The Mineralogy and Geochemistry of the Green Giant Vanadium-Graphite Deposit, S.W

The Mineralogy and Geochemistry of the Green Giant Vanadium-Graphite Deposit, S.W. Madagascar

Veronica Di Cecco

A thesis submitted in conformity with the requirements for the degree of Masters of Applied Science Department of Geology University of Toronto

The Mineralogy and Geochemistry of the Green Giant Vanadium-Graphite Deposit, S.W. Madagascar

Veronica Di Cecco

Masters of Applied Science

Department of Geology University of Toronto

2013 Abstract

The purpose of this project was to determine the vanadium bearing ore minerals present at the

Green Giant vanadium-graphite deposit in the S.W. of Madagascar owned by Toronto based

Energizer Resources Inc. The rocks are mainly quartzofeldspathic gneiss, with alternating bands of hornblende biotite gneiss, marble, granitoid, and amphibolite. Using X-ray diffraction, electron microprobe analysis, and Raman spectroscopy, the vanadium bearing minerals were identified as vanadium bearing rutile, schreyerite, berdesinskiite, karelianite, a member of the karelianite-eskolaite solid solution, V-bearing phlogopite, V-bearing pyrrhotite, V-bearing pyrite, goldmanite, dravite, uvite, actinolite, and unidentified “V-sulphide 1,” “V-sulphide 2,” “V- silicate 1.” The mineral assemblage present at Green Giant deposit is quite similar to that at Lake

Baikal, Russia. Vanadium-bearing phlogopite is primary vanadium host in the deposit, although

V-bearing oxides contribute substantially to the total V concentration, even where present in very trace amounts.

Acknowledgments

Thank you to Professors E.T.C Spooner and K. Tait for your assistance and guidance. Thanks to Brendt Hyde, Vincent Vertolli, Katherine Dunnell and Tony Steede at the Royal Ontario Museum Department of Natural History, Mineralogy section, Professor Mike Gorton, Colin Bray, George Kretchman, Allison Enright, Christopher White and Beata Opalinska at the University of Toronto Department of Earth Sciences, and Craig Scherba at Energizer Resources Inc. Last but not least, many thanks to Adam Duyvestyn and my family for their continued support.

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Table of Contents

Acknowledgments...... iii

Table of Contents ...... iv

List of Tables ...... vii

List of Figures ...... ix

List of Common Symbols and Abbreviations ...... xii

List of Appendices ...... xv

Chapter 1 Introduction ...... 1

1 Vanadium ...... 1

1.1 Geological Associations...... 2

Chapter 2 Madagascar...... 4

2 Geography ...... 4

2.1 Geology ...... 5

Chapter 3 The Green Giant Vanadium and Graphite Property ...... 8

3 Property Geology ...... 8

Chapter 4 Vanadium Host Minerals ...... 11

4 Introduction ...... 11

5 Methods ...... 11

5.1 Field Visit and Sampling ...... 11

5.2 Material for Study ...... 12

5.3 Examination of Material ...... 13

6 Results ...... 15

6.1 XRD and Hand Sample Identification ...... 15

6.2 X-Ray mapping ...... 17

6.3 Electron Microprobe Analysis ...... 19

7 Mineral Species ...... 20

7.1 V-Bearing Oxides ...... 20

7.1.1 Ti-Oxide: Vanadium Bearing Rutile ...... 20

7.1.2 V-Ti-oxide 1: “Schreyerite” ...... 23

7.1.3 V-Ti-Oxide 2: “Berdesinskiite” ...... 28

7.1.4 V-Cr-Oxide: a member of the karelianite – eskolaite solid solution ...... 33

7.1.5 V-oxide: “Karelianite” ...... 36

7.2 V-Bearing Sulphides ...... 38

7.2.1 V-sulphide 1: Unknown ...... 38

7.2.2 V-Sulphide 2: Unknown ...... 40

7.2.3 Fe-V-Sulphide 1: V-bearing Pyrrhotite ...... 42

7.2.4 Fe-V-Sulphide 2: Vanadium bearing pyrite ...... 43

7.3 V-silicates ...... 44

7.3.1 V-silicate 1: Unknown ...... 44

7.3.2 V-Silicate 2: V-phlogopite ...... 45

7.4 Summary table ...... 48

7.5 Comparison to Lake Baikal, Russia ...... 50

Chapter 5 Vanadium Reconciliation ...... 52

8 Methods ...... 52

9 Results ...... 52

10 Discussion ...... 53

Chapter 6 Conclusion ...... 55

References ...... 56

Appendix I Vanadium Concentrations as Provided by Energizer Resources Inc...... 61

Appendix II Mineral Identifications Performed at the Royal Ontario Museum ...... 63

Appendix III V-Rutile EMPA Data ...... 72

Appendix IV Schreyerite EMPA Data ...... 73

Appendix V Berdesinskiite EMPA Data ...... 74

Appendix VI Karelianite-Eskolaite SS EMPA Data ...... 75

Appendix VII V-Phlogopite EMPA Data ...... 76

Appendix VIII The Results of X-Ray Fluorescence Performed at the University of Toronto on the Working Set of Samples ...... 79

List of Tables

Table 1: Tectonic events recorded in the tectonic units of Madagascar, from Collins (2006) ...... 6

Table 2: A list of the number of samples which comprise the working set selected from each deposit, and each concentration level ...... 14

Table 3: Minerals identified in hand sample...... 16

Table 4: The average, standard deviation, minimum, and maximum values of microprobe analyses of vanadium bearing Ti-oxide in thin sections UT117, UT134, UT150 and UT159. .... 21

Table 5: The arithmetic mean, standard deviation, maximum and minimum oxide compositions of vanadium titanium oxide 1 from thin sections UT117, UT134, UT150 and UT159...... 24

Table 6: A comparison of the weight percent composition of type schreyerite (Medenbach, 1976), kyzylkumite (Raade, 2006) and berdesinskiite (Bernhardt et al., 1981) with that of V-Ti- Oxide 1...... 27

Table 7: The arithmetic mean, standard deviation, maximum and minimum oxide compositions of vanadium titanium oxide 2 from thin sections UT134, UT150 and UT159...... 31

Table 8: comparison of schreyerite (Medenbach, 1976), kyzylkumite (Raade, 2006) and berdesinskiite (Bernhardt et al., 1981) with V-Ti-Oxide 2...... 32

Table 9: The arithmetic mean, standard deviation, maximum and minimum oxide compositions of vanadium chromium oxide from thin section UT159...... 34

Table 10: Microprobe analyses of vanadium oxide from thin sections UT130 and UT150...... 37

Table 11: comparison of Karelianite (Long et al., 1963), Oxyvanite (Reznitsky et al., 2009) and average V-oxide compositions...... 38

Table 12: Microprobe analyses of V-Sulphide 1...... 39

Table 13: Microprobe analyses of V-Sulphide 2...... 41

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Table 14: Microprobe analyses of Fe-V-Sulphide 1...... 43

Table 15: Microprobe analyses of Fe-V-Sulphide 2 from thin sections UT150 and UT159...... 44

Table 16: The results of EPMA of V-Silicate 1...... 45

Table 17: The average, standard deviation (1σ), maximum and medium compositions of V- silicate 2...... 45

Table 18: Summary table of the vanadium bearing minerals identified at Green Giant ...... 49

Table 19: Calculations to determine the contribution of vanadium to the bulk rock vanadium content for thin sections UT130, UT134, UT150 and UT159...... 53

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List of Figures

Figure 1: Location of Green Giant vanadium property on the island of Madagascar after Energizer Resources (2011)...... 4

Figure 2: Geological basement map of Madagascar (after Collins, 2006)...... 5

Figure 3: Geology of the Green Giant Vanadium Property (after Energizer Resources Inc., 2011) ...... 10

Figure 4: Drill core from hole M-87; a 2 m long rule is included for scale...... 12

Figure 5A: X-Ray map of vanadium in UT159...... 18

Figure 6: Ternary diagram of weight percent iron, vanadium and sulphur in vanadium-bearing sulphides as determined by EPMA in thin sections UT130, UT150 and UT159...... 19

Figure 7: Ternary diagram of weight percent TiO2, VO1.5 and CrO1.5 in vanadium-bearing oxides as determined by EPMA in thin sections UT117, UT130, UT134, UT150 and UT159...... 20

Figure 8: A BSEI of UT159 circle 1. Analysis 30 is of V-Ti-oxide 1...... 22

Figure 9: A reflected light photomicrograph of UT159 circle 1...... 23

Figure 10: Back Scattered Electron Image of UT117 spot 4. Rutile was found at analyses 27 and 28, V-Ti-oxide 1 was examined at analyses 25 and 26...... 25

Figure 11: A BSEI of UT150 spot 1. In this grain V-Ti-Oxide 1 (analyses 17 and 18) is the major mineral and rutile (analyses 15 and 16) is the minor mineral...... 26

Figure 12A: An oil immersion reflected light image of rutile with fine exsolution lamellae of schreyerite from Kwale District, Kenya (Medenbach 1976). B: A BSEI of exsolution induced lamellae of schreyerite (light) in rutile (grey) from Lake Baikal, Russia (Koneva 2002). The scale bar represents 100 μm...... 27

Figure 13: A BSEI of UT134 Spot 2. Analysis 8 is of V-Ti-Oxide 2 and analysis 9 is of “schreyerite” ...... 28

Figure 14: A BSEI in UT159 spot 4. Analyses 41, 42 and 43 are of V-Ti-Oxide 2, analyses 44, 45 and 46 are of “schreyerite,” and analysis 47 is of Nb-rich rutile ...... 29

Figure 15: A BSEI of UT130 spot 6 where analyses 5 and 6 are of V-Ti-Oxide 2. Analyses Phl- 37 and Phl-36 are of vanadium bearing phlogopite with results shown in Appendix VII...... 30

Figure 16: Images from Bernhardt et al. (1983) of type berdesinskiite. A: An electron beam scanning image showing the distribution of vanadium. B: A sketch of the mineral phases identified from Figure 17A...... 33

Figure 17: A BSEI of UT159 spot 4. Analyses 48, 49, 50, 51, 52 and 53 are of V-Cr-Oxide. .... 34

Figure 18: Eskolaite – karelianite solid solution series on a Cr2O3 – V2O3 – Fe2O3 diagram after Koneva (2002)...... 35

Figure 19: BSEI of UT150 spot 5 where analyses 21 and 24 are of V-oxide. Analysis 23 is of V bearing rutile. Analysis 22 is of “berdesinskiite”...... 36

Figure 20: A Fe-V-S diagram with the vanadium bearing sulphide species present at green giant plotted, as well as patrónite [calculated from synthetic composition (Hewett, 1906)]...... 39

Figure 21: A BSEI of UT150 spot 1 where analyses 14 and 15 are of V-Sulphide 1.. Analyses 12 and 13 correspond to V-bearing pyrrhotite...... 40

Figure 22: Back Scattered Electron Image of UT130 spot 1 bearing V-Sulphide 2 indicated by points 1, 2, 3 and 4. Also present in this region is “karelianite” and V-silicate 1...... 42

Figure 23: Transmitted light photomicrographs of UT130 spot 6. Top: Plane polarized light. Bottom: Cross polarized light. The scale bar represents 100 μm. V-Silicate 2 is pale brown in plane polarized light...... 47

Figure 24: The determined V2O3 content of phlogopites...... 48

Figure 25: Vanadium concentration with depth in drill core M-87; based on data provided by Energizer Resources Inc...... 61

Figure 26: Vanadium concentrations with depth in Mainty core K-02; based on data provided by Energizer Resources Inc...... 62

Figure 27: Vanadium concentration with depth in Jaky core J-07; based on data provided by Energizer Resources Inc………………………………………………………………………..63

List of Common Symbols and Abbreviations

< less than

> greater than

≤ equal to or less than

≥ equal to or greater than

~ approximately

% percent

$ dollar

°C degrees Celsius avg. average

BSEI back scattered electron imaging

CCD charge coupled device cm centimetre

EPMA electron probe micro-analysis

EDS energy dispersive spectrometry

FEG field emission gun

GDP gross domestic product

GLIER Great Lakes Institute for Environmental Research g gram g/ton grams per tonne

ID identification

IMA International Mineralogical Association kbar kilobar kg kilogram

xii

km kilometre kV kilovolt lb pound m metre

Ma mega-annum before present

Mlb million pounds mm milimetre

Mt megatonne

MWh mega-watt hour nA nanoamp ppm parts per milion

PGE platinum-group elements

R:G:B red:green:blue

ROM Royal Ontario Museum

SEM scanning electron microscope t tonne

USA United States of America

USD United States Dollars

USGS United States Geological Survey

UTM universal transverse mercator

VRB vanadium redox battery

WDS wavelength dispersive spectrometry wt % weight percent

XRD X-ray diffraction

XRF X-ray fluorescence

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xiv

List of Appendices

Appendix I: Vanadium Concentrations as Provided by Energizer Resources Inc.

Appendix II: Mineral Identifications performed at the Royal Ontario Museum

Appendix III: V-Rutile EMPA Data

Appendix IV: Schreyerite EMPA Data

Appendix V: Berdesinskiite EMPA Data

Appendix VI: Karelianite-Eskolaite SS EMPA Data

Appendix VII: V-Phlogopite EMPA Data

Appendix VIII: The Results of X-Ray Fluorescence Performed at the University of Toronto on the Working Set of Samples

xv 1

Chapter 1 Introduction

Vanadium is a transition metal used mainly in alloys and it is irreplaceable in aerospace applications (Moskalky, 2003; Goonan, 2011). Recent developments in the application of vanadium in the field of “green” battery technology are anticipated to have a large impact on the vanadium market in coming years (Dunn, 2011).

The Green Giant vanadium and graphite property is located in southwest Madagascar and is owned by Energizer Resources Inc. The purpose of this research project was to determine the residence of vanadium in the ore body. This was done using mineralogical and geochemical analytical techniques. Knowledge of the mineralogical hosts of vanadium should assist in the refinement process and provide further insight into the behavior of vanadium-bearing minerals. Detailed geochemical analysis of the hanging wall, main vanadium enriched zone and footwall of the deposit has resulted in physical constraints and a more accurate depiction of the ore body.

1 Vanadium

The metal vanadium (chemical symbol V) is the 23rd element in the periodic table. and is a transition metal. It has valence states of +5, +4, +3, +2, +1 and -1 but most typically exists in +3, +4, and +5. V is the 23rd most common element in the earth's crust, with an average crustal abundance of 160 ppm (Groonan, 2011; Rose, 1973). It is more abundant in the earth’s crust than zinc, twice as abundant as nickel and copper, and ten times as abundant as lead (Rose, 1973).

There are 65 recognized vanadium minerals. The most common are patrónite (VS4; Hewett, . 1906), vanadinite (Pb5(VO4)3Cl; von Kobell, 1838) and carnotite (K2(UO2)2(VO4)2 3H2O; Friedel, 1899; Groonan, 2011).

Vanadium minerals occur in one of four mineralogical host types in which vanadium is concentrated (Evans, 1974; Groonan, 2011). The first is in vanadium sulphide compounds where vanadium occurs as V4+ (Evans, 1974). Vanadium sulphide minerals include patrónite, sulvanite

(Cu3VS4; Goyder, 1900), and colusite (Cu12VAs3S16; Landon, 1933). The second is in secondary vanadate zones, above copper, lead, or zinc ore, where the oxidation state of vanadium is 5+ (Evans, 1974). The third host variety is vanadium micas where vanadium (III) and some iron (II) replaces aluminum in the octahedral layer of muscovite (KAl2(Si3Al)O10(OH)2) to form 3+ + roscoelite (KV 2(Si3Al)O10(OH)2; Blake, 1876;Evans, 1974). In these micas, V is in the 4 oxidation state and within the octahedral layer of the mineral (Evans, 1974). The fourth host is oxide deposits in some sandstone horizons where vanadium deposited as an oxide and can be weathered to produce a wide variety of minerals (Evans, 1974). Vanadium in this environment typically has valence states ranging from 3+ to 5+. The vanadium minerals which are produced in any environment are dependent on the V oxidation state, pH and redox state of the environment (Landergreen, 1974). However, there exist no magmatically produced minerals which have vanadium as a major component; it is only present as a minor constituent. Minerals containing vanadium as a major component are only secondary and are formed from chemical reactions involving montroseite ((V3+, Fe2+, V4+)O(OH); Weeks et al., 1950) or silicates (Landergren, 1974).

1.1 Geological Associations

Vanadium is generally associated with uranium, niobium, aluminum, and sometimes rare earths and phosphorous, however the elements with which it associates are dependent on the geochemical environment (Rose, 1973).

According to Rose (1973) there are twelve types of geological associations with vanadium. The types related to the rocks of the Green Giant project are listed below.

1) Carbonate complexes – Vanadium dissolved in sea water can be complexed, reduced and adsorbed, favouring accumulation of vanadium in sediments which are rich in organic carbon (Breit et al., 1991). During diagenesis vanadium-organic complexes are often removed from carbonaceous rocks with petroleum but vanadium remains in refractory organic matter or associated clay minerals (Breit et al., 1991). During metamorphism, the carbon in the rock is converted to graphite while vanadium is incorporated into silicate minerals (Breit et al., 1991). This group of vanadium-rich rocks is often stratigraphically associated with

phosphate-bearing units and tends to have high concentrations of organically bound sulphur (Breit et al., 1991).

2) Titaniferous magnetic deposits - In such deposits vanadium is associated with titanomagnetite as well as, in more minor amounts, with pyroxene, hornblende, biotite and chlorite (Rose, 1973). This deposit type is the most economically significant in terms of vanadium content (Rose, 1973). The Bushveld intrusion of South Africa is one example of this deposit type, where strongly fractionated magma leads to high V concentrations (Reynolds, 1985).

3) Dark shales and variegated shales - There are four varieties of black shales, which are differentiated based on redox state and pH. These conditions result in four chemical groupings with characteristic levels of manganese, iron and vanadium (Quinby-Hunt, 1994). Three of these varieties are characterized by low vanadium content, while the fourth is characterized by high vanadium content and low manganese and iron content (Quinby-Hunt, 1994). Vanadium can be used to indicate the amount of organic carbon which was compacted in diagenesis (Quinby-Hunt, 1994). Vanadium occurs as V-tetrapyrrole complexes within organic matter and is concentrated especially from marine plankton (Quinby-Hunt, 1994). These complexes are preserved best in low-pH, anoxic, aphotic and highly reducing environments (Quinby-Hunt, 1994).

4) Asphalt, asphaltite, bitumen, bituminous sandstone, lignite, coal, oil, shale and graphite occurrences - Knowledge of vanadium-bearing graphite occurrences is quite limited. When rocks rich in organic carbon are metamorphosed, graphite is produced. Graphite quartzites with vanadium muscovite have been reported in the upper Visean conglomerates of the Drahany Uplands of the Czech Republic (Houzar, 2001). Coal-bearing metapelites within the Ogcheon supergroup of the Republic of Korea are also known to contain vanadium mineralization (Lee, 2003).

Chapter 2 Madagascar

2 Geography

Madagascar is the world’s fourth largest island, over 587 000 km2 and is located in the Indian Ocean (Dahl, 2005). The Green Giant vanadium property is located in the southwest of Madagascar in the Tulear region (Figure 1). The region it is arid and low-lying, particularly in the interior of the island where the property is located. The property located at UTM coordinates 510 000 E, 7 350 000 N and covers an area of 188 km2 (Energizer Resources Inc., 2011). Located on the southwestern edge of the Green Giant property is the village of Fotodrevo (Energizer Resources Inc., 2011).

Figure 1: Location of Green Giant vanadium property on the island of Madagascar after Energizer Resources (2011).

2.1 Geology

The geologic history of Madagascar is closely tied to the evolution of the supercontinent, Gondwana, due to its previous position. At the end of the Paleozoic the island of Madagascar was adjacent to Kenya and Tanzania (Lardeaux, 1999). During the formation of Gondwana, the island was located in a continental collision zone (Collins, 2006). This resulted in a strain imposed on the basement rocks causing metamorphism and deformation (Collins, 2006). The main basement tectonic units span in age from 3127 Ma gneisses in the Antongil Block, to 539 Ma when post tectonic granitoids were intruded into the Antananarivo block (Collins, 2006). These tectonic units are represented in Figure 2. Table 1, after Collins (2006), summarizes the main tectonic events which are recorded in the tectonic units shown in Figure 2. The western third of the island is covered by Phanerozoic sediments (Schreurs et al., 2006). Since the late Jurassic to early Cretaceous, the island has been isolated from the African continent and has drifted over time to its current location (Lardeaux, 1999).

Figure 2: Geological basement map of Madagascar (after Collins, 2006).

Table 1: Tectonic events recorded in the tectonic units of Madagascar, from Collins (2006)

Tectonic Unit Sub-unit Major Tectonic Events  717 – 754 Ma granite magmatism Bemarivo Belt  715 Ma rhyolite extrusion coeval with deposition of sandstones and conglomerates  510 – 520 Ma granulite-grade metamorphism coeval with south – west directed thrusting

 Post 720 Ma deposition of protolith mudrocks Neoproterozoic Betsimisaraka  Post 620 Ma deposition of protolith quartzites and Metasediments Molo mudrocks  Metamorphism between 645 – 545 Ma  750 – 630 Ma deposition of protolith mudstones, Androyen sandstones and limestones  Intrusion by ~630 Ma anorthosites  Metamorphism between 645 – 545 Ma  Post 850 Ma deposition of protolith mudrocks, Vohibory carbonates and possible coeval basic volcanism. No earlier detritus  2747 – 2494 Ma granitoid intrusion through crust Tsaratanana dating back to 3260 Ma Sheet  Deformation and emplacement over Antananarivo Block  787 – 779 Ma gabbro magmatism coeval with high temperature metamorphism in the country rock  637 – 627 Ma granitoid intrusion  Intense deformation transposing earlier rocks into gneissic tectonites  549 Ma late dioritic magmatism  Deformation  ~ 2500 Ma crust formation Antananarivo  2189 – 1007 Ma zircon xenocrysts in later granites, Block whose significance is unknown (including the  Post 1850 Ma deposition of Itremo Group- quartzites Itremo Group) mudrocks and carbonates  Pre ~ 820 Ma deformation into large recumbent

 isoclinal folds  824 – 719 Ma supra-subduction zone gabbro and granitoid intrusion  633 – 561 Ma granitoid magmatism  Pre-550 Ma granulite-grade metamorphism and contractional deformation  Intrusion of post-tectonic granitoids 572 – 530 Ma possibly coeval with extensional deformation along the Betsileo shear zone  3200 – 2500 Ma Granite intrusion Antongil Block  Paleozoic sediments deposited on erosion surface

Chapter 3 The Green Giant Vanadium and Graphite Property

3 Property Geology

The Green Giant Vanadium Property is situated in the Vohibory unit, bordering the Androyen unit and within the Ampanihy transpressive shear zone (Energizer Resources Inc., 2011). Both units contain Neoproterozoic metasediments. The Androyen unit includes metapelites, quartzites and marbles, originally deposited as sediment between 750 and 630 Ma. This unit then underwent regional transpression and high thermal conditions of up to 800 oC leading to peak amphibolite to granulite facies between 645 and 545 Ma (Martelat, 1997; Collins, 2006).

The Vohibory unit contains pelites, marbles, amphibolites and granitoids, deposited after 850 Ma, which underwent the highest metamorphic conditions on the island, greater than 10 kbar of pressure, from an orogenic event (Collins, 2006). This unit contains evidence for a Pan-African deformation event which produced vertical shear zones and is interpreted to be the result of an E- W bulk horizontal shortening of the Precambrian crust (Lardeaux, 1999). This horizontal shortening resulted in high pressure, high temperature metamorphic grade rocks (Lardeaux, 1999)

Both supracrustal and plutonic rocks are present in the Green Giant property from the Androyen and Vohibory units (Energizer Resources Inc., 2011). The supracrustal rocks are migmatitic quartzofeldspathic gneiss, marble, chert, quartzite and amphibolite gneiss (Energizer Resources Inc., 2011). The plutonic rocks are migmatitic feldspathic gneiss of monzodioritic to syenitic composition, biotite granodiorite and leucogranite (Energizer Resources Inc., 2011). Amphibolite gneisses in the eastern region are recognized as the Androyen unit and a predominately quartzofeldspathic gneiss region in the west is termed the Vohibory unit (Energizer Resources Inc., 2011). The rocks on the property typically form narrow, alternating bands trending NNE and dipping steeply to the WNW (Energizer Resources Inc., 2011). Stratiform zones which are parallel over a 2-km wide region occur in the east of the Green Giant property and are termed “siliceous ferruginous gossans” (Energizer Resources Inc., 2011).

Despite this it is unclear whether these are true gossans. The geology of the Green Giant property is shown in Figure 3 and is mainly composed of quartzofeldspathic gneiss, with bands of hornblende biotite gneiss, marble, granitoid, and amphibolite.

The property contains three vanadium deposits: Mainty in the northwest, Manga in the center, and Jaky in the southeastern area (Figure 3), along with other small occurrences (Energizer Resources Inc., 2011). Jaky has been followed over a trend of 1800 m and drill cores indicate there may be two or more mineralized zones within the deposit (Energizer Resources Inc., 2011).

Mainty was followed for a strike length of 1000 m with high grade V2O5 assay values (greater than 0.5% V2O5) over a 450 m trend (Energizer Resources Inc., 2011). Manga has been divided into Manga North, Manga Main, and Manga South (Energizer Resources Inc., 2011). Manga extends from section 47 500 N to 46 100 N with a high grade core assaying over 0.8% V2O5 surrounded by lower grade material (Energizer Resources Inc., 2011).

Since 2007, 21,957 m of drill core has been collected and 17,105 m of trenches have been dug (Energizer Resources Inc., 2011). The material collected from the drill core and trenches has been examined by X-Ray Fluorescence (XRF) and the results modeled to determine the mineral resources of the deposit (Energizer Resources Inc., 2011). As no feasibility study has been undertaken on the mineral project only mineral resources are estimated (Energizer Resources

Inc., 2011). If a 0.5% V2O5 cutoff is used there are 49.5 Mt of indicated resources at an average of 0.693% V2O5 for a total of 756.3 Mlb of V2O5 and 9.7 Mt of inferred resources at an average grade of 0.632% V2O5 for a total of 134.5 Mlb of V2O5 at the Green Giant Property (Energizer

Resources Inc., 2011).

Figure 3: Geology of the Green Giant Vanadium Property (after Energizer Resources Inc., 2011)

Chapter 4 Vanadium Host Minerals 4 Introduction

The types of vanadium minerals found in different geochemical environments were described above in Section 1.2. To determine which of these mineral types, (i.e. sulphides, secondary vanadates, vanadium micas or oxide deposits), if any, are present at the Green Giant property, a variety of analytical techniques were employed.

5 Methods 5.1 Field Visit and Sampling

Between September 1st and Sept 18th 2011, a visit was made to the Energizer Resources Green Giant camp to collect samples for analysis. For each of the three main deposits within the property a drill core spanning the main vanadium bearing horizon and the hanging and footwalls was sampled. This ensured that concentrations of deposit materials could be compared to background levels in the region. Quarter cores were selected for samples because half of the width of core was required for assaying, and the company is required to keep samples of the core it extracts. A photograph of uncut core is presented in Figure 4. Samples forty cm in length were collected every 2 m of drill core to produce an even distribution of samples through the drill depth, providing a substantial, yet not excessive, quantity of material for analysis. In some cases, slight adjustment to the sampling interval was made to accommodate and work around the presence of poorly consolidated weathering products in the core. In these cases the next closest section of consolidated rock was sampled as a substitute.

Figure 4: Drill core from hole M-87; a 2 m long rule is included for scale.

The drill core selected from Mainty was from hole number K-02, from Manga, number M-87 and from Jaky were numbers J-07 and J-09. Core K-02 was drilled in 2010 at an inclination of 45o, and at collar UTM coordinates 503 986 E, 7 354 392 N for a depth down core of 233 m. Core M-87 was also drilled in 2010 at an inclination of 45o, and at collar UTM coordinates 503 070 E, 7 346 000 N for a depth down core of 306.5 m. Hole J-07 was drilled in 2009 at a 45o inclination, collar UTM coordinates 501 315 E, 7 336 900 N and for a depth down core of 276.5 m whereas J-09 was drilled in 2009 at a 45o inclination, collar UTM coordinates 501 442 E, 7 336 902 N for a depth of 141 m.

5.2 Material for Study

In total, 314 quarter core samples were collected. In addition, twenty-seven hand samples were collected from various locations on the property for mineralogical analysis. From Manga, 106 quarter core samples were collected from M-87, as were 70 drill core samples from Mainty K- 02, and 99 drill core samples from Jaky’s J-07 and J-09.

5.3 Examination of Material

Each of the core samples, trench samples and hand samples was inspected under a binocular microscope. No previous mineralogical studies had been completed on these rocks, so thorough mineralogical analysis was necessary. Samples bearing minerals which are atypical in comparison to the suite were identified, although thin sections which best represented the main rock-forming minerals of the host rocks were also analyzed. A working set of approximately 44 samples was selected to provide an overview of the Manga, Mainty and Jaky deposits. The number of samples in the working set selected for each deposit is listed below in Table 2. The samples are divided into hanging and footwall sections, and into low (<0.2% V2O5), medium

(0.2% ≤ V2O5 ≤ 0.5%) and high (V2O5 > 0.5%) vanadium concentrations as reported by X-ray

Fluorescence (XRF) assay results provided by Energizer Resources Inc. The 0.2 wt % V2O5 cutoff represents the regional background level (Appendix I). Representative pieces of each sample were sent to Vancouver Petrographics Ltd. for polished thin sections.

Minerals isolated in hand sample were examined with a Vicker Instruments Nanolab LE2100 Scanning Electron Microscope (SEM) equipped with a Kevex energy dispersive spectrometer (EDS) and GW Electronics backscatter detector currently located at the Royal Ontario Museum. This technique was used to identify the elemental constituents of each mineral.

Following this technique, powder X-ray Diffraction (XRD) was used to produce the powder XRD pattern of each mineral, which was then compared to a database together with the elemental information to identify the mineral. Due to the small grain size of the samples analyzed, powder XRD patterns were obtained on a single crystal X-ray diffractometer. The machine used was a Bruker Kappa Apex II with a molybdenum source, 0.5 mm collimator and 4K CCD detector at the Royal Ontario Museum. Raman spectra were also used to supplement these techniques to identify minerals. The Raman spectrometer used was a Horiba LabRAM Aramis Confocal Raman Microscope which has three lasers, at 532, 633 and 785 nm equipped with an Olympus BX41 microscope, at the Royal Ontario Museum. Raman spectroscopy

14 produces a characteristic spectrum for each mineral which can be compared to the mineral spectra in the RRUFF database1.

Table 2: A list of the number of samples which comprise the working set selected from each deposit, and each concentration level

Mainty Manga Jaky Hanging Wall 1 2 1

Low Concentration (<0.2% V2O5) 4 6 4

Medium Concentration (0.2% ≤ V2O5 ≤ 0.5%) 4 6 4

High Concentration (V2O5 > 0.5%) 4 6 4

Footwall 1 2 1

Vanadium and iron have similar atomic masses, making it difficult to locate vanadium-bearing minerals in thin section by Back Scattered Electron Imaging (BSEI) analysis with an SEM. Compounding this difficulty, vanadium minerals do not have any particular features to distinguish them from those of other elements. Therefore x-ray element mapping was employed. Polished thin sections of five high and medium concentration representative samples of the Manga drill core M-87 were made and X-ray element maps were produced. These thin sections were of samples UT117, UT130, UT134, UT150 and UT159. These maps were developed at the University of Windsor Great Lakes Institute for Environmental Research (GLIER) in Ontario, Canada using a FEI Quanta 200 Field Emission Gun (FEG) Environmental SEM equipped with EDAX Energy Dispersive Spectrometry (EDS). A 20 kV accelerating voltage was used and images were captured at 70x magnification. Maps were made for the elements Al, Ca, Cr, Fe, K, Si, S, Ti, U, V, Mg, Mn, and P. Then using photographic software, overlays were made of various combinations of spectra in an attempt to identify different vanadium phases. These vanadium phases and surrounding material were examined at the Department of Geological Sciences and Geological Engineering of Queen’s University in Ontario, Canada using a JEOL

1 Available through the University of Arizona at

JXA-8230 Electron Probe Microanalyzer. For silicates the conditions used were an accelerating potential of 15 kV, a beam current of 10 nA and a spot size of 7 microns. Sulphides and oxides were analyzed with an accelerating potential of 15 kV, and a fully focused static beam with a current of 30 nA. Combining this information with observations made in reflected and transmitted light photomicrographs, as well as identification by Raman spectroscopy and powder XRD, the vanadium host minerals were identified to the highest level of confidence possible permitted by the data.

6 Results 6.1 XRD and Hand Sample Identification

In Table 3 is a list of minerals identified by Raman spectroscopy or powder XRD, as well as the mineral chemistry and distinguishing features. Minerals which contain significant quantities of vanadium are highlighted in grey. These results were then used to identify the vanadium bearing minerals in thin section.

Mineral ID Method Colour Diaphaneity Lustre Habit

Phosphates apatite R colourless transparent vitreous massive alabandite X silver opaque metallic massive molybdenite R silver blue opaque metallic plates pyrite X bronze opaque metallic massive Sulphides pyrrhotite X bronze opaque metallic massive marcasite and X iridescent opaque metallic mottled pyrite red to pale siderite X transparent vitreous equant yellow calcite X white opaque vitreous massive Carbonates rhodochrosite- X black opaque dull sub-botryoidal siderite series Native Elements graphite R grey opaque metallic flakes montmorillonite X white translucent vitreous fibrous Phyllosilicates clinochlore X black opaque dull coating phlogopite X brown translucent pearly platy

kaolinite X white opaque dull crusts muscovite X grey transparent pearly plates talc X white opaque greasy platy vermiculite R dark green opaque subvitreous blades V-muscovite peacock with up to 10% X, Chem opaque vitreous platy green V spinel R pink transparent vitreous massive Oxides hematite X red opaque earthy crusts rutile X black opaque dull massive Sulphates gypsum X white transparent vitreous fibrous augite R brown opaque dull equant pale green tremolite X to translucent pearly fibrous colourless Inosilicates actinolite X green translucent waxy platy

pale green diopside R transparent vitreous small blades yellow white chabazite-Ca X opaque dull crusts yellow laumontite X white opaque pearly needles Tectosilicates golden semi anorthite X opaque massive yellow vitreous quartz X white opaque dull powdery goldmanite X green transparent vitreous granular (garnet group) Nesosilicates sillimanite X white opaque greasy needles titanite X brown opaque sub-metallic tabular pyrope X pale red translucent vitreous massive dravite (tourmaline X green translucent vitreous massive Cyclosilicates group) uvite (tourmaline X green transparent vitreous euhedral group)

Table 3: Minerals identified in hand sample. For method of identification, R denotes Raman spectroscopy and X denotes powder XRD. Grey subdivisions indicate vanadium- bearing species.

6.2 X-Ray mapping

X-ray mapping by SEM-EDS was employed to identify the presence and distribution of vanadium-bearing phases. X-ray mapping was used on five polished sections (UT117, UT130, UT134, UT150 and UT159), with medium or high grade mineralization from the Manga Green Giant prospect. The data gathered from these X-ray maps were used as a guide for subsequent SEM-EDS and Electron Microprobe Analysis (EMPA). An example of a vanadium X-ray map is in Figure 5A (UT159). Black pixels indicate the absence of vanadium and white pixels indicate the largest count rates for vanadium detected. All other pixels are shades of grey scaled to fit between these two values.

A false colour red-green-blue band image was produced using the Kα lines for vanadium (red), chromium (green) and titanium (blue). The resulting map (Figure 5B) displays the presence of V-Cr (yellow), V-Ti (purple) and V-bearing (red) phases.

To identify vanadium silicates separately from other vanadium phases a second spectrum combination was produced for vanadium (red), iron (blue) and silicon (green). The map produced (Figure 5C) displays not only the presence of the V-bearing phases from the previous image (red), but also the presence of Fe-V phases (blue purple) and Si-V (light green). The latter group of minerals is difficult to distinguish due to the presence of V-free silicates which make up the majority of the image.

The phases illuminated by X-ray mapping which appeared to have the highest concentration of vanadium were then used as the focus of EMPA as these were likely the ore minerals.

A B C

Figure 5A: X-Ray map of vanadium in UT159. The field of view is 4.0 cm by 2.3 cm; B: A spectrum combination of UT159 where R:G:B is V:Cr:Ti. The field of view is 4.0 cm by 2.3 cm; C: A spectrum combination of UT159 where R:G:B is V:Fe:Si. The field of view is 4.0 cm by 2.3 cm.

6.3 Electron Microprobe Analysis

V-bearing phases from thin sections UT117, UT130, UT134, UT150 and UT159 were analyzed by electron microprobe, and when combined with the X-ray maps, four vanadium-bearing sulphide species were identified, in addition to five vanadium-bearing oxide species, vanadium- bearing phlogopite, and an unknown vanadium-bearing silicate.

The microprobe results of the vanadium sulphide species plotted on a ternary diagram consisting of weight percent Fe, V and S, are given in Figure 6. The red circle corresponds to the analyses of V-sulphide 1, the purple circle to V-sulphide 2; the green circle to Fe-V-sulphide 1; and the dashed black circle to Fe-V-sulphide 2.

Figure 7 depicts microprobe results of the vanadium oxide species in a ternary diagram consisting of weight percent TiO2, VO1.5 and CrO1.5. The red circle encloses Ti oxide 1; green corresponds to V-Ti-oxide 1: black to V-Ti-oxide 2; the black dashed circle to V-oxide ; and the blue circle to V-Cr-oxide 1.

Figure 6: Ternary diagram of weight percent iron, vanadium and sulphur in vanadium- bearing sulphides as determined by EPMA in thin sections UT130, UT150 and UT159. The red circle corresponds to the analyses of V-sulphide 1; the purple circle to V-sulphide 2; the green circle to Fe-V-sulphide 1; and the dashed black circle to Fe-V-sulphide 2.

Figure 7: Ternary diagram of weight percent TiO2, VO1.5 and CrO1.5 in vanadium-bearing oxides as determined by EPMA in thin sections UT117, UT130, UT134, UT150 and UT159. The red circle encloses Ti oxide 1; green corresponds to V-Ti-oxide 1; black to V-Ti-oxide 2; the black dashed circle to V-oxide and the blue circle to V-Cr-oxide 1.

7 Mineral Species 7.1 V-Bearing Oxides 7.1.1 Ti-Oxide: Vanadium Bearing Rutile2

The most common vanadium-bearing oxide species examined in the polished thin sections studied was V-bearing rutile. There were an estimated 20 to 30 grains of this mineral in each thin section located. These grains range in size from 240 to 740 μm and did not appear to show preferential association with a particular phase. However, the majority of grains examined have exsolution of the vanadium rich phases V-Ti-oxide 1 and V-Ti-oxide 2. Ti-oxide is very dark

2 In this notation the name before the colon indicates the name given to the phase based on chemical composition, whereas the mineral name after the colon refers to the identification of the mineral as determined by analyses to follow. The mineral names in quotations indicates such identification could not be confirmed by structural methods.

21 brown to opaque in transmitted light and has a reflectance of approximately 40% in reflected light as can be seen below in the reflected light photomicrograph shown in Figure 9 with a red arrow. The green arrow indicates a pyrite grain for comparison.

Standard Arithmetic Analysis Deviation Mean (1σ) Minimum Maximum

TiO2 95.72 2.31 88.95 97.25

Nb2O5 0.829 1.15 0.204 4.51

Cr2O3 0.05 0.06 0.00 0.22

V2O3 3.08 0.95 2.00 5.97 Total 99.72 0.71 98.13 100.63

Table 4: The average, standard deviation, minimum, and maximum values of microprobe analyses of vanadium bearing Ti-oxide in thin sections UT117, UT134, UT150 and UT159. All values are reported in weight percent.

On average this species has a V2O3 content of 3.08 +/- 0.95 wt% with a range of 2.00 to 5.97 wt%. Minor amounts of Nb2O5 were also detected, ranging from 0.20 to 4.51 wt%. Only one grain examined, UT159 spot 4 analysis 7, has significant Nb2O5. The abundance of ions was averaged and the calculated mineral formula on the basis of two oxygens was

(Ti0.97V0.031Nb0.004Cr0.001)O2. A back scattered electron image (BSEI) of one grain is shown below in Figure 8 indicated by point 29. The results for analysis 29 is shown above in Table 4.

The correlation coefficient between TiO2 and V2O3 is -0.964, indicating a substitution of V for Ti.

Figure 8: BSEI of UT159 circle 1. The results for analysis 29 are in Table 4. Analysis 30 is of V-Ti-oxide 1.

Based on the mineral chemistry, the appearance in transmitted and reflected light and the identification of rutile in the suite of drill core samples, this mineral was identified as V-bearing rutile.

Figure 9: A reflected light photomicrograph of UT159 circle 1. The unknown Ti-oxide is indicated with a red arrow. For reference pyrite is indicated with a green arrow.

The significant vanadium contents found in the rutile of Green Giant are not unique. Scott et al. (2011) list compositions of rutiles in the Green Leader lode mineralization of the Kalgoorlie Goldfields. Of the data from Kalgoorlie Goldfields, the maximum vanadium weight percent reported is 2.5 wt% V2O3 and the median composition of rutiles is 1.48 wt% V2O3. These vanadium bearing grains at Green Giant are more enriched but are still of reasonable composition to confirm the identifications as V-bearing rutile.

7.1.2 V-Ti-oxide 1: “Schreyerite”

The first vanadium titanium oxide species examined in the polished thin sections studied is V-Ti- oxide 1. Four grains were examined and range in size from 200 to 700 μm. Five examples of this mineral exsolving from another were examined. V-Ti-oxide 1 is shown in Figure 8 denoted by analysis point 30 as intergrowths within rutile. Other examples of this mineral are shown in

Figures 10 and 11. In Figures 8 and 10, rutile is the major phase and V-Ti-Oxide the minor phase, whereas in Figure 11 the reverse is true. This mineral was primarily found in association with V-Rutile and V-Ti-oxide 2 and was not observed using a petrographic microscope or in hand sample.

This species has a mean V2O3 content of 34.73 +/- 1.442 wt% as determined by EMPA. The range is 31.51 to 36.57 wt % V2O3. It has a mean TiO2 content of 61.35 +/- 0.84 wt% and trace amounts of Cr2O3, Al2O3 and FeO as (Table 5).

Table 5: The arithmetic mean, standard deviation, maximum and minimum oxide compositions of vanadium titanium oxide 1 from thin sections UT117, UT134, UT150 and UT159. All results are reported in weight percent. Arithmetic Standard Oxide Mean Deviation Minimum Maximum (n=15) (1σ) TiO2 61.35 0.84 59.43 62.94 Al2O3 0.48 0.14 0.25 0.75 Cr2O3 2.26 1.41 0.23 3.97 V2O3 34.73 1.44 31.51 36.57 FeO 0.08 0.03 0.02 0.13 Total 98.96 0.34 98.07 99.28

According to the International Mineralogical Association (IMA) list of IMA approved minerals (2013), there are only three minerals which are composed exclusively of V, Ti and O: schreyerite 3+ 4+ 3+ [V 2Ti 3O9; Medenbach et al., 1976]; kyzulkumite [Ti2V O5(OH); Smyslova et al., 1981; 3+ Armbruster, 2013]; and berdesinskiite [V 2TiO5; Bernhardt et al., 1981]. Schreyerite has only been identified in five localities worldwide, berdesinskiite from three localities, and kyzulkumite from one locality (MinDat, 2013).

Shown in Table 6 are the weight percents of oxides as reported for schreyerite (Medenbach, 1976), kyzylkumite (Armbruster et al., 2013), and berdesinskiite (Bernhardt et al., 1981) alongside the average composition of V-Ti-Oxide 1. It is apparent that in terms of chemistry V- Ti-Oxide 1 is very similar in comparison to schreyerite. Two examples of schreyerite

25 morphology from the literature are shown in Figure 12. Image A is of a rutile grain with schreyerite lamellae from Kwale District, Kenya in oil immersion reflected light microscopy from Medenbach (1978). Image B is also BSEI of a rutile with schreyerite present as lamellae from Lake Baikal, Russia (Koneva 2002). These images are strikingly similar to those of V-Ti- Oxide 1, particularly to that shown in Figure 10.

Figure 10: Back Scattered Electron Image of UT117 spot 4. The scale bar represents 10 μm. Rutile was found at analyses 27 and 28, the results of which are shown in Appendix III. V-Ti-oxide 1 was examined at analyses 25 and 26, the results of which are shown in Appendix IV.

Figure 11: A BSEI of UT150 spot 1. In this grain V-Ti-Oxide 1 (analyses 17 and 18) is the major mineral and rutile (analyses 15 and 16) is the minor mineral. The results of these analyses can be seen Appendices III and IV.

The formula of V-Ti-oxide 1 was calculated on the basis of nine oxygens using the average weight percent oxide data from Table 5 and was found to be (V0.91Cr0.06Al0.02)2Ti3.02O9 which is quite similar to the formula calculated by Medenbach (1978) of (V0.93Cr0.06Al0.01)2Ti3O9.

As there is no reference Raman spectrum for schreyerite, this method cannot be used for confirmation. As no grains were found in hand sample, XRD was not undertaken. Therefore based on chemistry and habit alone, V-Ti-oxide 1 is identified as “schreyerite”.

Table 6: A comparison of the weight percent composition of type schreyerite (Medenbach, 1976), kyzylkumite (Raade, 2006) and berdesinskiite (Bernhardt et al., 1981) with that of V-Ti-Oxide 1.

V-Ti-oxide 1 Schreyerite Kyzylkumite Berdesinskiite (this study)

TiO2 61.07 66.21 34.13 61.35

Al2O3 0.43 0.06 0.76 0.481

V2O3 35.93 24.71 64.35 34.73

Cr2O3 2.23 1.72 1.39 2.263 FeO 0.10 1.37 0.00 0.081 MnO 0.00 No data 0.01 0.036 Total 99.87 94.07 100.64 98.96

7.1.3 V-Ti-Oxide 2: “Berdesinskiite”

Seven grains of V-Ti-Oxide 2 were examined, ranging in size from 60 to 250 μm. These grains were typically associated with V-Ti-Oxide 1, but also occurred independently from this mineral and with silicates. This mineral was not seen in thin section. Shown below in Figures 13, 14, and 15, are BSE images of V-Ti-Oxide 2. Figures 13 and 14 show replacement of “schreyerite” by V-Ti-Oxide 2. In Figure 14, Nb-bearing rutile, indicated with an arrow, has exsolved from “schreyerite.”

Figure 13: A BSEI of UT134 Spot 2. Analysis 8 is of V-Ti-Oxide 2 and analysis 9 is of “schreyerite”, the results of which can be seen in Appendices IV and V. The scale bar represents 10 μm.

Figure 14: A BSEI in UT159 spot 4. Analyses 41, 42 and 43 are of V-Ti-Oxide 2 and the results are in Appendix V. Analyses 44, 45 and 46 are of “schreyerite” and the results are in Appendix IV. Analysis 47 is of Nb-rich rutile and the results are in Appendix III. The scale bar represents 10 μm.

Figure 15: A BSEI of UT130 spot 6 where analyses 5 and 6 are of V-Ti-Oxide 2, with results in Appendix V. Analyses Phl-37 and Phl-36 are of vanadium bearing phlogopite with results in Appendix VII. The scale bar represents 100 μm.

The calculated arithmetic mean, standard deviation, minimum and maximum weight percent of oxides determined by EPMA on V-Ti-Oxide 2 are in Table 7. The average V2O3 content is 59.04

+/- 0.86 wt% and the average TiO2 content is 32.66 +/- 1.53 wt%. The Cr2O3 contents are highly variable, with a mean concentration of 4.19 +/- 2.05 wt%. The average of the total weight percent of the oxides was 96.80 +/- 0.41 wt% which is quite low. As there were no other oxides present than those analyzed for, as determined by wavelength dispersive spectrometry (WDS), it is likely that vanadium is present in multiple oxidation states. Calculations were performed to determine the amount of vanadium present as V2O5 and analyzed as V2O3 which would be required to raise the totals of these oxide weight percents to 100. It was determined that if approximately 18 wt% of the mineral existed as V2O5 instead of V2O3, the total weight percent of

31 oxides would equal 100. This would leave approximately 45 wt% of the mineral existing as

V2O3. These values correspond to the maximum about of vanadium which could exist as V2O5.

Table 7: The arithmetic mean, standard deviation, maximum and minimum oxide compositions of vanadium titanium oxide 2 from thin sections UT134, UT150 and UT159. All results are reported in weight percent. Arithmetic Standard Oxide Mean Deviation Minimum Maximum (n=11) (1σ) TiO2 32.66 1.53 30.83 34.85 Al2O3 0.70 0.14 0.54 0.99 Cr2O3 4.19 2.05 1.39 6.77 V2O3 59.04 0.86 55.67 62.36 FeO 0.21 0.04 0.08 0.45 MnO 0.041 0.01 0.01 0.1 Total 96.80 0.41 96.16 97.46

A comparison of this species with the three known vanadium titanium oxide species is shown below in Table 8. Based on chemistry, V-Ti-Oxide 2 is most similar to berdesinskiite; however, there are differences. For instance there is 1.4 wt% less TiO2, 5.3 wt% less V2O3, and two times more Cr2O3 (~4 wt %) in V-Ti-Oxide 2 than in type berdesinskiite. The correlation coefficient between V2O3 and Cr2O3 was calculated and was found to be -0.891 which indicates that there is some substitution of Cr2O3 for V2O3.

Table 8: comparison of schreyerite (Medenbach, 1976), kyzylkumite (Raade, 2006) and berdesinskiite (Bernhardt et al., 1981) with V-Ti-Oxide 2. All values are reported in weight percent oxide.

V-Ti-oxide 2 Schreyerite Kyzylkumite Berdesinskiite (this study)

TiO2 61.07 66.21 34.13 32.7

Al2O3 0.43 0.06 0.76 0.70

V2O3 35.93 24.71 64.35 59.00

Cr2O3 2.23 1.72 1.39 4.12 FeO 0.10 1.37 0.00 0.21 MnO 0.00 No data 0.01 0.04 MgO 0.11 No data No data No data Total 99.87 94.07 100.64 96.8

The formula calculated from the average oxide compositions on the basis of 5 oxygens is (V1.871

Al0.033Cr0.129)Ti0.97O5 or (V1.952 Al0.032Cr0.075)Ti0.952O5 for Cr poor V-Ti-Oxide 2 and (V1.77

Al0.034Cr0.193)Ti0.993O5 for Cr rich V-Ti-Oxide 2. The formula of berdesinskiite is

(V1.96Al0.03Cr0.05)Ti0.98O5 (Bernhardt et al., 1981), which is very similar to the results for V-Ti- Oxide 2.

The morphology of V-Ti-Oxide 2 (Figure 14) was also compared to that of type berdesinskiite, Figure 16 (Bernhardt et al., 1983). In Figures 14 and 16 rutile exsolution lamellae occur being exsolved from an interior region of “schreyerite” and in both images, schreyerite replacement by a berdesinskiite (Bernhardt et al., 1983).

As there is no known Raman pattern of berdesinskiite, Raman spectroscopy could not be used to confirm the identification of these grains as berdesinskiite and the grains are too small and could not be isolated to obtain XRD patterns for comparison. Therefore comparing chemistry and morphology to known minerals, V-Ti-Oxide 2 is identified as “berdesinskiite”.

7.1.4 V-Cr-Oxide: a member of the karelianite – eskolaite solid solution

Six grains of V-Cr-oxide were analyzed and were only found in thin section UT159. The grains range in size from 70 to 280 μm. All of the grains examined were adjacent to pyrrhotite. A BSEI of V-Cr-oxide is shown in Figure 17.

The calculated arithmetic mean, standard deviation, minimum and maximum weight percent of oxides determined by EMPA on V-Cr-oxide are in Table 9. The average V2O3 content of this mineral is 79.30 +/-1.02 wt% with an average Cr2O3 content of 16.02 +/- 0.64 wt%. It should be noted that the totals for these analyses are low, averaging 95.81 +/- 0.34 wt%, but the cause of this is not known. No other elements were recognized by WDS and this is not a hydrous phase. It is again possible that vanadium exists in multiple oxidation states in this mineral. It was calculated that in order to reach a total of the weight percent of oxides of 100 percent with only vanadium existing in multiple oxidation states, approximately 60 wt% of the mineral would be comprised of V2O3 and 24 wt% would be comprised of V2O5.

Table 9: The arithmetic mean, standard deviation, maximum and minimum oxide compositions of vanadium chromium oxide from thin section UT159. All results are reported in weight percent oxide. Standard Arithmetic Oxide Deviation Minimum Maximum Mean (1σ) TiO2 0.12 0.11 0.02 0.30 Al2O3 0.09 0.12 0.00 0.34 Cr2O3 16.02 0.64 14.65 16.73 V2O3 79.30 1.02 77.63 80.96 FeO 0.24 0.13 0.12 0.53 MnO 0.04 0.01 0.02 0.06 Total 95.81 0.34 95.11 96.18

Figure 3: A BSEI of UT159 spot 4. Analyses 48, 49, 50, 51, 52 and 53 are of V-Cr-Oxide, the results of which can be seen in Appendix VI. The scale bar represents 100 μm.

A correlation coefficient of -0.906 was calculated for V2O3 and Cr2O3 indicating mutual of these two oxides. It was shown by Höller and Stumpfl (1995) that a solid solution exists between karelianite (V2O3; Long et al., 1963) and eskolaite (Cr2O3; Kouvo et al., 1958) in the rocks of Rampura Agucha, India. This solid solution also exists in the samples from Lake Baikal, Russia (Koneva 2002). A diagram with the compositions of the samples in the karelianite – eskolaite solid solution from Lake Baikal and Rampura Agucha is in Figure 18 (after Koneva, 2002). The average formula calculated on the basis of three oxygens for V-Cr-Oxide from Green Giant is

V1.659Cr0.330O3 and the average composition of V-Cr-Oxide is indicated by the red circle in Figure 19.

Figure 4: Eskolaite – karelianite solid solution series on a Cr2O3 – V2O3 – Fe2O3 diagram after Koneva (2002). The red circle indicates the average composition of V-Cr-oxide from the Green Giant deposit.

Based on chemistry, V-Cr-Oxide is classified as a member of the solid solution series karelianite – eskolaite, closer to the karelianite (V) end-member (~80 mol% karelianite). As shown in the following section, near end member karelianite is also likely present at Green Giant. However, due to the small grain size, this mineral could not be isolated for identificationusing XRD.

7.1.5 V-oxide: “Karelianite”

Five grains of V-oxide were examined, ranging in size from 25 to 250 μm in thin sections UT130 and UT150. A BSEI of V-oxide, indicated by analyses 21 and 24 in Figure 19. This mineral was only identified adjacent to pyrrhotite.

Figure 19: BSEI of UT150 spot 5 where analyses 21 and 24 are of V-oxide and the results of EMPA in Table 10. Analysis 23 is of V bearing rutile and the results of EMPA in Appendix III. Analysis 22 is of “berdesinskiite” and the results of EMPA are in Appendix V.

The average V2O3 content of V-oxide is 91.3 +/- 0.76 wt% (Table 10). Cr2O3 contents average 2.15 +/- 0.87 wt%.

Table 10: Microprobe analyses of vanadium oxide from thin sections UT130 and UT150. All data are reported in weight percent.

UT130 UT150 UT150 UT150 UT150 1-3 1-5 1-6 5-1 5-4 Standard Deviation Analysis 1 19 20 21 24 Average (1σ)

TiO2 0.04 0.57 0.47 0.54 0.51 0.42 0.19 Al2O3 0.20 0.31 0.32 0.15 0.37 0.27 0.08 Cr2O3 0.42 2.60 2.55 2.60 2.59 2.15 0.87 V2O3 92.69 90.82 91.28 90.50 91.06 91.3 0.76 FeO 0.39 0.42 0.44 0.16 0.19 0.32 0.05 Total 93.77 94.77 95.08 93.99 94.72 94.5 0.5

It is noted that the totals of EPMA are low. The possible causes of this are the existence of vanadium in more than one oxidation state, or of this being a hydrous phase. According to the IMA list of approved minerals (International Mineralogical Association, 2013) there are two minerals which have vanadium oxide as the sole constituent, karelianite (V2O3; Long et al., 1963) and oxyvanite (V3O5; Reznitsky et al., 2009). The chemical compositions of these two minerals are compared to that of V-oxide in Table 11. V-oxide is most similar in composition to karelianite. It was calculated that in order to raise the total oxide weight percent to 100, assuming that only vanadium occurs in multiple oxidation states, approximately 36 wt% of the mineral would exist as V2O5 and the remaining approximately 63 wt% would exist as V2O3.

Based on the identification of a member of the karelianite – eskolaite solid solution above in section 7.1.4, and the similarity in composition to karelianite shown in Table 11, this mineral is likely to be karelianite. However, as this phase was only located in thin section and was unable to be isolated, no powder XRD pattern could be gathered. As well, no reference Raman pattern exists. Therefore this identification cannot be confirmed by structural methods.

Table 11: comparison of Karelianite (Long et al., 1963), Oxyvanite (Reznitsky et al., 2009) and average V-oxide compositions. All values are reported in weight percent. Where blank, no data were reported. Karelianite Oxyvanite V-Oxide (Long et al., 1963) (Reznitsky et al., 2009) TiO2 14.04 0.42 Al2O3 0.01 0.27 Cr2O3 3.7 10.76 2.15 V2O3 92.9 73.13 91.3 FeO 4.1 (Fe2O3) 0.04 (Fe2O3) 0.32 MnO 1.5 0.01 MgO 0.02 Total 102.2 100.03 94.5

7.2 V-Bearing Sulphides

7.2.1 V-sulphide 1: Unknown

Five grains of V-Sulphide 1 were analyzed in thin section UT150 ranging in size from 100 to 250 μm. This mineral was always found with V-rich pyrrhotite exsolving from it, as can be seen in Figure and compositions of this mineral are in Table 12.

There are no IMA approved V-Fe-sulphide minerals (International Mineralogical Association,

2013). There is however one vanadium sulphide, patrónite (VS4; Hewett, 1906). The Fe-V-S minerals present at Green Giant, as well as patrónite, have been plotted on a ternary diagram as shown in Figure 20. It can be seen that neither V-sulphide 1 nor any of the other V-Fe-sulphide minerals found at Green Giant are similar in composition to patrónite. However, there appears to be a trend in compositional change from V-sulphide 2, through V-sulphide 1 and up to pyrrhotite. A correlation coefficient was calculated for V and Fe and was found to be -0.972, indicating that V is substituting for iron.

As the grains of V-Sulphide 1 were unable to be isolated, it is not possible to gather X-ray diffraction data and there are no known minerals which resemble this species in composition. Therefore this species remains unidentified.

Table 12: Microprobe analyses of V-Sulphide 1. All analyses are from thin section UT150 and all values are reported in mass percent.

Sample UT150 UT150 UT150 UT150 UT150 UT150 Name 3-2 2-2 1-3 1-4 6-1 7-1 Standard Deviation Analysis 9 11 14 15 17 21 Average (1σ) V 18.50 19.67 20.24 20.31 21.03 18.84 19.77 0.87 Cr 0.27 0.27 0.16 0.17 0.00 0.21 0.18 0.09 S 43.96 44.37 44.33 44.05 44.54 43.96 44.20 0.22 Fe 36.45 35.00 34.68 34.41 33.74 35.48 34.96 0.85 Total 99.19 99.30 99.38 98.92 99.23 98.49 99.09 0.30

Figure 20: A Fe-V-S diagram with the vanadium bearing sulphide species present at green giant plotted, as well as patrónite [calculated from synthetic composition (Hewett, 1906)].

Figure 21: A BSEI of UT150 spot 1 where analyses 14 and 15 are of V-Sulphide 1. The results of these analyses in Table 12. Analyses 12 and 13 correspond to V-bearing pyrrhotite and the results in Table 14. The scale bar represents 100 μm.

7.2.2 V-Sulphide 2: Unknown

Five grains of V-sulphide 2 were analyzed in thin section UT130, ranging in size from 25 to 150 μm. These grains were found adjacent to V-pyrrhotite and V-silicate 1. The average vanadium content of V-Sulphide 2 is 33.29 wt% +/- 0.87 wt% (Table 13). Iron contents average 20.17 +/- 1.18 wt% and sulphur contents average 44.48 +/- 0.14 wt%. The correlation coefficient for V and Fe is -0.993, indicating that vanadium substitutes for iron.

Figure 22 depicts a BSEI of V-Sulphide 2. Planar fractures are visible in the image and this species occurs in association with pyrrhotite, “karelianite,” and V-silicate 1. It appears that V- pyrrhotite exsolved from V-sulphide and displaced V-silicate 1. As all that is known about this

41 mineral is the chemistry and habit, and there are no known V-Fe-Sulphide species in existence, this phase was not identified.

Table 13: Microprobe analyses of V-Sulphide 2. All analyses are from thin section UT130 and all values are reported in mass percent.

Sample UT130 UT130 UT130 UT130 UT130 UT130 UT130 Name 1-1 1-2 1-3 1-4 2-1 2-2 2-3 Standard Deviation Analysis 1 2 3 4 5 6 7 Avg. (1σ) V 34.29 33.33 34.11 34.21 32.48 32.05 32.54 33.29 0.87 Cr 0.13 0.11 0.15 0.00 0.09 0.08 0.07 0.09 0.04 S 44.63 44.54 44.40 44.60 44.62 44.29 44.29 44.48 0.14 Mn 0.06 0.05 0.04 0.06 0.04 0.05 0.04 0.05 0.01 Fe 19.02 20.08 18.79 18.96 21.25 21.76 21.33 20.17 1.18 Total 98.12 98.09 97.49 97.80 98.47 98.23 98.28 98.07 0.30

Figure 23: Back Scattered Electron Image of UT130 spot 1 bearing V-Sulphide 2 indicated by points 1, 2, 3 and 4. These analyses are in Table 13. Also present in this region is “karelianite” and V-silicate 1. The scale bar shown represents 10 μm.

7.2.3 Fe-V-Sulphide 1: V-bearing Pyrrhotite

Eight grains of Fe-V-sulphide were analyzed, ranging in size from 100 to 500 μm. Grains of Fe- V-sulphide were found adjacent to V-oxide, berdesinskiite, and exsolving from V-sulphide 1 (e.g. Figures 19 and 22). The results of EPMA of Fe-V-sulphide 1, including average, standard deviation, minimum and maximum values are in Table 14. The average vanadium content is 1.87 +/- 0.98 wt%. The average iron content of Fe-V-sulphide 1 is 58.66 +/- 0.97 wt% and the average sulphur content is 39.88 +/- 0.25 wt%. The iron and sulphur contents of Fe-V-sulphide 1 almost overlap pyrrhotite, indicated by a yellow triangle (Figure 20). Although there are no known Fe-V-sulphides, vanadium can substitute for iron in some minerals. The correlation

43 coefficient for V and Fe was calculated and determined to be -0.987, indicating that vanadium is substituting for iron. Based on chemistry and the identification of pyrrhotite in hand sample, this mineral has been identified as pyrrhotite bearing up to 2.99 wt% vanadium.

Table 14: Microprobe analyses of Fe-V-Sulphide 1. All analyses are from thin section UT150; values are reported in weight percent. Standard Minimum Maximum Deviation Avg. (1σ) V 1.87 0.98 0.19 2.99 Cr 0.13 0.04 0.05 0.19 S 39.88 0.25 39.47 40.31 Fe 58.66 0.97 57.66 60.30 Total 100.54 0.31 99.99 101.06

7.2.4 Fe-V-Sulphide 2: Vanadium bearing pyrite

One grain of Fe-V-sulphide 2 was examined in thin section UT150, measuring 50 μm. This was the only grain of this mineral found and it was adjacent to a silicate which contained a grain of V-sulphide 1. The average vanadium content of Fe-V-Sulphide 2 is 0.22 +/- 0.05 wt%, the average iron content, 46.29 +/- 0.04 wt% and the average sulphur content 53.53 +/- 0.01 wt%. For comparison, the composition of end member pyrite is indicated in Figure 22 with an open circle and the composition of Fe-V-Sulphide 2 with an orange square. It is apparent that the compositions overlap. Therefore, based on the chemical similarity to pyrite and the identification of pyrite by XRD, Fe-V-Sulphide 2 is identified as pyrite containing up to 0.27 wt% V.

Table 15: Microprobe analyses of Fe-V-Sulphide 2 from thin sections UT150 and UT159. Values are reported in weight percent.

UT150 UT150 6-2 6-3 Standard Deviation Analysis 18 19 Average (1σ) V 0.27 0.16 0.22 0.05 S 53.54 53.52 53.53 0.01 Fe 46.33 46.25 46.29 0.04 Total 100.23 99.96 100.09 0.14

7.3 V-silicates

7.3.1 V-silicate 1: Unknown

Two vanadium-bearing silicates were identified in the polished thin sections using EPMA. Two grains were analyzed of V-silicate 1 in thin section UT130, which has an average V2O3 content of 61.39 wt%, average SiO2 content of 27.72 wt% and average Al2O3 content of 1.23 wt% (Table 16).

A BSE image showing its position between grains of V-Sulphide 2 and V-pyrrhotite is in Figure 22. The totals determined for this mineral are quite low, averaging 90.99 wt%. No elements were present under WDS examination that were not analyzed for and it is possible that this is a hydrous phase. There are no IMA approved minerals which have this composition (International Mineralogical Association, 2013).

So this phase was only found in thin section and XRD was not used, it is possible that this is an amorphous phase. Since no identifications could be made, this phase remains an unknown.

Table 16: The results of EPMA of V-Silicate 1. All values are reported in weight percent. UT130 1-1 UT130 1-2 Analysis 1 2 Average

SiO2 27.54 27.90 27.72

Al2O3 0.96 1.50 1.23

Cr2O3 0.14 0.00 0.07

V2O3 61.86 60.91 61.39 FeO 0.41 0.13 0.27 MnO 0.00 0.04 0.02 CaO 0.01 0.03 0.02

Na2O 0.06 0.06 0.06

K2O 0.06 0.14 0.10 F 0.09 0.10 0.09 Total 91.14 90.85 90.99

7.3.2 V-Silicate 2: V-phlogopite

Sixty-two analyses of V-silicate 2 in 43 grains were performed and the results of EPMA of V- Silicate 2 are in Appendix V. V-silicate 2 ranges in size from 150 to 450 μm and has average compositions as shown below in Table 17. Standard Deviation Minimum Maximum Oxide Average (1σ)

SiO2 38.99 0.57 37.87 40.18

Al2O3 17.46 1.23 15.92 18.88

TiO2 2.30 0.77 0.16 3.44

Cr2O3 0.36 0.39 0.00 1.43

V2O3 4.87 2.27 1.48 9.7 FeO 0.17 0.09 0.00 0.40 MnO 0.08 0.06 0.01 0.28 MgO 20.14 1.58 16.71 22.4 BaO 0.65 0.60 0.01 2.12

Na2O 0.11 0.03 0.06 0.29

K2O 9.93 0.28 0.06 10.28 F 0.58 0.18 0.13 0.93

H2O 3.9 0.39 1.41 4.47 Total 99.33 0.81 96.22 100.57

Table 17: The average, standard deviation (1σ), maximum and medium compositions of V- silicate 2.

A back scattered electron image of V-silicate 2 is in Figure 15 indicated by analyses phl-36 and phl-37 where V-silicate 2 has a platy habit. Transmitted light photomicrographs of UT130 spot 6 are in Figure 23. Based on the appearance in transmitted light and the identifications of minerals in hand sample, V-silicate 2 is identified as vanadium-bearing phlogopite with an average vanadium content of 4.87 wt% V2O3. Correlation coefficients were calculated and the oxides 2 with the strongest R value with V2O3 were Cr2O3 at -0.827 and MgO at -0.867, indicating substitution is occurring between V2O3 and these oxides.

There is a range in vanadium content in the vanadium bearing phlogopites (1.48 to 9.69 wt%

V2O3). Figure 24 depicts a histogram of the vanadium contents of the phlogopites. There is a bimodal distribution with one peak centered on 2.72 weight percent and one peak centered on

7.13 weight percent. There is a random distribution of high and low concentrations of V2O3 present in each of the thin sections; therefore it is not a spatial relationship. The cause of the bimodal distribution is unknown at this time.

Histogram of wt% V2O3 in Phlogopites

y c

n 8

e r

F 6

0 0 2 4 6 8 10 % V2O3

Figure 24: The determined V2O3 content of phlogopites

7.4 Summary table

In Table 18 is a summary of the vanadium bearing minerals identified at Green Giant.

Table 18: Summary table of the vanadium bearing minerals identified at Green Giant

Average Vanadium Identification Mineral Type Content Associated phases method (wt%) Vanadium Bearing oxide 2.88 XRD, EMPA exsolved “schreyerite” Rutile

“Schreyerite” oxide 34.73 EMPA exsolved from rutile

“Berdesinskiite” oxide 59.00 EMPA replacing “schreyerite” Karelianite - pyrrhotite and Eskolaite Solid oxide 79.3 EMPA alabandite Solution “berdesinskiite,” "Karelianite" oxide 91.3 EMPA V bearing rutile

V-Sulphide 1 sulphide 19.77 - V-bearing pyrrhotite pyrrhotite V-Sulphide 2 sulphide 33.29 - "karelianite", V-silicate 1 other vanadium bearing V-Bearing Pyrrhotite sulphide 1.87 XRD, EMPA sulphides

other vanadium bearing V-Bearing Pyrite sulphide 0.22 XRD, EMPA sulphides

"karelianite" V-Silicate 1 silicate 61.39 - V-Sulphide 1

V-Phlogopite silicate 7.63 XRD, EMPA silicates

silicate, XRD, Dravite tourmaline Minor3 silicates SEM-EDS group silicate, garnet 18.33 Goldmanite XRD marbles group (Moench, 1964)

XRD, Actinolite silicate 0.2853 silicates SEM-EDS silicate, XRD, Uvite tourmaline Minor4 silicates SEM-EDS group XRD, V-Muscovite silicate 2.272 silicates SEM-EDS

3 SEM results 4 No quantitative analyses performed, however amount of vanadium present is minor

7.5 Comparison to Lake Baikal, Russia

There are several similarities between the Green Giant deposit and the high-grade metamorphic rocks of the Olkhon series of the Lake Baikal area, Russia. The rocks of the western Lake Baikal coast are a folded sequence of interlayered metasediments, including quartzites, basic schists, marbles and gneisses which have been metamorphosed to upper amphibolite and granulite facies (Koneva, 2002). The rocks types hosting the Green Giant prospects are similar to those at Lake Baikal and have also undergone upper amphibolite to granulite facies metamorphism. The rocks at Lake Baikal have high background levels of Cr and V and few modally significant concentrations of Cr-V bearing minerals have been reported and are irregularly distributed in carbonate and quartzitic rocks (Koneva, 2002). The distribution of V-bearing minerals at the Green Giant deposit is similar, although highl concentrations of Cr have not been documented.

The principal Cr-V-bearing minerals of Lake Baikal area are silicates (muscovite, diopside, tourmaline and garnet) and spinel, with less Cr-V-oxides in graphitic schists occurring in close association with rutile. The associations of Cr-V- oxides with rutile, as well as the presence of V- bearing muscovite, V-bearing tourmaline, and V-bearing garnet, as well as graphite, sillimanite, and rutile at Lake Baikal are similar to the mineral associations at Green Giant. The Cr-V-oxides at Lake Baikal include schreyerite, karelianite, eskolaite, berdesinskiite, vourelainenite 2+ 3+ 2+ (Mn V 2O4), manganochromite (Mn Cr2O4), and olkhonskite, (Cr2Ti3O9) (Koneva, 2002). The V-Ti-oxides are equivalent to those at Green Giant. However, the other oxides identified at Lake Baikal are more chromium and manganese rich than those at the Green Giant property. Rutiles from the two properties have between 1.00 and 3.86 wt % V2O3. However, like the other oxides present, the Lake Baikal rutiles have higher Cr2O3 contents (0.46 to 1.93 wt %). At Green Giant the average is 0.07 wt % Cr2O3. The similarities in petrographic description and mineralogy suggest that the mineral identifications made in this study are correct and that similar processes that formed the Olkhon series of Lake Baikal, formed Green Giant. At Lake Baikal schreyerite was most likely exsolved from V-Cr oversaturated rutile during retrograde metamorphism (Koneva, 2002), which, based on similar mineralogy and morphology, is therefore also the likely method of formation at Green Giant. In the Olkhon series it was speculated by Koneva (2002) that the Cr and V were preferentially associated with organic matter and clay minerals in

51 precursor sediments. During prograde metamorphism these elements have extremely low mobility and original sedimentary variations resulted in large variations in phase chemistry (Koneva, 2002). This is likely also the cause of vanadium enrichment and the formation of V-Ti- oxides at the Energizer Resources Inc. property.

Chapter 5 Vanadium Reconciliation

The goal of the mineral identification study was to determine the host minerals of vanadium. To confirm that the minerals identified are in fact those responsible for the whole rock concentrations of V observed at Green Giant, a reconciliation of vanadium data was performed.

8 Methods

X-Ray Fluorescence (XRF) analysis was performed for Energizer Resources Inc. by Mintek, located in Johannesburg, South Africa (Energizer Resources Inc., 2011). To confirm these results, and to obtain data for the specific core intervals examined in this study, the quarter core samples comprising the working set were analyzed at the University of Toronto and compared to those collected by Mintek. XRF pellets were produced as a 1 to 2 mm thick pressed disc on a borax substrate, producing a final disc approximately one centimetre thick. A Philips PW 2404 XRF was used with a 4 kW rhodium tube. Samples were calibrated using international reference materials and synthetic standards which were matched to the unknowns in both composition and grain size. Vanadium specifically was measured using the vanadium Kα x-ray peak and was corrected for the overlap of 6.4 % of the titanium Kβ x-ray.

Then, as the most abundant vanadium bearing mineral identified was phlogopite, it was tested if, for the estimated volume percent of phlogopite in polished thin sections UT130, UT134, UT150 and UT159, this mineral alone contributes substantially to the vanadium concentration found via XRF, or if trace minerals contribute significantly to this total.

9 Results

The results of XRF analyses at the University of Toronto are in Appendix IX. The results of calculations to determine the contribution of vanadium bearing phlogopite to the bulk rock V concentration are shown below in Table 19. As this did not account for the majority of the vanadium in the case of UT150, further calculations were performed to determine the contribution of vanadium bearing oxides. As it is very difficult to determine the exact abundance of trace minerals, particularly those with no distinguishing features, the oxide abundance

53 required to account for the remainder of the vanadium concentration was calculated. The results of these calculations are shown below in Table 20.

Phlogopite V in TS due to Vanadium abundance phlogopite XRF V data accounted for % ppm ppm % UT130 15 5421.926 6506.3 83.3 UT134 12 4337.541 5298 81.9 UT150 7 2530.232 5176 48.9 UT159 10 3614.617 5103 70.8

Table 19: Calculations to determine the contribution of vanadium to the bulk rock vanadium content for thin sections UT130, UT134, UT150 and UT159.

Required Average Vanadium Sum of oxide V in Thin XRF V accounted contributions abundance Section data for % ppm ppm % % UT130 0.155 1036.614 6506.3 15.9324659 99.27 UT134 0.15 1003.175 5298 18.9349729 100.81 UT150 0.4 2675.133 5176 51.6834037 100.57 UT159 0.22 1471.323 5103 28.8325129 99.67

Table 20: The results of calculations performed to determine the abundance of vanadium oxides required to account for the remainder of the bulk vanadium concentration in thin sections UT130, UT134, UT150, and UT159. The sum of the contributions from the vanadium oxides and vanadium bearing phlogopite is shown in the final column.

10 Discussion

Based on data in Table 19, it is concluded that phlogopite accounts for 49 to 83 percent of the bulk rock vanadium abundance. This is based on several assumptions: first that the material examined by XRF was representative of the material found at this location and depth; second

54 that the thin section examined to determine the phlogopite abundance is representative of the material examined by XRF. The abundance of phlogopite was determined by visual estimation, this value has the potential for uncertainty. The vanadium content of phlogopite used for the calculation was the average value of vanadium found from the phlogopite electron microprobe analyses. As there is large variation in these vanadium abundances, as well as a bimodal distribution of V content, this vanadium value used was only an approximation. Densities were calculated for representative rock samples of the thin sections examined and the densities were averaged to account for variation. Due to these assumptions and approximations, the contribution of phlogopite to the vanadium abundance can only be examined qualitatively and is shown here to be substantial.

Since the phlogopite abundances did not account for all of the vanadium present, it was then determined what the required abundance of the identified vanadium oxides would be in order to explain the remainder of the concentration found by XRF. For this calculation it was assumed that equal amounts of the identified vanadium oxides exist in each of the thin sections. The mean of the average concentrations of V2O3 from the identified vanadium oxides was used, as well as the mean of the densities reported in the Handbook of Mineralogy (2013) for each species. In Table 20 the required abundances of vanadium bearing oxides required to account for the remaining bulk rock V concentration are calculated to be very minor, between 0.15 and 0.4 %. Since other vanadium bearing phases exist in the rocks, such as vanadium bearing sulphides, tourmalines and garnets, which contribute to the total V concentration, the vanadium bearing oxides likely occur in a lower abundance than that calculated here. However this demonstrates how minor a concentration of vanadium bearing oxides is required to produce a high V concentration.

Chapter 6 Conclusion

As was determined through SEM-EDS, XRD, Raman Spectroscopy, and EMPA, the mineral phases present which host vanadium in order of increasing vanadium content are: pyrite, actinolite, dravite, uvite, pyrrhotite, muscovite, rutile, phlogopite, goldmanite, V-sulphide 1, V- sulphide 2, “schreyerite”, “berdesinskiite”, V-silicate 1, karelianite – eskolaite solid solution, and “karelianite.” The petrology and minerals identified are similar to those described by Koneva (2002) at Lake Baikal, Russia, indicating that Green Giant is not unique.

Based on calculations in Chapter 5, it is concluded that phlogopite is the primary vanadium host in the Green Giant deposit. However, vanadium bearing oxides contribute substantially to the V concentration even when the abundance of these oxides is in trace amounts. Therefore it would useful to locate these vanadium bearing oxides in higher concentrations. In order to accomplish this, fO2 – pH diagrams should be used to determine the region of stability for these minerals which would help to locate layers in the deposit rich in this material.

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Appendix I Vanadium Concentrations as Provided by Energizer Resources Inc.

Vanadium Concentrations in Manga (M-87) 1.40

1.20

1.00

0.80

% V2O5 % 0.60

0.40

0.20

0.00

5.00

15.50 26.00 36.50 47.00 57.50 68.00 78.50 89.00 99.50

215.00 225.50 110.00 120.50 131.00 141.50 152.00 162.50 173.00 183.50 194.00 204.50 236.00 246.50 257.00 267.50 278.00 288.50 299.00 Depth Down Core (m)

Figure 25: Vanadium concentration with depth in drill core M-87; based on data provided by Energizer Resources Inc.

Vanadium Concentrations in Mainty (K-02) 0.90 0.80 0.70

0.60 0.50 0.40 % V2O5 % 0.30 0.20 0.10

0.00

2.00 9.50

17.00 24.50 32.00 39.50 47.00 54.50 62.00 69.50 77.00 84.50 92.00 99.50

144.50 224.00 107.00 114.50 122.00 129.50 137.00 153.50 161.00 179.00 186.50 194.00 201.50 209.00 216.50 231.50 Depth Down Core (m)

Figure 26: Vanadium concentrations with depth in Mainty core K-02; based on data provided by Energizer Resources Inc.

Vanadium Concentrations in Jaky (J-07) 0.8

0.7

0.6

0.5

0.4 % V2O5 % 0.3

0.2

0.1

3.50

14.10 21.50 31.30 41.00 51.50 62.00 72.50 83.00 93.50

237.50 104.00 114.50 125.00 135.50 144.50 155.00 165.50 176.00 185.00 195.50 205.40 213.50 219.50 230.00 248.00 258.50 269.00 276.50 Depth Down Core (m)

Figure 27: Vanadium concentration with depth in Jaky core J-07; based on data provided by Energizer Resources Inc.

Appendix II Mineral Identifications Performed at the Royal Ontario Museum

Depth Mineral ID Sample Deposit Colour Diaphaneity lustre habit SEM elements ID (m) # Method O, Na, Mg, Al, K, Si, Ca, 1 green translucent vitreous massive dravite R, SX V,Ti 2 colourless transparent vitreous massive Si, O, Ca, P quartz & apatite R UT-11- Manga 241 3 grey opaque metallic flakes C graphite R 1 4 bronze opaque metallic massive Fe, S, O pyrite R 5 grey translucent vitreous massive Si, O quartz R 6 brown translucent pearly platy Si, Al, Mg, O, K, V, Ti phlogopite SX pale green montmorillonite, 1 opaque greasy fibrous Si, Al, Ca, Mg, O, Fe SX yellow Ca UT-11- yellow Manga 140 2 opaque metallic massive Fe, S pyrite R 2 bronze 3 white opaque dull flakey Si, Al, O kaolinite SX Micro- 1 white opaque dull Si, Al, Mg, O, Fe, Ca, K calcite R crystalline Micro- Si, Al, Mg, O, K, Na, Fe, UT-11- 2 green opaque dull Can’t isolate Manga 146 crystalline Ca 05 3 bronze opaque metallic massive pyrite R 4 dark grey opaque dull flakey graphite R 5 white opaque dull powdery quartz SX

Depth Mineral ID Sample Deposit Colour Diaphaneity Lustre Habit SEM elements ID (m) # Method

1 blue opaque dull massive Si, Al, Mg, O, Ca, Fe bentonite SX UT-11- Manga 162 15 2 white opaque vitreous massive calcite R, SX

3 pale bronze opaque metallic platy pyrite R UT-11- microcrystal Manga 168 1 brown opaque submetallic O, Al, Mg, O, Ca, Fe titanite SX 18 line

1 blue opaque dull crusts O, Al, Si, Ca, (Ti/Fe) no ID from R, PX UT-11- Manga 172 22 Gmelinite-Ca white 5 2 opaque dull crusts Si, Al, O, Ca, K, Na (Ra) Chabazite- SX yellow Ca (Sx)

3 pale red translucent vitreous massive Si, Al, Mg, Ca, O pyrope SX Si, Al, O, Mg, Ca, Na, Ti, kaolinite + 4 white opaque dull powdery SX Fe anorthite 5 green black opaque vitreous platy O, Si, Al, Mg, K, Ti, Fe hydrobiotite SX

5 Identified by different methods as Chabazite-Ca and Gmelinite-Ca. Potassium in sample indicate Chabazite-Ca is the proper identification.

Depth Mineral ID Sample Deposit Colour Diaphaneity Lustre Habit SEM elements ID (m) # Method wine hematite + 1 opaque dull crusts O, Al, Si, Ca, Fe R colour orthoclase powder kaolinite + 3 opaque dull massive O, Mg, Al, Si, Ca SX UT-11- blue graphite Manga 174 23 microcrysta 4 green opaque greasy O, Mg, Al, Si, S, Ca, Fe hydrobiotite SX lline 5 white translucent vitreous fibrous O, Si, Mg, Al, Ca montmorillonite SX

2 pale blue opaque dull matrix O, Al, Si, Ca, Fe (Na, Mg) kaolinite SX UT-11- Manga 176 24 golden Semi- 3 opaque massive O, Al, Si, Ca quartz + anorthite SX yellow vitreous hematite, 1 pinkish red opaque vitreous massive O, Al, Si, K graphite, R orthoclase UT-11- Manga 180 rotten 27 2 opaque dull massive O, Al, Si, Fe, Ca, Na Can’t isolate green yellow 3 translucent pearly platey O, S, Ca, Al, Si, Fe Can’t isolate green 6 1 green transparent vitreous granular O, Al, Si, Ca, V goldmanite R, SX vanadian 2 grey green opaque metallic blades O, Mg, Al, Si, K, V SX muscovite UT-11- Manga 188 dodecahedr 29 3 orange opaque dull O, Mg, Al, Si, S, Ca, V, Fe amorphous SX ons

4 brown opaque waxy platy O, Mg, Al, Si, K, Ti, V, Fe amorphous SX

6 Chemistry matches goldmannite. Crystal structure is same for uvarovite and goldmannite. Raman and powder spectra are also the same for these minerals, therefore based on the presence of a large quantity of vanadium, this mineral is identified as goldmannite.

Depth Mineral Sample Deposit Colour Diaphaneity Lustre Habit SEM elements ID (m) # ID Method O, Mg, Al, Fe, Si, Ca, V, 1 green translucent waxy platy Actinolite SX UT-11- Ti Manga 195 32 2 white opaque greasy platy O, Mg, Al, Si talc + muscovite SX 3 brown translucent vitreous platy O, Mg, Ak, Si, K, Mn, Fe biotite SX UT-11- Manga 220 1 bronze opaque metallic massive S, Fe pyrite R 35 O, Mg, Al, Si, Na, S, Ca, 1 green translucent vitreous massive dravite R V 2 grey transparent pearly plates O, Mg, Al, Si, K muscovite SX UT-11- Manga 223 Semi- rhodochrosite- 36 3 black opaque dull Mn, Fe, Ca SX botryoidal siderite series 4 black opaque dull massive O, Ti Rutile SX UT-11- Manga 258 1 bronze opaque metallic massive Fe, S pyrite R 40 UT-11- 1 silver opaque metallic massive S, Mn alabandite SX Manga 287 43 2 bronze opaque metallic massive S, Fe pyrrhotite SX UT-11- Manga 290 1 white opaque pearly needles O, Al, Si, Ca, Mn, K, Na laumontite SX 46 1 brown transparent pearly platey Si, Mg, O, K, Ti, K, V, Mn phlogopite R UT-11- Manga 294 2 green opaque pearly flakey S, Fe, O, Cu pyrite SX 49 silver 3 opaque metallic massive Fe, S pyrite Chem yellow

Depth Mineral Sample Deposit Colour Diaphaneity Lustre Habit SEM elements ID (m) # ID Method 1 white opaque dull needles O, Mg, Al, Si, Ca, Fe laumontite R 2 green transparent vitreous massive O, Al, Si dravite R UT-11- Manga 298 51 3 bronze opaque metallic flakey Fe, S pyrite R 4 red brown opaque dull platy Si, Al, Mg, O, Fe amorphous SX 5 black opaque dull coating O, Mg, Si, Al, Fe, Mn clinochlore SX red to pale 1 transparent vitreous equant O, Fe, Mg, Ca, Si siderite R, SX yellow UT-11- Mainty 80 56 2 white opaque dull powder Si, O, Al, K, Fe amorphous SX hematite + 3 grey opaque metallic massive Fe, O, Si, Al R feldspar Semi- siderite and 1 grey opaque dull O, Si, Al, Fe, Mg, Ca R, Sx UT-11- botryoidal hematite Mainty 88 60 2 yellow opaque metallic massive S, Fe, O pyrite Chem 3 white translucent vitreous massive Si, O quartz Chem 1 yellow translucent dull bladed O, Al, Si, Mg, Fe amorphous Sx UT-11- Mainty 90 marcasite and 61 2 iridescent opaque metallic mottled S, Fe, O SX pyrite siderite- semi UT-11- 1 red opaque vitreous O, Fe, Mg, Ca, Mn, Si rhodochrosite R Mainty 94 columnar 63 series 2 yellow opaque metallic plates S, Fe, O, Si pyrite R

Depth Mineral Sample Deposit Colour Diaphaneity Lustre Habit SEM elements ID (m) # ID Method 1 blue opaque pearly mica O, Si, Mg, Al, K, Fe, Ti phlogopite R

UT-11- 2 white translucent vitreous granular Si, O/ Si, O, Al, Mg, K quartz, phlogopite Chem Mainty 96 64 augite, could not 3 brown opaque dull equant O, Si, Al, Mg, Fe, Ca find any to R confirm by XRD UT-11- golden Mainty 98 1 transparent vitreous small xstls siderite eye 65 orange

UT-11- 1 red translucent vitreous massive O, Si, Al, Mg, Fe, Ca pyrope R, Sx Mainty 102 67 2 brown translucent vitreous blades Si, O, Mg, Al, K, Ti, V, Fe phlogopite Sx 2 cream opaque dull blades Si, Mg, Al, K, Ti, Fe, O muscovite eye UT-11- Mainty 106 eye, 69 3 green translucent pearly plates Mg, O, Si, Al, K muscovite chem 1 green translucent pearly plates O, Al, Si, Mg, K, V muscovite R coating on white 3 red opaque waxy plates Si, Al, Fe, Mg, O opaque, cant UT-11- Mainty 110 isolate 71 4 white transparent vitreous fibrous O, S, Ca gypsum R, SX 5 white opaque dull spheres O, S, Ca gypsum R 2 orange transparent vitreous crystals Fe, Ca, Mn, Fe siderite R 7 UT-11- 1 reddish pink opaque dull massive O, Si, Al, Mg, Fe, K, S, Na anatase/qtz +hm R Mainty 120 75 8 2 silver blue opaque metallic plates Mo, S molybdenite R

7 The minerals are intergrown and fine grained. Raman spectra were present for both minerals and it was not possible to isolate for XRD 8 It was not possible to distinguish the material with a Raman spectra matching molybdenite from graphite and therefore XRD was not performed.

Depth Mineral Sample Deposit Colour Diaphaneity Lustre Habit SEM elements ID (m) # ID Method hematite 1 salmon red opaque dull massive Fe, O; Si, O Chem UT-11- intergrown w quartz Mainty 137 83 peacock V-muscovite w up SX, 2 opaque vitreous platy O, Si, Al, K, V, Mg green to 10% V Chem UT-11- Mainty 212 1 green/blue opaque iridescent platy Mg, Si, O, Al, K, Fe, Ca phlogopite SX 99 UT-11- Mainty 218 1 pale bronze opaque metallic massive Fe, S pyrite chem 103 UT-11- sulphide w gypsum Mainty 220 1 copper opaque metallic leafy Fe, S, minor Se; Ca, S, O chem 104 coat UT-11- Mainty 230 1 pink transparent vitreous Al, Mg, O spinel R 109 pale green small Ca, S, Mg, O, (Fe), Al, 1 transparent vitreous diopside R UT-11- yellow blades (Ti, K), Cl Mainty 232 110 pale silver 2 translucent pearly plates Mg, Si, Al, O, K, Ti phlogopite R brown UT-11- 1 red opaque dull, earthy crusts Fe, O hematite SX Jaky 68 139 2 white opaque dull crusts Al, Si, O, very minor Mg kaolinite SX UT-11- Jaky 78 1 white opaque waxy crusts Ca, Mg, O calcite R 144 UT-11- Jaky 86 1 white opaque greasy needles Al, Si, O Sillimanite SX 146a UT-11- Jaky 82 1 green transparent vitreous columnar O, Mg, Al, Si, Ca Uvite SX 146b UT-11- Jaky 108 1 grey blue translucent vitreous prismatic Si, Al, O Sillimanite R 156

Depth Mineral Sample Deposit Colour Diaphaneity Lustre Habit SEM elements ID (m) # ID Method Si, Mg, Al, O, K, Ti, 1 dark amber translucent pearly blades fluorphlogopite R UT013 Mainty 188 Fe, F 2 white opaque greasy needles Si, Al, O, K orthoclase chem Al, Si, O, Mg, Ca UT114 Manga 186 2 pale green transparent vitreous columnar uvite R minor Ti, V, Na

Si, Mg, O, Ca, V, F SX, UT118 Manga 194 1 green translucent vitreous massive 9 (Ti) uvarovite chem

Al, Si, O, Mg, Ca, Ti, UT123 Manga 204 1 green transparent vitreous massive uvite R V, F 1 orange transparent vitreous angular siderite eye UT124 Manga 206 pale green 3 to translucent pearly fibrous Si, O, Mg, Al, Ca tremolite SX colourless 1 green translucent pearly plates Mg, O, Si, Al, K phlogopite R Si, Mg, Al, O, K, Ti, 2 peach translucent pearly plates phlogopite R V, Fe UT126 Manga 210 3 white opaque pearly fibres Si, Mg, O, minor Al talc R

5 grey opaque metallic vein O, Si, Al, Fe, Mn amorphous SX

UT131 Manga 220 1 white opaque waxy cryptocrystalline kaolinite eye

9 Chemistry matches uvarovite with minor vanadium. Crystal structure is same for uvarovite and goldmannite. Raman and powder spectra are also the same for these minerals, therefore based on the presence of only minor vanadium; this mineral is identified as uvarovite.

Depth Mineral Sample Deposit Colour Diaphaneity Lustre Habit SEM elements ID (m) # ID Method UT134 Manga 226 1 white trl to op. pearly fibrous Ca, S, O gypsum Chem UT137 Manga 232 1 green transparent vitreous massive Al, O, Si, Mg, Na, Ca uvite SX Si, Al, O, Mg, K (Ca, UT139 Manga 236 2 green opaque vitreous crystals uvite R Ti, Fe) UT156 Manga 270 1 dark green opaque subvitreous blades O, Mg, Al, Si Vermiculite R Al, Si, K, O, V, Ti, Vanadian 1 green opaque pearly blades SX UT158 Manga 274 Fe muscovite 2 green transparent vitreous prisms O, Al, Si, Mg, Ca Uvite R

Appendix III V-Rutile EMPA Data

Microprobe analyses of V-rutile in thin sections UT117, UT134, UT150 and UT159. All values are reported in weight percent oxide. UT134 UT134 UT134 UT134 UT134 UT150 UT150 UT150 UT150 oxide oxide oxide oxide oxide oxide oxide oxide oxide 1-1 1-2 2-3 5-1 5-2 3-2 1-1 1-2 5-3 Analysis 6 7 10 11 12 14 15 16 23

TiO2 94.73 95.05 94.93 95.60 95.58 97.01 96.63 96.51 96.04

Nb2O5 0.48 0.45 1.32 0.83 0.82 0.24 0.38 0.42 0.53

Cr2O3 0.03 0.08 0.04 0.04 0.01 0.01 0.00 0.00 0.01

V2O3 2.88 2.95 3.36 3.04 3.08 2.92 3.04 3.05 3.09 Total 98.13 98.55 99.75 99.53 99.51 100.20 100.08 100.01 99.68

UT117 UT117 UT159 UT159 UT159 UT159 UT159 UT159 UT159 oxide oxide oxide oxide oxide oxide oxide oxide oxide 4-3 4-4 1-1 2-3 2-4 4-7 8-1 8-2 7-2 Analysis 27 28 29 33 34 47 54 55 59 Avg .

TiO2 98.35 98.34 96.90 97.28 97.93 88.95 97.49 97.68 98.19 96.29

Nb2O5 0.37 0.36 0.17 0.40 0.33 4.51 0.20 0.25 0.34 0.69

Cr2O3 0.00 0.00 0.31 0.12 0.10 0.22 0.14 0.06 0.07 0.07

V2O3 2.09 2.14 2.71 2.53 2.25 5.97 2.30 2.39 2.00 2.88 Total 100.88 100.93 100.12 100.36 100.64 99.67 100.21 100.41 100.63 99.96

Appendix IV Schreyerite EMPA Data

Microprobe analyses of schreyerite in thin sections UT117, UT134, UT150 and UT159. All values are reported in weight percent oxide.

UT134 UT150 UT150 UT150 UT117 UT117 UT159 UT159 UT159 UT159 UT159 UT159 UT159 UT159 UT159 oxide oxide oxide oxide oxide oxide oxide oxide oxide oxide oxide oxide oxide oxide oxide 2-2 3-1 1-3 1-4 4-1 4-2 1-2 2-1 2-2 4-4 4-5 4-6 8-3 8-4 7-1 Arithmetic Analysis 9 13 17 18 25 26 30 31 32 44 45 46 56 57 58 Mean

TiO2 60.94 61.32 61.51 61.62 61.94 61.88 62.94 61.86 61.55 59.77 60.74 59.43 61.72 61.82 61.17 61.35

Al2O3 0.64 0.75 0.62 0.60 0.25 0.28 0.29 0.42 0.53 0.41 0.39 0.42 0.52 0.46 0.64 0.48

Cr2O3 1.16 0.35 0.28 0.23 0.76 0.75 3.97 3.13 3.41 3.66 3.39 3.60 3.39 2.79 3.07 2.26

V2O3 36.05 35.56 36.57 35.97 36.07 36.14 31.51 33.87 33.32 35.25 34.09 35.08 33.51 33.99 33.92 34.73 FeO 0.05 0.07 0.02 0.05 0.07 0.07 0.13 0.04 0.13 0.12 0.08 0.08 0.11 0.09 0.09 0.08 Total 98.96 98.07 99.04 98.48 99.20 99.16 98.91 99.38 99.00 99.28 98.80 98.71 99.31 99.20 98.97 98.96

Appendix V Berdesinskiite EMPA Data

Microprobe analyses of berdesinskiite in thin sections UT130, UT134, UT150 and UT159. All values are reported in weight percent oxide

UT130 UT130 UT130 UT130 UT134 UT150 UT159 UT159 UT159 UT159 UT159 oxide oxide oxide oxide oxide oxide oxide oxide oxide oxide oxide 5-1 5-2 6-1 6-2 2-1 5-2 2-5 3-1 4-1 4-2 4-3 Analysis 2 3 4 5 8 22 35 37 41 42 43 Average TiO2 31.00 31.05 31.16 30.83 34.85 32.59 33.16 32.51 32.94 34.35 34.79 32.7 SiO2 0.03 0.02 0.02 0.01 0.01 0.00 0.00 0.01 0.00 0.00 0.00 0.01 Nb2O5 0.04 0.05 0.02 0.03 0.00 0.00 0.02 0.00 0.00 0.01 0.02 0.02 Al2O3 0.54 0.56 0.59 0.61 0.99 0.79 0.83 0.77 0.71 0.60 0.71 0.7 Cr2O3 2.73 2.71 2.79 2.18 2.54 1.39 6.23 6.72 6.77 5.71 5.53 4.12 V2O3 61.87 62.17 61.72 62.36 58.63 61.42 56.30 56.83 56.39 56.09 55.67 59.00 FeO 0.17 0.14 0.14 0.14 0.43 0.08 0.45 0.22 0.15 0.22 0.21 0.21 MnO 0.02 0.03 0.03 0.01 0.01 0.01 0.04 0.03 0.10 0.07 0.09 0.04 Total 96.39 96.73 96.47 96.16 97.46 96.28 97.03 97.09 97.06 97.05 97.02 96.8

Appendix VI Karelianite-Eskolaite SS EMPA Data

Microprobe analyses of karelianite-eskolaite solid solution in thin section UT159. All values are reported in weight percent.

UT159 UT159 UT159 UT159 UT159 UT159 UT159 UT159 UT159 UT159 oxide oxide oxide oxide oxide oxide oxide oxide oxide oxide 2-6 3-2 3-3 3-4 4-8 4-9 4-10 4-11 4-12 4-13 Analysis 36 38 39 40 48 49 50 51 52 53 Average TiO2 0.30 0.18 0.02 0.02 0.23 0.27 0.02 0.04 0.06 0.03 0.12 SiO2 0.00 0.01 0.01 0.00 0.04 0.02 0.00 0.00 0.00 0.00 0.01 Nb2O5 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.00 Al2O3 0.34 0.10 0.02 0.01 0.32 0.04 0.03 0.01 0.00 0.01 0.09 Cr2O3 16.72 16.69 16.07 15.65 16.73 16.53 15.88 15.54 14.65 15.70 16.02 V2O3 77.63 78.20 79.23 80.33 78.23 78.92 80.01 79.29 80.96 80.19 79.30 FeO 0.53 0.23 0.22 0.12 0.34 0.36 0.12 0.18 0.16 0.12 0.24 MnO 0.06 0.04 0.04 0.04 0.04 0.05 0.02 0.05 0.04 0.04 0.04 Total 95.59 95.44 95.62 96.17 95.93 96.18 96.08 95.11 95.87 96.11 95.81

Appendix VII V-Phlogopite EMPA Data

The results of EPMA of vanadium bearing phlogopites in UT117, UT130, UT134, UT150 and UT159. All values are reported in weight percent wt% Analysis Sample SiO2 Al2O3 TiO2 Cr2O3 V2O3 FeO MnO MgO BaO Na2O K2O F H2O Total 1 UT134 1-2 39.02 17.42 3.01 0.08 1.89 0.15 0.06 22.26 0.25 0.08 10.17 0.65 3.85 98.64 2 UT134 1-3 39.24 17.52 3.01 0.04 1.97 0.10 0.05 22.12 0.08 0.07 10.00 0.69 4.10 98.71 3 UT134 2-1 38.27 17.76 2.21 0.39 6.49 0.20 0.09 18.83 0.20 0.11 10.12 0.49 3.82 98.80 4 UT134 2-2 38.74 17.43 2.17 0.43 6.39 0.14 0.05 18.94 0.05 0.07 10.08 0.53 3.82 98.63 5 UT134 2-3 38.57 17.75 1.42 0.53 8.45 0.25 0.05 17.70 0.32 0.11 10.06 0.33 3.82 99.24 6 UT134 2-4 38.19 17.69 1.43 0.42 7.87 0.27 0.02 17.90 0.01 0.09 9.93 0.49 3.88 97.98 7 UT134 3-1 38.89 17.43 1.82 0.33 6.84 0.20 0.05 18.54 0.51 0.12 9.98 0.52 3.88 98.93 8 UT134 3-2 38.80 17.66 2.07 0.49 6.85 0.14 0.05 18.52 0.29 0.11 10.18 0.37 3.87 99.24 9 UT134 3-3 38.93 17.64 2.02 0.53 7.05 0.20 0.05 18.34 0.09 0.06 10.10 0.46 3.86 99.14 10 UT134 3-4 39.15 17.40 2.35 0.32 6.24 0.38 0.03 19.03 0.25 0.09 10.14 0.57 3.94 99.64 11 UT134 3-5 39.25 17.49 3.41 0.02 1.48 0.09 0.02 22.09 0.02 0.11 10.21 0.74 4.09 98.70 13 UT134 4-1 39.05 17.83 2.87 0.18 3.34 0.07 0.05 20.99 0.53 0.09 10.10 0.77 3.95 99.51 14 UT134 4-2 39.44 17.84 2.94 0.04 2.97 0.11 0.04 21.27 0.18 0.12 10.18 0.62 4.40 99.91 15 UT134 4-3 39.12 17.76 2.76 0.12 3.51 0.15 0.06 20.78 0.63 0.09 9.99 0.84 3.90 99.36 16 UT134 4-4 39.48 17.78 2.83 0.22 3.40 0.10 0.01 20.86 0.27 0.10 10.19 0.80 4.05 99.77 17 UT134 6-1 40.18 17.62 2.83 0.09 2.63 0.16 0.02 21.57 0.27 0.10 10.08 0.86 4.19 100.25 18 UT134 6-2 39.62 17.72 2.77 0.15 2.53 0.18 0.03 21.67 0.24 0.09 10.20 0.63 4.11 99.70 19 UT134 6-3 39.71 17.80 2.46 0.20 2.84 0.16 0.03 21.68 0.34 0.10 10.25 0.86 4.03 100.10 20 UT134 6-4 39.44 17.69 2.50 0.07 2.95 0.16 0.08 21.78 0.58 0.12 10.15 0.58 4.47 100.33 21 UT134 6-5 39.73 17.74 2.79 0.08 2.39 0.09 0.05 21.98 0.54 0.10 10.09 0.42 4.07 99.90 22 UT134 6-6 39.64 17.95 2.81 0.12 2.42 0.10 0.04 22.18 0.25 0.06 10.13 0.85 4.07 100.26

77 23 UT134 6-7 39.77 17.55 2.90 0.02 2.47 0.11 0.04 22.19 0.55 0.10 10.28 0.77 4.08 100.52 24 UT134 6-8 39.51 17.68 2.62 0.04 2.41 0.10 0.08 22.40 0.30 0.08 10.05 0.74 4.07 99.77 25 UT134 6-9 39.70 17.80 3.05 0.13 2.24 0.14 0.06 21.92 0.29 0.08 10.18 0.93 4.07 100.21 26 UT134 6-10 39.36 18.06 2.91 0.06 2.28 0.17 0.05 21.96 0.38 0.10 10.23 0.79 4.31 100.33 27 UT134 7-1 39.86 17.94 2.87 0.15 2.24 0.14 0.07 21.81 0.38 0.07 10.16 0.72 4.13 100.25 28 UT134 7-2 39.79 17.91 2.79 0.13 2.60 0.10 0.05 21.52 0.38 0.11 10.26 0.79 4.09 100.19 30 UT134 8-1 39.26 17.56 3.14 0.02 3.78 0.14 0.06 20.13 0.20 0.08 10.02 0.68 1.41 96.22 31 UT134 8-2 39.88 17.84 2.95 0.06 3.80 0.19 0.06 19.96 0.26 0.10 9.98 0.55 4.12 99.56 32 UT130 5-1 38.67 15.94 1.22 0.63 7.05 0.20 0.10 20.18 1.75 0.12 9.51 0.69 3.85 99.63 33 UT130 5-2 38.73 15.95 1.22 0.50 7.73 0.22 0.09 19.79 1.67 0.19 9.45 0.73 3.85 99.85 34 UT130 5-3 38.18 15.92 2.05 0.26 6.30 0.25 0.16 20.34 1.61 0.15 9.33 0.74 3.94 98.93 35 UT130 5-4 38.14 16.04 1.20 0.63 7.71 0.31 0.09 20.11 2.12 0.14 9.34 0.89 3.98 100.35 36 UT130 6-1 38.56 16.40 1.47 0.48 7.25 0.23 0.11 19.86 1.35 0.11 9.45 0.64 3.97 99.61 37 UT130 6-2 38.68 16.19 1.32 0.53 7.27 0.18 0.10 19.63 1.16 0.29 9.47 0.57 3.85 99.10 38 UT130 6-3 38.47 16.35 1.18 0.61 7.31 0.15 0.12 19.58 1.96 0.22 9.46 0.71 3.76 99.63 39 UT130 6-4 38.53 16.06 1.21 0.66 7.62 0.24 0.10 19.67 1.48 0.12 9.47 0.65 3.91 99.45 40 UT130 4-1 38.36 16.25 2.21 0.32 6.79 0.17 0.16 19.62 1.47 0.14 9.43 0.75 3.78 99.13 41 UT130 4-2 38.77 16.14 2.17 0.28 6.95 0.19 0.17 19.79 2.10 0.12 9.51 0.53 3.68 100.19 42 UT130 3-1 38.22 18.42 0.16 0.04 7.30 0.02 0.02 19.47 1.97 0.15 9.46 0.44 3.80 99.31 43 UT130 3-2 38.10 17.36 0.17 0.00 9.69 0.26 0.01 17.87 1.94 0.13 9.43 0.40 3.88 99.12 49 UT159 1-1 38.37 18.23 1.80 1.22 4.21 0.24 0.20 19.16 0.68 0.13 9.93 0.54 3.72 98.19 50 UT159 1-2 38.56 18.05 1.83 1.23 4.16 0.26 0.23 19.62 0.93 0.08 9.89 0.64 3.80 99.02 51 UT159 1-3 38.83 18.33 1.69 0.88 3.88 0.29 0.21 19.74 0.54 0.12 9.69 0.45 3.91 98.37 52 UT159 1-4 39.17 18.00 2.07 1.01 4.10 0.40 0.28 20.39 1.01 0.12 9.83 0.43 3.91 100.57 53 UT159 3-1 38.94 18.24 1.76 0.87 5.90 0.22 0.23 17.93 0.75 0.14 10.04 0.38 3.88 99.13 54 UT159 3-2 38.32 17.33 1.65 1.44 7.03 0.22 0.23 17.81 1.31 0.17 9.69 0.45 3.77 99.23 55 UT159 4-1 38.45 17.36 1.75 1.43 7.26 0.24 0.14 17.51 0.54 0.12 9.80 0.50 3.86 98.79 57 UT159 9-1 38.27 18.88 2.13 1.00 6.49 0.16 0.14 16.71 0.63 0.13 9.93 0.67 3.87 98.74 58 UT159 9-2 38.02 18.10 1.66 1.39 6.59 0.22 0.10 17.71 0.75 0.11 9.73 0.61 3.92 98.66 59 UT150 6-1 39.48 17.59 3.35 0.00 2.41 0.00 0.02 21.92 0.38 0.10 10.14 0.27 4.00 99.55

78 60 UT150 6-2 39.23 17.72 3.10 0.01 2.16 0.02 0.01 21.91 0.13 0.11 9.94 0.50 4.02 98.67 61 UT150 6-3 39.58 17.59 3.31 0.00 2.28 0.03 0.04 21.77 0.35 0.10 9.99 0.45 4.11 99.43 62 UT150 6-4 39.76 17.53 3.39 0.00 2.58 0.05 0.06 21.56 0.38 0.11 10.17 0.37 4.19 100.01 63 UT150 6-5 39.51 17.47 3.37 0.01 2.55 0.01 0.03 21.93 0.15 0.09 10.19 0.44 4.11 99.70 64 UT150 6-6 39.90 17.61 3.44 0.01 2.56 0.00 0.06 21.87 0.09 0.06 10.13 0.19 4.23 100.07 65 UT150 4-1 38.22 17.16 2.33 0.35 7.79 0.28 0.09 17.46 0.02 0.14 9.98 0.40 2.78 96.86 66 UT150 4-2 37.87 17.50 2.25 0.35 7.44 0.21 0.06 18.12 0.42 0.11 10.16 0.13 3.99 98.56 67 UT150 4-3 39.09 17.11 2.93 0.13 6.10 0.10 0.09 19.17 0.44 0.07 9.97 0.36 3.92 99.35 68 UT150 4-4 38.67 17.49 2.87 0.14 5.60 0.10 0.07 19.27 0.34 0.06 10.06 0.34 3.76 98.64 Average 38.99 17.46 2.29 0.37 4.92 0.17 0.08 20.10 0.66 0.11 9.93 0.58 3.91 99.34

Appendix VIII The Results of X-Ray Fluorescence Performed at the University of Toronto on the Working Set of Samples

Sample Depth Down Core U of T XRF Results Deposit Number (m) (ppm V)

UT-11-8 152-152.4 112.7 UT-11-14 160-160.4 555.7 UT-11-18 168-168.4 783.9 UT-11-24 176-176.4 535.8 UT-11-28 182-182.4 575.1 UT-114 186-186.4 2672.7 UT-117 192-192.4 3572.2 UT-122 202-202.4 4022.6 UT-126 210-210.4 5111.9 UT-128 214-214.4 4662.5 UT-130 218-218.4 6506.3 Manga UT-134 226-226.4 5298.4 UT-141 240-240.4 5948.5 UT-150 258-258.4 5175.6 UT-154 266-266.4 5275.8 UT-159 276-276.4 5103 UT-161 280-280.4 5545.6 UT-163 284-284.4 3980.9 UT-165 288-288.4 1900.8 UT-11-49 294-294.4 3156.9 UT-11-52 300-300.4 437 UT-11-54 304-304.4 547.6 UT-11-111 8-8.4 356 UT-11-118 28-28.4 7535.5 UT-11-121 34.08-34.48 593.2 UT-11-129 52-52.4 1002.8 UT-11-146a 82-82.4 1031 Jaky UT-11-153 102.5-102.9 1658.5 UT-11-169 131.66-132.26 341.5 UT-11-181 156-156.4 5380.4 UT-11-187 168.5-168.9 1278.6 UT-11-193 180-180.4 393.5 UT-11-201 196-196.5 178.2

UT-11-61 90-90.4 133.1 UT-11-73 114-114.4 67.6 UT-11-79 128.3-128.82 750.9 UT-11-83 137-137.4 1971.9 UT-11-87 146-146.4 2221.8 Mainty UT-11-93 161-161.4 2252.8 UT-11-97 173-173.35 1053.6 UT-11-98 210-210.4 181.5 UT-11-100 214-214.4 225.3 UT-11-104 220-220.4 3359.8 UT-11-108 228-228.4 153.8