Indicator mineral exploration methodologies for VMS

Indicator mineral exploration methodologies for VMS deposits using geochemistry and physical characteristics of magnetite

Thèse

Sheida Makvandi

Doctorat interuniversitaire en sciences de la Terre Philosophiae doctor (Ph.D.)

Québec, Canada ! ! ! ! !

© Sheida Makvandi, 2015

Résumé Pour évaluer le potentiel de la magnétite en tant que minéral indicateur des dépôts de Sulfures Massifs Volcanogènes (SMV), la composition des éléments traces et les caractéristiques (morphologie, taille des grains et textures de surface) de la magnétite provenant de différents contextes ont été investiguées. Les caractéristiques physiques et les associations minérales de la magnétite du dépôt d’Izok Lake (Nunavut, Canada), de la roche encaissante et du till recouvrant la zone à proximité ont été étudiés en utilisant la microscopie optique, le Microscope Électronique à Balayage (MEB) et l’Analyseur de Libération Minérale (MLA). Les résultats permettent de distinguer la magnétite magmatique, métamorphique et supergène dans un environnement de SMV, et indiquent que 1) la taille des grains de magnétite et leur relation texturale avec les associations minérales caractérisent la roche encaissante, 2) l’angularité de la magnétite du till est indicatrice de la forme originel du minérale, et 3) les textures de surface de la magnétite détritique sont diagnostiques des processus affectant les grains durant l’érosion, le transport, et après la déposition dans les sédiments glaciaire. La composition de la magnétite provenant d’Izok Lake (Nunavut, Canada) et d’Halfmile Lake (Nouveau-Brunswick, Canada) et de leurs roches encaissantes a été étudiée en utilisant le MEB, la microsonde électronique, et l’ablation laser- spectrométrie de masse à plasma à couplage inductif (LA-ICP-MS). Les données censurées ont été transformées en utilisant la routine R robCompositions, puis converties en utilisant les log-ratios centrés pour éviter tout effet de fermeture. L’analyse en Composantes Principales (ACP) permet de discriminer différents types de roche encaissantes et des dépôts basés sur la teneur de la magnétite en Si, Ca, Zr, Al, Ga, Mn, Mg, Ti, Zn, Co, Ni et Cr. Les données de composition de la magnétite de seize dépôts SMV (mafique, bimodal mafique, bimodal felsique, felsique-silicoclastique), et de trois Formations de Fer Rubanées (FFR) associés à des SMV ont été investiguées par analyse discriminante par les moindres carrés partiels (PLS-DA) pour distinguer les différentes compositions de magnétite basées sur les teneurs en Si, Ca, Al, Mn, Mg, Ti, Zn, Co et Ni. Le résultat indique quatre types de magnétite en association avec les dépôts de SMV: magmatique, hydrothermale, métamorphique, et la magnétite zonée. L’analyse des données par PLS-DA sépare la

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magnétite des SMV et BIF des autres types de gites minéraux. Les analyses en PCA et PLS-DA des échantillons de la roche encaissante/dépôt SMV et FFR produisent un modèle de discrimination de la composition de la magnétite dans le till qui peut être utilisé pour identifier, en exploration minérale, la magnétite dérivée de l'érosion d'un SMV par un glacier.

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Abstract To evaluate the potential of magnetite as an indicator mineral for Volcanogenic Massive Sulfide (VMS) deposits, trace element compositions and physical characteristics (morphology, grain size, and surface textures) of magnetite from various VMS settings were investigated. Physical characteristics and mineral associations of magnetite from the Izok Lake deposit (Nunavut, Canada), its host bedrocks, and till covering the nearby area were studied using optical microscopy, Scanning Electron Microscopy (SEM), and Mineral Liberation Analysis (MLA). The results distinguish magmatic, metamorphic and supergene magnetite in the VMS setting, and indicate that 1) the grain-size distribution of magnetite and its textural relationships with mineral associations fingerprint the host bedrocks, 2) the angularity of magnetite in till is indicative of the original shape of the mineral, and 3) the surface textures of detrital magnetite are diagnostic of processes affecting grains during erosion, transport, and after deposition in glacial sediments. Variation in magnetite composition from the Izok Lake (Nunavut, Canada) and Halfmile Lake (New Brunswick, Canada) deposits and their host rocks were studied using SEM, Electron Probe Micro-Analyzer (EPMA), and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). The data were transformed for censored values using the R-package robCompositions. Transformed data were converted using centered log-ratio to overcome the closure effect, and then were investigated by Principal Component Analysis (PCA) to discriminate different rock/deposit samples based on Si, Ca, Zr, Al, Ga, Mn, Mg, Ti, Zn, Co, Ni and Cr contents of magnetite. The data from sixteen VMS deposits from four subtypes (mafic, bimodal-mafic, bimodalfelsic, and felsic-siliciclastic), and three VMS-associated Banded Iron Formations (BIF) were also investigated by Partial Least Squares Discriminant Analysis (PLS-DA). PLS-DA to distinguish different compositions of magnetite based on Si, Ca, Al, Mn, Mg, Ti, Zn, Co and Ni contents. The results indicate four types of magnetite in association with VMS deposits: 1) magmatic, 2) hydrothermal, 3) metamorphic, and 4) zoned magnetite. PLS-DA separates VMS and VMS-associated BIF magnetite from that of other mineral deposit types including Ni-Cu, porphyry, IOCG and IOA deposits. PCA and PLS-DA of magnetite data

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from VMS bedrock/deposit and BIF samples yield discrimination models that can be used to classify magnetite compositions in till samples for mineral exploration.

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Table of Content

Résumé .......................................................................................................................................... iii Abstract ...........................................................................................................................................v List of Tables ................................................................................................................................ ix List of Figures ............................................................................................................................... xi Acknowledgments ........................................................................................................................xv Foreword .................................................................................................................................... xvii

Chapter 1 Introduction ........................................................................................................ 1 1.1.

Bckground .........................................................................................................................1

1.2.

Research objectives ...........................................................................................................7

1.3.

Thesis outline ....................................................................................................................8

Chapter 2 “The surface texture and morphology of magnetite from the Izok Lake volcanogenic massive sulfide deposit and local glacial sediments, Nunavut, Canada: Application to mineral exploration” ................................................................................. 11 Résumé: .....................................................................................................................................11 Abstract:.....................................................................................................................................12 2.1.

Introduction: ....................................................................................................................13

2.2.

Methodology ...................................................................................................................18

2.3.

Results .............................................................................................................................21

2.4.

Discussion .......................................................................................................................41

2.5.

Conclusions .....................................................................................................................51

Chapter 3 “Principal Component Analysis of magnetite composition from volcanogenic massive sulfide deposits: Case studies from the Izok Lake (Nunavut, Canada) and Halfmile Lake (New Brunswick, Canada) deposits” ................................ 53 Résumé: .....................................................................................................................................53 Abstract:.....................................................................................................................................54 3.1.

Introduction .....................................................................................................................55

3.2.

Geologic settings .............................................................................................................60

3.3.

Methodology ...................................................................................................................62

3.4.

Results .............................................................................................................................69

3.5.

Discussion .......................................................................................................................93

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3.6.

Conclusions .................................................................................................................. 104

Chapter 4 “Partial Least Squares Discriminant Analysis of trace element compositions of magnetite from various VMS deposit subtypes: Application to mineral exploration” ........................................................................................................ 107 Résumé:................................................................................................................................... 107 Abstract: .................................................................................................................................. 108 4.1.

Introduction .................................................................................................................. 109

4.2.

Sample selection and compositional diversity in selected VMS deposits .................... 113

4.3.

Methodology................................................................................................................. 116

4.4.

Results .......................................................................................................................... 121

4.5.

Discussion..................................................................................................................... 134

4.6.

Conclusions .................................................................................................................. 146

Chapter 5 Thesis conclusions and recommendations for future work ........................ 149 5.1.

General conclusions...................................................................................................... 150

5.2.

Recommendations for future work ............................................................................... 152

Bibliography ..................................................................................................................... 155 Appendices ........................................................................................................................ 187 Appendix-I: Variable contributions for Mag from VMS deposits in Fig. 4-4B……………..187 Appendix-II: Variable contributions for Mag from the VMS deposits Fig. 4-6B…………...189 Appendix-III: Variable contributions for Mag from mineral deposits in Fig. 4-7B………....191 Appendix-IV: The range of detection limits for A) EMPA and B) LA-ICP-MS analyes…...192 Appendix-V: EMPA raw data for Mag from the Izok Lake area……………………………193 Appendix-VI: LA-ICP-MS raw data for Mag from the Izok Lake area……………………..203 Appendix-VII: EPMA raw data for Mag from the Halfmile Lake area……………………..209 Appendix-VIII: LA-ICP-MS raw data for Mag from the Halfmile Lake area………………222 Appendix-IX: EPMA raw data for Mag from the other VMS settings……………………...227 Appendix-X: LA-ICP-MS raw data for Mag from the other VMS settings…………………231

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List of Tables Table 2-1. The Izok Lake studied bedrock samples description. .......................................................................22! Table 2-2. The Izok Lake studied till samples description.................................................................................24! Table 2-3. The proportion of microtextures found on the surface of magnetite in bedrock samples. ...............24! Table 2-4. The proportion of microtextures found on the surface of magnetite in till samples from the Izok Lake area. ..........................................................................................................................................29! Table 3-1. Trace element compositions of associated spinel group minerals in Figure 3-2G, obtained by EPMA (in wt%). ................................................................................................................................70! Table 3-2. Average compositions and standard deviations (Std) for minor and trace elements (in ppm; obtained by LA-ICP-MS) in magnetite from Izok Lake bedrock samples. ......................................77! Table 3-3. Average compositions and standard deviations (Std) for minor and trace elements (in ppm; obtained by LA-ICP-MS) in magnetite from Halfmile Lake bedrock samples. ...............................83! Table 4-1. List of VMS deposits studied. .........................................................................................................117! Table 4-2. Mean compositions of magnetite (in ppm) from VMS deposits BIFs studied. ..............................130!

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List of Figures Figure 2-1. Simplified bedrock geology map of the Izok Lake deposit. ............................................................16! Figure 2-2. Locations of bedrock and till samples in the Izok Lake area ..........................................................19! Figure 2-3. Typical morphology and microtextures of magnetite from Izok Lake massive sulfide lenses. ......26! Figure 2-4. Typical surface textures of magnetite from gahnite- rich dacite (A to D), iron formations (E to G), and gabbro (H & I). ...........................................................................................................................27! Figure 2-5. Typical morphology of till magnetite ..............................................................................................28! Figure 2-6. A selection of mechanical textures on the surface of Izok Lake till magnetite. ..............................33! Figure 2-7. Different forms of dissolution characterizing the surface of till magnetite grains. .........................34! Figure 2-8. A to C) Precipitation texture overprinting dissolution texture (shown by arrows). D) Overgrowth rims of Mag2 precipitated on surfaces of till magnetite. E) Widespread precipitation of Mag2 masked mechanical microtextures. F) A dissolution pit filled by precipitation of Mag2. ................35! Figure 2-9. Histograms show the proportions of euhedral, subhedral, and anhedral crystals of magnetite from different Izok Lake bedrock samples. ...............................................................................................35! Figure 2-10. Izok Lake till magnetite grains classified into 5 roundness classes of Powers’ angularity chart. .37! Figure 2-11. Distribution of magnetite grains from Izok Lake till samples among different roundness classes. ...........................................................................................................................................................37! Figure 2-12. Equivalent Ellipse enclosed in a particle to calculate the angularity by the MLA. .......................38! Figure 2-13. Box-and-whisker plots showing values of angularity of magnetite grains obtained from equation (1) in Izok Lake bedrock and till samples. ........................................................................................38! Figure 2-14. Cumulative weight percent passing graphs showing grain size distribution of magnetite in A) bedrock samples and B) till samples. ................................................................................................40! Figure 2-15. The diagram shows comparison between frequency of occurrences of microtextures in Izok Lake till magnetite, Wahianoa magnetite, and Weichselian quartz. ..........................................................46! Figure 3-1. A) Location map of the Halfmile Lake area in eastern Canada. B) Simplified bedrock geology map of the Halfmile Lake district. C) Locations of till samples in the Halfmile Lake area.. ...........61! Figure 3-2. Backscattered electron images of mineral grains in the Izok Lake bedrock samples .....................72! Figure 3-3. Backscattered electron images of mineral grains in the Halfmile Lake bedrock samples. .............76! Figure 3-4. Principle component analysis results of electron microprobe data for magnetite from the Izok Lake bedrock samples. ......................................................................................................................80! Figure 3-5. Principle component analysis results of laser ablation inductively coupled mass spectrometry data for magnetite from the Izok Lake bedrock samples. .........................................................................81! Figure 3-6. Projection of A) EPMA and B) LA-ICP-MS data of magnetite in till samples from the Izok Lake deposit area into t1-t2 models defined by p1-p2 in Figure 3-4B and Figure 3-5B. C) Histograms show proportions of magnetite grains in till with the signature of mineralization, unmineralized bedrock, and unclassified grains in A. ..............................................................................................82! Figure 3-7. PCA results of EPMA data for magnetite from Halfmile Lake bedrock samples. ..........................85! Figure 3-8. PCA results of LA-ICP-MS data for magnetite from Halfmile Lake Lake bedrock samples. ........86! Figure 3-9. Projection of A) EPMA and B) LA-ICP-MS data of magnetite in till samples from the Halfmile Lake deposit area into t1-t2 models defined by p1-p2 in Figure 3-7B and Figure 3-8B. C) Proportion of magnetite grains in till with the signature of mineralization, unmineralized bedrock, and unclassified grains in A. .............................................................................................................91!

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Figure 3-10. PCA of EPMA data for Mag from Izok Lake and Halfmile Lake deposit districts ...................... 92! Figure 3-11. PCA of LA-ICP-MS data for Mag from Izok Lake and Halfmile Lake depoit districts. ............. 93! Figure 3-12. PCA of LA-ICP-MS data for magnetite from Izok Lake and Halfmile Lake depoit districts. ..... 94! Figure 3-13. Projection of A) EPMA and B) LA-ICP-MS data of till magnetite from Izok Lake and Halfmile Lake deposit districts into t1-t2 models defined by PCA in Figure 3-11B and Figure 3-12B. ........ 94! Figure 3-14. Chemical maps of zoned Mag from Halfmile Lake alteration zone by EPMA. ........................... 99! Figure 4-1. Locations of studied VMS deposits and VMS-associated BIFs on simplified bedrock geology maps of A) Canada and B) Oman. .................................................................................................. 118! Figure 4-2. A selection of figures showing mineral aggregates from VMS deposits and VMS-associated BIFs studied. ............................................................................................................................................ 126! Figure 4-3. Chemical maps of zoned Mag from the Ansil bimodal-mafic VMS deposit by EPMA .............. 127! Figure 4-4. PLS-DA of LA-ICP-MS data for Mag from various subtypes of VMS deposits, their host bedrocks, and VMS-associated BIFs. ............................................................................................. 131! Figure 4-5. PLS-DA of LA-ICP-MS data for Mag from the studied VMS deposits and VMS-associated BIFs of the Bathurst Mining Camp ......................................................................................................... 132! Figure 4-7. PLS-DA of LA-ICP-MS data for Mag from various ore deposit types including VMS, VMSassociated BIF, Ni-Cu, IOCG, IOA, porphyry and the Bayan Obo REE-Fe-Nb deposit. .............. 134!

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……dedicated to my loved ones: My Mother, My Father & My husband

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Acknowledgments My sincere gratitude is expressed to my dear supervisor, Professor Georges Beaudoin, for his professional guidance and continuous encouragement throughout my thesis work. His vast knowledge and incisive insight have been inspiring. His support, and valuable comments and suggestions have always lighted the way throughout my PhD research. I sincerely appreciate M. Beth McClenaghan, Massoud Ghasemzadeh-Barvarz, Eric C. Grunsky, Daniel Layton-Matthews and Carl Duchesne for their contributions to this research, and also for their suggestions and scientific/technical support. I would also like to acknowledge my committee members who graciously agreed to serve on my committee, when they were probably up to their neck in work. Thank you and the best of luck in your future endeavors. I also wish to acknowledge the kind, cordial and helpful staffs of Département de géologie et de génie géologique of Université Laval, especially Marc Choquette for his technical supports for SEM and EPMA, and also the secretarial staffs for putting up with me and answering all my questions. I would like to thank my colleagues and friends (Émilie Boutroy, Erik Lalonde, Marion Lesbros, Thomas Raskevicius, Nelly Maneglia, Clovis Cameron Auger, and Anne-Aurélie Sappin) for their moral support, and for creating such a good atmosphere in our office/research group. Finally, but most importantly, I would like to extend my deepest gratitude to my family for allowing me to realize my own potential. All the support they have provided me over the years was the greatest gift anyone has ever given me. Without my parents’ encouragement, sacrifices and patience, I may never have gotten to where I am today. Also, I need to thank my best friend, my husband, Mousa, for his endless support, inspiration, and encouragement throughout this research effort, and always at difficult times. This dissertation would not have been accomplished without the help and moral support of my loved ones.

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Foreword Magnetite is common in many different mineral deposit types. This widespread distribution as well as the potential of magnetite to fingerprint the chemistry of its host rocks has caused an increasing interest in investigating trace element compositions of magnetite from different mineral deposit types. Despite numerous studies demonstrating the application of magnetite chemistry in provenance studies and mineral exploration, magnetite compositions from volcanogenic massive sulfide settings is almost unstudied. In addition, in the majority of magnetite studies, the potential of detrital magnetite chemistry and physical characteristics (e.g., shape, grain-size distribution, and surface textures) to track mineral deposits from distances have not been considered. Thus, my PhD studies have been done with the aim of 1) characterizing physical and chemical characteristics of magnetite from various VMS deposits, their host bedrocks, and from till covering the deposit nearby areas, and 2) establishing criteria to use these characteristics of magnetite in exploration for VMS deposits under layers of overburden cover. This doctoral thesis presented to the department of Geology and Geological engineering of Laval University, has been carried out under supervision of Professor Georges Beaudoin. This research was funded by a partnership between the Geological Survey of Canada under its Geo-mapping for Energy and Minerals 1 (GEM-1) program (2008-2013), Natural Science and Engineering Research Council (NSERC) of Canada, and industrial partners Overburden Drilling Management Limited, MMG Limited, Teck Resources Limited, and AREVA Resources Canada. The thesis includes three research papers in which I have been the principal researcher and the first author. Two articles have already been published and the third is under revision at the time of the thesis submission. My contribution to this PhD project has been: 1) to write the research plan, 2) to do sample selection, preparation, examination by various analytical techniques such as SEM, MLA, EMPA, and LA-ICP-MS, and data collection, 3) to establish statistical methodology to transform geochemical censored data, to overcome the effect of closure of compositional data, and to present data using state of the art discrimination techniques, and 4) to write up research papers.

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As it is mentioned above, this PhD thesis includes three research papers. The first paper entitled “The surface texture and morphology of magnetite from the Izok Lake volcanogenic massive sulfide deposit and local glacial sediments, Nunavut, Canada: Application to mineral exploration” is co-authored by Georges Beaudoin (research supervisor from ULaval), M. Beth McClenaghan (research scientist from the GSC, Ottawa), and Daniel Layton-Matthews (associate professor in economic geology and petrology from the Queen's University). The article is already published in the Journal of Geochemical Exploration, 2015, V. 150, pages 84-103. The second paper entitled “Principal component analysis of magnetite composition from volcanogenic massive sulfide deposits: Case studies from the Izok Lake (Nunavut, Canada) and Halfmile Lake (New Brunswick, Canada) deposits” is co-authored by Massoud Ghasemzadeh-Barvarz (PhD in chemical engineering, postdoctoral fellow at Pfizer Inc.), Georges Beaudoin, Eric C. Grunsky (retired GSC research geostatistician, and current adjunct professor at the University of Waterloo), M. Beth McClenaghan, and Carl Duchesne (professor in in chemical engineering from ULaval). This article is already published in the journal of Ore Geology Reviews, 2016, V. 72, pages 60-85. The third manuscript is entitled “Partial Least Squares Discriminant Analysis of trace element compositions of magnetite from various subtypes of VMS deposits: Application to mineral exploration. It is also co-authored by M. Ghasemzadeh-Barvarz, G. Beaudoin, E.C. Grunsky, M.B. McClenaghan, and C. Duchesne, and is submitted to the journal of Ore Geology Reviews at the time of the thesis submission.

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Chapter 1

1.1.

Introduction

Bckground

1.1.1. Indicator mineral methods Growing demands of industries for raw materials have always forced the human to find better ways to discover mineral resources. Development of indicator mineral methods may be considered part of the mineral’s industry efforts to discover new resources. These methods may be the result of innovative uses of some former exploration methods (e.g., traditional geochemical analysis and heavy minerals). A great advantage of indicator mineral methods is tracing the dispersion of eroded mineral deposits in surficial sediments. In contrast to indicator mineral methods, traditional mineral exploration techniques such as geophysical exploration cannot trace ore bodies or alteration zones from distances. These methods face challenges when applied to areas of transported cover (Jackson, 2009). Overall, different mineral exploration methods are complementary to each other. Study of different characteristics of indicator minerals may provide information applicable to evaluate mineral potential of the study area, determine mineral deposit types, distinguish specific sources (for gold e.g. Desborough, 1970; Antweiler and Campbell, 1977; Antweiler and Campbell, 1982; Von Gehlen, 1983; Knight and McTaggart, 1986; Hallbauer and Utter, 1977), determine secondary from primary deposits (for gold e.g. Wilson, 1984), and to determine the location of deposits. Presence of indicator minerals such as omphacite, pyrope and manganiferous ilmenite in sediments fingerprints kimberlitic bodies, and the chemistry of these minerals is useful to assess the fertility for diamonds (Golubev, 1995; Dredge et al., 1996; Clements et al., 2009; Kaminsky and Belousova, 2009). Grant et al. (1991) also indicated that the integration of morphological and chemical data of indicator minerals would provide more effective exploration tools. Changes in physical characteristics of minerals might be related to chemical alteration 1

affecting grains during weathering and/or transport. For instance, rims in gold grains are commonly generated by the removal of Ag, Hg and Cu, and not because of Au precipitation (Grant et al., 1991). The two most fundamental properties that characterize a mineral and make it distinguishable from other minerals are its chemical composition and crystal structure. In nature, there is no truly pure mineral because similarity in atomic number/radius always allows some elements substituting for mineral forming elements. Some minerals, such as magnetite, are able to preferentially incorporate extensive substituting elements in their crystallographic structure that results in exhibition of extensive variation in chemical composition, called a solid solution. The extent of the elemental substitution and the type of substituting elements are strongly controlled by the environment in which the mineral has formed (Barnes and Roeder, 2001). The chemistry of some indicator minerals is useful for tracing more than one type of mineral deposits. For instance, cinnabar is an indicator for mercury (Plouffe, 2001), and gold mineralization (Stendal and Theobald, 1994), whereas fluorite is an indicator for tungsten Mississippi Valley Type Pb-Zn, molybdenum and/or tin mineralization (Stendal and Theobald, 1994; Friske et al., 2001). The chemistry of some indicator minerals is a discriminant tool to determine the mineral deposit type. For instance, gold grains from epithermal environments are Ag-rich and Cu-poor, whereas gold grains from Au-Cu porphyry deposits are Cu-rich with variable content of Ag (Townley et al., 2003). Apatite is a ubiquitous accessory mineral in a wide range of rock types and useful to record trace elements chemistry of rock systems at the time of its crystallization (Sha and Chapell, 1999; Belousova et al., 2001). Similarly, magnetite is a major to accessory mineral in many types of mineral deposits/geologic settings. The composition of magnetite has been used to distinguish various mineral deposit types including Ni-Cu, porphyry, iron oxide copper gold (IOCG), iron oxide-apatite (IOA), banded iron formation, skarn, Mg-skarn, and the Bayan Obo REE-Fe-Nb deposit (Lindsley, 1976; Ghiorso and Sack, 1991; Razjigaeva and Naumova, 1992; Carew, 2004; McClenaghan, 2005; Singoyi et al., 2006; Gosselin et al., 2006; Beaudoin and Dupuis, 2009; Dupuis and Beaudoin, 2011; Gao et al., 2013; Hu et al., 2014; Boutroy, 2013; Boutroy et al., 2012a,b, 2014; Dare et a., 2012, 2014, 2015; Nadoll et

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al., 2012, 2014, 2015; Huang et al., 2015; Chung et al., 2015; Chen et al., 2015a,b; Liu et al., 2015a,b; Zhao and Zhou, 2015). Indicator mineral studies often result in obtaining multiple beneficial information applicable in other geological domains. The study of a single indicator mineral, such as zircon, enables geologists to extract data about crystal structure, chemistry of major and trace elements, patterns of REEs, U-Pb ratios, and Hf isotope ratios (Jackson, 2009). The chemistry of minerals can also be used as a petrogenetic indicator. Zircon from different igneous rocks shows a variable composition with an increase in trace elements concentration from ultramafic through mafic to granitic rocks. Belousova et al. (2002) used binary diagrams as well as classification trees to discriminate different host rocks of zircon. Dare et al. (2014) suggested using trace element compositions of magnetite as petrogenetic indicators for various magmatic and hydrothermal mineral deposits. The study of indicator mineral inclusions also provides useful information about genetic history of minerals, the composition of host rocks or the type of deposits (Slansky et al., 1991; Auge and Legendre, 1992; Cabri et al., 1996; Leake et al., 1998; Mortensen et al., 2005; Shcheka, 2004; Shcheka et al., 2004; Podlipsky et al., 2007). For instance, chromite inclusions in xenomorphic Pt-Fe alloy grains indicate an association with dunite (Shcheka, 2004). Enargite inclusions in gold grains represent a high sulfidation epithermal source, however, argentite inclusions indicate a mesothermal provenance for gold (Mortensen et al., 2005). In Pt-group minerals, there is a correlation between the presence of inclusions with the minerals morphology and/or chemistry. Iridium, Ru and Os inclusions are observed in small xenomorphic Pt-Fe alloy crystals, whereas they are completely absent in coarse idiomorphic grains. Lack of inclusions indicates a low concentration of PGEs, and also association with the late apatite-magnetite-phlogopite clinopyroxenite intrusions (Shcheka, 2004). Furthermore, the inclusions mineral chemistry can be used to develop trace element criteria and discriminant diagrams that are applicable in recognition of the mineral potential of an area (Jackson, 2009). For example, the majority of garnet inclusions in diamond have depleted trace element patterns characterized by low contents of Zr (800 m. These textures have never been observed on grains transported by cirque glaciers with thicknesses of less than ~200m. In this study, we examine the micro-scale surface textures and morphological features of magnetite grains from the ferromagnetic fractions of bedrock and till at the Izok Lake volcanogenic massive sulfide deposit (Nunavut, Canada) to evaluate if they may be useful for mineral exploration. Specifically, the objectives are to determine if the surface textures and morphological features in till can be used to 1) identify the nature of host bedrock, 2) determine the transport mechanisms, 3) estimate the distance of transport from the source, and 4) identify supergene processes that affected grains after deposition in sedimentary basins. Surface textures and morphology of magnetite grains from massive sulfides and host rocks are compared to that of magnetite grains in up- and down-ice till collected from various distances from the Izok Lake deposit to document the textures formed during erosion, transport and/or deposition. Magnetite is the focus of this study because: 1) it is a common iron oxide mineral found in different geological environments, 2) it is easily separated from sediments/disaggregated samples because it has the highest magnetic susceptibility among all naturally occurring minerals, 3) its physical properties (e.g. hardness, lack of cleavage) and mechanical behaviour (conchoidal fractures) are similar to quartz (Mandolla and Brook, 2010), and therefore surface textures of magnetite can be studied as indicators of transport media as well as depositional environments, and 4) its chemical composition allows discrimination of different types of mineral deposits (e.g. Beaudoin et al., 2007, 2009; Dupuis and Beaudoin, 2011; Dare et al., 2011, 2012; Nadoll et al., 2012, 2014; Sappin et al., 2014).

2.1.1. Geological setting The Izok Lake deposit is an Archean bimodal-felsic Zn-Pb-Cu-Ag volcanogenic massive sulfide deposit located at 65° 38' 00'' N, 112° 47' 45'' W in the northern part of the Slave Structural Province, Nunavut Territory, Canada (Figure 2-1; Morrison, 2004; Hicken, 2012; Paulen et al., 2013). The deposit is situated under Izok Lake, which is 20 km west of Itchen Lake and 30 km north of Point Lake. The deposit is hosted within 2.7-2.67 Ga granite greenstone terrain of folded, faulted, and metamorphosed rocks of the Point Lake Formation (PLF), which is a sub-division of the Yellowknife Supergroup (Padgham and 15

Fyson, 1992; Morrison, 2004; Bleeker and Hall, 2007; Paulen et al., 2013). In the Izok Lake area, the PLF consists of felsic to mafic meta-volcanic, and meta-sedimentary rocks (Figure 2-1), and has been intruded by 2.68 and 2.58 Ga syn-volcanic to post-volcanic granitic plutons, and by the Helikian Mackenzie gabbro dikes swarm (Bleeker et al., 1999). These intrusive bodies seem to be volcanic feeders to the overlying flows. The gabbro is typically medium to coarse-grained, with an equigranular texture, and is massive to weakly foliated (Morrison, 2004). The gabbro dykes trend north to northwest, and cut the massive sulfide lenses of the Izok Lake deposit (Buchan and Ernst, 2004).

Figure 2-1. Simplified bedrock geology map of the Izok Lake deposit showing lithologies and massive sulfide lenses (modified from Morrison, 2004), and Location map of the Izok Lake area in Canada.

East of Izok Lake, the end of felsic volcanism is marked by a series of dacitic flows overlying rhyolite (Figure 2-1; Morrison, 2004). Felsic volcaniclastic rocks, dacitic, andesitic and basaltic flows, thin sulfide-rich iron formations, and turbiditic sedimentary rocks form the hanging wall of the Izok Lake deposit (Figure 2-1). Irregular granitic pegmatite, and diabase dikes subsequently cut all these lithologies (Morrison, 2004; Hicken, 2012). Carbonate and sulfide facies iron formations overlay dacite and basalt to the

16

east and north of Izok Lake (Thomas, 1978). Carbonate facies iron formation is wellbedded and consists of carbonate layers interbedded with cherty beds. In southeast of the deposit, carbonate facies grades into a sulfide facies iron formation containing pods of zincrich massive sulfides. The volcanic rocks in the Izok Lake belt have been altered by hydrothermal fluids followed by metamorphic overprint (Thomas, 1978; Money and Heslop; 1972; Morrison, 2004). A large, Na-depleted, sericitic alteration zone encloses the Izok Lake massive sulfide lenses, whereas the immediate footwall and hanging-wall rocks to the deposit are affected by aluminous alteration typified by the assemblage muscovite-biotite-sillimanite (Morrison, 2004). A metamorphosed magnesium enrichment alteration zone composed of chlorite, biotite and cordierite, formed in close association with the Izok Lake orebody (Thomas, 1978). Thomas (1978) suggested that the Mg alteration has been overprinted by locally intense silicification and sodium metasomatism. Volcanic and sedimentary rocks in the northern and central parts of the Izok Lake area are metamorphosed to the upper amphibolite-sillimanite grade forming a gahnite-rich zone at the margin of the massive sulfide bodies and the underlying stringer zone (Thomas, 1978; Bostock, 1980; Morrison and Balint, 1993, 1999). The gahnite-rich dacite hosting the stringer zone consists of gahnite, sillimanite, magnetite, illmenite, pyrite, pyrrhotite, chalcopyrite, sphalerite, quartz, biotite, plagioclase, and hornblende (Thomas, 1978; Bostock, 1980; Morrison and Balint, 1993, 1999; Morrison, 2004; Hicken, 2012; Hicken et al., 2013a). South of the Izok Lake area, the metamorphic grade decreases to the greenschist facies. The Izok Lake deposit comprises 5 massive sulfide lenses with 14.8 Mt indicated resources grading 12.8% Zn, 2.5% Cu, 1.3% Pb, and 71 g/t Ag (Costello et al., 2012). The massive sulfides contain 25% pyrite, 24% sphalerite, 9% chalcopyrite, 8% pyrrhotite, 3% galena, and 3% magnetite (Morrison, 2004). In addition to these massive sulfide lenses, several gossans have been discovered in the Izok Lake area including a zinc-rich gossan on the west side of Iznogoudh Lake, referred to as the WIZ showing (Heslop, 1976; Money and Heslop, 1976; Figure 2-2). Several diabase dikes of the Mackenzie Swarm, trend north to northwest, crosscut the massive sulfide lenses of the Izok Lake deposit (Buchan and Ernst, 2004). The Mackenzie dikes are composed of plagioclase, pyroxenes, and 1-15% fine-

17

grained Fe-Ti oxides (Baragar et al., 1996). Magnetite is dominant in Mackenzie dikes, whereas ilmenite is subordinate or rare. The Izok Lake area is a glaciated terrain affected by four phases of ice flow (Kerr et al., 1995; Dredge et al., 1996; Stea et al., 2009). Figure 2-2 shows the ice flow patterns in the Izok Lake region. Paulen et al. (2013) demonstrated that the oldest ice flow was directed towards the southwest (210° to 254°) followed by a flow directed towards the northwest (300° to 325°). The third ice flow from east to west-northwest (279° to 296°) was the dominant phase that shaped the present-day landscape of the area. Evidence of the youngest glacial flow direction towards the northwest (296° to 318°) is faint and rare, and are only found on outcrops east of Iznogoudh Lake (Paulen et al., 2013). Undulating topography, glacially streamlined bedrock hills surrounded by surficial sediments and abundant lakes are characteristic of the area. Till cover in the Izok area is generally thin, varying between < 0.5 m to 3 m (Dredge et al., 1996; Hicken et al, 2013).

2.2.

Methodology

2.2.1. Sampling methods A total of 22 bedrock samples and 85 till samples were collected by Geological Survey of Canada (GSC) in the Izok Lake region in 2009 and 2010 (McClenaghan et al., 2012b; Hicken et al., 2013a,b). Heavy mineral concentrates (HMC) of GSC bedrock and till were prepared by the Overburden Drilling Management Limited (ODM; Ottawa, Canada) using methods described in McClenaghan et al. (2012b). Massive sulfide and host rock samples were disaggregated using Electric Pulse Disaggregation (EPD). Electric Pulse Disaggregation liberates minerals from rock by applying a high-voltage electric current, which breaks the rock along grain boundaries. The resulting mineral morphologies after EDP reflect the original shape and grain size (Rudashevski et al., 2002; Cabri et al., 2008). A heavy mineral preconcentrate was then produced for each disaggregated rock and for till samples using a shaking table (McClenaghan, 2011). The table preconcentrate was refined using methylene iodide diluted to a specific gravity of 3.2. The heavy mineral concentrate was then further separated into ferromagnetic and non-ferromagnetic fractions using a hand magnet. The ferromagnetic fraction contains mainly mineral grains and aggregates in which 18

magnetite and/or pyrrhotite are principle components. The < 0.25 mm ferromagnetic fraction was archived, whereas the 2 to 0.25 mm ferromagnetic fractions of selected GSC till and bedrock samples were shipped to Université Laval (ULaval) for further preparation and examination of grains.

Figure 2-2. Locations of bedrock and till samples in the Izok Lake area (modified from Hicken, 2012). In the map, the prefix 09-MPB has been removed from the sample names, as sample 09-MPB-R64 is shown as R64.

Each ferromagnetic fraction was homogenized by hand shaking the container. Each sample was poured onto a sheet of paper and divided into four sections, and one of the four sections was selected as a subsample, according to the method described by Gerlach and Nocerino, (2003). The minimum number of grains for a representative subsample, based on previous microtexture investigations, has been determined to be 25 (Krinsley and Doornkamp, 1973; Baker, 1976; Mahaney, 2002; Townley et al., 2003; Madhavaraju et al., 2009). Townley et al. (2003) indicated that examination of at least 25 grains is required to 19

document the range in shape of gold grains in stream sediments. Krinsley and Doornkamp (1973), Baker (1976), and Mahaney (2002), also stated that study of at least 25 quartz grains was sufficient to record variations in surface textures and morphology of quartz in a sample. The splitting procedure was repeated until the subsample contained between 25 and 50 ferromagnetic particles. A ferromagnetic particle is a mineral aggregate in which magnetite may be a component. In this study, 150 magnetite grains from 6 bedrock samples, and 225 magnetite grains identified in ferromagnetic fractions of 9 till samples were examined for their surface textures using Scanning Electron Microscopy (SEM). The 6 rock samples include 1) sample 09-MPB-R60 from massive sulfides, 2) sample 09-MPBR64 from massive sulfides adjacent to gahnite-rich zone, 3) sample 09-MPB-R61 from gahnite-rich dacite within the deposit stringer zone, 4) samples 09-MPB-R42 and 5) 09MPB-R90 from iron formations located 6 km up ice to the east of the deposit, and 6) sample 09-MPB-R92 from the bedrock gabbro. The location of till samples, and directions of ice flows as identified by Paulen et al. (2013) are illustrated in Figure 2-2. Other subsamples were also prepared from the bedrock and till samples to determine modal mineralogy, mineral association, grain size distribution, and angularity of magnetite grains using Mineral Liberation Analysis (MLA).

2.2.2. Analytical methods 2.2.2.1. Scanning Electron Microscopy (SEM)

The SEM was used to examine and document the surface microtextures, morphological features, and shape of magnetite grains in the ferromagnetic fraction. Subsamples were cleaned using acetone in an ultrasonic bath for 5 minutes. Longer immersion in ultrasonic baths may alter existing surface textures and even create new microtextures (Porter, 1962; 1973; Vos et al., 2014). Grains were mounted on 3 mm thick carbon discs taped to 12.5 mm aluminum stubs. Grains were coated with gold and palladium. A JEOL JSM-840A SEM at ULaval equipped with Back-Scattered Electron (BSE) and Secondary Electron (SE) modes were used to examine magnetite grains. The accelerating voltage was 15 KeV and the beam current was 60 µA, at a working distance of 20 mm. Magnetite grains in each subsample were identified during Scanning Electron Microscopy using Energy Dispersive X-ray.

20

2.2.2.2. Mineral Liberation analysis (MLA)

The subsamples for the MLA were mounted in epoxy, and the surface of the mounts was polished. The analyses were performed using the MLA 650 Field Emission Gun Environmental SEM at Queen’s University, using an accelerating voltage of 25 kV and beam currents of 10-15 nA. The MLA software collects BSE images over the sample frame to automatically discriminate mineral grain boundaries and map distribution. Each particle is subdivided into grains, and grain boundaries are distinguished based the greyscale variations in the BSE images. Each grain is further analyzed by X-ray, and the collected spectra are compared to the library of reference spectra for mineral identification (Fandrich et al., 2007; Sylvester, 2012). For each sample, MLA produces different data sets including modal mineralogy, mineral association, particle properties, grain properties (including angularity, area, perimeter, weight proportion, length, breadth, angle length, aspect ratio, and form factor), particle size distribution, and grain size distribution (Fandrich et al., 2007). Quantitative mineralogical data (e.g. modal mineralogy, and grain properties and size distribution) generated by the MLA measurement software for each sample are presented by DataView software and can be exported by the operator (Fandrich et al., 2007). Table 2-1 and Table 2-2 summarize the modal mineralogy and weight proportion of minerals in the ferromagnetic fractions of the Izok Lake bedrock and till samples, respectively.

2.3.

Results

2.3.1. Surface textures of magnetite in bedrock samples Table 2-3 summarizes the proportion of different microtextures found on the surface of magnetite grains in bedrock samples. The proportion of a surface texture in bedrock samples indicates the percentage of grains that are characterized by the given texture. The occurrence of each surface texture has been assessed independently to that of other microtextures, as even if one texture is overprinted by another both textures have been counted.

21

Table 2-1. The Izok Lake studied bedrock samples description. Weight proportions of minerals in ferromagnetic fractions of each sample are presented. Samples

MS (09MPB-60)

MS (09-MPBR64)

Dacite (09MPB-R61)

IF (09-MPBR42)

IF (09-MPBR90)

Gabbro (09MPB-R92)

Sampling depth (m)

49.8

111

52

140

141

11

UTM East

417291

417314

417291

417291

418032

418684

UTM North

7279944

7279934

7279944

7279944

7281312

7279626

Mag

16

23

29.88

2.2

2.6

5.2

Hem

0.5

2.2

3.08

3

7.69

2.5

Sp

58.06

32

0.48

0.006

0

0

Py

10.92

18

0.07

0.004

0

0.01

Gn

0.02

0.7

0

0

0

0

Po

4.75

0

3.32

0

0.03

0.73

Ccp

5.34

7.74

0.03

0

0

0.02

Gnh

0

0.6

12

0

0

0

Grt

0.72

0.9

0.85

12.5

25

0.03

Ti-m

0

0

1

0.02

0.02

7

Qz

0

0

16.37

17

3

0.6

Amp

3.67

11.8

0.17

52

39.59

60

Mic

0.01

3

3.48

13

16

17.4

Fds

0.009

0.06

29.1

0.1

0.002

6

Ap

0

0

0

0.06

0.01

0

Zrn

0

0

0.05

0.09

0.05

0

Mnz

0

0

0.02

0.02

0.01

0

Ax

0

0

0

0

6

0.04

Sil

0

0

0.1

0

0

0.46

Abbreviations. MS: massive sulfides. IF: iron formations. Mag: Magnetite. Hem: Hematite. Sp: Sphalerite. Py: Pyrite. Gn: Galena. Po: Pyrrhotite. Ccp: Chalcopyrite. Ghn: Gahnite. Grt: Garnet group minerals such as pyrope, almandine, spessartine, and andradite. Ti-m: Ti-bearing minerals such as ilmenite, titanomagnetite, and titanite. Qz: Quartz. Amp: Amphibole group minerals such as actinolite, hornblende, and grunerite. Mic: Mica group minerals such as biotite and muscovite. Fds: Feldspare group minerals such as albite, anorthite, and orthoclase. Ap: Apatite. Zrn: Zircon. Mnz: Monazite. Ax: Axinite. Sil: Sillimanite.

A variety of grain morphologies and surface microtextures were observed on magnetite from the Izok Lake massive sulfides (Figure 2-3). Grains from massive sulfide samples are dominated by mineral aggregates in which magnetite is associated with sulfide and silicate minerals (Figure 2-3A). Magnetite from massive sulfides (MS-Mag) is subhedral to anhedral, medium to coarse grained (0.05-0.8 mm), and commonly hosts sphalerite and chalcopyrite inclusions (Figure 2-3B). Pyrite, sphalerite, and chalcopyrite are the abundant sulfide minerals in association with MS-Mag. Pyrite is typically cubic shaped, whereas

22

MS-Mag is intergrown with sphalerite and contains inclusions of muscovite and sphalerite. Muscovite, biotite, and amphibole (actinolite with lesser amounts of hornblende) are either associated with sulfides and MS-Mag, or are inclusions in these minerals. Mineral aggregates from the central parts of massive sulfide lenses (sample 09-MPB-R60) tend to be coarse-grained, whereas samples from margins of the massive sulfides (sample 09MPB-R64) are characterized by fine-grained magnetite with sulfide inclusions (Figure 2-3A & B). Figure 2-3C shows irregular grains of magnetite in sphalerite. Sphalerite contains inclusions of chalcopyrite, whereas magnetite contains inclusions of both sphalerite and chalcopyrite. Despite the central parts of massive sulfides where magnetite is intergrown with actinolite (Figure 2-3B), towards the margins, near the contact between massive sulfides and gahnite-rich host rocks, banded actinolite and magnetite are common (Figure 2-3D). In massive sulfides, parting planes are a characteristic texture in 10% of magnetite grains (Figure 2-3E). Parting planes form as a result of external stress in minerals, without formation of cleavage planes (Chang et al., 1998). External stress breaks minerals along their planes of structural weakness. Parallel micro-intergrowths of fine layers of magnetite in sphalerite can cause octahedral parting planes (Figure 2-3E). Dissolution textures are the most widespread surface texture characterizing 50% of MS-Mag (Figure 2-3F). Dissolution textures are commonly overprinted by precipitation textures. Porous magnetite (Mag2) is a precipitation product observed on the surface of 20% of the grains (Figure 2-3G). In Figure 2-3H, the surface of an actinolite aggregate is covered by a thin layer of porous Mag2. Mag2 precipitated on the surface of early-formed grains locally forms layers of non-porous crystals as shown in Figure 2-3I.

23

Table 2-2. The Izok Lake studied till samples description. Weight proportions of minerals in ferromagnetic fractions of each sample are presented. )*%%(+09MPB-,-,.(

)*%%(+09MPB-,/-.(

)*%%(+09MPB-,--.(

)*%%(+09MPB-,01.(

)*%%(+09MPB-,20.(

)*%%(+09MPB-,22.(

)*%%(+09MPB-,1,.(

)*%%(+09MPB-,31.(

)*%%(+09MPB-,,1.(

8/9298(

8/-010(

8/-1,8(

8/0082(

8/88/3(

8/8992(

8//223(

8/3/08(

8/,082(

219,1,1(

219,/93(

212>1-,(

219,-30(

219//,3(

219,9/1(

219/0>8(

2190322(

2191/,2(

5"?(

3,(

/0(

11(

/1(

/>(

/1(

/-@,9(

11@0(

13(

A&#(

6.5

6

1,(

0@1>(

//(

/3(

//(

10@/1(

7

B;(

0

0

,@,1(

,(

,(

,(

,(

,(

0

CD=(

,(

,(

,(

,@,/(

,(

,@0(

,@,,0(

,@,,0(

,(

C@0(

/,@0(

0@0(

/1(

0(

>(

9(

/,(

JK'(

8(

0(

3@0(

1(

/@1(

0(

8@1(

1@0(

/@98(

H$(

0.2

0.5

,@8(

,@1(

,@/(

1(

,@1(

/@0(

0.65

L(

,@,/(

0

BM(

/-(

33@0(

/-(

39(

1,(

33(

/9(

/2(

/2(

N 500 °C) hydrothermal fluids. Hitzman et al. (1992) also found out that magnetite from IOCG deposits is commonly depleted in Ti. Boutroy et al. (2012b) compared magnetite from Ni-Cu-PGE and IOCG deposits and realized that primary magnetite from Ni-Cu-PGE deposits contains higher Ni, Cu and Cr, and lower Ti, Al and Si relative to ore-stage magnetite from IOCG deposits. Magnetite from the IOA deposits can be discriminated from that of other deposit types due to their higher Ti and Co values (Figure 4-7A & C; Appendix-III). The IOA magnetite also contains higher Ni content relative to magnetite from the other deposit types other than NiCu deposits. Boutroy et al. (2012b) showed that magnetite from IOA deposits is rich in Al and Mg or in Ca. Knipping et al. (2015) investigated trace element contents of magnetite from the Cretaceous Kiruna-type Los Colorados IOA deposit (Chile), and realized that the chemistry of Los Colorados magnetite is similar to that from high temperature hydrothermal systems, such as porphyry Cu deposits, in which magnetite contains high Al, Ti, V and Ga. Higher Ca content relative to the other deposit types is the main contributor clustering the Bayan Obo REE-Fe-Nb magnetite in the left side of the t1-t2 plot (Figure 4-7A & B).

144

Huang et al. (2015), however, did not used the Ca content of magnetite in characterizing different types of magnetite associated to the Bayan Obo deposit. They excluded some elements such as Ca from their analyses because their concentrations were close to or below the detection limit of LA-ICP-MS, or because of considerable variation in their contents. The VIP plot (Figure 4-7C) reveals that Si, Ca, Al, Mn, Zn, Co and Ni are discriminator for magnetite from various mineral deposit types, whereas Mg and Ti are not useful.

4.5.4. Application of magnetite composition to provenance studies and mineral exploration Makvandi et al. (2016) used PCA models to classify magnetite compositions in till covering the areas nearby the Izok Lake and Halfmile Lake VMS deposits. They showed that in the Izok Lake area a high proportion of till magnetite have been derived either from the Izok Lake mineralization (massive sulfides and gahnite-rich dacite stringer zone) or the host bedrocks (gabbro or silicate facies iron formations). The PCA results displayed that in the Halfmile Lake area, a high proportion of till magnetite have been eroded from the deposit host rocks (felsic ash tuff, rhyolite, or andesite), whereas a low proportion of the grains show the chemistry of magnetite from the Halfmile Lake gossans, massive sulfides, or the associated magnetite alteration zone. Makvandi et al. (2016) showed that in both Izok Lake and Halfmile Lake areas, a low proportion of till magnetite is also from unclassified sources. Projecting the Halfmile Lake till data from Makvandi et al. (2016) in PLS-DA model formed by magnetite data from the BMC VMS deposits and BIFs (Figure 4-5B) results in projecting the majority of till magnetite grains in the region for the Halfmile Lake deposit or close to its boundaries (Figure 4-5D). Considering that Halfmile Lake till magnetite is mostly derived from the host bedrocks (Makvandi et al., 2016), the accumulation of till magnetite in the field for the Halfmile Lake gossans (Figure 4-5D) indicates that magnetite from the Halfmile Lake deposit and its host rocks are characterized by local chemical signatures, which separate them from that of the other deposits in the BMC.

145

Projecting the till data from both Izok Lake and Halfmile Lake VMS areas (Makvandi et al., 2016) into the PLS-DA subspace estimated magnetite data from various mineral deposit types (Figure 4-7B) also displays that a high proportion of till magnetite grains cluster in the same region as for the VMS deposits and VMS-associated BIFs (Figure 4-7D). Considering that a proportion of till magnetite from both VMS settings were derived from host bedrocks or unclassified sources, plotting a low proportion of till magnetite outside, but very close to the boundaries of the VMS deposits and BIFs field is inevitable. The results in Figure 4-5D and Figure 4-7D reveal the potential of magnetite chemistry in provenance studies and exploration of VMS deposits, and also demonstrate the ability of PLS-DA to classify different compositions of magnetite in unconsolidated sediments.

4.6.

Conclusions

Investigation of a representative number of magnetite grains from various VMS deposits, their host bedrocks, and VMS-associated BIFs by petrography, and chemical and statistical analyses identifies three types of magnetite in these geologic settings: magmatic, hydrothermal, and metamorphic. In VMS deposits, hydrothermal magnetite co-formed with sulfides, whereas metamorphic magnetite replaced sulfides and is intergrown with the chlorite ± calcite ± sericite ± quartz ± biotite ± anthophyllite assemblage. Metamorphic magnetite from BIFs formed as a result of Fe-silicate decomposition, or by exsolving from high temperature precursors during slow cooling or recrystallization during metamorphism at the expense of early forming minerals. Magmatic magnetite, however, shows metamorphic overprint. The composition of hydrothermal and metamorphic magnetite associated to massive sulfides varies over a wide range. Both types are rich in Mn, but mostly depleted in Si, Ca, Zr, Al, Ti, and Ni. Enrichment of some magnetite in Ti, Co and/or Zn suggests their crystallization from high temperature hydrothermal fluids or at high-grade metamorphism. It may also fingerprint the chemistry of sulfides or silicates replaced by magnetite. Magnetite from different VMS-associated BIFs shows distinct chemical and petrographic characteristics suggesting its formation from different sources. BIF-mag may form during

146

metamorphism or early stages of diagenesis by: 1) decomposition of Fe-bearing silicates, 2) recrystallization of precursor magnetite, hematite and/or silicates, and/or 3) exsolving from a high temperature precursor such as almandine. PLS-DA identifies Al, Ti and Zn as main contributors in classification of BIF-mag. Magmatic magnetite from the VMS deposits host bedrocks is characterized by ilmenite exsolution, and contains higher concentration of Ti relative to the other types of magnetite. Magmatic magnetite is commonly rich in Mn, Zn, Co, and/or Ni. PLS-DA classifies different VMS deposits and BIFs based on Si, Ca, Zr, Al, Mg, Ti, Zn, Co and Ni contents of magnetite. It is also a powerful method to discriminate between different mineral deposit types such as VMS, BIF, Ni-Cu, IOCG, IOA, and porphyry using the distribution of Si, Ca, Al, Mn, Mg, Ti, Zn, Co and Ni in magnetite. PLS-DA classifies different compositions of magnetite in sediments as a high proportion of Halfmile Lake till magnetite plot in the field for the Halfmile Lake gossans in the model formed by the BMC deposits data, and a high proportion of Halfmile Lake and Izok Lake till magnetite plot in the field for VMS deposits and BIFs in the model formed by different mineral deposit types data. PLS-DA indicates that the distribution of samples in score plots is controlled by 1) the origin of magnetite (magmatic, hydrothermal, or metamorphic), 2) the formation temperature of magnetite, 3) the grade of metamorphism, 4) the mineral deposit type, and 4) the geologic setting.

147

Chapter 5

Thesis conclusions and recommendations for future work

Over the last few decades, magnetite composition has been the focus of many studies as a petrogenetic indicator and a pathfinder for some mineral deposit types or geologic settings (Lindsley, 1976; Ghiorso and Sack, 1991; Razjigaeva and Naumova, 1992; McClenaghan, 2005; Dupuis and Beaudoin, 2011; Gao et al., 2013; Boutroy et al., 2014; Dare et a., 2012, 2014, 2015; Nadoll et al., 2012, 2014, 2015; Chung et al., 2015; Chen et al., 2015a,b; Liu et al., 2015a,b; Zhao and Zhou, 2015). Despite numerous studies of magnetite, the chemistry of the iron oxide from VMS settings remained almost unstudied. In addition, chemical and physical characteristics of magnetite in unconsolidated sediments for applying to sediment provenance and mineral exploration were not considered. My research presents the first comprehensive assessment of the minor and trace element geochemistry as well as physical characteristics of magnetite from VMS deposits, their host rocks, and respective alteration zones. It also presents a novel approach to classify different compositions of magnetite in till. Furthermore, this study develops the indicator mineral methods by establishing criteria for using the shape, angularity, grain size, surface textures, and mineral associations of detrital magnetite in discovery of VMS deposits.

149

5.1.

General conclusions

The major achievements of the present study are as following: 1) This study is the first using morphology, grain size distribution, surface textures, and mineral associations of magnetite in mineral exploration. Magnetite in mineralized zone and host bedrocks of the Izok Lake massive sulfide deposit was characterized and then the criteria to classify magnetite in till and to distinguish source rocks were established. This study shows that morphology and surface textures of magnetite are indicative of the conditions under which the mineral formed, and also processes affecting grains during erosion, transport, and after deposition in sedimentary environments. A high percentage of magnetite from till from the Izok Lake area are characterized by surface textures typical of glacial transport (e.g., crescentic gouges, deep grooves, arc-shaped steps, and troughs), whereas a low proportion of grains contain V-shaped percussion cracks indicating fluvial and/or glaciofluvial environments. Abundance of magnetite with surfaces characterized by different textures overprinting each other is consistent with 4 phases of ice flow affecting the Izok Lake area through time. The grain size distribution of till magnetite also fingerprints its origin. In vicinity of the Izok Lake deposit, the grain size of a high proportion of detrital magnetite is similar to that of magnetite from the mineralization. Mineral associations of magnetite are also useful to distinguish the composition of host rocks. For instance, ilmenite is a common association of magnetite from Izok Lake bedrock gabbro, whereas magnetite from the gahnite-rich dacite is associated to gahnite, silimanite and ilmenite. Integration of classified data for magnetite shape, angularity, grains size, surface textures, and mineral associations helps in identification of host bedrocks, and to estimate the proximity to the source. This research emphasizes the importance of the study of magnetite physical features for indicator mineral exploration methods. 2) This study provides a comprehensive statistical methodology for compositional data analysis, and establishes criteria to treat geochemical censored values and to overcome closure of compositional data. The small size of magnetite or lack of inclusion free surfaces, using small laser beam size, and high detection limits for some elements are main reasons for percentage of censored values in EPMA and/or LA-ICP-MS data. Excluding censored values or arbitrary substitutions (with zero, & DL or DL) cause

150

over/underestimating the statistical parameters of the data. In this study, censored geochemical data have been imputed using the impKNNa function from the R-package robCompostions yielding the smallest error in comparison with conventional techniques. This study also uses centered log-ratio transformation (clr) to overcome the closure problem of compositional data. In this transformation, each variable of a component is divided by the geometric mean of the variable concentration. clr is recommended for multivariate statistical techniques, and geometric mean is an appropriate, natural parameter for lognormal random variables. 3) In this study, five types of magnetite were identified in association with VMS deposits: 1) hydrothermal, 2) metamorphic, 3) magmatic, 4) zoned, and 5) supergene. In massive sulfides, hydrothermal magnetite is intergrown with sulfides, whereas metamorphic magnetite commonly replaces sulfides and is intergrown with typical metamorphic minerals such as chlorite, sericite, anthophylite, and/or actinolite. At Izok Lake, metamorphic magnetite in the deposit stringer zone is intergrown with gahnite. In VMSassociated BIFs, metamorphic magnetite is a product of a) decomposition of Fe-bearing silicates (biotite, hornblende) during metamorphism, b) exsolution from a high temperature (almandine) precursor during slow cooling, or c) recrystallization of magnetite, hematite, or Fe-bearing sulfides/silicates. Magmatic magnetite is commonly characterized by ilmenite exsolution, and fingerprints VMS deposits host bedrocks. Zoned magnetite may indicate retrograde skarn alteration associated to VMS mineralization. The growth zoning of magnetite can be the result of changes in the composition of hydrothermal fluids, the grade of metamorphism, and/or oxygen fugacity. Intrusion of seawater in volcanic sub-seafloor environments may also cause retrograde skarn alteration. Supergene magnetite overprints hypogene minerals and fingerprints supergene environments where low temperatures and high oxygen fugacity are prevalent. 4) This is the first study to combine high-resolution LA-ICP-MS analyses and PCA to determine variations in minor and trace element composition of magnetite from different VMS deposits and geologic settings. PCA discriminates the Izok Lake bimodal-felsic and Halfmile Lake felsic-siliciclastic VMS deposits, their host bedrocks, and alteration zones based on Si, Ca, Zr, Al, Ga, Mn, Mg, Ti, Zn, Co, Ni and Cr contents of magnetite. This research suggests that magnetite grains of the same origin share similar chemistry 151

clustering them in PCA models. However, the results show that the composition of metamorphic and hydrothermal magnetite vary over a wider range of trace elements concentration than that of magmatic magnetite. Magmatic magnetite from VMS settings is commonly rich in Ti but depleted in Si, Ca and Mg. 5) PLS-DA, a supervised classification technique, has also been used for the first time to classify LA-ICP-MS data of magnetite from various VMS deposits, host bedrocks, and VMS-associated BIFs. PLS-DA suggests that Si, Ca, Zr, Al, Mg, Ti, Zn, Co and Ni as discriminator elements isolating various VMS settings. PLS-DA of magnetite composition discriminates VMS deposits and VMS-associated BIFs from other deposit types including Ni-Cu, IOCG, IOA, porphyry, and the Bayan Obo REE-Fe-Nb deposit. Magnetite from VMS settings contains lower concentration of trace elements than that from mentioned mineral deposit types. 6) PCA and PLS-DA of magnetite compositions from various VMS deposits, their host rocks, alteration zones, and VMS-associated BIFs yield discrimination models for discovery of VMS deposits using the chemistry of magnetite in Quaternary sediments. This study indicates that magnetite forms a characteristic dispersal halo around the host deposit in which the percentage of magnetite with chemical signatures of VMS deposits shows the proximity to the source. My research also suggests that magnetite grains of each geologic environment carry local signatures plotting them in the fields for the bedrock samples of their host area in PLS-DA and PCA models.

5.2.

Recommendations for future work

This PhD project has been directed to meet its research objectives; thus it answered many questions regarding the application of magnetite chemistry and physical characteristics to mineral exploration for VMS deposits, while new questions have risen. Answering these new questions requires carrying out new research and investigations. To evaluate the reproducibility of the results, and to develop the established methods in this dissertation, recommendations for future works are listed as followings:

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- Integrating magnetite data with that of other indicator minerals, and till geochemistry from the Izok Lake and Halfmile Lake areas to develop indicator mineral methodologies. - Characterizing surface textures, shape, grains size distribution and mineral associations of magnetite transported by geologic environments other than glaciers (e.g., aeolian, fluivial) and comparing the results with that of the Izok Lake area to get insight into the application of these characteristics for remote discovery of new mineral deposits/potentials using magnetite. - Using multivariate statistical methods to investigate the MLA data and establish more sophisticated classification methods for using surface textures, grain size, shape and modal mineralogy of magnetite to indicator mineral exploration. - Integrating magnetite geochemical and morphological data to 1) distinguish relations between physical and chemical alterations of magnetite grains during erosion and liberation from host rocks, transport by geologic environments, and deposition in sedimentary basins; and 2) develop indicator mineral exploration methologies using magnetite. - Improving PLS-DA and PCA classification methods by implementing boundary classifiers such as using Probabilistic Principal Component Analysis (PPCA), or the nonlinear KNN classifier. - Compiling data on magnetite compositions from various mineral deposit types from the literature to establish a comprehensive dataset that is useful for validating future works as well as establishing comprehensive discrimination models.

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185

Appendices Appendix-I: Variable contributions for magnetite from different VMS deposits and BIFs investigated in Figure 4-4B.

187

188

Appendix-II: Variable contributions for magnetite from the VMS deposits investigated in Figure 4-6B.

189

190

Appendix-III: Variable contributions for magnetite from various mineral deposits investigated in Figure 4-7B.

191

Appendix-IV: The range of detection limits (in ppm) for A) EMPA and B) LA-ICPMS analyes.

A

B

Beam size

V

Cr

Zn

Cu

Ni

Mn

K

Sn

Ca

Ti

Al

Si

Mg

10 μm

#$##%&' #$##&(!

#$##)*' #$#+(+!

#$##+' #$#++%!

#$##,-' #$##-!

#$##.*' #$##-&!

#$##(,' #$##%&!

#$##+%' #$##))!

#$##%' #$##%-!

#$##+.' #$##)&!

#$##+,' #$##)-!

#$##+*' #$##(!

#$##+%' #$##)&!

#$##)+' #$##%,!

Beam size

192

20 μm

35 μm

43 μm !

20 μm

35 μm

43 μm

Nb

0.01- 0.2

0.004-0.06

0.05- 5.5

0.08- 1.38

0.026-0.53

0.19- 88.54

Mg

0.03- 0.26

0.01-0.083

0.00176- 0.07

Al

0.21- 1.8

0.325-1.8

0.01- 1.38

Mo

P

0.72- 5.84

1.39-6.3

0.0365- 1.57

Ag

0.03- 0.5

0.007-0.077

0.83- 9.04

K

0.93- 7.26

178-809

0.0146- 1.05

Cd

0.09- 1.09

0.03-0.36

20.75- 435.38

Sc

0.09- 0.8

0.025-0.17

0.00379- 0.15

In

0.01- 0.21

0.003-0.097

0.02- 0.57

Ti

0.28- 2.89

0.056-1.6

0.04- 1.17

Sn

0.17- 1.88

0.12-0.6

0.03- 4.82

V

0.07- 0.59

0.05-0.3

0.03- 1.24

Sb

0.07- 0.79

0.58-3.07

0.03- 1.1

Cr

1.29- 8.14

2.23-9.03

0.0055-0.12

Eu

0.02- 0.16

0.004-0.076

0.47- 16.29

Mn

1.19- 6.91

0.8-4.6

0.01- 0.32

Yb

0.05- 0.28

0.009-0.14

0.32- 11.47

Co

0.02- 0.36

0.004-0.04

0.0068- 0.41

Hf

0.04- 0.23

0.007-0.11

0.003- 11.91

Ni

0.23- 2.04

0.16-1.25

0.0018- 0.06

Ta

0.01-0.09

0.003-0.044

0.99- 3.53

Cu

0.14- 1.62

0.03-0.26

0.00713- 0.3

W

0.04- 0.66

0.016-0.23

0.054- 1.93

Zn

0.35- 3.22

0.29-2.09

0.005- 0.25

Re

0.04-0.34

0.01-0.12

0.14- 5.3

Ga

0.14- 0.79

0.056-0.4

0.02-2.62

Ir

0.12- 2.1

0.04-1.09

0.02- 0.9

Ge

0.2- 1.22

0.17-1.08

0.014- 2.79

Pt

0.13- 1.45

0.03-2.03

0.08- 2.71

As

0.3- 3.31

0.73-4.3

0.0054- 0.39

Au

0.02- 0.37

0.01-0.21

0.22- 6.81

Y

0.01- 0.1

0.003-0.035

0.02- 0.66

Pb

0.05- 0.36

0.04-0.31

0.0019- 0.17

Zr

0.01- 0.13

0.006-0.06

0.003- 0.15

Bi

0.07- 0.62

0.64-4.32

0.01-0.16

Appendix-V: EMPA raw data (in wt.%) for magnetite from the Izok Lake area ID !"#$%&#'"()!*++ !"#$%&#'"()!(++ !"#$%&#'"()!1++ !"#$%&#'"()!5++ !"#$%&#'"()!4+ !"#$%&#'"()!2+ !"#$%&#'"()!"+ !"#$%&#'"()*!++ !"#$%&#'"()**++ !"#$%&#'"()*3++ !"#$%&#'"()*1+ !"#$%&#'"()*5++ !"#$%&#'"()*4++ !"#$%&#'"()*2+ !"#$%&#'"()(!++ !"#$%&#'"()(*++ !"#$%&#'"()((++ !"#$%&#'"()(3++ !"#$%&#'"()(1++ !"#$%&#'"()(6++ !"#$%&#'"()(5++ !"#$%&#'"()3*++ !"#$%&#'"()3(++ !"#$%&#'"()33++ !"#$%&#'"()36++ !"#$%&#'"()34++ !"#$%&#'"()32++ !"#$%&#'"()3"++ !"#$%&#'"()1!++ !"#$%&#'"()1*++ !"#$%&#'"()11++ !"#$%&#'"()16++ !"#$%&#'"()15++ !"#$%&#'"()14++ !"#$%&#'"()12++ !"#$%&#'"()1"++ !"#$%&#'"()6!++ !"#$%&#'"()6*++ !"#$%&#'"()6(++ !"#$%&#'"()61++ !"#$%&#'"()65++ !"#$%&#'"()64++ !"#$%&#'"()62++ !"#$%&#'"()6"++ !"#$%&#'"()5!++ !"#$%&#'"()5*++ !"#$%&#'"()5(++ !"#$%&#'"()53++ !"#$%&#'"()56++ !"#$%&#'"()55++

Sample !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+

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Al !)!1*2+ !)!3*"+ !)!335+ !)!111+ !)(3(4+ !)!1*(+ !)!(16+ !)!"51+ !)!362+ !)!(56+ !)*3*4+ !)!(12+ !)!311+ *)33("+ !)!366+ !)!36*+ !)!("2+ !)!1!"+ !)!162+ !)!3"5+ !)!133+ !)!2*6+ !)!3*4+ !)!32+ !)!35*+ 6)666(+ !)!35*+ !)!1(*+ !)!("5+ !)!1*"+ 1)445+ *)146*+ !)!363+ !)!153+ !)!33(+ !)!122+ !)124"+ !)!3!3+ !)!345+ !)!11(+ !)!332+ !)3151+ !)!3(1+ !)!(26+ !)!332+ !)!13+ !)*5!1+ !)!(16+ !)!656+ !)!3(*+

Ca !)!*34+ !)!*!6+ !)!*(3+ !)!!(*+ !)!562+ !)!*42+ !)!((3+ !)!341+ !)!!63+ !)!((4+ !)*(34+ !)!64*+ !)!(!4+ !)**"4+ !)!5((+ !)!6(*+ !)!1!5+ !)!*5+ !)!!"3+ !)!*13+ !)!646+ !)!!54+ !)!"!6+ !)!!66+ !)!!55+ *)1"((+ !)!*26+ !)!(6+ !)!*15+ !)!354+ 3)4*5+ !)4*5*+ !)!6"(+ !)!555+ !)!!1"+ !)!*54+ !)1161+ !)!3!3+ !)!(*"+ !)!!52+ !)*(31+ 3)6551+ !)!2(3+ !)!**"+ !)!4*"+ !)!!2"+ !)!**1+ !)!6("+ !)!!"5+ !)!6"+

Cr !)*25(+ !)(6("+ !)33!5+ !)*464+ !)(242+ !)(*(5+ !)!"22+ !)*361+ !)*"*1+ !)*3!5+ !)1!*5+ !)*!2+ !)*245+ !)(!"4+ !)!1"(+ !)(42+ !)*31(+ !)("*+ !)*6*+ !)(5"4+ !)!"!1+ !)*63"+ !)*623+ !)*(6"+ !)*"4+ *)!3*1+ !)(511+ !)(***+ !)(!13+ !)3*!1+ !)"3(1+ !)(625+ !)**52+ !)*2""+ !)(2(1+ !)3"53+ !)*!3(+ !)*!!6+ !)*4("+ !)*"!"+ !)!""+ !)(""+ !)3!*2+ !)(!""+ !)**56+ !)*5*5+ !)"61(+ !)*3"6+ !)(13(+ !)3**1+

Cu !)!!3+ !)!!*1+ !)!!3(+ !)!!*"+ !)!!33+ + + !)!!66+ !)!!65+ !)!*1+ !)!!52+ + + + !)!!6*+ !)!!25+ !)!!3+ + + !)!**(+ !)!!36+ !)!!*+ !)!!41+ + + + + !)!!*"+ !)!!5*+ + !)!!65+ + + !)!!"6+ !)!!12+ !)!!11+ !)!*63+ + + !)!!12+ + + !)!**3+ !)!!3+ !)!!(6+ !)!!66+ + !)!(3(+ + +

K !)!!2+ !)!!!*+ + !)!!5*+ !)!!!5+ !)!!!6+ !)!!!(+ !)!!(*+ + + !)!3!3+ !)!*("+ !)!!*5+ !)!!4*+ !)!!*1+ + + + !)!!!5+ !)!!!4+ + + + !)!!*+ + !)!*"6+ !)!!!*+ + !)!!"2+ !)!**1+ !)!*!6+ !)!1"+ !)!!65+ !)!!!5+ + + !)!*+ + !)!!*(+ !)!!65+ !)!!**+ !)!!1"+ !)!!"1+ !)!!3(+ !)!!*(+ + !)!!!1+ !)!!5(+ !)!!(+ !)!!!2+

Mg !)!!14+ !)!!65+ + !)!!*1+ !)!!5+ !)!!32+ !)!!(6+ !)!152+ !)!!3(+ !)!!*6+ !)!5*4+ !)!!5"+ !)!!54+ !)*"56+ !)!!1*+ !)!!!3+ + !)!!35+ !)!!24+ !)!!(1+ + !)!(4*+ !)!!"1+ !)!!64+ !)!!(5+ + !)!!!1+ !)!!(*+ !)!!(2+ !)!!4+ !)2122+ *)**!5+ !)!!53+ !)!!!1+ !)!!26+ !)!!62+ !)*2(+ + + !)!!13+ + !)*5"2+ !)!*+ !)!!6(+ !)!!!6+ !)!!4(+ !)!(!6+ !)!!(1+ !)!6""+ !)!!2(+

Mn !)!**6+ !)!!6*+ !)!*1+ !)!!"(+ !)!*!(+ !)!!2"+ !)!!""+ !)!*2+ !)!!6"+ !)!!53+ !)!!53+ !)!!"3+ !)!!2"+ !)!(2"+ !)!!"5+ !)!*+ !)!!25+ !)!!"5+ !)!*16+ !)!!26+ + !)!"51+ !)!**1+ !)!33+ !)!!5*+ !)!*36+ !)!!1*+ !)!**2+ !)!!41+ !)!*(6+ !)!6!4+ !)!5*3+ !)!*11+ !)!!12+ !)!!(3+ !)!**5+ !)!*"1+ !)!*53+ !)!!2*+ !)!*!5+ !)!*4*+ !)!*5(+ !)!*((+ !)!***+ !)!!66+ !)!**6+ !)!*3"+ !)!*22+ !)!!21+ !)!*(4+

Ni !)!!2"+ !)!*54+ !)!!16+ !)!!!5+ !)!!"+ !)!!4(+ !)!!22+ !)!*33+ !)!*!1+ !)!*(2+ !)!!5"+ !)!*!"+ !)!!63+ !)!*!"+ !)!!6+ !)!!"4+ !)!!3"+ !)!!11+ !)!!51+ !)!!*3+ !)!*3+ !)!!4"+ !)!!33+ !)!!62+ !)!*3*+ + + !)!!6(+ !)!*!1+ !)!!12+ !)!!16+ !)!!2*+ !)!!52+ !)!**(+ !)!**1+ !)!*6+ !)!!36+ !)!*!4+ !)!!24+ + !)!!"1+ !)!!3(+ + !)!!*"+ !)!!54+ !)!!6*+ !)!!22+ !)!*65+ !)!!11+ !)!*1+

Si !)!*64+ !)!*6*+ !)!(!*+ !)!*42+ !)!(32+ !)!*23+ !)!*44+ !)!"2+ !)!*5+ !)!*56+ !)*("1+ !)!(**+ !)!*64+ *)616"+ !)!*23+ !)!(!5+ !)!*44+ !)!*(*+ !)!(**+ !)!*4"+ !)!*5"+ !)!335+ !)!*23+ !)!*6+ !)!*4*+ **)6(*(+ !)!*43+ !)!*22+ !)!*41+ !)!*43+ 4)3*"4+ 3)""56+ !)!*4"+ !)!*"1+ !)!*(3+ !)!*4(+ !)1!13+ !)!*"+ !)!((2+ !)!*4+ !)!*"1+ !)34(*+ !)*((2+ !)!((3+ !)!*56+ !)!*56+ !)*5+ !)!*43+ !)!*45+ !)!(5+

+ +

Sn !)!!(*+ + !)!!(*+ !)!!!"+ + !)!!65+ !)!!(1+ + !)!!!1+ + !)!!35+ + !)!!(6+ + !)!!56+ + + !)!!1"+ + !)!!6*+ + + !)!!13+ + + !)!!**+ !)!!*4+ !)!!!4+ !)!!*3+ + !)!!!"+ !)!!(3+ + + + !)!!65+ !)!!31+ + !)!!64+ + !)!!3"+ + + + !)!!*+ + !)!!*3+ + !)!!13+

Ti !)!34(+ !)!4(6+ !)(14"+ !)!16+ !)*((2+ !)!324+ !)!453+ !)!125+ !)!132+ !)!25"+ !)!6!6+ !)!322+ !)!633+ !)!33"+ !)!16(+ !)!1*"+ !)!15*+ !)!322+ !)*!5(+ !)!133+ !)!166+ *)(211+ !)!613+ !)3333+ !)!44*+ !)!3*2+ !)!22(+ !)!16+ !)!6(3+ !)!162+ !)2"(3+ !)!6(2+ !)*!*4+ !)!11+ !)!32(+ !)!133+ !)11*+ !)!1*+ !)!155+ !)!1"5+ !)!136+ !)!*"+ !)!1*"+ !)!1*(+ !)!35+ !)!655+ !)!664+ !)!251+ !)!141+ !)!4(3+

V !)5"6*+ !)246*+ !)61+ !)5566+ !)564"+ !)1636+ *)3(42+ !)5!!(+ !)6416+ !)442*+ !)5"34+ *)4"**+ !)"163+ !)6"62+ !)65!1+ !)(64(+ !)4(43+ !)136*+ !)26"3+ !)1(!5+ !)6452+ !)44*+ !)4!12+ !)466(+ !)633*+ !)11*+ !)345(+ !)664"+ !)421(+ *)!!12+ !)2(!1+ !)6""2+ *)*64+ !)46("+ !)5*(4+ !)156"+ !)526*+ !)24(*+ !)6!4*+ !)221"+ !)4524+ *)1142+ *)!*4*+ !)534+ !)"!5(+ !)6"!5+ !)1164+ !)"611+ !)6152+ !)6(*2+

Zn !)!!*"+ !)!!6"+ + !)!!"+ !)!!63+ + !)!*3+ !)!*1"+ + !)!!*1+ + !)!*(*+ !)!!32+ + !)!!"1+ + !)!*(1+ !)!*53+ !)!!64+ !)!!45+ + !)!(41+ + !)!!"(+ + !)!!44+ !)!!2"+ !)!!3"+ !)!!!6+ !)!(!4+ !)!(*5+ + !)!*+ !)!*36+ !)!!(3+ + !)!!62+ !)!!52+ + + + !)!*5(+ !)!**4+ + + !)!!14+ + !)!!44+ !)!(43+ + +

ID !"#$%&#'"()54++ !"#$%&#'"()52++ !"#$%&#'"()5"++ !"#$%&#'"()4*++ !"#$%&#'"()4(++ !"#$%&#'"()43++ !"#$%&#'"()41++ !"#$%&#'"()46++ !"#$%&#'"()44++ !"#$%&#'"()42++ !"#$%&#'"()4"++ !"#$%&#'"()2!++ !"#$%&#'"()2*++ !"#$%&#'"()23++ !"#$%&#'"()21++ !"#$%&#'"()26++ !"#$%&#'"()25++ !"#$%&#'5*)!*++ !"#$%&#'5*)!(++ !"#$%&#'5*)!3++ !"#$%&#'5*)!1++ !"#$%&#'5*)!6++ !"#$%&#'5*)!4++ !"#$%&#'5*)*!++ !"#$%&#'5*)**++ !"#$%&#'5*)*(++ !"#$%&#'5*)*3++ !"#$%&#'5*)*1++ !"#$%&#'5*)*6++ !"#$%&#'5*)*5++ !"#$%&#'5*)*4++ !"#$%&#'5*)(!++ !"#$%&#'5*)(*++ !"#$%&#'5*)((++ !"#$%&#'5*)(3++ !"#$%&#'5*)(1++ !"#$%&#'5*)(6++ !"#$%&#'5*)(5++ !"#$%&#'5*)(4++ !"#$%&#'5*)(2++ !"#$%&#'5*)("++ !"#$%&#'5*)3!++ !"#$%&#'5*)3*++ !"#$%&#'5*)3(++ !"#$%&#'5*)33++ !"#$%&#'5*)31++ !"#$%&#'5*)36++ !"#$%&#'5*)34++ !"#$%&#'5*)32++ !"#$%&#'5*)3"++

194

Sample !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'"(+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+ !"#$%&#'5*+

Sample type ,-../0+ ,-../0+ ,-../0+ ,-../0+ ,-../0+ ,-../0+ ,-../0+ ,-../0+ ,-../0+ ,-../0+ ,-../0+ ,-../0+ ,-../0+ ,-../0+ ,-../0+ ,-../0+ ,-../0+ ,-789:;#/9/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+ >/08+?0/@-:908+

Al !)!((1+ !)!(51+ !)!*"4+ !)!(14+ !)!6*"+ !)!3!3+ !)!153+ !)!33+ !)!64"+ !)!1*5+ !)!4("+ !)!3(*+ !)!(4"+ !)**35+ !)!(2"+ !)!4*4+ !)!3((+ !)!(36+ !)!3+ !)!("4+ !)!(51+ !)!(("+ !)!*36+ !)!33+ !)!3*3+ !)!3!*+ !)!(6+ !)!3*5+ !)!6"(+ !)!335+ !)!(5(+ !)!(45+ !)!324+ !)!*""+ !)!3!4+ !)**3*+ !)!(62+ !)!11"+ !)!""3+ !)!((3+ !)!*"3+ !)!556+ !)!2"+ !)!(12+ !)!3!4+ !)!(21+ !)!("1+ !)*!3+ !)!356+

Ca !)!*11+ !)!(24+ !)!3(2+ !)!(23+ !)!*42+ !)!334+ !)!!4(+ !)!(*5+ !)!52*+ !)!*51+ !)!**1+ !)!*6+ !)!!(4+ !)(4"6+ !)!!6"+ !)!!24+ !)!!23+ !)!363+ !)!624+ !)!(((+ !)!151+ !)!!"5+ !)!*55+ !)!*3"+ !)!1!"+ !)!!66+ !)!*!(+ !)!!2*+ !)*!(+ !)!3(4+ !)!(33+ !)!6*+ !)!*"5+ !)!(*(+ !)!("+ !)!4!3+ !)*36(+ !)!(1"+ !)!"41+ !)!!2(+ !)!*"5+ !)!52+ !)*!2+ !)!!62+ !)!!41+ !)!3!2+ !)!!(2+ !)!1*3+ !)!!24+

Cr + + + + + + + + + + + + + + + + + + + + !)!!*+ + + + + + + + + + + !)!!33+ + + + + + + + + + + + + !)!!!2+ + + !)!!*1+ +

Cu !)!!31+ + !)!!**+ !)!!44+ !)!!!4+ !)!!(4+ + !)!!!*+ + !)!!16+ + + + + !)!!42+ + !)!!4"+ + !)!!42+ + + !)!!!*+ + + + !)!!*3+ + + !)!!21+ + + !)!!1(+ !)!!*(+ + !)!!1"+ + !)!*(*+ !)!!(3+ !)!!45+ !)!!"(+ + + + !)!!(6+ !)!!"3+ + + + !)!!*"+

K !)!!!*+ !)!!45+ !)!!*+ !)!!!2+ !)!*!1+ !)!!65+ + !)!!*1+ !)!22+ + + !)!!!*+ !)!!!1+ !)!!3+ !)!!34+ !)!!("+ !)!!*3+ + !)!!*6+ !)!!*2+ !)!!(6+ + !)!!!5+ !)!!*3+ !)!!!5+ !)!!5"+ !)!!(3+ !)!!!2+ !)!(23+ !)!!*3+ !)!*!*+ !)!!(3+ + !)!!6"+ + !)!*"5+ !)!!26+ !)!!*1+ !)!452+ !)!!24+ !)!!35+ !)!!15+ !)!*22+ !)!!*2+ !)!!*3+ + + !)!!(4+ !)!!!4+

Mg !)!!*+ !)!!33+ !)!!31+ !)!!5(+ !)!((5+ !)!!*6+ !)!!33+ !)!!*3+ !)!(62+ !)!!*"+ !)!!56+ !)!!5*+ !)!!1(+ !)!2(1+ !)!!53+ !)!51*+ !)!!3+ !)!!(*+ !)!6(1+ !)!!*3+ !)!!66+ !)!!6*+ !)!!*4+ !)!!!"+ !)!!**+ !)!!(6+ !)!!62+ !)!!11+ !)!4!4+ !)!!65+ !)!!*"+ !)!!6(+ !)!123+ !)!!*3+ !)!!!2+ !)!!33+ !)(113+ !)!((2+ !)**!6+ !)!!(+ !)!!34+ !)!661+ !)((+ !)!!32+ !)!!65+ !)!!!5+ !)!!12+ !)!42*+ !)!!3"+

Mn !)!46*+ !)!426+ !)!1("+ !)!6(+ !)!41(+ !)!4*6+ !)!1(+ !)!441+ !)*!(3+ !)!1("+ !)**64+ !)!464+ !)!3(6+ !)!52+ !)!216+ !)!663+ !)!1(6+ !)!545+ !)!145+ !)!32*+ !)!224+ !)!634+ !)!3*4+ !)!31"+ !)!6"*+ !)*!4"+ !)*(13+ !)!356+ !)!121+ !)!1*(+ !)!(44+ !)!2""+ !)!252+ !)!4*+ !)!5*6+ !)*!52+ !)*31"+ !)!455+ !)!565+ !)!33+ !)!((3+ !)!144+ !)!252+ !)!"*(+ !)!325+ !)!413+ !)!32"+ !)!51(+ !)!12+

Ni !)!!4"+ + !)!!14+ !)!!61+ + !)!!*4+ !)!!**+ + + !)!!!(+ + !)!*("+ !)!!3+ !)!!13+ !)!!12+ !)!!"+ !)!!*5+ !)!!11+ !)!!54+ + + + !)!!1"+ !)!!36+ + + + !)!*+ !)!!!*+ + + !)!!**+ !)!!34+ !)!!(3+ !)!!!4+ + !)!!45+ !)!!51+ !)!!("+ + !)!!(1+ + !)!!32+ + + !)!!45+ + + !)!!4"+

Si !)!3(*+ !)!16*+ !)!1(4+ !)!6(2+ !)*!24+ !)!335+ !)!3"1+ !)!36+ !)*4*3+ !)!1!5+ !)!3"(+ !)!5!*+ !)!31*+ !)1535+ !)!32+ !)*533+ !)!316+ !)!31"+ !)(5*6+ !)!3(2+ !)!312+ !)!342+ !)!3(5+ !)!356+ !)!353+ !)!344+ !)!362+ !)!311+ !)33**+ !)!153+ !)!1!6+ !)!322+ !)3!*1+ !)!33(+ !)!355+ !)!11*+ *)363(+ !)**(2+ !)5*15+ !)!35*+ !)!34(+ !)("!*+ !)2323+ !)!35"+ !)!34*+ !)!1!3+ !)!32*+ !)645+ !)!1!1+

Sn + + + !)!!51+ + !)!!!(+ + + + !)!!!"+ + !)!!**+ + !)!!3+ + + + + !)!!5+ + + !)!!(+ + + !)!!13+ + !)!!(5+ !)!!55+ + !)!!*6+ !)!!!(+ !)!!**+ + !)!!*1+ + + !)!!1(+ !)!!5+ !)!!14+ + + + !)!!(6+ + !)!!*3+ + + !)!!*3+ +

Ti !)!625+ !)!143+ !)!12*+ !)!6(5+ !)!4(4+ !)!6(3+ !)!4*1+ !)!54*+ !)!1*2+ !)!64*+ !)3"25+ !)*(!1+ !)!431+ !)!35(+ !)3*!2+ !)*3"5+ !)!452+ !)!356+ !)!(4(+ !)!6(6+ !)!144+ !)*(*"+ !)!663+ !)!5!3+ !)!5("+ !)5!1(+ !)1461+ !)!63*+ !)!65+ !)!536+ !)!521+ !)!312+ !)!5*(+ !)!114+ !)!5(+ !)!244+ !)!1(4+ !)!111+ !)!65*+ !)!465+ !)!5!4+ !)!63*+ !)!56+ !)14!6+ !)!161+ !)!(6(+ !)!3*"+ !)!645+ !)!11+

V + !)!!36+ !)!!*5+ + !)!!5(+ + + + !)!!(5+ !)!!!(+ !)!!43+ + + + + + !)!!*(+ !)!!6+ !)!!!"+ !)!*!5+ + !)!*!3+ !)!!32+ !)!!62+ + + !)!*56+ + !)!!*1+ !)!!15+ + !)!!(6+ + !)!!16+ !)!!14+ !)!*13+ !)!!5(+ !)!**4+ !)!!66+ !)!!*6+ !)!!3"+ !)!!6(+ + !)!**2+ !)!!46+ + !)!!!2+ !)!!3(+ !)!!56+

Zn !)!*6+ + !)!*(3+ + !)!!(2+ !)!!"5+ !)!!45+ + !)!*26+ + !)!!5*+ !)!*1"+ + !)!*66+ !)!!53+ + + + !)!!61+ !)!!64+ + !)!!(*+ !)!*5(+ + !)!*51+ !)!*53+ + !)!!1(+ !)!*33+ !)!!*2+ !)!*4(+ + !)!!!*+ + + + + !)!!!2+ !)!!!4+ + !)!**"+ !)!*!1+ + !)!!16+ !)!!3+ !)!!2+ !)!*12+ + !)!!51+

ID !"#$%&#'"!)13++

Sample !"#$%&#'"!+

Sample type >/08+?0/@-:908+

Al !)!((6+

Ca !)!!33+

Cr

Cu !)!!!6+

K !)!!4+

Mg

Mn !)!3"*+

Ni

Si !)!313+

Sn

Ti !)!445+

V

!"#$%&#'"!)11++ !"#$%&#'"!)16++

!"#$%&#'"!+ !"#$%&#'"!+

>/08+?0/@-:908+ >/08+?0/@-:908+

!)!*!2+ !)!45*+

!)!6!6+ !)*!43+

+ +

!)!!!4+ !)!((4+

!)!!63+ !)!*(3+

+ !)!!6(+ !)!415+

!)!36+ !)!("6+

+ !)!!*+ !)!*!(+

!)!443+ !)*423+

+ !)!!*2+

!)!1!5+ !)!662+

+ + !)!!((+

!"#$%&#'"!)15++ !"#$%&#'"!)14++

!"#$%&#'"!+ !"#$%&#'"!+

>/08+?0/@-:908+ >/08+?0/@-:908+

!)!365+ !)!53*+

!)!*3*+ !)!!"3+

+ +

+ !)!!((+

!)!!34+ !)!!*+

!)!!1+ !)!!34+

!)!612+ !)!342+

!)!**5+

!)!346+ !)!321+

+ +

!)!(34+ !)!62"+

!"#$%&#'"!)12++ !"#$%&#'5!)!*++

!"#$%&#'"!+ !"#$%&#'5!+

>/08+?0/@-:908+ $-AA9B;+ACD?9=;A+

!)!3(4+ !)!!*4+

!)!(66+ !)!*!6+

+ +

!)!!"4+ !)!!4*+

!)!!!(+ !)!!*(+

!)!!3(+ *)554*+

!)!15*+ !)(5*+

+ +

!)!353+ !)!*64+

+ + !)!!3"+

!)!56+

!)!!1*+ !)!!!6+

+ !)!*53+

!"#$%&#'5!)!(++ !"#$%&#'5!)!3++

!"#$%&#'5!+ !"#$%&#'5!+

$-AA9B;+ACD?9=;A+ $-AA9B;+ACD?9=;A+

!)!!!4+

!)!!31+ !)!!(+

+ +

!)!((*+ !)!*"3+

+

!)3*26+ !)*"34+

!)*6(6+ !)34!"+

+ + !)!!51+

!)!!**+ !)!!*+

+

+ +

!)!!5(+ !)!!25+

+ !)3451+ !)(4(+

!"#$%&#'5!)!1++ !"#$%&#'5!)!6++

!"#$%&#'5!+ !"#$%&#'5!+

$-AA9B;+ACD?9=;A+ $-AA9B;+ACD?9=;A+

+ + !)!!**+

!)!*11+ !)!!*2+

+ +

!)!((2+

+ + !)!!*+

!)1*13+ !)5*""+

!)*66(+ !)3352+

+ !)!!*+

!)!*!6+ !)!3!1+

+ + !)!!62+

+ !)!!(1+

!)!!14+

!)(522+ !)!*62+

!"#$%&#'5!)!4++ !"#$%&#'5!)!"++

!"#$%&#'5!+ !"#$%&#'5!+

$-AA9B;+ACD?9=;A+ $-AA9B;+ACD?9=;A+

+

!)!!(*+ !)!("1+

+ +

+ !)!!12+ !)!**4+

+

*)"2"+ !)!*2(+

!)((!*+ !)!3*+

!)!!5+

+ *)*32*+

!)!!13+ !)!*21+

+ +

+ !)!!*(+ !)!!!5+

!)!32(+

!"#$%&#'5!)**++ !"#$%&#'5!)*(++

!"#$%&#'5!+ !"#$%&#'5!+

$-AA9B;+ACD?9=;A+ $-AA9B;+ACD?9=;A+

+ !)!!*6+

!)!!("+ !)!!(4+

+ +

!)!!65+

+ !)!!!2+

()!*34+ *)6(23+

!)(6((+ !)(436+

+ !)!!*4+ !)!!64+

!)!!6*+ !)!!11+

+ !)!!!2+

!"#$%&#'5!)*3++ !"#$%&#'5!)*1++

!"#$%&#'5!+ !"#$%&#'5!+

$-AA9B;+ACD?9=;A+ $-AA9B;+ACD?9=;A+

+ +

!)!!*2+ !)!!(1+

+ +

+ !)!!61+ !)!!64+

+ +

!)!1"2+ *)(!(5+

!)34!5+ !)(6!*+

+ !)!!!6+

!)!!35+ !)!!!4+

!)!!(1+ !)!!!4+

+ +

+ !)!!35+ !)!!*3+

+ !)!(53+ !)!(((+

!"#$%&#'5!)*5++ !"#$%&#'5!)*4++

!"#$%&#'5!+ !"#$%&#'5!+

$-AA9B;+ACD?9=;A+ $-AA9B;+ACD?9=;A+

+ + !)!!!*+

!)!!!5+ !)!!12+

+ +

+

+ !)!!!4+ !)!!(1+

*)2553+ *)6!4"+

!)(62+ !)(("4+

+ !)!!44+

!)!!(4+ !)!!1*+

!)!!!"+

+ + !)!!!1+

!)!!11+ !)!!!4+

!)!(!5+ !)!(!5+

!"#$%&#'5!)*2++ !"#$%&#'5!)*"++

!"#$%&#'5!+ !"#$%&#'5!+

$-AA9B;+ACD?9=;A+ $-AA9B;+ACD?9=;A+

+

!)!!!"+ !)!!(3+

+ +

+ + !)!!41+

+

*)1354+ !)!("+

!)(15"+ !)(112+

!)!!34+

!)!!*2+ !)!*23+

+ +

!)!!!(+

!)!!12+

!)!*32+ !)!*42+

!"#$%&#'5!)(!++ !"#$%&#'5!)(*++

!"#$%&#'5!+ !"#$%&#'5!+

$-AA9B;+ACD?9=;A+ $-AA9B;+ACD?9=;A+

+ +

!)!!33+

+ +

!)!*2"+

+ !)!!!5+ !)!!!*+

!)*6"3+ *)1*(3+

!)*524+ !)(*1(+

+ + !)!!44+

!)!!42+ !)!!*6+

+ +

+ +

+ +

!)*164+ !)!(61+

!"#$%&#'5!)((++ !"#$%&#'5!)(3++

!"#$%&#'5!+ !"#$%&#'5!+

$-AA9B;+ACD?9=;A+ $-AA9B;+ACD?9=;A+

+ +

+ !)!!(5+ !)!!33+

+ +

+ +

+

!)156(+ *)"41*+

!)*6*4+ !)(14(+

+

!)!!31+ !)!!(3+

+ !)!!52+

+ + !)!!!6+

+ +

!)4!"2+ !)!!*(+

!"#$%&#'5!)(1++ !"#$%&#'5!)(6++

!"#$%&#'5!+ !"#$%&#'5!+

$-AA9B;+ACD?9=;A+ $-AA9B;+ACD?9=;A+

+ + !)!!!"+

!)!!!1+ !)!!!4+

+ +

+ + !)!!("+

+ + !)!!!6+

*)3!"2+ *)3*32+

!)(3!"+ !)((46+

+ !)!!5*+

!)!!(1+ !)!!32+

+ !)!!(1+

+ !)!!6+

!)!5*5+ !)!12+

!"#$%&#'5!)(4++ !"#$%&#'5!)(2++

!"#$%&#'5!+ !"#$%&#'5!+

$-AA9B;+ACD?9=;A+ $-AA9B;+ACD?9=;A+

!)!!!"+

!)!!!"+ !)!!*2+

+ +

!)("**+ !)!!3+

+

!)*54*+ ()!(2*+

!)*(5*+ !)(3(5+

+ +

!)!!(+ !)!!32+

+ !)!!25+ !)!!*3+

+ +

+ !)!!4*+

!)*551+ !)*!43+

!"#$%&#'5!)("++ !"#$%&#'5!)3!++

!"#$%&#'5!+ !"#$%&#'5!+

$-AA9B;+ACD?9=;A+ $-AA9B;+ACD?9=;A+

+ +

!)!!44+ !)!!*+

+ +

!)!!54+

+ +

*)**5+ !)326"+

!)*2!3+ !)(("4+

+ !)!!(5+ !)!!1(+

!)!!(4+ !)!!*4+

+ !)!!54+

+ !)!!*3+

+ !)!!26+

!)*!23+ !)!324+

!"#$%&#'5!)3*++ !"#$%&#'5!)3(++

!"#$%&#'5!+ !"#$%&#'5!+

$-AA9B;+ACD?9=;A+ $-AA9B;+ACD?9=;A+

+ +

!)!!3+ !)!!!(+

+ +

+ !)!!2+ !)!!5+

+ !)!!*5+

()346"+ *)4*42+

!)(164+ !)(*"5+

!)!!6(+

!)!!33+ !)!!(4+

+

+ !)!!2*+ !)!!*2+

+ + !)!!4*+

!)!(""+ !)!!44+

!"#$%&#'5!)33++ !"#$%&#'5!)36++

!"#$%&#'5!+ !"#$%&#'5!+

$-AA9B;+ACD?9=;A+ $-AA9B;+ACD?9=;A+

+ +

!)!!*4+ !)!!(2+

+ +

!)!!!5+ !)!!46+

+ !)!!*+ !)!!!1+

()!3!"+ !)6!46+

!)(1""+ !)*535+

+ + !)!!((+

!)!!*4+ !)!!*+

+ !)!!3*+ !)!!15+

+ !)!!(+

!)!!43+ !)!!63+

!)!!*5+ !)!"4+

!"#$%&#'5!)35++ !"#$%&#'5!)34++

!"#$%&#'5!+ !"#$%&#'5!+

$-AA9B;+ACD?9=;A+ $-AA9B;+ACD?9=;A+

+ +

!)!!!5+ !)!!31+

+ + !)!!*(+

+ !)!!24+

+

*)5*42+ *)3222+

!)(31"+ !)(3!*+

+

!)!!12+ !)!!11+

!)!!32+

+

+ !)!!46+

+

!"#$%&#'5!)32++ !"#$%&#'5!)3"++

!"#$%&#'5!+ !"#$%&#'5!+

$-AA9B;+ACD?9=;A+ $-AA9B;+ACD?9=;A+

+ +

+ !)!!((+

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!)!!44+

!)!*12+ !)!**5+

+

!)!6"*+ !)*4(1+

!)3"51+ !)!6(3+

+ !)!*3+ !)!*(1+

!"#$%&#!(!)*1!++ !"#$%&#!(!)*16++

!"#$%&#!(!+ !"#$%&#!(!+

H9DD+ H9DD+

!)!*4(+ !)!!*1+

!)!**2+ !)!(44+

!)!162+ !)*512+

+ !)!!(1+ !)!*!1+

!)!!((+ !)!!1+

!)!!(4+ !)!!*(+

!)!!"3+ !)!631+

+ !)!*(1+ !)!!63+

!)!*!*+ !)!!45+

+ +

!)!*(2+ !)!!*6+

!)("*(+ !)*6"6+

+ !)!!(6+

!)!!61+

+

199

200

ID !"#$%&#!(!)*12++

Sample !"#$%&#!(!+

Sample type H9DD+

Al !)!!25+

Ca

Cr !)!165+

Cu

K !)!!*6+

Mg !)!!12+

Mn !)!56*+

Ni !)!!61+

Si !)!!14+

Sn

Ti !)!!(3+

V !)*441+

Zn

!"#$%&#!(!)*6++ !"#$%&#!(!)*6!.++

!"#$%&#!(!+ !"#$%&#!(!+

H9DD+ H9DD+

!)!(34+ !)!*56+

+ !)!3(3+ !)!!3(+

!)!***+

+ + !)!!46+

!)!!6"+ !)!!*2+

!)!!34+ !)!!((+

!)!!2(+ !)!*2"+

!)!!*3+

!)!63*+ !)!!"5+

+ +

!)!622+ !)!!55+

!)!1!1+ !)!*1"+

+ + !)!!1+

!"#$%&#!(!)*6*++ !"#$%&#!(!)(*++

!"#$%&#!(!+ !"#$%&#!(!+

H9DD+ H9DD+

!)!363+ !)*!*2+

!)!!(5+ !)!415+

+ + *)!31(+

!)!!*(+ !)!*!6+

!)!!*6+ !)!!*"+

!)!!(3+ !)!!64+

!)!(24+ !)!3*"+

+ !)!!15+ !)!14"+

!)!(!(+ !)!!"5+

+ +

!)!(4(+ !)**51+

!)!23(+ !)1221+

!)!!51+ !)!("3+

!"#$%&#!(!)(3++ !"#$%&#!(!)(2++

!"#$%&#!(!+ !"#$%&#!(!+

H9DD+ H9DD+

!)**!4+ !)!*3*+

!)!!14+ !)!*64+

+ !)12"6+

!)!!11+

!)*"(+ !)!61(+

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!)!(34+ !)!!4*+

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!)*32"+ !)!!5(+

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!)!(*5+ !)!(12+

!"#$%&#!(!)3*++ !"#$%&#!(!)15++

!"#$%&#!(!+ !"#$%&#!(!+

H9DD+ H9DD+

!)*345+ !)!!*"+

*)2656+ !)!1**+

!)!!(+ !)234+

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!)!!43+ !)!!3+

+ !)!65+ !)!!1*+

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!)!!*3+ !)!*12+

!)(564+ !)!*2*+

!)!!62+

!)*5*4+ !)!!32+

!)!!44+ !)(!5"+

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!"#$%&#!(!)12++ !"#$%&#!(!)6!++

!"#$%&#!(!+ !"#$%&#!(!+

H9DD+ H9DD+

!)!*!*+ !)(1"*+

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!)!*65+

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!)!!3+ !)!!(1+

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!)!!(*+ !)!(5+

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!)!*"2+ !)!1*1+

!)!35+ !)*4"*+

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!"#$%&#!(!)65++ !"#$%&#!(!)64++

!"#$%&#!(!+ !"#$%&#!(!+

H9DD+ H9DD+

!)!(4*+ !)!3*(+

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!)!!5"+ !)!!!5+

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!)!3(3+ !)*!**+

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!)!3*2+ !)!**+

!)!!6*+ !)!36(+

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!"#$%&#!(!)6"++ !"#$%&#!(!)5"++

!"#$%&#!(!+ !"#$%&#!(!+

H9DD+ H9DD+

!)!(14+ !)!*!*+

!)!!*5+ !)!(!3+

+ !)!!52+ !)("45+

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!)!!3(+ !)!!6*+

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!)!1(3+ !)6*+

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!"#$%&#!(!)4!++ !"#$%&#!(!)4*++

!"#$%&#!(!+ !"#$%&#!(!+

H9DD+ H9DD+

!)!("+ !)!33(+

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!"#$%&#!(!)41++ !"#$%&#!(!)46++

!"#$%&#!(!+ !"#$%&#!(!+

H9DD+ H9DD+

!)!5*2+ !)!(!5+

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!)!!13+ !)!("4+

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!)!*22+

!)!6*1+ !)!!6(+

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+

!)5"35+ !)!*13+

+ !)!!(+

!)(6"1+ !)!*+

!)*5""+ !)!3!5+

+

!"#$%&#!(!)45++ !"#$%&#!(!)44++

!"#$%&#!(!+ !"#$%&#!(!+

H9DD+ H9DD+

!)!16*+ !)53"5+

!)!!1*+ !)!!!2+

+

+

+ !)!!44+

!)!!35+ !)!*23+

!)!(5*+ !)!6(3+

+ !)!!45+ !)!*3(+

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!)!!!"+ !)!!4*+

!)!342+ !)*!6*+

!)!222+ !)!2!5+

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!"#$%&#!(!)4"++ !"#$%&#!(!)2(++

!"#$%&#!(!+ !"#$%&#!(!+

H9DD+ H9DD+

!)!((+ !)!*"1+

!)!!*2+ !)!*26+

+ !)!!64+

+ + !)!!24+

+ !)!!!"+ !)!!(3+

!)!!13+ !)!!6"+

!)!*"3+ !)!!(4+

+ !)!!(+

!)!!"+ !)!(54+

+ !)!!*5+

!)!*43+ !)!1!*+

!)!!45+

!"#$%&#!(!)23++ !"#$%&#!(!)26++

!"#$%&#!(!+ !"#$%&#!(!+

H9DD+ H9DD+

!)11!"+ !)!*(2+

!)!!((+ !)!142+

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!)!!2"+ !)!!36+

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+ !)!(5"+

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!)!*(+ !)!*6"+

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!"#$%&#!3()!*++ !"#$%&#!3()!(++

!"#$%&#!3(+ !"#$%&#!3(+

H9DD+ H9DD+

!)***6+ !)!*53+

!)!!6"+ !)!!(2+

+ !)!!2*+

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!)!!*2+

!)!!*3+ !)!!(2+

!)!!(2+ !)!*66+

!)!*64+ !)!*(2+

!)!3+ !)!!""+

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!)*553+ !)!*4(+

!)!!"3+ !)*46+

!)!!((+ !)!**"+

!"#$%&#!3()!3++ !"#$%&#!3()!5++

!"#$%&#!3(+ !"#$%&#!3(+

H9DD+ H9DD+

!)!(4(+ !)!314+

!)!!2+ !)!!!6+

+

+

+

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!)!!24+ !)!*26+

!)!(3+ !)!*32+

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!"#$%&#!3(+ !"#$%&#!3(+

H9DD+ H9DD+

!)!1*6+ !)!62"+

!)!!**+ !)!!!1+

+ !)!!!3+

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!)!!!(+

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!)!!!5+ !)!116+

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!)!1!"+ !)!*!"+

+ !)*142+

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!"#$%&#!3()*"++ !"#$%&#!3()((++

!"#$%&#!3(+ !"#$%&#!3(+

H9DD+ H9DD+

!)!(!4+ !)!*!1+

!)!!!6+ !)!**6+

+ +

+ +

+ + !)!!*1+

!)!!*4+ !)!!33+

!)!!44+ !)*5!2+

+

!)!!4*+ !)!!(5+

+ !)!!3*+

!)!*!(+ !)!!34+

!)!334+ !)!*32+

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!"#$%&#!3()3(++ !"#$%&#!3()36++

!"#$%&#!3(+ !"#$%&#!3(+

H9DD+ H9DD+

!)!*!3+ !)!*(1+

!)!(!6+ !)!!*5+

+ *)5""+

+ !)!!!(+ !)!!*5+

!)!((3+

!)!!(6+ !)!!6*+

!)!!"2+ !)!(1(+

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!)!*("+ !)!!41+

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!)!5*6+ !)!!"2+

!)!!43+ !)!!62+

!"#$%&#!3()32++ !"#$%&#!3()1!++

!"#$%&#!3(+ !"#$%&#!3(+

H9DD+ H9DD+

!)!52"+ !)*(5(+

!)!3"4+

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!)!!(6+

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!)!1!5+ !)!*61+

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!)!!1(+

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!"#$%&#!3()1(++ !"#$%&#!3()15++

!"#$%&#!3(+ !"#$%&#!3(+

H9DD+ H9DD+

!)!*"6+ !)!*15+

+ + !)!251+

+ !)!!2"+ !)*35*+

+ + !)!!16+

+ !)!!!1+ !)!!!2+

!)!!3+ !)!!!6+

!)!2("+ !)!6!(+

+ + !)!!53+

!)!!4+ !)!!4*+

+ !)!!!"+

!)!!24+ !)**3"+

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!)!***+ !)!*!6+

!"#$%&#!3()6!++ !"#$%&#!3()64++

!"#$%&#!3(+ !"#$%&#!3(+

H9DD+ H9DD+

!)!42"+ !)!**"+

!)!!!4+ !)!!*1+

+ !)**2*+

+

+ !)!!**+

!)!!!2+ !)!!3*+

!)!635+ !)!666+

+ !)!*56+

!)!*1"+ !)!!44+

+

!)!(13+ !)!!22+

!)*!63+ !)*41"+

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!"#$%&#!3()57++

!"#$%&#!3(+

H9DD+

!)!12*+

!)!*65+

!)!!*1+

!)!13(+

!)!(!2+

+ +

!)!(2+

!)!6!"+

!)!*11+

+

!)!!4(+

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+ !)!!14+

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+

+

+

ID !"#$%&#!6()*5++

Sample !"#$%&#!6(+

Sample type H9DD+

Al !)*2*(+

Ca !)!!22+

Cr !)!!24+

Cu !)!!3(+

K !)!!3*+

Mg !)!(!3+

Mn !)!((+

!"#$%&#!6()*2++ !"#$%&#!6()(*++

!"#$%&#!6(+ !"#$%&#!6(+

H9DD+ H9DD+

!)!316+ !)!411+

!)!1"4+ !)!!*6+

+

+ !)!!1(+

!"#$%&#!6()(1++ !"#$%&#!6()(5++

!"#$%&#!6(+ !"#$%&#!6(+

H9DD+ H9DD+

!)!351+ !)!45+

!)!!25+ !)!(1(+

+ !)!63*+

!)!*25+ !)!*!6+

!"#$%&#!6()3!++ !"#$%&#!6()3(++

!"#$%&#!6(+ !"#$%&#!6(+

H9DD+ H9DD+

!)!!3"+ !)!*36+

!)!!6*+ !)!!46+

+ + !)(62+

!"#$%&#!6()6!++ !"#$%&#!6()6*++

!"#$%&#!6(+ !"#$%&#!6(+

H9DD+ H9DD+

!)!(33+ !)!14(+

!)!!*2+ !)!!35+

!"#$%&#!6()61++ !"#$%&#!5!)!*++

!"#$%&#!6(+ !"#$%&#!5!+

H9DD+ H9DD+

!)!34(+ !)!(1"+

!"#$%&#!5!)!6++ !"#$%&#!5!)*4++

!"#$%&#!5!+ !"#$%&#!5!+

H9DD+ H9DD+

!"#$%&#!5!)(!++ !"#$%&#!5!)3(++

!"#$%&#!5!+ !"#$%&#!5!+

!"#$%&#!5!)31++ !"#$%&#!5!)63++

Ni !)!633+

Sn !)!!!2+

Ti !)!(21+

V !)*245+

Zn

!)!*31+

!)!**3+ !)!!6+

!)!!33+

+

!)!!*+ !)*!2+

!)!**(+ !)*!"(+

+ !)!*5"+ !)!!42+

+ + !)!!!6+

!)!!14+ !)!"65+

+ !)!*2+ !)!!(5+

!)!!*1+ !)!!""+

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+ !)!!(*+

!)*32*+ !)!**(+

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+ !)!!*2+

!)!!(6+ !)!!*4+

!)!!3"+ !)!643+

!)!*(5+ !)!*!6+

+

!)*!"+ !)!**3+

+ +

!)!!!6+ !)!!64+

!)*!3(+ !)(*(+

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!)!3(3+ !)!!(1+

!)!*!3+ !)!!13+

+

!)!!31+ !)!!31+

!)!544+

!)!*3(+

!)!!"2+ !)!654+

+ + !)!!!5+

!)!(5*+ !)!145+

!)!""*+ !)!!(5+

!)!*"+ !)!*(3+

+ !)!!*3+

!)*!"3+ !)!"12+

+

+ +

!)!!6"+ !)!!65+

+ !)!24*+ !)!1*6+

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!)*45"+ !)!"64+

!)!!54+ !)!!32+

!)!(((+ !)*!46+

!)!!!5+ !)!*5+

!)!*16+ !)!!1(+

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!)!!*6+ !)!!4+

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!)!*(1+ !)!!"4+

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H9DD+ H9DD+

!)!661+ !)**!*+

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!)!1"+

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!)!!2(+

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+ !)!!4*+ !)!!24+

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!)!!66+

!)!366+ !)!((4+

!)*511+ !)36"4+

!"#$%&#!5!+ !"#$%&#!5!+

H9DD+ H9DD+

!)!(!2+ !)!62*+

!)!!!3+ !)!!5*+

+ !)!!(4+

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!)!11"+ !)!!62+

!)!!!1+

!)!!"6+ !)!3"4+

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!)!!64+ !)45*6+

!)!6!5+ !)!!6*+

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!"#$%&#!5!)61++ !"#$%&#!5!)66++

!"#$%&#!5!+ !"#$%&#!5!+

H9DD+ H9DD+

!)!(13+ !)!1!6+

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+ !)!*(1+

!)!(!4+ !)!!5+

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!)!!2(+

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!)!!52+ !)!*63+

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!)!**3+ !)!*66+

!)*431+ !)!111+

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!"#$%&#!5!)5*++ !"#$%&#!5!)5(++

!"#$%&#!5!+ !"#$%&#!5!+

H9DD+ H9DD+

!)!!31+ !)!!61+

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+ !)**(+ !)3!55+

!)!!(3+ !)!!43+

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!)!1!1+ !)!6(2+

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!)!!((+ !)!!1+

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!)!!(6+

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!)!!4(+

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!"#$%&#!5!+ !"#$%&#!55+

H9DD+ H9DD+

!)*144+ !)!*54+

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!)*"55+ !)!*1*+

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!)!!5(+

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+ !)!45"+ !)!*3"+

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!"#$%&#!55)!6++ !"#$%&#!55)*2++

!"#$%&#!55+ !"#$%&#!55+

H9DD+ H9DD+

!)!1(*+ !)!3"5+

!)!!13+

!)!!5*+

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!)!31(+ !)!*+

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!)(341+ !)!5*"+

!)!((*+ !)!(!5+

!"#$%&#!55)(3++ !"#$%&#!55)(1++

+

!"#$%&#!55+ !"#$%&#!55+

H9DD+ H9DD+

!)!(*(+ !)!3!(+

+ !)!*!3+

+ + !)!6!3+

+ !)!!24+

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!)!6!2+ !)!("(+

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!"#$%&#!55+ !"#$%&#!55+

H9DD+ H9DD+

!)!1!*+ !)!*!1+

+ !)!!*"+ !)!(5"+

!)!252+ !)!535+

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!)!!!1+ !)!!*6+

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!)!*1+ !)!!5+

!)*"14+ !)*6*"+

!)!*23+ !)!3(1+

!"#$%&#!55)3(++ !"#$%&#!55)31++

!"#$%&#!55+ !"#$%&#!55+

H9DD+ H9DD+

!)!(3+ !)!*22+

!)!!!4+ !)!**5+

!)*51"+ !)*333+

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!)!656+ !)!1(+

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!"#$%&#!55+ !"#$%&#!55+

H9DD+ H9DD+

!)!*6+ !)!*!2+

+ !)!!1*+

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!)!26*+ !)!432+

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!)!!21+ !)!!23+

+ + !)!!*5+

!)!!51+ !)!!41+

!)*(35+ !)*!(5+

+ !)!166+ !)!!26+

!"#$%&#!55)3"++ !"#$%&#!55)1!++

!"#$%&#!55+ !"#$%&#!55+

H9DD+ H9DD+

!)!444+ !)!3*(+

!)!!(2+ !)!!33+

!)!!3(+

+

!)!!43+ !)!!**+

!)!!(1+

!)!!15+ !)!22+

!)!*31+ !)!!"4+

!)!**4+ !)!*!*+

+

!)!*1(+ !)*13"+

!)15""+ !)*(14+

+ !)!!6(+

!"#$%&#!55)13++ !"#$%&#!55)11++

!"#$%&#!55+ !"#$%&#!55+

H9DD+ H9DD+

!)!354+ !)!111+

!)!!!4+ !)!***+

+ +

+ !)!!3"+

!)!!**+

+ !)!!(+ !)!!52+

!)!635+ !)*6*(+

+

!)!!4"+ !)!*44+

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!)!**1+ !)*1(*+

!)*364+ !)!*35+

!)!*31+ !)!*!6+

!"#$%&#!55)14++ !"#$%&#!55)1"++

!"#$%&#!55+ !"#$%&#!55+

H9DD+ H9DD+

!)*!*1+ !)!*(2+

!)!!("+ !)!!*"+

+ + !)!!13+

+ !)!**"+

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!)!!3*+

!)!(*4+ !)!55*+

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!)!!"2+ !)!!5(+

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!)!*6*+ !)**("+

!)!*14+ !)!!"2+

!"#$%&#!55)6!++ !"#$%&#!55)61++

!"#$%&#!55+ !"#$%&#!55+

H9DD+ H9DD+

!)!**"+ !)!*1+

+ !)!!!3+

+ !)*(12+

+ + !)!!!1+

+ +

+ +

!)!2"6+ !)!541+

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!)!!34+

!)!**(+ !)!!46+

!)!261+ !)*632+

!)!212+ !)!*(4+

!"#$%&#!55)64++ !"#$%&#!55)6"++

!"#$%&#!55+ !"#$%&#!55+

H9DD+ H9DD+

!)!*(1+ !)!152+

+ !)!!*+

!)!*!4+ !)!!(6+

!)!!62+ !)!!!2+

+ + !)!!!*+

+ !)!!!5+

!)!543+ !)!1!(+

!)!!"2+ !)!*"2+

!)!!2"+ !)!!4*+

+ +

!)!**5+ !)!**2+

!)!45*+ !)*5!2+

!)!*(2+ !)!!6(+

!"#$%&#!55)5!++

!"#$%&#!55+

H9DD+

!)!1*3+

!)!!(5+

+

+

!)!!*4+

+ !)!!*+

!)!(43+

!)!*14+

+ !)!!!(+

!)!*"2+

!)!(43+

!)!!1*+

+ !)!!63+

+

Si !)**4*+ !)1131+

+

201

ID !"#$%&#!46)!(++

Sample !"#$%&#!46+

Sample type H9DD+

Al !)!(24+

Ca !)!!(5+

Cr !)!!!(+

Cu !)!!6+

K !)!!("+

Mg !)!!*"+

Mn !)!((*+

Ni !)!*!"+

Si !)!*!6+

Sn

Ti !)!(("+

V !)*435+

Zn

!"#$%&#!46)!6++ !"#$%&#!46)*5++

!"#$%&#!46+ !"#$%&#!46+

H9DD+ H9DD+

!)!*1+ !)!3*3+

!)!!("+ !)!*(5+

!)**"5+ !)!!43+

!)!!22+

+

!)!!55+ !)!!12+

!)!6*"+ !)!*32+

!)!**3+

!)!!"*+ !)!*64+

+ !)!!!1+

!)!!53+ !)!35+

!)*51(+ !)1*3"+

+ !)!!*6+ !)!*6(+

!"#$%&#!46)("++ !"#$%&#!46)3*++

!"#$%&#!46+ !"#$%&#!46+

H9DD+ H9DD+

!)!!46+ !)!335+

!)!(("+ !)!!3(+

!)161(+

+ +

+ !)!!!3+

!)!!3+ !)!!12+

!)!2*4+ !)!*2+

+ !)!(1"+ !)!!1*+

!)!!15+ !)!*(5+

+ !)!!*3+ !)!!(1+

!)!(45+ !)!3(*+

!)*51*+ !)1155+

!)!(4*+ !)!!(6+

!"#$%&#!46)33++ !"#$%&#!46)34++

!"#$%&#!46+ !"#$%&#!46+

H9DD+ H9DD+

!)!!("+ !)!133+

!)!*6+ !)!!5"+

+ !)!12"+ !)!**+

+ + !)!!36+

+ +

!)!!((+ !)!!61+

!)!*(5+ !)!!!2+

!)!*1(+

!)*!(2+ !)!*12+

+

!)!!!"+ !)!246+

!)!566+ !)131"+

!"#$%&#!46)3"++ !"#$%&#!46)1!++

!"#$%&#!46+ !"#$%&#!46+

H9DD+ H9DD+

!)!!*3+ !)!33*+

!)!(25+ !)!!33+

!)*!22+

+ !)!!6"+

+ !)!!34+

+ + !)!!!(+

!)!*15+ !)!!62+

!)!!"5+ !)!*"*+

+ !)!(*(+

!)*32"+ !)!*+

+ +

!)!!44+ !)!*51+

!)!142+ !)!55"+

!)!*45+ !)!!"(+

!"#$%&#!44)!4++ !"#$%&#!44)*!++

!"#$%&#!44+ !"#$%&#!44+

H9DD+ H9DD+

!)!*"2+ !)!14"+

!)!!3+ !)!!3(+

+ !)**21+ !)!!"4+

+ !)!!26+

!)!!!(+ !)!!!1+

!)!!2*+ !)!!4*+

!)!"6+ !)!(42+

+ !)!**"+ !)!!26+

!)!!65+ !)!*64+

+ +

!)!!"3+ !)!*24+

!)*"6+ !)*5((+

!)!(41+

!"#$%&#!44)**++ !"#$%&#!44)*(++

!"#$%&#!44+ !"#$%&#!44+

H9DD+ H9DD+

!)55!2+ !)!!63+

!)!(5(+ !)!!*6+

+ !)*!"(+

!)!*(1+ !)!!42+

+ !)!!!6+

!)!31(+ !)!!66+

!)!24+ !)!(25+

+ !)!!21+

!)!366+ !)!!6*+

+ !)!!11+

()*!!5+ !)!!32+

!)!*2(+ !)*6""+

+ !)(1*"+ !)!!13+

!"#$%&#!44)*1++ !"#$%&#!44)*2++

!"#$%&#!44+ !"#$%&#!44+

H9DD+ H9DD+

!)*"64+ !)!!4+

!)!!*4+ !)!!*"+

!)!(3+ !)!!*4+

!)!!3"+ !)!!33+

+

!)!!1(+ !)!!4*+

!)((12+ !)!51(+

!)!!(*+

!)!!63+ !)!!4"+

+ !)!!4*+

!)(!(5+ !)!!33+

!)*6!3+ !)**31+

!)!(1*+ !)!6!(+

!"#$%&#!44)((++ !"#$%&#!44)(5++

!"#$%&#!44+ !"#$%&#!44+

H9DD+ H9DD+

!)!123+ !)!2!"+

!)!!1*+ !)!!(1+

+ !)!(33+

+ !)!!35+

+ !)!!*4+ !)!!3(+

!)!!11+ !)!!"*+

!)!!*3+ !)!!3"+

+ + !)!*5*+

!)!((2+ !)!!42+

+ !)!!!3+ !)!!*4+

!)3*33+ !)!!4(+

!)!*3"+ !)(25+

!)!!2+ !)!!31+

!"#$%&#!44)(4++ !"#$%&#!44)(2++

!"#$%&#!44+ !"#$%&#!44+

H9DD+ H9DD+

!)!!42+ !)!*1*+

!)!!**+ !)!!!5+

!)(433+

!)!!1"+ !)!!(4+

!)!!55+ !)!!!1+

!)!!*(+

!)!4*3+ !)!*6*+

+

!)!!66+ !)!**2+

+

!)!!1(+ !)!*25+

!)*1*6+ !)!!!2+

+ !)!!63+

!"#$%&#!44)32++ !"#$%&#!44)3"++

!"#$%&#!44+ !"#$%&#!44+

H9DD+ H9DD+

!)!121+ !)!("4+

!)!!""+ !)!!*(+

+ + !)!!((+

!)!!2(+ !)!!!1+

!)!!21+ !)!!36+

+ !)!!36+ !)!!63+

+ !)!5!3+

+ + !)!*(4+

!)*!""+ !)!!21+

+ !)!!(6+

!)*!6+ !)!**4+

!)!!""+ !)*5"1+

+ !)!*+

!"#$%&#!44)6!++ !"#$%&#!44)6(++

!"#$%&#!44+ !"#$%&#!44+

H9DD+ H9DD+

!)!!23+ !)*(((+

!)!!!5+

+

!)!!!3+ !)!!!5+

!)!!51+ !)!!63+

!)*!5*+ !)*(*"+

!)!!4+ !)!!6(+

!)!*!3+ !)!*(3+

+ +

!)!*!"+ !)!*4(+

!)*(15+ !)!6"6+

!)!*"+ !)!264+

+

202

+ !)!!(4+

+

+

Appendix-VI: LA-ICP-MS raw data (in wt.%) for magnetite from the Izok Lake area ID !"#$%&#'"()(1-++

Sample !"#$%&#'"(+

Sample type ,-../0+

Ag !)!!!*+

Al !)!32!+

Au

As !)!!!(+

Bi

!"#$%&#'"()(1.++ !"#$%&#'"()(1