitic field of composition for phyllite, schist and quartzite rocks while

calcareous field for limestone rock. The pelitic and calcareous composition also

supported by the CaO(Fe+MgO)-Al2O3 (Fig. 7.35) ternary plots after Wronkiewicz and

Condie (1989). The alumina concentration is high in the phyllite, schist and

manganiferous phyllite samples of the study area which may be due to sedimentary and

metasedimentary nature of source rock protolith. The ternary plot of

MgO-FeO-(Na2O+K2O) after Kuno (1968) shows that all samples of host rocks

showing calc-alkaline nature (Fig. 7.38). The host rocks were classified using binary

plot after Roddaz et al. (2006) between the Log(Fe2O3 /K2O) vs Log(SiO2 /Al2O3)

shown that the schist, phyllite and manganiferous phyllite fall close to shale-greywacke

fields while quartzite samples near arkose field (Fig. 7.37).

The geochemical data (Major oxides-Trace Elements-Rare Earth Elements) of

host rocks have been useful to determine the plate tectonic setting for the

metasediments of the study area. To know the tectonic setting various binary plots after

Bhatia (1983), Roser and Korsch (1986) and ternary-plots after Bhatia and Crook

(1986) draw and interpreted. The binary plots of Fe2O3+MgO vs A12O3/SiO2 (Fig.

7.41), Fe2O3+MgO vs Al2O3/(CaO+Na2O) (Fig. 7.42) suggest the active and passive

continental margin type tectonic setting for the host rocks of the study area. These

settings also supported by binary plots of K2O/Na2O vs SiO2 (Fig. 7.40) after Roser and

Korsch (1986) for the studied samples. Due to immobility of La, Sc, Th and Zr these

233

elements are used to find out the tectonic settings for the host rocks in the study area.

These elements are resistant during secondary processes like erosion, weathering,

digenesis and metamorphism. The binary discrimination diagram after Mc Lennan et

al. (1993) between the Th/Sc vs Zr/Sc shows close affinity of host rocks with UCC and

felsic compositional field in the study area (Fig. 7.43). The ternary plots of Sc-Th-Zr/10

and La-Th-Sc (Fig. 7.44 and 7.45) after Bhatia and Crook (1986) suggested active and

passive continental margin type tectonic settings for the host rocks (Phyllite-

Manganiferous phyllite-Schist-Quartzite and limestone) of the study area.

234

Fig. 7.34 A-C-F ternary plot (after Eskola, 1915) shows the pelitic field for Schist

(SCH), Manganiferous phyllite (MNP), Phyllite (PHY), Quartzite (QTZ) and

calcareous field for limestone (LST) rocks, Banswara district, Rajasthan.

Fig. 7.35 The ternary plot of Ca-Fe+MgO-Al2O3 (after Wronkiewicz and Condie, 1989)

shows the pelitic rock fields for schist (SCH), manganiferous phyllite (MNP),

phyllite (PHY), quartzite (QTZ) and calcareous protolith for limestone (LST)


235

Fig. 7.36 The binary plot of K2O/Al2O3 vs Na2O/Al2O3 (after MacDonald and Katsura,

1964) shows the samples are lying in the sedimentary and metasedimentary

field for the host rocks Manganiferous phyllite (MNP), Phyllite (PHY),

Schist (SCH), Quartzite (QTZ) and Limestone (LST), of Banswara


Fig. 7.37 The binary plot Fe2O3/K2O vs SiO2/A12O3 (after Roddaz et al., 2006), shows

the shale-arkose sequence field for the host rocks Manganiferous phyllite

(MNP), Phyllite (PHY), Schist (SCH), Quartzite (QTZ) and Limestone

(LST), of Banswara manganese ores, Banswara district, Rajasthan.

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Fig. 7.38 The ternary plot of MgO-FeO-(Na2O+K2O) (after Kuno, 1968) shows all the

host rock Manganiferous phyllite (MNP), Phyllite (PHY), Schist (SCH),

Quartzite (QTZ) and Limestone (LST), samples fall in the calc-alkaline field,


Fig. 7.39 The binary plot of Zr vs TiO2 (after Hayashi et al., 1997) shows felsic rock

composition for the host rocks Manganiferous phyllite (MNP), Phyllite

(PHY), Schist (SCH), Quartzite (QTZ) and Limestone (LST), of Banswara


237

Fig. 7.40 The binary plot of K2O/Na2O vs SiO2 (after Roser and Korsch, 1986) shows

PCM type tectonic setting for the host rocks of Banswara manganese ores,


Fig. 7.41 Binary plot of Fe2O3+MgO vs A12O3/SiO2 (after Bhatia, 1983) shows the

active and passive continental margin type tectonic settings for the host rocks

of Banswara manganese ores, Banswara district, Rajasthan.

238

Fig. 7.42 The binary plot of Fe2O3+MgO vs A12O3 /CaO+Na2O (after Bhatia, 1983)

shows the ACM and PCM type tectonic settings for the host rocks of


Fig. 7.43 Zr/Sc vs Th/Sc plot (after McLennan et al., 1993) showing UCC (Upper

continental crust) and felsic rock affinity for the host rocks of Banswara


239

Fig. 7.44 La-Th-Sc discrimination diagram (after Bhatia and Crook, 1986) showing

PCM type tectonic setting for the host rocks of Banswara manganese ores,


240

Fig. 7.45 Sc-Th-Zr/10 discrimination diagram (after Bhatia and Crook, 1986) shows the

PCM type tectonic settings for the host rocks of Banswara manganese ores,


241

CHAPTER-8

SUMMARY AND CONCLUSIONS

Manganese (symbol Mn) has a high seek of key significance in this modern era

and one of the primary metals for ferroalloy industries. India is an independent country

about her manganese deposits and a major continental manganese ore producer in the

world and also accounting 6th place in respect of manganese production in the world. The

country has a solid position about its manganese assets. In India, Madhya Pradesh is the

largest and Rajasthan is the smallest producer of manganese ores among all the Indian

states. The Rajasthan state is contributing only 5.80 million tons of total assets of

manganese mineral, out of these assets, the Banswara district (Present study area) of

Rajasthan state consisting 5.3 million tons of manganese ores, out of which 1780(000'

tons) in reserve category while 3520(000' tons) as a remaining resources.

The current research work is carried out only to investigate the geochemistry of

manganese ores but due to lack of complete geoscientific research, published and

unpublished research material in the study area, the present author also focused on host

rocks geochemistry and petrography, occurrence of manganese ores, tectonics in relation

of ore deposits, lithological and structural controls as well as field characters of the ore

deposits, hand specimen and optical studies to evaluate the genetic assessment of the

present manganese ore deposits. The geochemical studies of the present manganese ore

deposits of Banswara, is an important piece of research work to serve the economic

geologist, entrepreneurs and industrialists for opting the low grade manganese ores of the

study area, as an alternate mineral resource to cope up with the stress on the existing high

grade oceanic manganese from PMN (Polymetallic Nodules) and other manganese ores.

The study area is situated in Banswara district, which lies in southern most part of

Rajasthan state of India. The manganese ore deposits of Banswara district mainly occur

in a linear belt, which is stretching about 20 km in NE-SW direction except Talwara

village (small manganese producing locality). The manganese belt is situated in a

sequence from Gararia to Ratimauri village in between 23˚12'-23˚20'N to 74˚15'-74˚25'E

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(Toposheet no. 46 I/7) and Talwara manganese at 230 33' - 740 19' (Toposheet no. 46I/6).

The major ore deposit sites are Kalakhunta, Ghatia, Gararia and Tambesara in which

active mining is going on, in Kalakhunta and Ghatia mining areas only. Except above

deposits the other manganese hosted blocks are in Itala, Sagwa, Loharia, Kheria,

Rupakhera and Ratimauri villages etc. At present the Geological Survey of India and

Department of Mines and Geology, Udaipur (Rajasthan) is investigating the area like

Tambesara etc., to explore higher grade of manganese ores in the Banswara district. The

present manganese ore deposits categorized as low to medium grade manganese ores with

average Mn content around 40.23%.

Geologically, the district comprises Deccan traps, Aravallis and Pre-Aravalli

banded gneissic complex and the manganese ore deposits hosted in Aravallis only. The

manganese ores of Banswara district occurred in Kalinjara formation of Lunavada group

which is the younger group of Aravalli Supergroup of Paleo-Proterozoic age. The

manganese bearing Kalinjara formation comprises dominantly of an intimate association

of meta-subgreywacke, manganiferous phyllites, meta semi-pelite, petromictic

conglomerate and quartz-biotite-sericite schist. These manganese ores are interbedded in

a repetitive sequence throughout the belt and the manganiferous beds are generally

striking by following the regional strike of its associated rocks. The manganese ores of

the study area classified as stratified, metasedimentary, metamorphosed deposits and

mainly associated with Aravalli phyllite, quartzite, schist, and limestone etc., which are

the predominant identified host rocks and responsible in relation of mineralization in the

study area.

Structurally, the study area is very much disturbed due to complex structural

pattern, which is in support that the area has passed away with severe tectonism and

deformational episodes. This concluded that the manganiferous beds and associated rocks

suffered greatly by intense deformational phases resulting in to co-folded ores deposits of

the study area. The main structural control of ores in the area is foliation plane, shear

zone, fissure plane and weak zone of phyllite etc. Moreover, fissure planes, foliation

planes and shear zones also provided excellent path for circulation of water to precipitate

dissolved manganese minerals as a secondary product. Various prominent structures like

243

ptygmatic folding, lineation and joint sets, etc., are present in the manganese bearing

rocks and played important role in controlling the manganese mineralization. The

alternate bedding of host and ores also well preserved in the study area. The present

lithology, structural features and their relation in form of strict conformity of manganese

horizon with bedding of phyllite and quartzites, sharp contact with the overlying and

underlying rocks, uniformity in quality of ores, suggested the primary syngenetic origin

for these deposits.

Megascopically, the argillaceous composition are represented by phyllite which is

the dominant rock types of Banswara manganese ores belt while the schist rocks are

highly foliated and marked by parallel orientation of several disconnected lamellar or

flaky micaceous constituents. The petrographic studies of host rocks suggest that the

prevailing mineral assemblages belong to greenschist to lower amphibolite facies in

manganese bearing phyllite and schist. In phyllite and schist rocks samples manganese

minerals consistently associated along the foliation planes or along the mineral

boundaries indicating that the mineralization may be occurred along the foliation plane or

shear zones. Manganese ores also found as encrustation, in the form of inclusion within

various minerals. The quartzite are disposed conformably with the phyllite and

microscopic studies concluded that the manganese ores found as encrustation, inclusions

and in the form of embedded in quartzitic assemblage. The rock type showing

granoblastic texture. The bedding of limestone is in conformity with phyllites and

quartzites and various structures like irregular joints, fissure, cavernous pockets are its

characteristic features in which manganese ores deposited in Talwara. The petrographic

studies reveal that mostly limestone are dolomitic in composition and the manganese ores

are distributed very irregularly and in scattered form in the limestone. Manganese ores

replacing limestone constituents around minerals boundaries. Texturally, the rock is

medium to coarse grained and showing all the mineral grains are approximately equal in

size which referred mosaic structure.

The textures, structures and prevailing mineral assemblages suggest that low

grade regional metamorphism has played an important role in metamorphism of these

pelitic-psammitic and calcareous sediments which turn into the prominent manganese

244

comprising rocks of the study area and finally metamorphosed to present day rock types

viz, phyllite, schist and quartzite. These metasediments occur as inter-banded with

present manganese ores and enriched in silica, alumina and iron contents. The prevailing

mineral assemblages are as follows:

Phyllite: Muscovite + Chlorite + Quartz ± Garnet ± Biotite + Opaque ore

minerals

Schist: Muscovite + Chlorite + Quartz + Garnet ± Biotite + Opaque ore

minerals

Quartzite: Quartz + Plagioclase + Orthoclase + Microcline ± Sericite ±

Calcite + Opaque ore minerals

Limestone: Calcite + Dolomite + Quartz ± Magnetite ± Tremolite ±

Hematite ± Chert + Opaque ore minerals

The manganese ores are co-folded with the interbedded phyllite and quartzite and

dispersed throughout the manganese belt except Talwara area where the manganese

occurred in caverns, pockets, and cavities, resulting from solution effects in ferruginous

limestone which indicates local leaching and infiltration of meteoric waters. The deposits

of manganese belt of study area having varying shapes and sizes and also occurred as

bedded deposits or irregular veins, pockets, stringers and as lenticular bodies. The

manganese ores which were collected from study area are megascopically examined and

found to be largely composed of braunite, pyrolusite, cryptomelane, psilomelane and

wad. In respect of physical properties, the manganese ores are very much different in

form, feel, colour etc. Optically the manganese ores are also different in properties due to

presence of various gangue minerals like quartz, garnet, feldspar, limonite, hematite and

ochre. The manganese ores divided into two types in the study area on the basis of field

and laboratory studies.

1. Stratified/Primary/Metamorphosed/Syngenetic/Meta-sedimentary ores

Braunite

Bixbyite

Pyroxmangite

Hollandite

Spessartine

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2. Secondary recrystallised/ Supergene/ Reworked ores

Pyrolusite

Cryptomelane

Psilomelane

Coronadite

Wad

Optically the various microstructures and textures recognized through these

manganese ores which are as follows:

1. Textures and Structures

Colloform Texture

Replacement Texture

Banded Texture

Veined Texture

Granular Texture

Spherulitic Texture

Comb Structure

Crystallographic Intergrowth

Relict Texture

Mutual Boundary Relation

The mineragraphic and XRD studies reveal that braunite is abundant mineral in

study area and identified almost in all polished blocks, with gonditic assemblages spotted

in few polished ore blocks (Orthoclase-Pyroxmangite-Spessartine). Presence of these

minerals reveal that the primary manganese ores of study area similar to gonditic type

deposits. The mineragraphic and textural relation studies concluded that the original

manganiferous sediments were metamorphosed under low grade metamorphism with the

formation of braunite first followed by bixbyite. There is no presence of minerals like

jacobsite and hausmannite in mineralogical assemblages which indicates that the stability

field of mineral bixbyite was not much exceeded. And geochemical data also confirmed

that the iron content in manganese ores is low and not sufficient for the formation of

these two minerals. The second generation braunite also recorded which possibly formed

246

by transformation of bixbyite in an undeformed manner with decreasing metamorphic

conditions. The acicular alteration growth of pyrolusite is the common feature of

supergene enrichment presented in prevailing ore mineral assemblages of the study area.

While on other side colloform texture indicates derivation of ore minerals from colloidal

aqueous hydrothermal solution. And the neocrsytallized pyrolusite with totally different

orientation can be considered as a product of supergene enrichment. Apart from these ore

minerals the hollandite ore mineral occurring with first generation braunite and replacing

it. Due to dominance of braunite with characteristic banded texture, bedding and

conformable relations with the enclosing rocks, textural and mineralogical studies of

other ore minerals assemblages supported that the ore body formed by regional

metamorphism of syngenetic manganiferous sediments, however hydrothermal

manganese bearing solution also played an important role in the enrichment of

manganese in the study area at later stage.

The geochemistry of manganese ores samples reveal that the MnO wt % is in

high category (i.e. 30.99 to 76.75 %) with enrichment of silica, iron and alumina

contents. The high concentration of MnO in most of the manganese samples is due to the

presence of braunite, pyrolusite and hollandite etc. The manganese is showing

antipathetic relation with Si, Al, Mg, Na and P, which indicate increase in manganese

proportion at the expanse of these oxides. The samples of study area lies near braunite-

rhodonite composition in Fe-Mn-Si triad and suggest that braunite present as main

minerals due to high content of silica in the study area. The alumina concentration is

showing very much similar concentration in manganese ores samples of the study area

and suggested more resemblance in mineralogy. The alumina also showing positive

relation with Si and negative relation with Ti. The higher Al/Ti ratio of manganese ores

indicate felsic source for Banswara manganese deposits. The manganese ores of present

study area are characterized by lower concentration of iron and showing less variation in

Fe values. The lower values of iron oxide in the manganese ores of study area may be

due to the presence of braunite as a main mineral and absence of iron rich manganese

minerals such as bixbyite, hausmannite and jacobsite in the study area. Fe showing

sympathetic relation with Mn which indicate the same source for iron and manganese. In

manganese ores of study area it seems that the iron may also concentrated by

247

hydrogenous and terrigenous supply from the host rocks rather than direct hydrothermal

influx. The lower values of Mn/Fe ratio are related to the primary manganese ores while

higher Mn/Fe values attributed to secondary or supergene ores in the study area. The

mineralogical studies suggest that the calcium incorporated by various processes from

initial stage to final stage (Precipitation to supergene enrichment) and Ca shows positive

correlation with manganese. The positive relation of Ca with Mn and negative relation

with Fe referred early digenesis and carbonate replacement by manganese minerals

while positive relation between Ca and Mn indicate that Mn is mainly enriched in the

carbonate sediments. Both magnesia and soda have negative correlation with manganese

in study area. In study area samples, potassium oxide content is higher in comparison of

soda content which depict that the source of these higher values of K2O due to the

presence of feldspar and mica which are the prominent constituent of the host rocks of

the study area. The phosphorous concentration is not much high and therefore the main

source of P is due to the presence of apatite and garnet minerals. The ternary plot

between CaO-Na2O-MgO showing marine field for most of the manganese samples

while Na-Mg discrimination diagram suggesting shallow water shelf conditions for the

manganese deposits of the study area.

The manganese ores of the study area is abnormally enriched in Co, V, Cu, Ni,

Zn, Zr, Sr, Pb, and Ba concentration which signify sedimentary to metasedimentary

nature of the manganese deposits. The higher concentration of these trace elements also

suggest involvement of secondary processes and supergene enrichment. The calculated

CaO/(CaO+MgO) ratio is too high and is possibly due to the involvement of supergene

enrichment in present manganese deposits which is indicated by the presence of

pyrolusite, cryptomelane, in the ores associated with braunite, bixbyite, hematite and

quartz. The sympathetic relation of Pb with Cu and Zn is supported Cu-Pb-Zn

association in the manganese minerals. The low Co/Ni ratio (.40) suggested sedimentary

environment for the formation of present manganese ore deposits. A number of

manganese ore samples of study area providing hydrothermal source for the present

manganese deposits in shallow marine shelf environment. The higher concentration of

trace elements like Cu, Ni, Co and Zn, compared to their lower concentration in

hydrogenous deposits also indicate sub-marine hydrothermal affinity of manganese

248

oxide ores. The higher concentration of Ba in the manganese ore samples of the study

area could be due to the supergene enrichment process or volcanic activity. The trace

elements and major oxides studies of manganese ore samples like MnO/Fe2O3 ratio

(16.93), Co/Zn ratio (.20), Fe-Si*2-Mn (Toth, 1980), Mn-Fe-(Ni+Co+Cu)*x10 (Bonatti

et al.,1972; Crerar et al., 1982), Zn-Ni-Co (Choi and Hariya, 1992), Co/Zn vs

Co+Ni+Cu (Toth, 1980), Cu+Ni vs Cu+Pb+V+Zn (Nicholson, 1992) ternary and binary

plot respectively suggested hydrothermal source for present manganese ores while SiO2

vs Al2O3 (Wonder et al., 1988) and Si vs Al (Choi and Hariya, 1992) binary plot showed

hydrothermal-hydrogenous origin for the manganese ores of study area and this may be

due to terrigenous weathering (detrital sediments) involvement.

The rare earth elements (REE) analysis provided various important signatures

regarding genesis and environment of deposition of manganese ores. The study area

show that total REE is decreasing from low to high grade manganese ores in the study

area. The chondrite normalized after Taylor and Mclennan (1985) data of manganese

ores show enriched light rare earth elements (LREE) and depleted heavy rare earth

elements (HREE). The enriched LREE and depleted HREE pattern in manganese ores of

the study area suggest that the source is more felsic rather than the mafic for the

manganese deposits. The analyzed geochemical data suggest positive Eu* and Ce*

values for the manganese ores of the study area. The slight positive Ce* indicated

enrichment of manganese ores from continental source which is also supported by high

Ce/La ratio of manganese ores. The Ba vs P2O5 diagram of Maynard (2010) indicated

both oxygen minimum zone and near euxinic basin type deposits which suggest

manganese deposition under anoxic and oxygen deficient environment. The manganese

ores or manganese rich sediments were precipitated in form of manganese oxides or

hydroxides above the anoxic and oxic interface on shelf as a consequence of upwelling

anoxic deep ocean water while continental weathering also played an important role for

the formation of Mn in present manganese ores deposits, supplied to the depositional

paleo-basin. The strong sympathetic relation between Si-Al and Ti-Al with high

amounts of Si, Al and Ti in the Banswara manganese ores belt may be due to the

admixture of terrigenous material during precipitation.

249

The major, trace and REE analysis of manganese ores of present study area

interpreted that the marine hydrothermal solution was enriched in manganese which was

carried in solution through upwelling of anoxic deep oceanic water and were delivered

to the shelf zone during favorable conditions of their precipitation and deposition. Later

activities like deformation and low grade metamorphism (greenschist facies) which

effected locally and resulted in textural, structural and mineralogical reconstitution in the

present manganese ores and host rocks of the study area. The rare earth elements data of

Banswara manganese deposits show lanthanum enrichment, la/Ce ratio and strong Eu

anomalies which indicate both basinal hydrothermal fluids and terrigenous materials as

source for the manganese deposits, in which major contribution from the former one.

While the positive Eu and Ce anomaly also suggest reducing environment conditions for

the deposition of present manganese ore deposits of Banswara district. The positive Eu

anomaly is clearly seen in all the manganese ore samples of study area and it increasing

towards the high grade ores and this positive values of europium shows reducing

environmental conditions due to change in Eu+3 to Eu+2.

The analyzed samples of host rocks data after chondrite normalized (Taylor and

Mclennan, 1985) of manganese ores in the study area show enrichment of LREE while

depletion of HREE. The average ratio of LREE/HREE is 3.76 and shows positive

correlation which depict that the enrichment of LREE took place before the formation

mechanism of host rocks of the study area. The average (La/Yb)N values of studied

samples is 24.01. This average high value suggest that heavy rare earth elements may

have been retained for its higher existence by garnet during formation of source rocks

and also shows depletion in HREE. The chondrite normalized data after Taylor and

Mclennan (1985) show negative Eu and Ce anomaly, suggest deposition of host

sediments under anoxic condition. The pattern of LREE and HREE observed in PAAS

normalized spider diagram is very similar to chondrite normalized pattern. The

normalized average Upper Continental Crust (UCC) (Taylor and Mclennan, 1985) major

and trace elements data of host rocks show variable enrichment in MnO, Na2O, P2O5

while depletion of SiO2, Al2O3, TiO2, Fe2O3, CaO, K2O and MgO. In case of trace

elements UCC normalized diagram shows enrichment in V, Cr, Ni, Co, Rb, Y, La, Pb,

Hf and Th while depletion of Sc, Cu, Sr, Zr, Nb and U in the host rocks of study area.

250

The abundance and enrichment of Ba, Pb, Hf, Th, Rb and La suggest felsic source for

the host rocks of the study area.

The binary plot of K2O/Al2O3 vs Na2O/Al2O3 after Mcdonald and Katsura (1964)

suggested sedimentary to metasedimentary field for protolith. The alumina concentration

is high in the phyllite, schist and manganiferous phyllite samples of study area which

may be due to sedimentary and metasedimentary field of source rock. The binary plot of

Zr vs TiO2 after Hayashi et al. (1997) suggest the nature and composition of source rock

in which the host rocks of study area falls is more felsic to less intermediate field of

composition. The ternary plots of ACF after Eskola (1915) suggest pelitic field of

composition for phyllite, schist and quartzite rocks while calcareous field for limestone

rock. These pelitic and calcareous field of composition also supported by

CaO(Fe+MgO)-Al2O3 ternary plot After (Wronkiewicz and Condie, 1989). The binary

plots of Fe2O3+MgO vs A12O3/SiO2, Fe2O3+MgO vs A12O3/(CaO+Na2O) after Bhatia

(1983) suggest the active and passive continental margin type tectonic setting for the

host rocks of study area. The passive continental margin setting also supported by binary

and ternary plots of K2O/Na2O vs SiO2 after Roser and Korsch (1986), Sc-Th-Zr/10 and

La-Th-Sc, after Bhatia and Crook (1986) for the studied samples respectively. The

interpretation of the analyzed geochemical data reveal that the host rocks were most

probably deposited in passive continental margin environment. The binary

discrimination diagram after Mclennan et al. (1993) between the Th/Sc vs Zr/Sc also

shows close affinity of these host rocks metasediments with UCC and felsic

compositional field in the study area.

251

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