Heavy Minerals in Soils from the Athabasca Basin and the ...

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Heavy Minerals in Soils from the Athabasca Basin and the

Implications for Exploration Geochemistry of Uranium Deposits at

Depth

by

William R. Carlson

A thesis submitted to the Department of Geological Sciences and Geological Engineering

In conformity with the requirements for the

Degree of Master of Science

Queen’s University

Kingston, Ontario, Canada

(September, 2016)

Copyright ©William R. Carlson, 2016

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Abstract

The Centennial deposit is a high grade (~8% U3O8), deeply buried (~950m),

unconformity-related U deposit located in the south-central region of the Athabasca Basin in

northern Saskatchewan, Canada. The mineral chemistry of fine fractions (<63 μm) of soils from

grids above the Centennial deposit were examined to understand possible controls on the

geochemistry and radiogenic 207Pb/206Pb ratios measured in the clay-size (<2 μm) fractions used

for exploration. Soil samples distal and proximal to the deposit projection to the surface and

geophysically defined structures were selected. Mineral abundances were determined using the

scanning electron microscope and Mineral Liberation Analysis.

Zircon was the only U-rich mineral identified with modal abundances >0.02% by weight.

Monazite, which can be U-rich, was identified, but not in significant abundances. The source of

the zircon and other heavy minerals is interpreted to be from sub-cropping sources that are >100

km up-ice from Centennial. Trace element analysis using laser ablation inductively coupled

plasma mass spectrometry of hydroseparated zircon grains indicate that zircon abundances and

zircon Pb concentrations in surficial samples have minimal effect on the radiogenic 207Pb/206Pb

ratios in the clay-fraction of the samples, with the dominant source of radiogenic Pb being clay

mineral surfaces that trapped Pb during secondary dispersion from the Centennial uranium

deposit through faults and fractures to the surface. The REE patterns indicate HREE enrichment

in the clay-fractions of samples that have higher abundances of zircon in the <20 μm fraction.

Immobile elements such as HREE that are concentrated in zircon can be used as indicators of

radiogenic Pb being sourced from minerals at the surface rather than being sourced from

secondary dispersion from deeply buried U deposits.

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Co-Authorship

The thesis and manuscript contained herein are prepared by William R. Carlson. Chapter 2 is co-authored

by Dr. Dan Layton-Matthews (project co-supervisor) and Dr. Kurt Kyser (project supervisor) who

provided scientific and editorial support for this research. Uravan Minerals carried out the geochemical

survey that was the subject of this thesis.

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Acknowledgements

I am very grateful to my supervisors Dr. Kurt Kyser and Dr. Dan Layton-Matthews for the

guidance and support throughout this entire project. The SEM and MLA work for this project would not

have been possible without the great help that Agatha Dobosz offered in SEM operation. Evelyn Leduc

was very helpful and patient with LA-ICPMS work on grain mounts and also offered guidance in writing

of this thesis. Jerzey was helpful by offering friendly tips on polishing grain mounts for the SEM.

A very special thanks go to Dr. Steve Beyer and Paul Stewart for the help, constructive

conversations, and friendship during the course of this project. Thanks to Mike Gadd for always being in

the office and for being willing to talk about any questions I had regarding my project. Thanks to Brian

Joy for the help with the EPMA work. Thank you to all of my friends and family for encouragement and

support. Thank you to all of the staff and students I had the pleasure to work with at QFIR and the

Queen’s Geology Department. Thank you to my girlfriend Rachel Greco for her unconditional love and

always being there to talk to me.

Thanks to Uravan Minerals for allowing me to use geochemical samples collected from their

orientation survey of Centennial conducted in 2013.

Finally, this thesis is dedicated to my parents: Mark and Lee Carlson for their loving support

during my undergraduate and graduate degrees. I could not have made it where I am today without their

help.

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Table of Contents

Abstract ......................................................................................................................................................... ii

Co-Authorship.............................................................................................................................................. iii

Acknowledgements ...................................................................................................................................... iv

Chapter 1: Introduction ............................................................................................................................. 1

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

1.2 Geologic Setting of the Athabasca Basin ............................................................................................ 5

1.3 Genetic Models ................................................................................................................................... 9

1.4 The Centennial Deposit ..................................................................................................................... 11

1.5 Exploration Methods ......................................................................................................................... 12

1.6 Project Purpose ................................................................................................................................. 14

1.7 Thesis Layout .................................................................................................................................... 18

Chapter 2: Heavy minerals in soils from the Centennial Uranium Deposit in Athabasca Basin and

the implications for exploration geochemistry of uranium deposits at depth ..................................... 19

2.1 Introduction ....................................................................................................................................... 19

2.2 Regional and Local Geology............................................................................................................. 23

2.3 Pb isotopes and U concentrations in exploration for U deposits....................................................... 28

2.4 Methods............................................................................................................................................. 31

2.4.1 Sample Collection and Analysis from Surface Geochemical Survey ........................................ 31

2.4.2 Sample Selection and Preparation .............................................................................................. 33

2.4.3 Mineral Analysis ........................................................................................................................ 37

2.4.4 Maximum U and Pb Contribution from Heavy Mineral Content .............................................. 43

2.5 Results ............................................................................................................................................... 45

2.6 Discussion ......................................................................................................................................... 58

2.6.1 Mineral Quantification ............................................................................................................... 58

2.6.2 Radiogenic Pb Contribution from Minerals at the Surface ........................................................ 60

2.6.3 Identifying “false” Radiogenic Pb anomalies at the surface ...................................................... 66

2.8 Conclusions ....................................................................................................................................... 69

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Chapter 3: Conclusions and Future Work ............................................................................................. 72

References ................................................................................................................................................... 78

Appendix A ................................................................................................................................................. 96

Appendix B ................................................................................................................................................. 98

Appendix C ............................................................................................................................................... 101

Appendix D ............................................................................................................................................... 111

Appendix E ............................................................................................................................................... 117

Appendix F................................................................................................................................................ 127

Appendix G ............................................................................................................................................... 129

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List of Figures

Figure 1.1: Geologic map of the Athabasca Basin and its location in northern Saskatchewan ..... 4

Figure 1.2: Map of the Athabasca Basin showing the data from an airborne radiometric survey

and dominant ice flow directions .................................................................................................... 8

Figure 1.3: Schematic diagram showing the basement-hosted and sandstone-hosted end member

deposit types.................................................................................................................................. 10

Figure 1.4: Locations of selected samples with respect to the projected deposit outline,

207Pb/206Pb values from clay fraction (<2µm), and geophysical anomalies and lineaments ........ 17

Figure 2.1: Geologic map of the Athabasca Basin and its location in northern Saskatchewan ................. 21

Figure 2.2: Location of 13 selected samples (stars) with respect to the projected Centennial deposit

outline projected to surface, 207Pb/206Pb values from clay-fractions (<2 µm) separated from B/C horizon

soils (red stars = radiogenic Pb, black stars = common Pb), and geophysical anomalies and lineaments. . 25

Figure 2.3: Map showing the dominant direction of ice flow (black arrows) and the normalized eTh

(equivalent Th), K and eU from an airborne radiometric survey ................................................................ 27

Figure 2.4: Conceptual plot of U concentrations vs 207Pb/206Pb ratios in surficial media illustrating the

effects of syn-ore primary and post-ore secondary dispersion on U and radiogenic Pb ............................. 30

Figure 2.5: Normal probability plots indicating possible break points in 207Pb/206Pb ratios and

concentrations of U in ppm in the clay fraction separated from soils ......................................................... 36

Figure 2.6: BSE images of typical zircon grain morphologies in the <20 µm fraction ............................. 38

Figure 2.7: False color mosaic of an original sample and its heavy mineral concentrate .......................... 40

Figure 2.8: Photomicrographs of clay coated grains that were identified as aluminosilicates ................... 48

Figure 2.9: Proportions by count of extrabasinal material in 100 pebble counts compared to heavy

mineral contents by weight (S.G.>3.1) in <63 μm fractions ....................................................................... 50

Figure 2.10: Mean abundances in grain size fractions for feldspars and heavy minerals .......................... 59

Figure 2.11: Relationship between the 207Pb/206Pb ratios and U concentrations in selected clay fraction

samples of soils from the Centennial deposit area ...................................................................................... 63

Figure 2.12: Zircon and garnet abundances in <20 μm fraction vs. HREE/LREE in clay-size fraction (<2

μm) aqua regia digests. ............................................................................................................................... 67

Figure 2.13: Chondrite-normalized rare earth element-yttrium plot in the clay-size fraction (<2 μm) aqua

regia digests of samples and their zircon abundances in the <20 μm fraction ............................................ 68

Figure 3.1: Map of suggested locations for future studies ........................................................... 77

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List of Tables

Table 2.1: Descriptions and typical depths of podzol soil horizons ............................................ 33

Table 2.2: Initial and increased operating parameters for HS-11 hydroseparator ....................... 35

Table 2.3: Operating parameters for the laser and ICPMS .......................................................... 43

Table 2.4: Selected element concentrations of the soil clay-fraction .......................................... 46

Table 2.5: Average proportions by weight of heavy minerals with a S.G. > 3.2 in each size

fraction determined by MLA and the weight percent of heavy minerals in a concentrate produced

by heavy liquid separation by OBM ............................................................................................. 49

Table 2.6: Abundances in weight percent of minerals in non-hydroseparated sample and

hydroseparated sample in the <20 μm fraction ............................................................................. 51


hydroseparated sample in the 20-45 μm fraction .......................................................................... 53


hydroseparated sample in the 45-63 μm fraction .......................................................................... 55

Table 2.9: Summary of element concentrations in zircons from the <20 and 20-45 μm fractions

analyzed using EPMA................................................................................................................... 57

Table 2.10: Average U, 206Pb, 207Pb contributions from zircon grains in the <20µm size fraction,

the U, Pb and 207Pb/206Pb concentrations measured in the clay fraction aqua regia digest, and the

corrected U concentration and 207Pb/206Pb of the clay fraction assuming all the U and Pb from the

zircon had contributed to the measured U, Pb and 207Pb/206Pb. in the clay fraction ..................... 65

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Chapter 1: Introduction

1.1 Introduction

Unconformity-associated uranium deposits occur as semi massive replacements, veins,

and pods of mainly uraninite located near an unconformity between diagenetically-altered,

uranium-depleted, Proterozoic red bed basins and metamorphosed, uranium-rich, basement

rocks, such as supracrustal gneiss and graphitic metapelite (Kyser and Cuney, 2009). Two types

of deposits have been described, based on their location relative to the unconformity and their

respective genetic model: 1) basement-hosted deposits, which are located at or below the

unconformity and are generally “mono-metallic” or simple (consisting of mostly U), with a low

total concentration of rare earth elements (REEs), and 2) sandstone-hosted deposits, which are

located at and above the unconformity and are “poly-metallic” or complex (consisting of U, V,

Ni, Co, Cu, and As), with a high total concentration of REEs (Fayek and Kyser, 1997; Kyser and

Cuney, 2009).

The only unconformity-associated U deposits currently in production worldwide are

located in the Athabasca Basin of Saskatchewan, Canada and the McArthur Basin of the

Northern Territory, Australia (OECD Nuclear Energy Agency and the International Atomic

Energy Agency, 2012). Although production has been limited to these two localities,

unconformity-associated uranium deposits have accounted for over 15% of the total world

production of uranium up to 2007 (Cuney, 2008). These deposits are of particular importance in

Canada because they have been the only source of uranium production in the country for over 15

years; in 2010 Canada was the second largest producer of uranium in the world, with 18% of the

total yearly production (OECD Nuclear Energy Agency and the International Atomic Energy

Agency, 2012). The average ore grade in the Athabasca Basin is 1.97% (Gandhi, 2007), more

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than four times the average grade for unconformity-associated deposits in Australia (Jefferson et

al., 2007; Kyser and Cuney, 2009).

All currently producing deposits in the Athabasca Basin are located near the eastern

margin of the basin (Figure 1.1). Some deposits, such as McArthur River and Cigar Lake, are

buried under approximately 550 m (Marlatt et al., 1992) and 430 m (Bruneton, 1987) of

sandstone cover, respectively. Other deposits (Rabbit Lake, Eagle Point, Key Lake, and

Midwest) have no sandstone cover, but are only covered by glacial sediments. (Sopuck et al.,

1983; Sibbald, 1985). Uraniferous boulder trains have aided in the discovery of some sub-

cropping deposits including Key Lake, Rabbit Lake, and Midwest (Sopuck et al., 1983).

However, few recent discoveries have been at the surface (Marlett and Kyser, 2011); this has

prompted further development of exploration geochemistry techniques aimed at vectoring

towards deeper deposits (Cohen et al., 2010; Stewart, 2015; Kyser et al.; 2015).

Lithogeochemical boulder prospecting to identify alteration haloes of deposits at depth by their

clay mineralogy and elemental concentrations has been a widely used exploration technique

(Earle, 2001). However, occurrences of clay-alteration haloes not associated with economic

mineralization have also been observed, further encouraging the development of new exploration

techniques (Alexander et al., 2009).

High grade U deposits are a source for U, radiogenic Pb, and a suite of pathfinder

elements including Ni, Co, V, Cu, and As (Hoeve and Sibbald, 1978; Hoeve and Quirt, 1984;

Sibbald, 1985). Surface geochemical sampling programs may be conducted to identify

geochemical anomalies in radiogenic Pb and other pathfinder elements occurring from materials

that may have been mobilized to the surface from deeply buried deposits (Sibbald and Quirt,

1987; Stewart, 2015; Kyser et al., 2015). This upward movement of materials, such as radiogenic

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Pb, is thought to occur through faults and fractures in the rocks (Holk et al., 2003). The

remobilized elements are subsequently transferred to surface media such as vegetation, soil, and

till (Cameron, 2012). However, transported materials at the surface have been identified by

relatively higher eU than eTh and K in airborne and ground radiometric surveys (Campbell et al.,

2002; Campbell, 2007). Therefore, geochemical anomalies, especially of U and radiogenic Pb,

must be interpreted carefully to determine if they are sourced from a deposit at depth or materials

at the surface.

The objective of this thesis was to develop methods to quantitatively analyze the

mineralogy of fine fractions of soils from a surface geochemical orientation survey conducted

over the Centennial uranium deposit located in the south-central region of the Athabasca Basin

(Figure 1.1). The goal was to identify minerals that commonly have high concentrations of U and

radiogenic Pb and to calculate the maximum contributions of those elements from the U-rich

minerals to the geochemical signature, particularly radiogenic Pb, of the samples, in an effort to

better characterize any geochemical anomalies.

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Figure 1.1: Geologic map of the Athabasca Basin and its location in northern Saskatchewan, Canada. Locations of some major

deposits and prospects are indicated, as well as the approximate locations of three sub-basins within the basin. The location of the

Centennial prospect, which is the focus of this thesis, is indicated with the large black arrow. (Modified from Ramaekers, 1990;

Jefferson et al., 2007, and references therein).

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1.2 Geologic Setting of the Athabasca Basin

The Athabasca Basin is a large (~100,000 km2) Proterozoic intracratonic basin located in

northern Saskatchewan hosting a sedimentary sequence approximately 1.5 km in thickness,

consisting mainly of fluvial sandstone units known as the Athabasca Group (Ramaekers, 1990;

Ramaekers, 2007; Rainbird et al., 2007). The formation of the basin was a result of rapid uplift

and erosion of the Trans-Hudson Orogeny (Lewry and Sibbald, 1980; Ramaekers, 1990). The

Athabasca Basin has undergone extensive erosion, as suggested by fluid inclusion data that

indicated a paleo-depth of up to 6 km (Pagel et al., 1980).

The Athabasca Group unconformably overlies metamorphosed rocks of the Archean to

Paleoproterozoic Hearn and Rae Provinces that are divided by the Snowbird Tectonic Zone,

which is expressed at the surface as the Virgin River Shear Zone south of the basin, and as the

Black River Shear Zone in the north (Figure 1.1) (Hoffman, 1988). The Centennial project area

is located in the south-central region of the basin in the Virgin River Shear Zone (Figure 1.1).

The metamorphosed basement rocks are characterized by a paleoweathering profile that can

extend 50 m below the unconformity (Hoeve and Sibbald, 1978; Hoeve and Quirt, 1984;

Ramaekers, 1990). The basement rocks are dominantly deformed granitoid and supracrustal

gneisses, unconformably overlain by metamorphosed sedimentary rocks (Lewry and Sibbald,

1980).

The Athabasca Group was deposited from around 1760 Ma to 1500 Ma (Kyser et al.,

2000; Ramaekers, 2004). It is divided into four unconformity-bound sequences from the base to

the top of the basin: 1) the Manitou Falls (divided into a, b, c, and d members) and Fair Point

Formations, which are quartz rich, generally fining upward sequences with conglomerates being

more common near the base; 2) the Lazenby Lake and Wolverine Point Formations, consisting

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of fluvial to marine sandstones with few siltstones and mudstones; 3) the Locker Lake and

Otherside Formations, which are predominantly sandstones; and 4) the Douglas and Carswell

Formations, which form a cap of marine mudstone and stromatolitic dolostone that are only

found at the Carswell Structure, in the west-central region of the basin (Figure 1.1) (Hoeve and

Quirt, 1984; Armstrong and Ramaekers, 1984; Ramaekers, 1990; Hiatt and Kyser, 2007). The

stratigraphic sequences of the Athabasca Group were deposited in three distinct, northeast-

southwest-trending sub basins: the Cree Basin in the east, the Mirror Basin in the central portion,

and the Jackfish Basin in the western region (Figure 1.1) (Hoeve and Quirt, 1984; Armstrong and

Ramaekers, 1985; Ramaekers, 1990). The Athabasca Basin is intruded by a swarm of gabbroic

diabase dikes with an approximate age of 1300 Ma (Armstrong and Ramaekers, 1985), which is

likely related to the McKenzie Dike Swarm (Cumming and Krstic, 1992). Regional diagenetic

alteration occurred throughout the basin, resulting in a dominant mineralogy of quartz with trace

minerals such as zircon, tourmaline, rutile, ilmenite, and very rare mica and feldspar (Ramaekers,

1990).

Several different ice flow directions have been recorded in the Athabasca Basin

(Schreiner, 1984; Millard, 1988; Dyke and Dredge, 1989; Campbell, 2007) indicating it has been

subjected to multiple glaciation events. Different generations of glacial deposits can be buried

under meters of till, but the most recent, and main regional ice-flow record was a result of the

late stages of Late Wisconsonian glaciation and deglaciation (Campbell, 2007), which blanketed

the surface of the Athabasca Basin with glacial drift (~90-95% coverage). Large fields of

streamlined drumlins are present in the central and western regions of the basin, and indicate that

the most recent ice flow direction was west-southwestern (Campbell, 2007; Campbell et al.,

2002). In the northern and western regions of the basin, the ice flow direction is dominantly west

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and becomes more southwestern towards the southern and eastern regions of the basin (Figure

1.2). Glacial drift generally thins from west to east, and occurs only as a veneer at the eastern

margin of the basin (Campbell, 2007). At some sample locations, the boulders in the till can

consist entirely of extrabasinal clasts; erratics have been identified from several hundreds of

kilometers away (Campbell et al., 2002; Campbell, 2007).

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Figure 1.2: Map of the Athabasca Basin showing the data from an airborne radiometric survey

and dominant ice flow directions, with different generations indicated by colours of arrows.

Intense magenta and blue colors (stronger eU and K signal relative to eTh) indicate extrabasinal

surface material; less intense green, yellow colors (stronger eTh relative to K and eU) indicate

basin-derived surface material. The large black star indicates the location of the Centennial

deposit, the focus of this study. (Modified from Campbell et al., 2007 and references therein)

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1.3 Genetic Models

The proposed general model for the genesis of unconformity-associated uranium deposits

in the Athabasca Basin is based on spatial associations with reactivated pre-Athabasca structures

(Jefferson et al., 2007). Some deposits like Centennial, however, are not spatially associated with

major pre-Athabasca structures (Jiricka et al., 2006; Alexandre et al., 2012; Reid et al., 2014).

Oxidizing, U-rich, basinal brines flow through the unconformity and these structures if present,

become reduced, and deposit U in the form uraninite (Hoeve and Sibbald, 1978; Hoeve and

Quirt, 1984). It has been suggested that these fluids are reduced either through mixing with

reducing basement fluids being forced upward from the basement (Sibbald, 1985; Kotzer and

Kyser, 1995), or by downward movement of basinal oxidizing fluids resulting in direct contact

with reducing basement lithologies or fluids (Fayek and Kyser, 1997). These theories lead to two

end-member types of unconformity-associated uranium deposits: basement-hosted and

sandstone-hosted deposits (Figure 1.3), although many of them are hybrids because

mineralization is hosted in both the basement and sandstone (Kyser and Cuney, 2009). The

deposits are commonly associated with variable amounts of clay alteration minerals including

illite, chlorite, kaolinite, and dravite (Hoeve and Sibbald, 1978; Hoeve and Quirt, 1984; Sibbald,

1985; Kotzer and Kyser, 1995). The basement-hosted deposits formed from downward fluid

movement, which results in very subtle expression in the overlying sandstone (Fayek and Kyser,

1997). In sandstone-hosted deposits, reducing basement fluids are forced up through reactivated

structures and mix with oxidizing basinal fluids to deposit U; conditions of fluid mixing must

occur for extended periods of time to produce large, high-grade deposits (Kyser et al., 2000;

Kotzer & Kyser, 2007). Large clay mineral alteration haloes containing fractures and intervals

of silicification and desilicification are commonly associated with these deposits (Hoeve and

Quirt, 1984; Kotzer and Kyser, 1995; Kister et al., 2006).

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Figure 1.3: Schematic diagram showing the basement-hosted and sandstone-hosted end member deposit types and the potential

pathways for secondary dispersion of pathfinder elements. (Modified from Jefferson et al., 2007, and references therein).

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1.4 The Centennial Deposit

This thesis focuses on an orientation surface geochemical survey conducted over the

Centennial deposit. Centennial represents the first discovery of significant mineralization along

the Virgin River Shear Zone structural trend (Jiricka and Witt, 2008). Mineralization is

predominantly hosted in the basement and is “mono-metallic” as it has relatively low

concentrations of Ni, Cu, As, and V compared to “poly-metallic” type deposits (Jiricka et al.,

2006). There is significant brittle deformation at the deposit, but no spatial association with

graphite rich basement lithologies or significant post Athabasca displacement (Ried et al., 2014).

Secondary uranyl minerals are common up to 100m above the deposit (Jiricka et al., 2006) with

brittle structures allowing late fluid movement including recent meteoric water (Alexandre et al.,

2012; Ried et al., 2014). Several intervals of > 20% U3O8 over 0.5m have been intersected in

diamond drill core (Jiricka et al., 2006).

The basement rocks underlying the project area are interpreted to be Virgin River Schists

(within the Virgin River Shear Zone) (Reid et al., 2014). The Manitou Falls Formation is the

only formation of the Athabasca Group that is present in the Centennial project area (Jiricka et

al., 2006), but Lazenby Lake, Wolverine Point, Locker Lake, and Otherside formations are

exposed north and northeast (up ice) of the area (Figure 1.1).

Unconsolidated Quaternary glacial deposits in the area range in thickness of

approximately 0-15m and up to 5% of the surface is exposed bedrock of the Manitou Falls

Formation (Jiricka et al., 2005). Surficial deposits in the project area consist mostly of

glaciofluvial outwash and hummocky terrain, till moraines and ridges, and alluvial plain deposits

(Jiricka et al., 2006). The relatively thin glacial cover and exposed bedrock suggests that surface

geochemical sampling may be an effective exploration tool here (Jiricka et al., 2005).

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1.5 Exploration Methods

Large, Proterozoic, diagenetically-altered sandstone basins unconformably overlying

metamorphosed basement host all known unconformity-associated U deposits (Kyser and Cuney,

2009) and therefore are the first order exploration targets. In prospective basins, geophysical

methods including electromagnetic, gravity, seismic and magnetotelluric surveys may be

employed to identify conductivity trends from graphitic basement units related to reactivated

fault zones in the subsurface (Jefferson et al., 2007). Geochemical methods may then be applied

to target primary dispersion of mineralization-related minerals and their chemistry, or secondary

dispersion of elements related to mineralization through faults and fractures (Sopuck ., 1983;

Earl, 1983; Clark, 1987; Holk et al., 2003; Cohen et al., 2010; Stewart, 2015; Kyser et al., 2015).

There have been several proposed methods of secondary transport including fault related

dilatency pumping, ground water transport, and microbial activity (Aspandiar et al., 2008; Kelley

et al., 2006). The pathways for mineralizing fluids are faults and fractures in the bedrock. Large

clay alteration haloes may be important tools for geochemical exploration (Sopuck et al., 1983)

consisting of alteration-related mineralogy and brittle deformation creating pathways for element

dispersion through faults and fractures.

Geochemical surveys can involve sampling of various surface media including soil, till,

boulders, outcrops, vegetation, and near surface gases (Coker and Dunn, 1983; Dunn, 1983;

Hoeve and Quirt, 1984; Earle and Sopuck, 1989; Stewart, 2015; Kyser et al., 2015). For

geochemical soil surveys to be reliable, the proper soil horizon, size fraction, and extraction

methods must be employed (Hawkes and Webb, 1962; Rose et al., 1979). The soil type found in

northern Saskatchewan is podzol, which occurs in temperate humid climates where the dominant

vegetation is coniferous trees (Hawkes and Webb, 1962). Podzol consists of 3 profiles: A, B,

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and C which are further divided into A0, A1, A2, B1, B2, and C (Hawkes and Webb, 1962; Rose et

al., 1979). The A0 horizon is composed entirely of decomposing plant material, A1 transitions

downwards becoming more mineral based. The A2 horizon is mainly quartz without organic

matter that has been “eluviated” or leached and mechanically removed by percolating meteoric

water (Hawkes and Webb, 1962; Rose et al., 1979). The components that are eluviated from the

A horizon “illuviate” or accumulate in the B horizon which is stained a bright orange color.

(Hawkes and Webb, 1962; Rose et al., 1979). The B2 horizon is a lighter colored transition to the

C horizon. The C horizon, which is closest to bedrock, is dominantly silt, clay and sand

composed of weathered bedrock and till. A recent Study of radiogenic Pb ratios in soils above

the Cigar Lake deposit in the Athabasca Basin (Kyser et al., 2015) indicated that soils closest to

the surface had less radiogenic Pb signatures than soils deeper because of anthropogenic input of

common Pb near the surface.

Radiogenic Pb ratios may be an effective secondary dispersion exploration tool (Holk et

al., 2003; Alexandre et al., 2009; Stewart, 2015; Kyser et al., 2015). In some studies (Holk et al.,

2003; Alexandre et al., 2009), the Pb207/Pb206 has been found to be very low in rocks at

mineralization and can be traced along faults and fractures hundreds of meters above deposits.

Common lead Pb207/Pb206 values varied between approximately 0.7-0.9, whereas radiogenic

values associated with uranium mineralization were as low as 0.08 (Holk et al., 2003; Alexandre

et al., 2009). A mixing of these “radiogenic” Pb isotopes with “common” Pb isotopes can result

in anomalously low Pb207/Pb206 ratios in rocks that overly uranium mineralization (Holk et al.

2003).

The rocks of the Athabasca Basin are dominantly quartz-rich (Hoeve and Sibbald, 1978;

Sibbald, 1985; Ramaekers, 1990) containing a regional U background in unmineralized rocks of

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< 2 ppm (Fayek & Kyser, 1997); therefore, radiogenic Pb in unmineralized sandstone would be

unsupported and would indicate that the Pb was mobilized from an enriched U source (e.g. a

high grade deposit at depth) (Holk et al., 2003). Relative to the Athabasca Group, the basement

lithologies surrounding the basin area have much higher background concentrations in pathfinder

elements like U (7+ ppm) and radiogenic Pb, due to heavy minerals (> 3.1 g/cm3) such as zircon,

phosphates, and uraninite (Hecht and Cuney, 2000; Annesly et al., 2000). Uraninite has been

observed in pegmatoids near the eastern margin of the basin (Annesley and Madore, 1999).

Multiple glaciation events have dispersed basement lithologies across the Athabasca Basin

(Campbell et al, 2002; Campbell, 2007) possibly obscuring or overwhelming the surface

geochemical signature to produce anomalies that are related to glacially dispersed material,

rather than to a deposit at depth.

1.6 Project Purpose

The purpose of this project was to identify minerals in the fine fraction (< 63 µm) of soils

from an orientation surface geochemical survey, and to determine if there is a significant

contribution from these minerals to the surface geochemical signature, particularly radiogenic

Pb, of the soils.

A survey was conducted in the summer of 2013, at the Centennial uranium deposit

located in the south-central region of the Athabasca Basin (Figure 1.1). The clay sized (< 2 µm)

fraction was separated from the soil and digested in aqua regia to extract elements that had been

adsorbed to clay surfaces and the leachate was analyzed by Inductively-Coupled Plasma Mass

Spectrometry (ICP-MS) for 53 elements and Pb isotopic ratios. Although aqua regia is a

relatively strong acid solution, it cannot dissolve some minerals very easily, namely silicates

(Niskavaara et al., 1997). The reason for using aqua regia was to identify mobile elements in the

15

soil directly above the deposit outline, without getting a signal from minerals in the surficial

media. Radiogenic Pb signatures were found along geophysical lineaments related to brittle

deformation directly above the deposit, but some were not near the deposit outline or along

geophysical lineaments (Figure 1.4) (Uravan unpublished data, 2013).

For this thesis, samples from Centennial with radiogenic and common Pb signatures in

the clay sized fraction were selected for quantitative mineralogical analysis to determine if there

was a relationship between mineral abundances in soils, trace element concentrations in U-rich

minerals like zircon and monazite, and the geochemical signature in the clay sized fraction of

soils, particularly radiogenic Pb. Although zircon is generally chemically untouched by aqua

regia (Niskavaara et al., 1997; Evans et al., 2005), radiation can damage its crystal structure,

allowing it to be at least partially dissolved in acidic conditions (Ewing et al., 1982; Tole, 1985;

Balan et al., 2001). Regional airborne radiometric surveys (Campbell et al., 2002, 2003, 2007;

Campbell and Shives, 2000; Carson et al., 2002) measuring the relative K, eTh and eU signal of

the surface suggest that the eastern margin of the basin contains the most extrabasinal glacial

drift material, whereas the central and western regions of the basin contain glacial drift

dominantly derived from the basin (Figure 1.2). However, extrabasinal material is commonly

dominant in the core of streamlined glacial drift landforms such as drumlins (which are present

in the central and western regions of the basin directly up-ice of Centennial), whereas basinal

material is dominant near the surface of these landforms (Campbell, 2007). It is therefore evident

that some extrabasinal material at or near the surface may not be reflected in airborne

radiometric surveys. Several previous surficial studies, in addition to the surficial geochemical

exploration program of 2013, have identified extrabasinal material at Centennial (Jiricka et al.,

2005; Jiricka, et al., 2006; Uravan unpublished data, 2013).

16

Even in an area with limited abundance of extrabasinal material, a small abundance of U-

rich minerals such as zircon or monazite present in the soil may still have an effect on the

radiogenic Pb signature of the clay sized fraction. This thesis was completed to develop a method

for quantifying the mineralogy in the soil, and analyzing trace element concentrations of U-rich

minerals to determine the effect they may have on the radiogenic Pb signature of the clay sized

fraction at Centennial.

A process for heavy mineral concentration was developed using the HS-11 software-

controlled hydroseparator (CNT Minerals), to collect a representative population of the rare, U-

rich heavy minerals found in each sample. A method to mount the separated minerals whilst

preserving their representative distribution was also devised, and these mounts were then

analyzed using a Scanning Electron Microscope (SEM) for mineral identification, and Mineral

Liberation Analysis (MLA) technique for quantification. The trace element concentrations found

in the mineral separates were then analyzed using Laser Ablation Inductively Coupled Plasma

Mass-Spectrometry (LA-ICP-MS).

17

Figure 1.4: Locations of 14 selected samples (2 off map) (stars) with respect to the projected deposit outline, 207Pb/206Pb values from

clay fraction (<2µm), and geophysical anomalies and lineaments. Samples off the map had 207Pb/206Pb values >0.60. Stars labeled

with sample IDs represent samples chosen for this study. Black and red dots represent sample sites for the 2013 geochemical survey

(Uravan, 2013).

18

1.7 Thesis Layout

This thesis is divided into three chapters: introduction, manuscript, and conclusions. The

geographic location, the geologic setting, and the purpose of the project, and the reasoning

behind it, are outlined in the introduction. Chapter two includes a short introduction, a

description of the methods used and developed during this project, a presentation of the results,

as well as discussion of the results and conclusions to be drawn from them. The manuscript will

be submitted to Geochemistry: Exploration, Environment, Analysis (GEEA). The last chapter

will summarize and highlight the significance of the results and suggest future work. All data

that produced or used during the course of this project, and is not displayed in the manuscript

chapter is included in the Appendices.

19

Chapter 2: Zircon in soils from the Centennial Uranium Deposit in

Athabasca Basin and the implications for exploration geochemistry of

uranium deposits at depth

2.1 Introduction

Unconformity-related U deposits occur as semi-massive replacements, veins, and pods of

mainly uraninite located near the unconformity between Proterozoic, U-depleted, red-bed

sandstones, and metamorphosed, U-rich, Archean to Paleoproterozoic crystalline basement

rocks, including supracrustal gneiss and graphitic metapelite (e.g. Kyser and Cuney, 2015).

These deposits commonly form at major fault zones that exhibit a structural displacement of

basement and overlying sandstone rocks (Hoeve and Quirt, 1984). The genetic model for these

deposits involves reducing fluids originating from the basement and oxidizing basinal brines

mixing at a relatively immobile redox front controlled by structures in the basement and

overlying sandstone, commonly resulting in a large clay-mineral alteration halo above the

deposit (Hoeve and Sibbald, 1978; Sibbald, 1985). In addition, some unconformity-related

deposits form by oxidizing basinal brines being reduced directly by basement rocks or mafic

intrusives, resulting in dominantly basement-hosted mineralization with a subtle, less extensive

clay-mineral alteration halo (Fayek & Kyser 1997; Holk et al., 2003; Kyser and Cuney, 2015).

The Athabasca Basin is a large (~100,000 km2) Proterozoic intracratonic basin located in

northern Saskatchewan and Alberta (Figure 2.1). Although most deposits are located in the

eastern part of the basin (Figure 2.1), the Centennial U deposit, the focus of this study, is a high-

grade (~8 wt% U3O8) unconformity-related deposit that is located in the south-central region of

the Athabasca Basin (Figure 2.1). Airborne and ground geophysics (resistivity, electromagnetics

(EM), gravity) have delineated conductors, resistivity lows, gravity lows, and linear geophysical

20

trends (lineaments) related to structures (Figure 2.2) along a major regional fault zone at the

Centennial project (Uravan, 2013). The deposit, which is about 950 meters below the surface,

was outlined by several drill holes following the discovery hole drilled in 2004 (Jiricka et al.,

2006). Unlike typical unconformity-related U deposits, the Centennial deposit is not directly

associated with significant post-Athabasca structural displacement or graphitic conductors (Reid

et al., 2014). The Centennial deposit is dominantly basement hosted, but is associated with late

clay alteration and brittle structures that extend from the basement to the surface and host

perched secondary U mineralization up to 100m above the unconformity (Jiricka et al., 2006;

Alexandre et al., 2012; Reid et al., 2014). Surface media including soils from tills and tree-cores

were collected both proximal and distal to the deposit projection to the surface as part of an

orientation survey by Uravan Minerals in 2013, to evaluate the use of surface geochemistry in

detecting deep deposits.

21

Figure 2.1: Geologic map of the Athabasca Basin and its location in northern Saskatchewan. Locations of some major deposits and

prospects are indicated. The south-central location of the Centennial deposit is indicated with the red star. VRSZ = Virgin River Shear

Zone, BLSZ = Black Lake Shear Zone (Modified from Jefferson et al., 2007 and references therein.

22

Traditional mineral exploration for unconformity-related U deposits is focused in large,

Proterozoic sandstone basins where geophysical methods are used to delineate reactivated

basement structures and graphitic conductors (Sibbald and Quirt, 1987). Surface geochemical

surveys to identify anomalous concentrations of pathfinder elements such as Pb, Ni, Co, Cu, B,

As, Zn, Mn, Fe, V, Ag, Se, Au, S, and PGEs (Sibbald, 1985) are sometimes conducted to detect

primary dispersion of pathfinder elements or alteration clay mineralogy that formed syn-ore

(Hoeve and Quirt, 1984; Sopuck et al., 1983). In addition, 207Pb/206Pb ratios in surficial media

can reflect secondary post-ore dispersion of radiogenic Pb from the decay of U deposits at depth

(Holk et al., 2003; Alexandre et al., 2009; Stewart, 2015; Kyser et al., 2015), although such

components may also come from detrital material in the soils and tills and be unrelated to a

deposit below.

This study examined an area far down ice (>100 km) of any out-cropping Archean and

Paleoproterozoic basement rocks in the Athabasca Basin to determine what U-rich heavy

minerals are in glacial sediments at surface above the buried Centennial deposit and whether

these minerals can explain the Pb isotope anomalies in the clay fraction of soils from tills above

and near the deposit projected to the surface. The purpose of this study is to identify mineral

abundances, particularly in the small size fraction (<63 µm), of soil samples from above the

Centennial deposit, to calculate the contribution of radiogenic Pb and U from U-rich minerals in

the tills, and to suggest a method to identify “false” radiogenic Pb anomalies caused by U-rich

minerals at the surface. The premise of this study was to determine if there were significant

amounts of extrabasinal-derived sediments at the Centennial deposit; if there is significant

influence from extrabasinal derived material at Centennial, then areas more proximal to the

influence of down-ice sub-cropping basement rocks would be more likely to have higher

23

amounts of extrabasinal material at surface and higher potential for radiogenic Pb contamination

from the extrabasinal material.

2.2 Regional and Local Geology

The Athabasca Basin consists of fluvial to marine siliciclastic units of the Athabasca

Group (Ramaekers, 1990). The basin has a maximum thickness of approximately 1.5 km, but

regional homogenization studies of fluid inclusions from euhedral quartz indicates a possible

paleo-maximum thickness of up to 6 km (Pagel et al., 1980). Regional diagenesis occurred

across the entire basin and, as a result, the preserved detrital mineralogy of the Athabasca Group

is dominantly quartz that is interbedded with variably-altered rare heavy mineral (i.e., zircon,

rutile, and ilmenite) bands (Ramaekers, 1990). The basin unconformably overlies

metamorphosed sedimentary and igneous rocks of the Archean to Paleoproterozoic Hearne and

Rae provinces that are divided by the Virgin River and Black Lake Shear Zones (VRSZ and

BLSZ) (Fig. 2.1; Hoffman, 1988). The metamorphosed basement rocks display a regional

paleoweathering profile that can extend over 50 m below the unconformity (Ramaekers, 1990).

The Athabasca Basin is intruded by diabase dikes that are ca. 1300 Ma (Armstrong and

Ramaekers, 1985) and probably are related to the Mackenzie Dike Swarm (Cumming and Krstic,

1992).

The Centennial deposit is located in the south-central region of the Athabasca Basin on

the eastern side of the VRSZ adjacent to the Hearne Province (Figure 2.1). The inferred location

of the Dufferin Fault, which is a major reactivated post-Athabasca structure, is approximately

300m west of the deposit (Figure 2.2). The Dufferin fault is a W-NW dipping thrust fault that

may have acted as a major fluid conduit during mineralization (Jiricka, 2010). The VRSZ and the

Dufferin Fault in this area were the cause of a complex brittle structural framework that allowed

24

movement of mineralizing basinal fluids between the basin and basement rocks (Reid et al.,

2014). Mineralization is dominantly hosted in the basement with late, sub-economic perched

mineralization found up to 100m above the unconformity (Reid et al., 2014). The deposit is

intruded by diabase that is related to the Mackenzie Dike swarm (Reid et al., 2014). The brittle

structural framework in the area has allowed periodic fluid movement up to present day (Reid et

al. 2014).

25

Figure 2.2: Location of 13 selected samples (stars) with respect to the projected Centennial deposit outline projected to surface, 207Pb/206Pb values from clay-fractions (<2 µm) separated from B/C horizon soils (red stars = radiogenic Pb, black stars = common Pb),

and geophysical anomalies and lineaments. Black and red dots represent sample sites for the 2013 geochemical survey (Modified from

Uravan, 2013). Two additional samples are on the same sampling grid line as WL066, but off the map ~3 km to the NW (WL060) and

~4 km to the SE (WL087). Both off the map samples had 207Pb/206Pb values >0.60.

26

Regional surficial geology consists mainly of till, glaciofluvial, and glaciolacustrine

deposits (Campbell et al, 2002, Carson et al, 2002, Jiricka et al., 2006). Glaciolacustrine deposits

in the area commonly occur as large, flat-lying, silty sand deposits whereas other till and

glaciofluvial deposits typically occur as courser sediments (Campbell et al., 2007). The most

recent regional ice flow direction, indicated by streamlined glacial landforms, is dominantly

west-southwest (Figure 2.3). Regional airborne radiometric surveys (Campbell, 2007; Campbell

et al., 2002, 2003; Campbell and Shives, 2000; Carson et al., 2002) measuring K, eTh and eU

contents at the surface (Figure 2.3) indicate that the eastern margin of the basin contains the most

extrabasinal glacial drift material and the central and western regions of the basin contain

surficial glacial drift derived mainly from the basin (Campbell et al., 2002; Carson et al., 2002;

Campbell, 2007). Near the northern and eastern margins of the basin, the extrabasinal material

follows the direction of ice flow patterns. To the south and west of the basin, sandstone-rich till

also follows the directions of ice flow patterns (Figure 2.3). Surficial deposits at the Centennial

deposit consist mostly of basin-derived glaciofluvial outwash, glaciolacustrine plains,

hummocky terrain, till moraines and ridges, and alluvial plain deposits (Jiricka et al., 2006). The

surface geology dominantly represents the most recent dominant ice flow (Campbell, 2007), but

other generations of glacial deposits may be present deeper below the surface.

27

Figure 2.3: Map showing the dominant direction of ice flow (arrow colours indicate generation)

and the normalized eTh (equivalent Th), K and eU from an airborne radiometric survey. Intense

magenta, blue, green, and yellow colours indicate extrabasinal surface material; less intense

green, yellow, and white colors indicate basin derived surface material. The black star indicates

the location of the Centennial deposit. (Modified from Campbell, 2007, Campbell et al., 2002,

Carson et al., 2002, and references therein).

28

The Centennial deposit is down ice (>100 km; most recent ice flow event) from any

exposed basement lithologies (Figure 2.1; Figure 2.3). Regional radiometric surveys suggest very

little extrabasinal material in the Centennial project area (Figure 2.3), but some of the boulders

observed in a recent surface geochemical survey were extrabasinal granitoids and metapelites

(Unpublished Uravan data, 2013). Extrabasinal material was also observed in the pebble-size

fraction during earlier soil sampling programs in the area (Jiricka et al., 2005, Jiricka et al.,

2006). Extrabasinal material in the boulder, pebble, and smaller size fractions in till at the surface

or in till that is several meters below the surface may contain high abundances of U-rich minerals

that could affect radiogenic Pb and geochemical anomalies in surficial media above the

Centennial deposit.

2.3 Pb isotopes and U concentrations in exploration for U deposits

The 207Pb isotope is the stable decay product of the 235U isotope, which has a half-life of

ca. 0.70 Ga and the 206Pb isotope is the stable decay product of the 238U, which has a half-life of

ca. 4.46 Ga (Jaffey et al., 1971). About 99.28% of natural U is the 238U isotope whereas about

0.72% of natural U is the 235U isotope (Bievre and Taylor, 1993). Most rocks have Pb that

reflects a mixture from the original accretion of the Earth plus that produced from the decay of

U. Common Pb typically refers to 204Pb. However, Pb isotopic ratios (including 204Pb, 206Pb,

207Pb, and 208Pb) may be referred to as common or radiogenic Pb depending on the ratio. Given

that most rocks have similar U/Pb ratios, most Pb has a 207Pb/206Pb ratio referred to as “common

Pb” which is not to be confused with 204Pb. As a consequence of the relatively faster decay rate

of 235U, 207Pb/206Pb ratios of “common Pb” are about 0.91. However, in the presence of U-rich

29

sources, 207Pb/206Pb ratios as low as 0.07 occur due to the increasing relative abundance of 238U

(Catanzaro et al., 1968). Secondary dispersion of radiogenic Pb hundreds of metres from a high-

grade U deposit can result in anomalously low 207Pb/206Pb ratios in bedrock and surficial media

because of the increased 206Pb from U-rich sources (Holk et al., 2003; Alexandre et al., 2009;

Stewart, 2015; Kyser et al, 2015).

Elevated concentrations of U in the Athabasca Basin may be sourced from either primary

or secondary dispersion (Figure 2.4). Primary dispersion occurs at depth under relatively high

pressure and temperature (Hawkes and Webb, 1962), and in the Athabasca Basin, during a U

mineralizing event. Secondary dispersion occurs at relatively lower pressures and temperatures

and commonly occurs due to mobilization by post-ore fluids (Hawkes and Webb, 1962; Rose et

al., 1979). Secondary dispersion of U in the Athabasca Basin may occur over time from a deposit

at depth or from glacial dispersion of U-rich lithologies, such as U deposits near the surface or

basement rocks having U-rich phases such as monazite and zircon.

Radiogenic Pb dispersed from a U deposit at depth after the deposit formed is

unsupported, meaning that the Pb lacks the presence of U-rich source in the same sample (Figure

2.4). Radiogenic Pb in the presence of U may be a result of a combination of primary or

secondary U and secondary dispersion of radiogenic Pb (Figure 2.4). Elevated U contents

without radiogenic Pb is likely a result of recent secondary dispersion of U or removal of

radiogenic Pb (Figure 2.4).

30

Figure 2.4: Conceptual plot of U concentrations vs 207Pb/206Pb ratios in surficial media illustrating the effects of syn-ore primary and

post-ore secondary dispersion on U and radiogenic Pb. High 206Pb concentrations without high U concentrations are unsupported and

are a result of secondary dispersion of 206Pb (Holk et al., 2003).

31

The rocks of the Athabasca Basin are dominantly quartz-rich (Hoeve and Sibbald, 1978,

Sibbald, 1985, Ramaekers, 1990) containing a regional U background of approximately 1-2 ppm

(Fayek & Kyser, 1997). Therefore, radiogenic Pb in unmineralized sandstone that is unsupported

must have been mobilized from a U-rich source such as a high grade deposit at depth (Holk et

al., 2003). Basement lithologies surrounding the basin area have much higher concentrations of

pathfinder elements like U (ca. 15 ppm) and radiogenic Pb because of their inventory of heavy

minerals (specific gravity >3.1) such as zircon, phosphates, and uraninite (Hecht and Cuney,

2000; Annesley et al., 2000). The Athabasca Basin is more than 90% covered by glacial

sediments (Campbell, 2007), so the surface contains a mixture of basinal and extrabasinal

material. Heavy minerals within glacial sediments may be derived from sources outside of the

Athabasca Basin, and may therefore contain relatively high abundances of pathfinder elements

and radiogenic Pb that may cause surface anomalies not related to a deposit at depth (i.e. false

anomalies).

2.4 Methods

2.4.1 Sample Collection and Analysis from Surface Geochemical Survey

Soil samples were collected with 50m spacing on a grid around the projected surface

expression of the deposit outline. Spacing was spread to 100m and 200m moving away from the

deposit outline (Figure 2.2). Four hundred ninety-five samples of approximately 1 kg of A2, B2

or C horizon soils were collected from approximately 40-50 cm below the surface. The soil in

the study area is podzol, with A, B, and C horizons that were further divided into A0, A1, A2, B1,

B2, and C (Hawkes and Webb, 1962; Rose et al., 1979). Descriptions and typical depths of each

soil horizon are summarized in Table 2.1. The A2 horizon was only collected when its depth

32

continued below 50 cm; this commonly occurred near streams or on steep slopes. In most cases,

the B2 horizon was collected due to a poorly defined C horizon. At 45 of the soil sample sites, 2

kg ‘bulk soil’ samples were collected for heavy minerals in the 63-180 μm fraction. The bulk soil

samples were passed through methylene iodide heavy liquid separation and the mineralogy of

heavy minerals concentrates (HMC) in the 63-180µm size fraction was determined by

Overburden Drilling Management Inc. (ODM) on a subset of 100 grains.

Splits of the soils were taken and stored at Queen’s University. The clay-fraction of the

soil (<2 µm) was separated for analysis because clay minerals have charged surfaces that can

easily adsorb cations (Hawkes and Webb, 1962). The clay-sized fraction was separated from 2

mm sieved soil by ultrasonic disaggregation and centrifugation at Queen’s Facility for Isotope

Research. Clay-fraction samples (n=449) were sent to ACME Labs (now Bureau Veritas) in

Vancouver and digested in aqua regia (3:1 HCl:HNO3) for one hour at 90⁰ C and the leachate

analyzed for 53 elements and 204Pb, 206Pb, 207Pb, and 208Pb isotopes using ICP-MS. Aqua regia

was used to liberate elements adsorbed onto the clay surfaces because residual elements not

released by aqua regia are mostly bound to silicate lattices and are not important for analyzing

element mobility in soils (Niskavaara et al., 1997).

33

Table 2.1: Descriptions and typical depths of podzol soil horizons. Typically the

B2 horizon was collected at Centennial. Depths can vary significantly depending

on drainage. (Summarized from Hawkes and Webb, 1962; Rose et al., 1979)

Horizon Description Depth (cm)

A0 Composed entirely of decomposing plant material 0-5

A1 Transitions downwards becoming more mineral based 2 -12+

A2 Mainly quartz without organic matter which has been

“eluviated” or leached and mechanically removed by

percolating meteoric water 8-60+

B1 Components that are eluviated from the A horizon

“illuviate” or accumulate in the B1 horizon which is

stained a bright orange color 30-70+

B2 Lighter colored transition to the C horizon 40-70+

C

Dominantly composed of clay, silt and sand from eroded

till or bedrock and contains the least components from the

surface as the B horizon acts as a “filter” for percolating

components 40-70+

2.4.2 Sample Selection and Preparation

Fifteen soils were selected from the 2013 surface geochemical study based on their

chemical composition of the clay-fraction, particularly radiogenic Pb, and location with respect

to the projected surface outline of the deposit and geophysical anomalies (Figure 2.2). Samples

with 207Pb/206Pb ratios <0.60 were considered anomalously radiogenic and samples with U

concentrations >3.0 ppm were considered elevated based on break points in a normal probability

plot of the Pb ratios and concentrations of U of all the samples (Figure 2.5). The selected

samples were dried overnight at approximately 80⁰ C, weighed and split using a steel riffle

splitter. Sample splits were wet sieved into three size fractions (<20 µm, 20-45µm, 45-63µm)

using Retsch™ test sieves and shaker and dried at 80⁰ C. The >63 µm fraction was passed

through a 4 mm sieve and pebbles were separated for lithology using optical microscopy. The

size fractions were analyzed for mineral content using the SEM/MLA and the heavy minerals

concentrated using an HS-11 Hydroseparator (Rudashevsky et al., 2002). Zircon grains from

34

HMC were analyzed for U and Pb isotopic concentrations using LA-ICPMS and their

morphology analyzed using SEM.

An HS-11 software controlled hydroseparator was used to concentrate heavy minerals for

analysis by LA-ICPMS. The hydroseparator uses a gravity tank to create a constant hydraulic

head and a computer-controlled oscillating pulse-regulator to control a flow and pulse of water

through curved vertical glass separation tubes (GST) of different sizes. Within the GSTs,

minerals are sorted by size and density based on Stoke’s Law. The pulse regulator settings are

divided into modes 1.1-1.5 for concentration. As the mode number increases, the intensity of the

pulse increases and the pulse frequency decreases. The water flow was set at a constant rate of

25-95 ml/min that depended on the size fraction. Initial concentrates are produced using a large

glass separation tube (LGST) and final concentrates are produced using a small glass separation

tube (SGST).

Mineral abundances in the HMC were determined using the Mineral Liberation Analyzer

for the SEM. Concentration factors were calculated by dividing the HMC mineral abundances by

the non-hydroseparated mineral abundances. After initial concentration factors were calculated

on the first ten samples, higher flow rates and pulse regulator modes were used for the last five

samples to improve concentration factors. Table 2.2 summarizes the operating parameters used

for the HS-11 hydroseparator.

35

Table 2.2: Initial and increased operating parameters for HS-11 hydroseparator LGST = large glass

separation tube SGST = small glass separation tube

Size Fraction <20 µm 20-45µm 45-63µm

Initial Settings (LGST-SGST) 1.3-1.2 1.3-1.2 1.3-1.2

Initial Flow Rates ml/min (LGST-SGST) (50-55)-(50-55) (70-75)-(70-75) (90-95)-(90-95)

Increased Settings (LGST-SGST) 1.3-1.3 1.3-1.3 1.3-1.3

Increased Flow Rates ml/min (LGST-SGST) (50-55)-(20-25) (70-75)-(40-45) (90-95)-(90-95)

Increased Concentration Factors? no yes yes

36

Figure 2.5: Normal probability plots indicating possible break points in 207Pb/206Pb ratios (A) and concentrations of U in ppm (B) in

the clay fraction separated from soils. (Uravan unpublished data, 2013).

37

One hundred pebbles from each sample that contained pebbles were counted and split

into two categories based on their lithology. Sandstone pebbles were considered basinal material

because the Athabasca Basin is almost entirely sandstone (Ramaekers, 1990). All other

lithologies (commonly metapelite and granitoid) were considered extrabasinal material.

Proportions of lithologies were expressed as a percent. Pebble lithology counting was conducted

to compare proportions of extrabasinal material in the pebble fraction to proportions of heavy

minerals in the <63 μm fraction because extrabasinal material is assumed to be the dominant

source of heavy minerals.

2.4.3 Mineral Analysis

An FEI Quanta 650 FEG-MLA scanning electron microscope was used to analyze zircon

grain morphology in epoxy mounts from HMC of the <20 µm and 20-45 µm fractions (Figure

2.6) and automated mineralogy (MLA) of epoxy mounts from the <20 µm, 20-45µm, and 45-

63µm fractions. The clay-sized fraction (<2 µm) was not analyzed for mineral content because

mineral quantification using the MLA is limited to a minimum size of approximately 2-5 µm

(Gu, 2003, Fandrich et al., 2007). MLA analysis of grain mounts was conducted on 10-20 mg

subsamples that were separated using a rotary microriffler. A modified smear-mount method

(Poppe et al., 2001) of mounting grains in epoxy as a mono-layer was used for quantitative

mineral analysis of very fine grained material. Mono-layer grain mounts were necessary to avoid

density separation in the epoxy before it was fully cured (Mermollid-Blondin et al., 2011;

Blaskovich, 2013,).

38

Figure 2.6: BSE images of typical zircon grain morphologies in the <20 µm fraction from

samples WL008 (A), WL087 (B), and WL038 (C). WL087 has the lowest calculated radiogenic

Pb contribution from zircons (0.002), whereas WL038 has the highest (0.078). Chemical zoning

was commonly observed. The majority of the grains are broken pieces of larger grains (Left), but

some are unbroken zircon crystals (Right). Zr=zircon, Qtz=quartz, Hbl=Hornblende, Kspar= K-

feldspar

39

The MLA uses backscatter electron (BSE) imaging to define grain/background

boundaries along with energy dispersive x-ray spectrometry (EDS) and a library of EDS spectra

to identify mineral phases. The parameters for the MLA measurements included 25 kV, a beam

diameter of 4.8-5 nm, and a magnification of 400x for the 2-20 µm size fraction (referred to as

the <20 μm fraction) and 240x for the larger size fractions. Brightness and contrast for BSE

imaging were calibrated to a copper elemental standard. Minerals within the sample were

matched to modified EDS spectra (FEI Standard Mineral Reference Library; Severin, 2004) and

were used as standards for all of the samples. MLA was used to quantify the mineral content of

both unprocessed (non-hydroseparated) and heavy mineral concentrated samples (Fandrich et al.,

2007). An MLA false color mosaic (Figure 2.7) was created for each mount, which identified

grains (up to 350,000 particles) after assigning a color for each mineral EDS spectra. The MLA

mosaic was used to locate rare minerals in the grain mounts, like zircon, to be investigated using

LA-ICPMS. Minerals were assigned an average density (Klein and Dutrow, 2008; FEI Standard

Mineral Reference Library), such that mineral abundances by weight percent could be defined

using modal data produced by the MLA software.

40

Figure 2.7: False color mosaic of an original sample (WL518) (A) and its heavy mineral

concentrate (B). Background represents the epoxy/graphite powder between grains. These

examples are only 3-4 frames from the entire sample. Typically, one grain mount will contain

150-200 frames.

41

Electron probe microanalysis (EPMA) was used on 30 zircon grains from 4 different

HMC to determine U and Pb concentrations using an automated JOEL JXA-8230 with 5

wavelength dispersive spectrometers. Elements analyzed included Si, Zr, Hf, U, Th, Y and Pb,

although Pb concentrations were below detections limits (<150 ppm). Data were acquired using a

1-2 µm focused beam, 15 kV acceleration voltage and 100 nA beam current with peak and

background counting times of 10s for Zr and Si, 60s for Hf, 120s for Y, 200s for U and Pb, and

240s for Th. Zircon NMNH was the standard used for Zr, Hf and Si, synthetic UO2, ThO2 and

YO2 from the U.S. Atomic Energy Commission were used as standards for U, Th, and Y, and

Cerussite (Tsumbeb, GSC no. 66) was used for a Pb standard. Matrix-corrections were done

using JEOL PC-EPMA version 1.9.2.0, atomic number and absorption corrections were done

using XPP (Pouchou and Pichoir), the MAC database was FFAST from Chandler et al. (2005),

and the method of Reed (1990) was used for fluorescence correction. EPMA was performed to

determine a range of expected U and Pb concentrations so that proper standards could be used

for LA-ICPMS.

Laser ablation inductively-coupled-plasma mass spectrometry (LA-ICPMS) was done

with a ThermoScientific Element XR® ICP-MS and a ThermoScientific XSeries 2® quadrapole

ICP-MS coupled to an ESI NWR 193 nm ArF Excimer laser system. A total of 168 zircon grains

from the 20-45 µm fraction of the heavy mineral concentrate were analyzed. Isotopes analyzed

included 206Pb, 207Pb, 208Pb and 238U. Laser operating parameters are summarized in Table 2.3.

To cover the range of Pb and U content anticipated in some of the zircon grains (>400 ppm U

and >400 ppm Pb), a linear two point standard calibration curve was used with NIST 610

(National Institute of Standards and Technology, 1992a: 457.2 ppm U and 426 ppm Pb) and

NIST 612 (National Institute of Standards and Technology, 1992b: 37.4 ppm U and 38.6 ppm

42

Pb) glasses, and zircon 91500 (Wiedenbeck et al., 1995: 81.2 ppm U and 14.8 ppm Pb) to correct

all masses for ablation efficiency, mass bias, and instrumental drift. Published Pb isotopic ratios

were used to calculate concentrations of 206Pb, 207Pb, and 208Pb for each standard (Woodhead et

al., 2001; Weidenbeck et al., 1995; 2005). Fourteen of the 15 HMCs had large enough zircon

grains (30-40 μm diameter; limited by laser spot size of 35 μm) to be measured using LA-

ICPMS.

43

Table 2.3: Operating parameters for the laser and ICPMS

Laser Ablation System ICPMS

Model New Wave

Research

UP193HE

Model Element2,

ThermoFinnigan

Cooling

gas (Ar)

16 l/min

Type Excimer Type Magnetic Sector

field

Auxiliary

Gas (Ar)

0.75 l/min

Wavelength 193 nm Forward

Power

1300 W Sample

Gas (Ar)

0.9 l/min

Spot Size 35 µm Scan Mode E-Scan Carrier

Gas (He)

0.8 l/min

Repetition Rate 5-50Hz Scanned

Masses

202, 204, 206, 207,

208, 232, 235, 238

Laser Ablation System ICPMS

Model New Wave

Research

UP193HE

Model Xseries Cooling

gas (Ar)

13.0 l/min

Type Excimer Interface

cones

Xt Nickel Auxiliary

Gas (Ar)

0.90 l/min

Wavelength 193 nm RF Power 1404 W Nebulizer

Gas (Ar)

0.96 l/min

Spot Size 35 µm Detector SEM with PC and

Analogue

Carrier

Gas (He)

~1.0 l/min

Repetition Rate 5Hz Scanned

Masses

7-238

2.4.4 Maximum U and Pb Contribution from Heavy Mineral Content

To calculate maximum U (Uzircon), 206Pb (206Pbzircon), and 207Pb (207Pbzircon) contributions

from zircon grains to the clay-fraction chemistry, the mean 238U, 206Pb, and 207Pb concentrations

of all the grains measured using LA-ICPMS in each sample were combined with the zircon

abundances from the <20 µm fraction (Equations 1-3). The zircon abundances from the <20 µm

fraction were used because this was the closest size fraction to the clay-size (<2 µm) that was

quantified using MLA. Corrected values were calculated for U concentrations (Corr. Uclay-fraction)

and radiogenic Pb (Corr. 207Pb/206Pbclay-fraction) ratios in the clay-fraction aqua regia digest by

44

removing the contributions from zircon grains in the soil to the clay-fraction chemistry assuming

that all of the Uzircon, 206Pbzircon, and 207Pbzircon was contributed (Equations 4-5).

The following equations were used to make zircon contribution calculations:

Equation 1:

Uavg × Azircon = Uzircon

Where the average U content determined by LA-ICPMS (ppm) of zircon grains (Uavg) from a

given sample multiplied by the modal abundance determined by MLA (wt. %) of zircon (Azircon)

in the <20 μm fraction of that sample equals the maximum U contribution (ppm) to the clay-size

fraction chemistry (Uzircon) of that sample.

Equation 2:

206Pbavg × Azircon = 206Pbzircon

Where the average 206Pb content determined by LA-ICPMS (ppm) of zircon grains (206Pbavg)

from a given sample multiplied by the modal abundance determined by MLA (wt. %) of zircon

(Azircon) in the <20 μm fraction of that sample equals the maximum contribution (ppm) to the

clay-size fraction chemistry (206Pbzircon) of that sample.

45

Equation 3:

207Pbavg × Azircon = 207Pbzircon

Where the average 207Pb content determined by LA-ICPMS (ppm) of zircon grains (207Pbavg)

from a given sample multiplied by the modal abundance determined by MLA (Wt. %) of zircon

(Azircon) in the <20 μm fraction of that sample equals the maximum contribution (ppm) to the

clay-size fraction chemistry (207Pbzircon) of that sample.

Equation 4:

Uclay-fraction - Uzircon = Corr. Uclay-fraction

Where the U content from the clay-fraction (Uclay-fraction) minus the Uzircon equals the corrected U

content in the clay-fraction (Corr. Uclay-fraction)

Equation 5:

(207Pbclay-fraction − 207Pbzircon) ÷ (206Pbclay-fraction −

206Pbzircon) = Corr. 207Pb/206Pbclay-fraction

Where the 207Pb content from the clay fraction (207Pbclay-fraction) minus the 207Pbzircon divided by

206Pb content from the clay fraction (206Pbclay-fraction) minus the 206Pbzircon from a given sample

equals the corrected 207Pb/206Pb ratio (Corr. 207Pb/206Pbclay-fraction)

2.5 Results

Twenty-six samples of the clay-sized fraction from the 2013 Uravan survey have

207Pb/206Pb ratios <0.60 (Figure 2.2). The average 207Pb/206Pb for all samples with ratios greater

than 0.60 was 0.70. Table 2.4 shows the concentrations of elements of interest and 207Pb/206Pb

ratios in the clay-fraction from the 15 samples used for this study.

46

Table 2.4: Selected element concentrations of the soil clay-fraction analyzed using aqua regia digest used in this study (Uravan

unpublished data, 2013).

204Pb ppm 206Pb ppm 207Pb ppm 208Pb ppm 207Pb/206Pb U ppm LREE ppm HREE ppm

WL008 0.42 8.03 6.23 14.33 0.776 1.337 57.23 7.42

WL038 0.12 2.54 1.93 4.91 0.76 2.154 94.08 17.34

WL060 0.11 2.7 1.74 4.37 0.644 2.24 106.64 23.63

WL066 0.21 4.54 3.08 8.64 0.678 2.031 84.92 14.5

WL087 0.53 10.27 8.64 21.62 0.841 0.838 75.44 6.02

WL106 0.13 3.67 2.23 5.94 0.608 2.49 91.42 13.4

WL134 0.14 3.67 2.25 5.63 0.613 1.499 50.19 11.52

WL154 0.12 3.74 1.93 5.68 0.516 1.354 77.32 12.15

WL229 0.17 3.83 2.62 6.37 0.684 3.575 79.32 13.07

WL302 0.06 1.81 0.98 3.03 0.541 1.986 66.63 14.62

WL305 0.08 2.25 1.33 3.97 0.591 1.826 109.33 24.76

WL313 0.13 3.11 2.29 5.55 0.736 2.379 88.16 15.67

WL338 0.1 2.77 1.59 4.19 0.574 2.082 102.83 20.88

WL509 0.19 5.35 3 8.1 0.561 2.11 100.18 15.91

WL518 0.15 3.89 2.21 6.18 0.568 3.132 105.39 21.25

47

The most abundant heavy minerals identified in 100 grain counts in the 63-180 µm

fraction from bulk soil sites by OBDM included hematite, hornblende and garnet (Table 2.5).

Heavy mineral concentrates in the 63-500 µm fraction accounted for <0.30% by weight of the

entire size fraction. The original abundances and HMC abundances of all minerals from each

size fraction less than 63 μm are listed in Tables 2.6-2.8. The heavy mineral content in <20 µm

fraction ranges from 5.10%-10.75% by weight. The heavy mineral content in weight percent in

the 20-45µm and 45-63µm size fractions ranges from 2.82%-11.47% and 2.05%-12.64%,

respectively. The average heavy mineral content in all three size fractions was 5.3%, but the

range of heavy mineral contents increased with increasing size fraction. In all three size

fractions, the most abundant heavy minerals by weight were amphibole, garnet and hematite. The

heavy minerals zircon, rutile, and ilmenite had average abundances >0.10% in each size fraction.

Typically, the abundance of quartz was about 75%-90% and the abundance of feldspars was 5%-

20% with plagioclase > K-feldspar. The category “aluminosilicates” was used during MLA

classification for agglomerations of clay and for mineral grains completely coated in clay

minerals (Figure 2.8). WL 154 had a very high abundance of aluminosilicates in the <20 µm

(73.08%), 20-45 µm (69.32%), and 45-63 µm (38.18%) fractions. Unknown minerals were

<1.0% for all samples and all size fractions with the exception of one sample (WL 134) that had

1.41 % in the <20 µm fraction.

48

Figure 2.8: Photomicrographs of clay coated grains that were identified as aluminosilicates

(AlSi). Aluminosilicate grains showed rough surfaces (A – WL302), had lower BSE gray levels

than quartz (B - WL038) and in some cases had clay sized grains of hematite as well as clay

minerals coating them (C –WL305). Qtz = quartz, Plag = plagioclase, AlSi = aluminosilicates,

Hbl = Hornblende, Kspar = K-feldspar, Pyx = Pyroxene

49

Table 2.5: Average proportions by weight of heavy minerals with a S.G. > 3.2 in each size fraction

determined by MLA and the weight percent of heavy minerals in a concentrate produced by heavy

liquid separation by OBDM (Over Burden Drilling Management, 2013).

<20 µm 20-45 µm 45-63 µm 63-180 µm (OBDM)

HMC Total Wt% 4.23% 4.38% 3.80% 0.10%**

Amphibole 47.96% 34.12% 29.04% 10.43%

Apatite 0.30% 0.21% 0.32% 0.00%

Epidote 9.64% 6.17% 4.76% 2.64%

Garnet 9.03% 12.48% 13.54% 33.80%

Hematite 10.55% 11.91% 15.93% 40.91%

Ilmenite 4.51% 8.58% 8.37% 6.39%

Monazite 0.14% 0.21% 0.15% 1.07%

Olivine 0.51% 0.46% 0.69% 0.00%

Pyrite 1.01% 0.74% 0.99% 0.05%

Pyroxene 3.58% 5.27% 5.03% 3.43%

Rutile 8.50% 8.57% 6.84% 0.84%

Titanite 1.17% 1.28% 0.97% 0.30%

Zircon 3.11% 9.99% 13.38% 0.56%

Zircon grains examined using SEM were commonly broken zircon crystals (Figure 2.6).

In the <20 μm fraction, only 11% of the 73 grains examined were unbroken zircon crystals. In

the 20-45 μm fraction 21% of the 33 grains examined were unbroken zircon crystals.

Sandstone was the most common pebble type, followed by black metapelite and pink

granitoid. Extrabasinal material pebble counts were in the range of 6-23 pebbles out of 100

pebbles. Figure 2.9 shows the amount of extrabasinal material counted in each sample that

contained pebbles compared to the heavy mineral content of each size fraction of that sample

determined with MLA.

50

Figure 2.9: Proportions by count of extrabasinal material in 100 pebble counts compared to

heavy mineral contents by weight (S.G.>3.1) in <63 μm fractions in soils from the Centennial

area. WL518* only had 60 pebbles total in the pebble fraction so the proportion is percentage

rather than actual pebble counts.

0.00%

5.00%

10.00%

15.00%

20.00%

25.00%M

od

al a

bu

nd

ance

of

he

avy

min

era

ls b

y w

eig

ht

% a

nd

ext

rab

asin

al p

eb

ble

co

un

ts

Extrabasinal pebbles

<20 µm HMC

20-45 µm HMC

45-63 µm HMC

51

Table 2.6: Abundances in weight percent of minerals in non-hydroseparated sample and hydroseparated sample in the <20 μm

fraction. Gray highlighting indicates heavy mineral concentrate abundances *samples that concentrates were not analyzed using

MLA⁺ concentrate produced using increased flow rates and hydroseparator settings (Table 2.2.)

WL008 WL008 WL038 WL038 WL060 WL060 WL066 WL066 WL087 WL087 WL106* WL134* WL154*

Amphibole 0.75% 0.51% 2.40% 2.35% 2.24% 2.61% 2.08% 2.78% 1.08% 1.45% 3.26% 1.39% 1.09%

Apatite 0.01% 0.01% 0.01% 0.02% 0.03% 0.15% 0.00% 0.00% 0.00% 0.04% 0.02% 0.02% 0.02%

Aluminosilicates 3.85% 0.17% 3.71% 0.13% 3.64% 1.45% 3.53% 0.11% 9.30% 0.41% 5.29% 12.58% 73.08%

Epidote 0.17% 0.26% 0.36% 0.73% 0.38% 0.93% 0.42% 1.14% 0.18% 0.64% 0.70% 1.18% 0.36%

Garnet 0.26% 0.28% 0.41% 0.84% 0.30% 0.90% 0.27% 1.13% 0.12% 0.38% 0.41% 0.09% 0.22%

Hematite 0.37% 0.44% 0.11% 0.08% 0.49% 1.12% 0.35% 1.19% 0.18% 1.11% 0.32% 0.04% 0.09%

Ilmenite 0.14% 0.73% 0.16% 0.48% 0.19% 0.56% 0.28% 1.89% 0.07% 0.93% 0.20% 0.16% 0.06%

K-Feldspar 5.70% 2.85% 8.87% 7.27% 7.67% 6.10% 9.23% 7.79% 8.36% 6.57% 7.68% 12.15% 3.72%

Mica 0.50% 0.06% 0.20% 0.09% 0.13% 0.20% 0.13% 0.13% 0.21% 0.06% 0.10% 0.07% 0.10%

Monazite 0.02% 0.03% 0.01% 0.03% 0.00% 0.01% 0.01% 0.08% 0.00% 0.03% 0.01% 0.01% 0.01%

Olivine 0.03% 0.02% 0.04% 0.04% 0.02% 0.05% 0.01% 0.04% 0.02% 0.04% 0.02% 0.05% 0.02%

Plagioclase 6.59% 3.11% 12.95% 11.65% 8.52% 8.47% 12.17% 12.28% 8.97% 7.83% 11.17% 23.38% 5.50%

Pyrite 0.07% 0.13% 0.05% 0.08% 0.04% 0.07% 0.03% 0.03% 0.03% 0.16% 0.04% 0.07% 0.07%

Pyroxene 0.05% 0.08% 0.27% 0.45% 0.11% 0.66% 0.19% 0.50% 0.06% 0.24% 0.17% 0.24% 0.07%

Quartz 80.38% 89.76% 69.39% 73.73% 75.19% 74.12% 70.44% 68.26% 70.88% 78.55% 69.85% 46.68% 15.27%

Rutile 0.24% 0.59% 0.31% 0.76% 0.38% 1.27% 0.36% 1.21% 0.31% 0.63% 0.26% 0.32% 0.13%

Titanite 0.01% 0.02% 0.05% 0.12% 0.09% 0.18% 0.06% 0.24% 0.04% 0.13% 0.06% 0.12% 0.01%

Unknown 0.80% 0.53% 0.58% 0.65% 0.48% 0.55% 0.29% 0.29% 0.16% 0.39% 0.43% 1.41% 0.19%

Zircon 0.11% 0.43% 0.18% 0.56% 0.16% 0.57% 0.14% 0.97% 0.06% 0.43% 0.09% 0.07% 0.04%

52

WL229 WL229 WL302* WL305 WL305⁺ WL313 WL313 WL338* WL509* WL518*

Amphibole 1.94% 2.10% 1.62% 1.50% 1.56% 3.73% 2.20% 2.83% 2.42% 2.16%

Apatite 0.01% 0.02% 0.03% 0.02% 0.06% 0.04% 0.14% 0.00% 0.00% 0.00%

Aluminosilicates 6.88% 0.70% 14.90% 9.44% 17.36% 4.61% 0.17% 4.66% 2.33% 2.06%

Epidote 0.32% 0.63% 0.26% 0.21% 0.21% 0.38% 0.63% 0.36% 0.43% 0.44%

Garnet 0.27% 0.80% 0.63% 0.75% 0.88% 0.44% 1.31% 0.54% 0.47% 0.59%

Hematite 0.36% 1.10% 1.33% 1.16% 1.79% 0.42% 1.09% 0.34% 0.65% 0.52%

Ilmenite 0.21% 0.82% 0.17% 0.15% 0.14% 0.22% 0.46% 0.13% 0.45% 0.31%

K-Feldspar 8.28% 8.29% 11.91% 14.45% 15.40% 8.56% 6.93% 9.40% 11.92% 10.20%

Mica 0.15% 0.15% 0.00% 0.00% 0.00% 0.22% 0.14% 0.17% 0.20% 0.38%

Monazite 0.01% 0.03% 0.00% 0.00% 0.00% 0.00% 0.02% 0.01% 0.01% 0.02%

Olivine 0.02% 0.02% 0.02% 0.01% 0.02% 0.02% 0.06% 0.03% 0.03% 0.03%

Plagioclase 10.08% 10.16% 7.31% 9.92% 15.47% 10.39% 9.66% 12.29% 16.42% 14.20%

Pyrite 0.01% 0.04% 0.04% 0.05% 0.05% 0.06% 0.07% 0.05% 0.03% 0.03%

Pyroxene 0.12% 0.35% 0.13% 0.13% 0.15% 0.20% 0.47% 0.19% 0.22% 0.16%

Quartz 70.77% 73.43% 60.20% 60.42% 45.11% 69.91% 75.66% 68.27% 63.64% 68.04%

Rutile 0.26% 0.61% 0.83% 0.76% 0.84% 0.25% 0.50% 0.30% 0.34% 0.38%

Titanite 0.04% 0.08% 0.04% 0.03% 0.03% 0.07% 0.11% 0.03% 0.06% 0.05%

Unknown 0.13% 0.24% 0.37% 0.80% 0.68% 0.42% 0.14% 0.33% 0.28% 0.31%

Zircon 0.11% 0.44% 0.26% 0.23% 0.22% 0.11% 0.24% 0.13% 0.16% 0.16%

53

Table 2.7: Abundances in weight percent of minerals in non-hydroseparated sample and hydroseparated sample in the 20-45 μm

fraction. Gray highlighting indicates heavy mineral concentrate abundances *samples that concentrates were not analyzed using MLA

⁺concentrate produced using increased flow rates and hydroseparator settings (Table 2.2.)

WL008 WL008 WL038 WL038 WL060 WL060 WL066 WL066 WL087 WL087 WL106 WL106 WL134 WL134 WL154

Amphibole 0.56% 0.76% 0.91% 2.08% 1.52% 2.28% 0.93% 1.78% 1.30% 1.39% 1.56% 2.41% 1.01% 0.99% 1.80%

Apatite 0.00% 0.01% 0.00% 0.02% 0.01% 0.01% 0.00% 0.00% 0.00% 0.01% 0.02% 0.00% 0.00% 0.00% 0.02%

Aluminosilicates 4.61% 0.09% 0.70% 0.19% 1.14% 0.54% 1.88% 0.52% 2.05% 0.15% 2.55% 1.62% 2.12% 0.30% 69.32%

Epidote 0.10% 0.30% 0.18% 0.63% 0.33% 0.51% 0.18% 0.56% 0.30% 0.57% 0.31% 0.48% 0.57% 0.57% 0.12%

Garnet 0.14% 1.11% 0.30% 1.64% 0.56% 1.19% 0.34% 1.28% 0.59% 1.72% 0.72% 1.33% 0.59% 0.84% 0.13%

Hematite 0.24% 1.73% 0.03% 0.06% 0.69% 1.49% 0.16% 1.31% 1.24% 5.02% 0.30% 0.42% 0.03% 0.18% 0.09%

Ilmenite 0.17% 1.52% 0.19% 1.53% 0.26% 1.07% 0.19% 1.50% 0.96% 3.37% 0.47% 1.38% 0.41% 0.64% 0.09%

K-Feldspar 3.27% 1.70% 4.67% 4.75% 5.69% 5.21% 6.07% 4.71% 5.25% 3.71% 5.26% 4.95% 7.08% 7.14% 2.40%

Mica 0.06% 0.05% 0.02% 0.03% 0.05% 0.11% 0.07% 0.09% 0.05% 0.04% 0.04% 0.04% 0.01% 0.04% 0.02%

Monazite 0.00% 0.02% 0.00% 0.02% 0.01% 0.03% 0.01% 0.06% 0.03% 0.12% 0.02% 0.03% 0.01% 0.02% 0.01%

Olivine 0.03% 0.04% 0.01% 0.05% 0.02% 0.04% 0.02% 0.05% 0.02% 0.03% 0.03% 0.03% 0.03% 0.06% 0.03%

Plagioclase 3.96% 2.67% 7.03% 7.01% 8.03% 7.26% 8.78% 7.52% 7.20% 5.33% 8.60% 8.00% 12.65% 11.58% 4.37%

Pyrite 0.02% 0.08% 0.01% 0.08% 0.03% 0.04% 0.01% 0.02% 0.03% 0.02% 0.04% 0.02% 0.01% 0.03% 0.16%

Pyroxene 0.06% 0.18% 0.19% 0.44% 0.22% 0.49% 0.15% 0.49% 0.25% 0.35% 0.30% 0.54% 0.29% 0.20% 0.08%

Quartz 86.09% 85.39% 85.06% 77.00% 80.38% 77.01% 80.78% 76.76% 79.29% 73.45% 78.73% 75.59% 74.12% 75.67% 20.61%

Rutile 0.21% 1.20% 0.23% 1.22% 0.41% 0.93% 0.14% 1.03% 0.41% 1.13% 0.31% 0.96% 0.37% 0.43% 0.11%

Titanite 0.02% 0.05% 0.03% 0.10% 0.08% 0.09% 0.05% 0.12% 0.07% 0.15% 0.05% 0.13% 0.10% 0.12% 0.02%

Unknown 0.35% 0.71% 0.16% 0.51% 0.25% 0.48% 0.12% 0.31% 0.16% 0.28% 0.19% 0.20% 0.12% 0.31% 0.60%

Zircon 0.18% 2.38% 0.31% 2.69% 0.36% 1.23% 0.16% 1.94% 0.82% 3.16% 0.57% 1.86% 0.54% 0.90% 0.07%

54

WL154 WL229 WL229 WL302 WL302⁺ WL305 WL305⁺ WL313 WL313 WL338 WL338⁺ WL509 WL509⁺ WL518 WL518⁺

Amphibole 2.72% 1.36% 2.42% 1.09% 2.82% 1.16% 2.11% 4.59% 3.61% 1.39% 4.22% 1.76% 2.35% 1.54% 3.24%

Apatite 0.00% 0.01% 0.01% 0.01% 0.02% 0.01% 0.01% 0.08% 0.12% 0.00% 0.00% 0.00% 0.01% 0.00% 0.00%

Aluminosilicates 66.55% 2.35% 0.09% 4.50% 3.34% 2.82% 0.45% 1.55% 0.42% 1.63% 1.21% 1.79% 1.64% 1.71% 0.07%

Epidote 0.40% 0.31% 0.81% 0.22% 0.59% 0.24% 0.48% 0.56% 0.79% 0.24% 0.68% 0.22% 0.52% 0.22% 0.89%

Garnet 0.63% 0.58% 2.85% 0.48% 3.56% 0.61% 2.44% 2.06% 1.84% 0.52% 3.34% 0.38% 1.34% 0.25% 2.69%

Hematite 0.12% 1.14% 6.48% 0.98% 21.68% 1.22% 8.66% 0.85% 2.34% 0.25% 0.63% 0.38% 3.43% 0.27% 5.95%

Ilmenite 0.90% 0.67% 3.22% 0.28% 7.82% 0.42% 3.38% 0.69% 1.98% 0.24% 3.05% 0.32% 2.86% 0.33% 5.59%

K-Feldspar 2.16% 5.19% 4.57% 7.61% 2.61% 6.05% 7.93% 8.03% 6.04% 5.40% 3.14% 8.81% 5.72% 7.31% 4.20%

Mica 0.06% 0.04% 0.07% 0.14% 0.09% 0.16% 0.46% 0.16% 0.16% 0.02% 0.03% 0.05% 0.04% 0.04% 0.05%

Monazite 0.00% 0.03% 0.05% 0.01% 0.20% 0.02% 0.08% 0.01% 0.03% 0.01% 0.15% 0.01% 0.06% 0.00% 0.15%

Olivine 0.01% 0.02% 0.04% 0.03% 0.02% 0.02% 0.03% 0.02% 0.05% 0.02% 0.09% 0.02% 0.06% 0.02% 0.05%

Plagioclase 8.20% 6.75% 5.75% 5.37% 2.12% 5.43% 4.45% 13.01% 10.34% 8.27% 5.02% 12.26% 8.57% 10.28% 5.90%

Pyrite 0.13% 0.05% 0.02% 0.02% 0.05% 0.03% 0.04% 0.04% 0.05% 0.02% 0.05% 0.02% 0.04% 0.01% 0.05%

Pyroxene 0.32% 0.27% 0.61% 0.18% 0.82% 0.25% 0.60% 0.60% 0.69% 0.26% 1.17% 0.23% 0.54% 0.17% 0.53%

Quartz 17.14% 79.47% 65.79% 77.41% 36.28% 79.06% 59.63% 66.59% 68.07% 80.75% 67.90% 73.11% 69.17% 77.33% 64.23%

Rutile 0.03% 0.61% 1.97% 0.68% 4.16% 1.19% 2.94% 0.35% 1.05% 0.31% 1.82% 0.19% 1.01% 0.16% 1.38%

Titanite 0.01% 0.08% 0.14% 0.03% 0.15% 0.07% 0.08% 0.14% 0.20% 0.05% 0.20% 0.05% 0.10% 0.04% 0.16%

Unknown 0.58% 0.18% 0.49% 0.47% 0.50% 0.42% 1.14% 0.27% 0.60% 0.21% 0.41% 0.25% 0.35% 0.18% 0.45%

Zircon 0.03% 0.94% 4.62% 0.53% 13.17% 0.86% 5.08% 0.47% 1.62% 0.45% 6.88% 0.20% 2.19% 0.16% 4.43%

55

Table 2.8: Abundances in weight percent of minerals in non-hydroseparated sample and hydroseparated sample in the 45-63 μm

fraction. Gray highlighting indicates heavy mineral concentrate abundances *samples that concentrates were not analyzed using MLA

⁺concentrate produced using increased flow rates and hydroseparator settings (Table 2.2.)

WL008 WL008 WL038 WL038 WL060 WL060 WL066 WL066 WL087 WL087 WL106* WL134 WL134

Amphibole 0.62% 0.65% 0.49% 4.37% 0.93% 1.75% 0.62% 1.89% 1.34% 1.59% 0.86% 0.44% 0.59%

Apatite 0.00% 0.04% 0.00% 0.00% 0.01% 0.02% 0.01% 0.00% 0.01% 0.00% 0.00% 0.00% 0.00%

Aluminosilicates 4.36% 0.23% 0.45% 0.22% 1.06% 0.57% 2.10% 0.19% 2.13% 0.02% 2.81% 1.67% 0.15%

Epidote 0.10% 0.25% 0.15% 0.93% 0.21% 0.52% 0.10% 0.84% 0.31% 0.68% 0.19% 0.18% 0.32%

Garnet 0.22% 1.25% 0.35% 6.30% 0.43% 1.27% 0.31% 2.30% 1.47% 6.24% 0.65% 0.39% 1.86%

Hematite 0.29% 2.06% 0.04% 0.19% 0.43% 2.04% 0.19% 2.39% 3.80% 24.11% 0.13% 0.03% 0.36%

Ilmenite 0.13% 1.61% 0.12% 2.84% 0.18% 0.69% 0.17% 2.03% 1.79% 10.70% 0.30% 0.17% 1.01%

K-Feldspar 2.49% 1.17% 3.47% 2.57% 5.68% 5.18% 3.67% 3.00% 3.32% 0.97% 3.55% 4.60% 4.25%

Mica 0.04% 0.03% 0.03% 0.07% 0.07% 0.16% 0.09% 0.13% 0.05% 0.03% 0.03% 0.01% 0.02%

Monazite 0.01% 0.05% 0.00% 0.07% 0.00% 0.08% 0.00% 0.02% 0.04% 0.36% 0.00% 0.00% 0.00%

Olivine 0.01% 0.02% 0.06% 0.10% 0.02% 0.05% 0.02% 0.02% 0.04% 0.02% 0.02% 0.02% 0.06%

Plagioclase 3.86% 2.17% 4.80% 4.41% 7.58% 6.55% 5.66% 5.01% 5.27% 1.18% 5.46% 7.21% 4.95%

Pyrite 0.01% 0.03% 0.01% 0.05% 0.03% 0.07% 0.01% 0.01% 0.04% 0.02% 0.09% 0.02% 0.02%

Pyroxene 0.08% 0.18% 0.15% 1.34% 0.15% 0.26% 0.13% 1.03% 0.29% 0.63% 0.19% 0.18% 0.19%

Quartz 86.89% 85.33% 89.24% 66.95% 82.33% 78.12% 86.45% 75.99% 76.56% 30.97% 84.69% 84.45% 83.10%

Rutile 0.13% 0.93% 0.18% 2.22% 0.24% 0.62% 0.14% 1.17% 0.56% 3.39% 0.27% 0.17% 0.62%

Titanite 0.01% 0.04% 0.04% 0.25% 0.04% 0.07% 0.02% 0.21% 0.07% 0.25% 0.03% 0.03% 0.08%

Unknown 0.55% 0.66% 0.17% 0.82% 0.40% 0.49% 0.04% 0.32% 0.30% 0.51% 0.23% 0.11% 0.30%

Zircon 0.23% 3.29% 0.29% 6.32% 0.27% 1.50% 0.32% 3.45% 2.68% 18.34% 0.55% 0.34% 2.11%

56

WL154* WL229 WL229 WL302* WL305 WL305⁺ WL313 WL313 WL338* WL509* WL518 WL518⁺

Amphibole 1.87% 1.15% 3.37% 0.78% 0.57% 2.32% 4.62% 5.82% 0.74% 0.89% 0.65% 2.46%

Apatite 0.01% 0.01% 0.00% 0.01% 0.00% 0.00% 0.14% 0.32% 0.00% 0.00% 0.00% 0.00%

Aluminosilicates 38.18% 1.46% 0.14% 2.89% 8.35% 0.56% 3.47% 1.04% 0.85% 2.62% 1.07% 0.07%

Epidote 0.17% 0.22% 0.71% 0.18% 0.08% 0.42% 0.45% 0.75% 0.16% 0.15% 0.11% 0.45%

Garnet 0.48% 0.73% 4.81% 0.37% 0.18% 3.58% 1.20% 2.70% 0.53% 0.18% 0.26% 3.42%

Hematite 0.11% 1.01% 8.85% 0.85% 0.58% 11.65% 1.01% 2.88% 0.16% 0.29% 0.19% 5.73%

Ilmenite 0.19% 0.48% 3.85% 0.16% 0.12% 4.55% 0.62% 1.78% 0.16% 0.12% 0.11% 3.06%

K-Feldspar 2.73% 4.64% 3.53% 7.00% 3.03% 4.93% 7.94% 6.58% 4.11% 4.26% 4.24% 2.90%

Mica 0.01% 0.05% 0.09% 0.09% 0.03% 0.24% 0.14% 0.25% 0.02% 0.02% 0.06% 0.12%

Monazite 0.01% 0.01% 0.09% 0.00% 0.00% 0.13% 0.01% 0.06% 0.00% 0.02% 0.00% 0.12%

Olivine 0.05% 0.02% 0.10% 0.07% 0.01% 0.12% 0.05% 0.06% 0.01% 0.01% 0.02% 0.01%

Plagioclase 6.11% 5.72% 3.89% 4.99% 3.11% 3.27% 14.80% 10.48% 5.62% 6.12% 5.70% 4.10%

Pyrite 0.10% 0.08% 0.03% 0.02% 0.03% 0.09% 0.06% 0.10% 0.03% 0.03% 0.02% 0.06%

Pyroxene 0.15% 0.25% 0.99% 0.15% 0.12% 0.72% 0.63% 1.33% 0.17% 0.15% 0.11% 0.62%

Quartz 48.57% 82.65% 59.34% 80.88% 82.99% 53.01% 63.50% 62.37% 86.54% 84.70% 86.83% 69.82%

Rutile 0.15% 0.49% 2.23% 0.45% 0.29% 3.28% 0.37% 0.66% 0.24% 0.13% 0.12% 1.35%

Titanite 0.03% 0.05% 0.25% 0.02% 0.02% 0.12% 0.14% 0.41% 0.03% 0.03% 0.02% 0.12%

Unknown 0.94% 0.25% 0.61% 0.67% 0.25% 0.80% 0.41% 0.49% 0.30% 0.10% 0.31% 0.53%

Zircon 0.20% 0.79% 7.12% 0.45% 0.28% 10.19% 0.50% 1.93% 0.35% 0.22% 0.19% 5.06%

57

The Pb concentrations in zircon grains were not high enough to be accurately quantified

with EPMA (<150 ppm). The values from the LA-ICPMS varied consistently with most of the

values from the EPMA, however some grains that yielded concentrations of U ~1000 ppm on the

EPMA yielded significantly lower concentrations (~300 ppm) with LA-ICMPS. This likely

reflects sampling volume as the spot size used for LA-ICPMS (35 μm) measured the entire

grains whereas the spot size used for EPMA (1-2 μm) measured a smaller volume of an

individual grain that had different concentrations than an average of the entire grain (Table 2.9).

Table 2.9: Summary of element concentrations in zircons from the <20 and 20-45 μm fractions

analyzed using EPMA.

Si Wt. % Zr Wt. % Hf Wt. % Y ppm U ppm Th ppm

Minimum 14.59 47.80 0.79 120.07 20.26 0.00

Mean 15.05 49.30 1.06 948.47 231.15 117.84

Maximum 15.33 50.02 1.51 2957.49 1224.59 414.89

The mean U contents all of the zircon grains analyzed with LA-ICPMS was 402.37 ppm

and the mean 206Pb and 207Pb concentrations were 80.14 ppm and 10.83 ppm, respectively. The

median concentration of U was 200.33. The median concentrations of 206Pb and 207Pb were 45.84

ppm and 5.61, respectively. Maximum U concentrations exceeded 4000 ppm and maximum

206Pb concentrations exceeded 900 ppm. The standard deviations for 206Pb (117.28 ppm), 207Pb

(14.88 ppm), and U (519.22 ppm) were well above the mean concentrations. The maximum

contribution (assuming all zircon was digested in aqua regia) of U and Pb from zircon in the

clay-sized fraction of each sample was calculated (Table 2.10), with the exception of sample

58

WL154 (207Pb/206Pb ratio = 0.5160) because there were no zircon grains large enough (~30-40

μm) to be analyzed with LA-ICPMS.

2.6 Discussion

2.6.1 Mineral Quantification

Zircon was the only U-rich mineral in any size fraction to constitute greater than 0.02% by

weight (Tables 2.6-2.8). The mineral abundances showed a trend of increased feldspar

abundances with decreased size fraction (Figure 2.10A). Heavy minerals zircon, garnet and

ilmenite show a general decrease in average abundance with decreased size fraction (Figure

2.10B). These trends are likely the result of the physical and chemical durability of the minerals.

Feldspar is susceptible to chemical weathering and weathered feldspar is easily ground into small

grains during transport, resulting in increased feldspar abundance in the smallest size fractions

(Odom et al., 1975; Odom, 1976). Heavy minerals such as zircon, ilmenite, and garnet tend to be

more resistant to physical and chemical weathering (Freise, 1931; Thiel, 1945; Dietz, 1973;

Nickel, 1973; Bateman and Catt, 1985). The decreasing abundance of heavy minerals with

decreasing grain-size fraction from 45-63 μm fraction to the <20 μm fraction would suggest that

there are fewer heavy minerals in the clay-size fraction from the soils used in exploration.

Variations in the average proportions of heavy minerals in the <63 μm fraction analyzed by

MLA compared to the 63-180 μm fraction 100 grain counts by OBDM are similar, but the

overall abundance of heavy minerals is higher in the <63 μm fraction (Table 2.5) suggesting that

heavy minerals are concentrated in this smaller fraction, but decrease again in the clay size

fraction. There are two factors that likely played a role in concentrating heavy minerals in the

smaller size fraction: 1) distal transport distance from the dominant source of heavy minerals

(sub-cropping extrabasinal lithologies >100 km away) resulted in extensive grinding of

59

transported minerals, as evident from the majority of zircon grains being broken (Fig 2.6), and 2)

hydraulic equivalence, in which settling velocity is a function of grain size and grain density,

such that smaller, denser minerals are deposited with larger, less dense minerals (Rubey, 1933).

Glaciofluvial outwash and alluvial plain deposits are common surficial deposits at the Centennial

project area and their mineralogy may be influenced by hydraulic equivalence.

Figure 2.10: Mean abundances in grain size fractions for feldspars (A) and heavy minerals (B) in

all fifteen samples in this study.

4.00%

5.00%

6.00%

7.00%

8.00%

9.00%

10.00%

11.00%

12.00%

46-63µm 20-45µm <20µm

Mo

dal

ab

un

dan

ce b

y w

eigh

t %

K-Feldspar

Plagioclase

0.00%

0.10%

0.20%

0.30%

0.40%

0.50%

0.60%

0.70%

0.80%

0.90%

1.00%

46-63µm 20-45µm <20µm

Mo

dal

ab

un

dan

ce b

y w

eigh

t %

Zircon

Ilmenite

Garnet

A.

B.

60

The pebble fraction from soil samples in the Athabasca Basin can be divided into

extrabasinal material, which is a dominant source of U-rich minerals, and basinal material that is

dominantly quartz. Pebble counting is an effective estimate of the dominant source of sediment

in a given sample (Anderson, 1957; Gibbard, 1985; Woodward et l., 1992). The number of

extrabasinal pebbles in each sample from this project does not show any correlation with heavy

minerals in the smaller size fractions (Figure 2.9). However, proportions of extrabasinal pebbles

are very low (23% or less) in the 8 samples that had pebbles from Centennial. More conclusive

work needs to be conducted to test the viability of pebbles counting to determine provenance of

finer fractions in soils. However, pebble counts may still be a useful addition to surface

geochemical surveys to help identify patterns that may indicate sources of false anomalies or

even dispersal trains from sub-cropping mineralization.

2.6.2 Radiogenic Pb Contribution from Zircon at the Surface

The average 207Pb/206Pb ratio for the entire soil survey from 2013 excluding samples with

ratios <0.60 is 0.70, which is the background ratio for this area. For ratios lower than this, there

must be U-rich sources in the till or radiogenic Pb that has migrated to the surface from the

Centennial deposit at depth during secondary dispersion processes. The brittle structural

framework that resulted from the Virgin River Shear Zone and the Dufferin Fault may be the

pathways for secondary dispersion of radiogenic Pb. Many of the samples with the lowest

(<0.60) 207Pb/206Pb ratios are either within 100m of the surface projection of the deposit outline

or along brittle structures that are associated with the deposit (Figure 2.2), suggesting that the

most direct pathways from the deposit are associated with the lowest 207Pb/206Pb ratios.

The maximum contribution from zircons in the host till to the Pb isotopic composition and U

concentrations of the clay-fraction chemistry can be estimated using the Pb and U contents and

61

207Pb/206Pb in the zircons and the mass of the zircons in the smallest size fraction of this study,

the <20 μm fraction. This is a maximum contribution because, although metamict zircon grains

may dissolve in the aqua regia (Ewing et al., 1982; Tole et al., 1985; Belan et al., 2001), more

than 10% of the zircon grains in the <20 μm fraction of the host till were fully intact crystals so it

is not likely that all of the zircon grains were dissolved by aqua regia. In addition, the abundance

of zircons decreases with decreasing size fraction so there are fewer zircon grains in the clay-size

fraction than in the <20 μm fraction.

Six of the fifteen samples selected for this study have 207Pb/206Pb ratios <0.60. Three of these

(WL302, WL305, WL338) were within 100m of the surface projected deposit outline or along

structures associated with the deposit (Figure 2.2). The effect on the 207Pb/206Pb of the clay

fraction from the zircons in these three samples was ≤0.034 (Table 2.10). This suggests that the

dominant source of radiogenic 207Pb/206Pb ratios in these samples are not heavy minerals in the

soil at the surface. However, these three samples have relatively low U contents, (Table 2.4;

Figure 2.11) suggesting that the radiogenic Pb in the clay fraction was sourced from secondary

dispersion of radiogenic Pb, but not of U.

The lowest 207Pb/206Pb ratio in this study is 0.516 (WL154) located >200m away from any

geophysical evidence of brittle structures associated with the deposit (Figure 2.2). There is no

evidence of contamination from heavy minerals in WL154 as it has the lowest abundance of

zircon in the <20 μm fraction of any of the 15 samples analyzed with MLA. However, WL154

was the most clay-rich (73.08% aluminosilicates in the <20 μm fraction) of all the samples

analyzed with MLA and was located in a flat lying area. Fine-grained, silty sand in flat lying

areas is characteristic of glaciolacustrine deposits in the Athabasca Basin (Campbell, 2007). U

could have been removed from the sediments when a lake drained leaving behind radiogenic Pb

62

at WL154. WL134 was the only A2 horizon soil analyzed for mineralogy and it also has a

relatively low 207Pb/206Pb ratio (0.613) and relatively low zircon abundance in the <20 μm

fraction (0.07%). The A2 horizon at WL134 was sampled because of the proximity to a

streambed allowing deep, recent eluviation. The presence of meteoric water here could have

removed U but not radiogenic Pb. Indeed, these two samples have background U contents with

low 207Pb/206Pb ratios (Figure 2.11).

Samples WL518 and WL509 have radiogenic 207Pb/206Pb ratios and are located about 2 km

north-northeast of the surface projection of the deposit (Figure 2.2). WL518 has a calculated

change in the 207Pb/206Pb in the clay fraction of 0.045 to the ratio, suggesting that a small amount

of the radiogenic Pb could be the result of zircon in the soil at the surface. In contrast, zircons in

WL509 lowered the 207Pb/206Pb of the clay fraction by only 0.006. In both samples, the

207Pb/206Pb is not affected by the zircons in the soil enough to account for their 207Pb/206Pb ratios

being <0.60, so there must be another source of radiogenic Pb. The area 2 km N-NE of the

deposit outline hosts a group of radiogenic Pb anomalies in the clay fraction centered on a

resistivity low corridor (Figure 2.2) that may be related to brittle structures in the bedrock that

could act as pathways for radiogenic Pb from U-mineralization at the unconformity.

63

Figure 2.11: Relationship between the 207Pb/206Pb ratios and U concentrations in selected clay fraction samples of soils from the

Centennial deposit area, with the abundance in wt% of zircon in the <20 μm fraction represented by colours of points: Green <0.12%,

Blue 0.13-0.14%, Red >0.15.

64

Samples with background 207Pb/206Pb ratios generally have smaller corrections to their

207Pb/206Pb from the zircons (Table 2.10), assuming that the Pb in the zircons from the <20 μm

fraction affected the Pb in the clay fraction. For example, the sample with the highest “common”

207Pb/206Pb ratio of 0.84 (WL087) also has the smallest corrections to its 207Pb/206Pb (0.002) and

is located >2km away from the deposit. However, the sample with the largest correction to its

207Pb/206Pb of 0.078 is WL038, but the 207Pb/206Pb in the clay fraction was 0.760, well above the

background 207Pb/206Pb ratio in the area. Sample WL060 has a relatively low 207Pb/206Pb ratio

(0.644) despite being located >2 km from the deposit, but it also has one of the largest

corrections to its 207Pb/206Pb (0.027). This correction could, in part, account for the low

207Pb/206Pb ratio in the clay fraction of WL060. Samples WL060 and WL038 lie west of the

deposit and near the inferred Dufferin Fault zone and have 207Pb/206Pb ratios >0.60, as do all of

the samples just west of the deposit and the Dufferin Fault zone (Figure 2.2).

The densest grouping of samples with 207Pb/206Pb ratios <0.60 lie along geophysically

defined structures associated with the deposit (Figure 2.2), consistent with the most direct

pathways from high grade U mineralization being associated with the most radiogenic clay

fractions.

The corrections were calculated only taking zircon grains into account because monazite, the

other U-rich mineral present, was in very insignificant abundances. However, there are other

minerals that are not as rich in uranium but still may have trace concentrations; minerals like

apatite, rutile, ilmenite, titanite, and garnet may all contain trace concentration of uranium.

Therefore, the abundances and U and Pb concentrations of heavy minerals other than zircon

should be considered when interpreting surface geochemical surveys.

65

Table 2.10: Average U, 206Pb, 207Pb contributions from zircon grains in the <20µm size fraction, the U, Pb and 207Pb/206Pb

concentrations measured in the clay fraction aqua regia digest, and the corrected U concentration and 207Pb/206Pb of the clay fraction

assuming all the U and Pb from the zircon had contributed to the measured U, Pb and 207Pb/206Pb. in the clay fraction. The corrections

amounted to changes in the 207Pb/206Pb rations of the clay fractions ranging from 0.002 to 0.078.

Sample Uzircon

(ppm)

206Pbzircon

(ppm)

207 Pbzircon

(ppm)

Uclay-fraction

(ppm)

206Pbclay-fraction

(ppm)

207 Pbclay-fraction

(ppm) 207Pb/206Pbclay-fraction

Corr. Uclay-

fraction (ppm) Corr. 207Pb/206Pbclay-fraction

WL008 0.566 0.108 0.016 1.337 8.030 6.230 0.776 0.771 0.784

WL038 0.754 0.289 0.043 2.154 2.540 1.930 0.760 1.400 0.838

WL060 0.944 0.135 0.018 2.240 2.700 1.740 0.644 1.296 0.671

WL066 0.322 0.057 0.007 2.031 4.540 3.080 0.678 1.709 0.685

WL087 0.135 0.032 0.005 0.838 10.270 8.640 0.841 0.703 0.843

WL106 0.277 0.059 0.008 2.490 3.670 2.230 0.608 2.213 0.616

WL134 0.254 0.039 0.005 1.499 3.670 2.250 0.613 1.245 0.618

WL229 0.127 0.034 0.004 3.575 3.830 2.620 0.684 3.448 0.689

WL302 0.789 0.136 0.016 1.986 1.810 0.980 0.541 1.197 0.575

WL305 1.082 0.153 0.019 1.826 2.250 1.330 0.591 0.744 0.625

WL313 0.265 0.060 0.009 2.379 3.110 2.290 0.736 2.114 0.748

WL338 0.613 0.122 0.019 2.082 2.770 1.590 0.574 1.469 0.594

WL509 1.002 0.071 0.010 2.110 5.350 3.000 0.561 1.108 0.567

WL518 1.082 0.339 0.032 3.132 3.890 2.210 0.568 2.050 0.613

66

2.6.3 Identifying “false” Radiogenic Pb anomalies at the surface

Uraninite samples from the Athabasca Basin have a convex REE pattern (Fayek and

Kyser, 1997; Mercadier et al., 2011a; Mercadier et al., 2011b), whereas altered and unaltered

sandstone in the Athabasca Basin is LREE enriched (Fayek and Kyser, 1997). Zircon can contain

concentrations of up to 10% REE2O3 (Speer, 1982) and garnet can have up to 1% REE2O3 (Jaffe

1951; Wakita et al. 1969; Meagher 1982). In both minerals, chondrite-normalized patterns

indicate that HREE are relatively enriched compared to LREE (Hanchar, 2001; Whitehorse and

Platt, 2003). Therefore, the LREE enriched patterns recorded by the clay separates from

Centennial (Figure 2.12) do not resemble zircon and garnet REE patterns, nor do they reflect

primary or secondary dispersion of REE from the Centennial deposit, but are most similar to the

REE patterns in the sandstones of the basin.

There is no correlation between zircon abundances, their U concentrations, or the

corrections they impart on the 207Pb/206Pb ratios of the clay fractions. However, there is a

moderate positive correlation (r2=0.61) between the combined abundances of zircon and garnet

in the <20 μm fraction and HREE/LREE in the clay fractions and between zircon and garnet

abundances in the <20 μm fraction (r2=0.64). WL134 is an exception to the correlation between

HREE/LREE and combined zircon and garnet abundances (Figure 2.12), but the recent

eluviation resulting in a deep A2 horizon likely effected the chemistry and mineralogy at that

sample. Zircon can contain U, radiogenic Pb, and HREE (Ahrens et al., 1967; Hanchar and

Westrenen, 2007) so that enrichment of HREE accompanied by radiogenic Pb and U anomalies

in clay-fraction chemistry may be indicative of detrital zircon in a sample. Chondrite-normalized

REE patterns in the clay fractions of the 15 samples analyzed for mineral abundances (Figure

2.13) illustrate that the samples with higher abundances of zircon in the <20 μm fraction also

67

have relatively higher concentrations of HREE that may be due to both zircon and garnet

abundances. This, along with the high correlation between zircon and garnet abundances,

suggests that the presence of zircon or garnet may have a small effect on the clay-fraction

chemistry, so that slightly HREE enriched patterns may reflect U and Pb isotope anomalies

caused by detrital zircon or garnet in surface media as opposed to anomalies from a buried U

deposit.

Figure 2.12: Zircon and garnet abundances in <20 μm fraction vs. HREE/LREE in clay-size

fraction (<2 μm) aqua regia digests. Trend line disregards WL134.

68

Figure 2.13: Chondrite-normalized rare earth element-yttrium plot in the clay-size fraction (<2 μm) aqua regia digests of samples and

their zircon abundances in the <20 μm fraction. Samples with higher zircon abundances typically have higher REE contents than

samples with lower zircon abundances.

69

2.7 Conclusions

Heavy minerals commonly found in soils such as zircon and monazite can contain high

concentrations of U and radiogenic Pb that may affect the geochemical signature of the soils.

Above the Centennial deposit, which is >100 km down ice of basement sources of

contamination, the surficial geochemistry is not significantly affected by glacially transported

material. Zircon was the only U-rich mineral found in any significant abundance (>0.02%) in the

<63 μm fractions of soil samples analyzed above the Centennial deposit. Zircon appears to be

concentrated in the <63 μm fraction (Max. = 2.69%), but the abundance decreases an order of

magnitude in the <20 μm fraction (Max. = 0.26%) and is likely even less abundant in the clay-

fraction (<2 μm). The maximum effect that zircon would have on 207Pb/206Pb ratios of the clay-

fraction at the Centennial deposit is 0.078 and the maximum contribution to U is 1.08 ppm.

Six samples were selected because their clay fractions have radiogenic 207Pb/206Pb ratios

of <0.6. The greatest possible effect on the Pb isotope ratios of these samples from zircons in the

soils is a decrease in their 207Pb/206Pb ratios of only 0.045. None of the samples with radiogenic

207Pb/206Pb ratios analyzed were significantly affected by zircon in the host soils at the surface.

Therefore, the radiogenic Pb came from another source, such as U-rich lithologies at depth or U-

rich minerals in till meters below the surface where the samples were collected. All of the

samples with radiogenic 207Pb/206Pb ratios <0.6 show evidence of secondary dispersion of

radiogenic Pb or U and radiogenic Pb, but not of U (Figure 2.11).

Seven of the nine samples with background 207Pb/206Pb ratios of >0.6 would have a

correction to their 207Pb/206Pb ratios of 0.012 or less, suggesting that these were not affected by

minerals in the soils at the surface. However, one sample (WL106) has a 207Pb/206Pb ratio in the

clay fraction of 0.608, which is low for a background ratio. WL106 is located near a

geophysically defined structure associated with the deposit (Figure 2.2) suggesting that the

70

relatively low 207Pb/206Pb ratio is related to the deposit at depth. The two samples with

background 207Pb/206Pb ratios in the clay fraction, but potentially large corrections to their

207Pb/206Pb ratios from zircons (WL060 = 0.027 and WL038 = 0.078) are not associated with the

deposit outline or geophysically defined structures. This suggests that these 207Pb/206Pb ratios

could have been affected by minerals at surface, but not enough to produce “false” radiogenic Pb

anomalies.

The contributions from transported zircon to surface geochemical anomalies at the

Centennial deposit are minimal because of the great distance from potential sources of

contamination. However, other minerals such as apatite, rutile, ilmenite, and garnet may also

contain trace concentrations of U and the abundances and geochemistry of these minerals should

be considered in future studies. Only the minerals in the near surface environment were taken

into account for this project, but other generations of glacial deposits deeper below the surface

may contain minerals that could be potential sources of secondary dispersion of pathfinder

elements. Therefore, glacial stratigraphy should also be taken into account. The materials at or

near the surface may more significantly affect exploration geochemical surveys carried out closer

to sources of U-rich mineral contamination (i.e., outcropping basement rocks). For example, if

the abundance of zircon was 4 times higher (~1% zircon) in the clay fraction of soils, U

contributions could exceed 4 ppm and 207Pb/206Pb ratios could be lowered by up to 0.3.

Although the pebble counts of extrabasinal material from Centennial samples showed no

correlation with the heavy mineral content in the <63 μm fraction (Figure 2.9), there is a minimal

amount (23% or less) of extrabasinal pebbles at Centennial. Only 8 samples from Centennial

contained pebbles and extrabasinal lithologies also contain lighter minerals like k-feldspar and

quartz. Therefore, pebble counting in surface geochemical exploration programs should be

71

studied further as a possible cost effective way to identify sediment sources that could contribute

to U, radiogenic Pb, and other pathfinder element anomalies.

Although minimal abundances of U-rich minerals may affect the 207Pb/206Pb ratios, they

commonly contain other, less mobile, elements. Zircon and garnet are commonly associated and

are relatively enriched in HREE compared to LREE and HREE are relatively immobile

compared to radiogenic Pb mobilized from a U deposit (Holk et al., 2003, Alexandre et al., 2009,

Stewart, 2015, Kyser et al., 2015). Zircon and garnet abundances in the <20 μm fraction at

Centennial showed a strong correlation with HREE concentrations in clay fraction chemistry.

Radiogenic Pb anomalies accompanied by higher concentrations of HREE relative to

background may be possible “red flags” for false anomalies being produced by zircon at the

surface.

Exploration for deeply buried unconformity-related U deposits using radiogenic Pb ratios

in clay-size fractions of soils at the surface combined with geophysical exploration methods is a

viable technique. However, awareness of local surficial deposits, local and regional ice flow

directions, and distance from near surface sources of contamination is critical for interpretation

of radiogenic Pb anomalies.

72

Chapter 3: Conclusions and Future Work

There are commonly heavy minerals in soils that can contain high concentrations of U

and radiogenic Pb. Minerals, such as zircon or monazite, are u-rich and may affect the

geochemical signature of the soils. Other minerals including apatite, rutile, ilmenite, and garnet

may all contain trace concentration of U and may affect the geochemical signature of the soils.

The Athabasca Group sandstone consists of dominantly quartz (Ramaekers, 1990) so surficial

sediments sourced from the Athabasca Group will have minimal heavy minerals. However,

Proterozoic and Archean basement lithologies that are exposed at the surface around the

Athabasca Basin can contain significant abundances of U-rich heavy minerals (Hecht and Cuney,

2000; Annesley et al., 2000). The surficial geochemistry at Centennial is not significantly

affected by zircon in the glacial sediments because the Centennial deposit is located >100 km

down ice (most recent ice flow) of any exposed basement lithologies. However, other heavy

minerals that could contain elevated U concentrations should be considered and minerals other

generations of glacial deposits deeper below the surface should be considered as potential

sources for secondary dispersion of pathfinder elements.

Zircon was the only U-rich mineral found in any significant abundance (>0.02%) in the

<63 μm fractions of soil samples analyzed above the Centennial deposit. The maximum

abundance of zircon decreases an order of magnitude from the <63 μm fraction (Max. = 2.69%)

to the <20 μm fraction (Max. = 0.26%) and is likely even less abundant in the clay-fraction (<2

μm). The estimate of the effect that zircon had on 207Pb/206Pb ratios was calculated using zircon

abundances from the <20 μm fraction and the highest change to the 207Pb/206Pb ratio was 0.078 at

WL038. Even with the highest calculated effect on the 207Pb/206Pb ratio, WL038 has a

73

207Pb/206Pb ratio of 0.760 so it was not effected by zircon enough to generate a “false” radiogenic

Pb anomaly.

The greatest possible effect zircon in the soil had on the Pb isotope ratios of the 6

selected samples with radiogenic 207Pb/206Pb ratios is a decrease of only 0.045 in their 207Pb/206Pb

ratios. There are not enough U-rich minerals in any of the radiogenic samples analyzed to

account for their 207Pb/206Pb ratios being well below 0.600 and all of the samples with radiogenic

207Pb/206Pb ratios <0.6 show evidence of secondary dispersion of radiogenic Pb or U and

radiogenic Pb, but not of U alone. Therefore, the radiogenic Pb is more likely sourced from

secondary dispersion from some type of U-rich source below the surface. These sources could

include U-rich lithologies at depth, a U deposit at depth, or U-rich minerals in till meters below

the surface where the samples were collected.

Nearly all of the selected samples with background 207Pb/206Pb ratios of >0.6 would have

a correction to their 207Pb/206Pb ratios of 0.012 or less, suggesting that these were not

significantly affected by minerals in the soil at the surface. WL106 had 207Pb/206Pb ratio in the

clay fraction of 0.608, which is low for a background ratio, and it is located near a geophysically

defined structure associated with the deposit. The low effect zircon in the soil would have on the

207Pb/206Pb ratio (decrease of only 0.008) and the proximity to structures related to the deposit

suggests that the relatively low 207Pb/206Pb ratio at WL106 is related to the deposit at depth.

WL060 and WL038 both had potentially large corrections to their 207Pb/206Pb ratios from zircons

(decreases of 0.027 and 0.078, respectively). However, these samples had 207Pb/206Pb ratios well

above background and they are not spatially associated with the deposit outline or geophysically

defined structures. Therefore, the 207Pb/206Pb ratios at WL060 and WL038 may have been

74

affected by the minerals at the surface, but not enough to produce “false” radiogenic Pb

anomalies.

The minimal effect that U-rich minerals in the soil have on the surface geochemical

survey at Centennial is a result of the transport distance from any exposed basement lithologies

containing high abundances of U-rich minerals. However, surface geochemical surveys carried

out more proximally down ice of exposed basement lithologies may be significantly affected. If

the abundance of zircon is 4 times higher (~1% zircon) in the clay fraction of soils, U

contributions from zircon could exceed 4 ppm and 207Pb/206Pb ratios could be decreased by up to

0.3. Therefore, exploration for deeply buried U-deposits using radiogenic Pb ratios in the clay-

size fraction of soils is a viable technique when combined with geophysical exploration methods,

but awareness of local and regional surficial deposits and ice flow directions is important for

interpretation of radiogenic Pb anomalies.

At Centennial, the dominant source of U-rich minerals is glacially transported

extrabasinal material. The pebble counts of extrabasinal material showed no correlation with the

heavy mineral content in the <63 μm fraction. However, there were only 8 samples with pebbles

in them and minimal abundances of extrabasinal material. Pebble counting in surface

geochemical exploration programs may still be a cost effective way to identify sediment sources

that could contribute to U, radiogenic Pb, and other pathfinder element anomalies especially in

areas with significantly more extrabasinal material at the surface. Large groups of geochemical

anomalies, especially ones that coincide with high extrabasinal pebble counts and ice flow

directions, may be possible “red flags” for false anomalies being produced by U-rich minerals in

the soil at the surface.

75

U-rich minerals may affect the 207Pb/206Pb ratios, but they commonly contain other, less

mobile, elements. For example, zircon and garnet are relatively enriched in HREE compared to

LREE (Hanchar, 2001, Whitehorse and Platt, 2003). HREE are relatively immobile (Fayek and

Kyser, 1997) compared to radiogenic Pb mobilized from a U deposit (Holk et al., 2003,

Alexandre et al., 2009, Stewart, 2015, Kyser et al., 2015). At Centennial, there is a strong

correlation between zircon and garnet in the <20 μm fraction (r2=0.61) suggesting that they were

transported from the same source. Radiogenic Pb anomalies accompanied by higher

concentrations of HREE relative to background may be possible “red flags” for false anomalies

being produced by zircon accompanied by garnet in the soil at the surface.

3.5 Future Work

Minerals at the surface did not significantly affect the clay-fraction chemistry at the

Centennial deposit, but clay-fraction chemistry at different locations more proximally down ice

of exposed extrabasinal material could be affected. Therefore, carrying out the same type of

study at a location where a geochemical survey has been carried out that is more likely to be

affected (e.g. eastern region of the Athabasca Basin) would be helpful for characterizing “false”

radiogenic Pb anomalies. Fine fraction mineral abundance identification using MLA, identifying

and counting extrabasinal pebbles, and calculating effects that U-rich minerals would have on

clay-fraction geochemistry will help to identify characteristics of soils that generate “false”

radiogenic Pb anomalies. Other minerals that may have trace amounts of U should also be

considered and the concentrations of REE in minerals studied should also be determined to

identify potential sources of higher HREE/LREE patterns. This study focused on minerals very

close to the surface, but other generations of glacial deposits may be below the surface and these

76

should be considered as potential sources of secondary dispersion of pathfinder elements.

Locations in the Athabasca Basin where airborne radiometrics identify dominantly extrabasinal

material (Figure 3.1) at the surface would be suitable for future investigations.

Using HREE/LREE ratios combined with pebble counting and surficial geology mapping

may be an effective way to distinguish “false” from “true” radiogenic Pb and U anomalies.

Carrying out similar studies on the eastern margin of the Athabasca Basin would be important

for testing this hypothesis. The maximum proportion of extrabasinal pebbles in the samples

analyzed at Centennial was 23 % and the maximum abundances of zircon and garnet in the <20

μm fraction were 0.26% and 0.75%, respectively. If samples taken near the eastern margin of the

Athabasca Basin had proportions of extrabasinal pebbles in the 60-80% range, there would likely

be higher abundances of zircon and garnet as well. Increased zircon could result in “false”

radiogenic Pb anomalies, but the increased abundance of both zircon and garnet could result in

higher HREE/LREE ratios.

77

Figure 3.1: Airborne radiometrics and ice flow directions map with suggestions on sites for

futures studies of surface radiogenic Pb anomalies related to minerals at the surface. (Modified

from Campbell, 2007, Campbell et al., 2002, Carson et al., 2002, and references therein)

78

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96

Appendix A

Initial, Split, Size Fraction, and Concentrate Weights

Sample ID WL008 A WL008 B WL038 WL060 WL066

Initial Weight (g) 372.1 372.1 595.2 278.1 375.2

Split 1 (g) 187.3 187.3 282.3 147.4 224.2

Split 2 (g) 181.2 181.2 312.5 130 150

Yield (%) 99.03% 99.93% 99.93% 99.75% 99.73%

<20µm (g) 5.5 3.6 1.4 0.5 3.8

<20µm % of Sample 2.94% 1.99% 0.50% 0.34% 1.69%

<20µm Concentrate (mg) 64 45 16 12 9

<20µm Concentrate (% of Size Fraction) 1.16% 1.25% 1.14% 2.40% 0.24%

20-45µm (g) 5.1 7.1 3.5 0.8 4.3

20-45µm % of Sample 2.72% 3.92% 1.24% 0.54% 1.92%

20-45µm Concentrate (mg) 19 32 60 56 59

20-45µm Concentrate (% of Size Fraction) 0.37% 0.45% 1.71% 7.00% 1.37%

45-63µm (g) 5.1 5.6 4.2 0.7 3.3

45-63µm % of Sample 2.72% 3.09% 1.49% 0.47% 1.47%

45-63µm Concentrate (mg) 37 50 70 75 31

45-63µm Concentrate (% of Size Fraction) 0.73% 0.89% 1.67% 10.71% 0.94%

Notes: Weights of samples, splits, size fractions and concentrates for each sample. Gray

highlighting indicates which split was used for sieving and heavy mineral concentration.

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Initial, Split, Size Fraction, and Concentrate Weights (Continued)

Sample ID WL087 WL106 WL134 WL154 WL229 WL302 WL305 WL313 WL338 WL509 WL518

Initial Weight (g) 962.6 675.6 435.5 426.7 341.9 622.2 724.8 276.6 438.1 405.8 446.8

Split 1 (g) 474.3 358.1 200.5 212.3 188.7 311.9 373.9 135.3 220 206.1 222.2

Split 2 (g) 486.5 316.9 234.8 214.3 152.7 309.5 338.2 140.6 218 198.5 223.5

Yield (%) 99.81% 99.91% 99.95% 99.98% 99.85% 99.87% 98.25% 99.75% 99.98% 99.70% 99.75%

<20µm (g) 8.8 0.2 0.1 0.3 1.6 1.8 1.9 0.7 0.4 4.1 3.3

<20µm % of Sample 1.86% 0.06% 0.05% 0.14% 0.85% 0.58% 0.50% 0.52% 0.16% 1.97% 1.47%

<20µm Concentrate (mg) 7 11 9 46 98 16 8 11 14 37 0

<20µm Concentrate (% of Size Fraction) 0.08% 5.50% 9.00% 15.92% 6.13% 0.88% 0.43% 1.57% 3.98% 0.91% 0.00%

20-45µm (g) 3 0.5 0.2 0.3 3.1 6.1 7.4 0.3 0.7 5.9 6.2

20-45µm % of Sample 0.63% 0.14% 0.10% 0.14% 1.64% 1.97% 1.98% 0.22% 0.30% 2.87% 2.77%

20-45µm Concentrate (mg) 60 58 20 4 118 17 19 17 7 34 11

20-45µm Concentrate (% of Size Fraction) 2.00% 11.60% 10.00% 1.33% 3.81% 0.28% 0.26% 5.67% 1.08% 0.57% 0.18%

45-63µm (g) 2.3 1.5 0.3 0.1 5.2 10.2 10.7 0.2 1.2 3.3 2.6

45-63µm % of Sample 0.48% 0.42% 0.15% 0.03% 2.76% 3.26% 2.87% 0.15% 0.56% 1.58% 1.19%

45-63µm Concentrate (mg) 117 114 24 19 147 74 40 8 30 9 20

45-63µm Concentrate (% of Size Fraction) 5.09% 7.60% 8.00% 34.55% 2.83% 0.73% 0.37% 4.00% 2.46% 0.28% 0.76%

Notes: Weights of samples, splits, size fractions and concentrates for each sample. Gray highlighting indicates which split was used

for sieving and heavy mineral concentration.

98

Appendix B

Microriffle Splitting and Mono-layer Grain Mounting

A Quantachrome Rotary Micro-Riffler was used to make subsamples into small enough

aliquots (10-20 mg) to mount in epoxy. The microriffler splits individual grain or powder

samples into 8 subsamples. A representative subsample of the desired weight was achieved by

repetitive division of the 8 collected subsamples. One aliquot was collected for each size fraction

of heavy mineral concentrates because the whole concentrate, which is representative of the

heavy mineral content of the sample, was a small fraction (e.g. <1%) of the unprocessed sample

weight.

Simply adding subsamples to epoxy before curing may result in dense minerals settling to

the bottom of the epoxy mold and being overrepresented (Mermollid-Blondin, 2007). By

creating a monolayer of grains directly against a flat surface, there is no room for density

separation. Double sided tape was placed on polished epoxy caps and 10-20 mg subsamples of

grains mixed with 5-10 mg (ca. half the weight of the subsample) of micronized graphite powder

were spread on to the tape using a small plastic spatula. Graphite reduces grain clumping and

poor separation during MLA (Blaskovich, 2013). EpoxyCure 2 epoxy (Buehler Scientific,

Canada) was poured into the epoxy molds and placed in a vacuum chamber for about 5 minutes

to allow any bubbles to float to the top of the epoxy. Following the vacuum chamber, the grain

mounts set for at least 24 hours until fully cured. Mounts were then carefully polished with 1µm

diamond compound and carbon coated in preparation for MLA. Care was taken during the

polishing process to minimize grain loss.

To test the efficiency of the micro-riffler subsampling and mon-layer grain mounting

methods, 8 subsamples of 10-20 mg were from each size fraction (<20 μm, 20-45 μm, 45-63 μm)

99

were analyzed using MLA and the relative standard deviation (standard deviation of mineral

abundances divide by the mean) of each mineral abundance was calculated. The relative standard

deviations (RSD) were below 30% in all of the minerals except those that had average mineral

abundances below 0.10 wt%. This is reasonable because only 3 or 4 grains out of thousands

could change the mineral abundance by more than 30% of the average. The mineral category

“aluminosilicates” also had high RSDs because one clump of clay could change the abundance

by more than to 2 wt%. Aluminosilicates were labeled as mica by MLA in some of the

subsamples of the <20 µm fraction because of the similar chemistries of mica and clay minerals

so this also had a high RSD.

Once this subsampling method was developed, two subsamples of each size fraction were

made for mono-layer epoxy grain mounting and the average mineral abundances of these two

subsamples were used for the final mineral abundances of all the samples. Two subsamples of

unprocessed (non-hydroseparated) samples were analyzed for each size fraction so that an

average mineral abundance between the two would be more representative of the entire sample

than just one.

100

Relative Standard Deviations of Mineral Abundances Mineral RSD <20µm RSD 20-45µm RSD 45-63µm

Amphibole 7.02% 7.09% 11.22%

Apatite 32.40% 53.45% 282.84%

Aluminosilicates 28.84% 48.63% 30.42%

Epidote 16.62% 12.15% 11.45%

Garnet 12.13% 10.82% 20.11%

Hematite 9.53% 10.93% 26.74%

Ilmenite 25.94% 20.02% 26.21%

K-Feldspar 18.48% 10.01% 3.39%

Mica 43.78% 12.96% 42.25%

Monazite 170.78% 94.28% NA

Olivine 48.45% 66.48% 56.38%

Plagioclase 23.67% 4.55% 3.30%

Pyrite 23.60% 36.03% 53.45%

Pyroxene 20.89% 16.07% 23.81%

Quartz 4.81% 0.68% 0.47%

Rutile 8.74% 9.71% 10.46%

Titanite 37.11% 19.72% 46.29%

Zircon 12.74% 17.49% 26.16%

Notes: Relative standard deviations (RSD = Standard deviation of mineral abundance divided by

the mean) of mineral abundances for each size fraction are based on the average mineral

abundances of 8 micro-riffled sub-samples. Minerals that have an RSD> 30% (highlighted in

gray) had average abundances of <0.10% so even the smallest variation, which can be caused by

3 or 4 grains out of thousands, from the average results in a high RSD. The category labeled

aluminosilicates has high RSD because it can be affected by 1 large clump of clay in the

subsample. The RSD labeled NA was a result of monazite having an average abundance of

0.00% by weight.

101

Appendix C

HS-11 Hydroseparator & Heavy Liquid Separation

The hydroseparator uses curved vertical glass tubes (GST), a software controlled pulse

regulator, and a manually controlled flow rate regulator connected to a gravity controlled water

tank. The hydroseparator has two GST sizes: the large GST (LGST) is for initial concentration

and the small GST (SGST) is for final concentration. Heavier minerals stay at the bottom of the

GST and lighter minerals flow out the top of the GST (Figure A.1). Pulse regulator modes are

split into two categories: 1.1-1.5 and 2.1-2.5. When there is a large difference in densities

between light and target minerals (e.g., quartz and zircon) modes 1.1-1.5 are used. Modes 2.1-2.5

are used only for initial concentration when the difference in densities is closer (CNT Minerals,

2010). For this project, only modes 1.1-1.5 were tested.

Trial runs with heavy mineral-doped quartz powders were most successful (visual checks

of concentrates on SEM) with modes 1.2 and 1.3 so these were the only modes used. Calgon®

was added to the water used for hydroseparation to reduce clumping of samples in the GSTs

(some clumping is unavoidable in the <20 µm size fraction because not all the clay could be

removed during preparation). For initial concentrations, aliquots of approximately 4 g or less

were mixed with water to create a slurry that was poured into the top of the LGST. Each aliquot

was processed for 2-3 minutes until no grains were visibly flowing out of the top of the LGST.

The initial concentrates for all of the <4 g aliquots were combined and processed in the SGST for

1-2 minutes to produce a final HMC.

One sample (WL008) was run twice on the hydroseparator with the same setting to test

the reproducibility of concentration factors. The reproducibility of concentration factors was

102

close for the same sample, however there was no reproducibility between different samples. A

number of variables could account for different concentration factors between samples including

original mineral abundances and clay content, original weight of the size fraction, shapes of

heavy minerals, and human or instrumental error of hydroseparator operation.

Sub-splits of four samples (<63 μm) were sent to Laurentian University in Sudbury, ON

to be passed through methylene iodide (S.G. = 3.33; Brauns, 1912) for heavy liquid density

separation to compare the efficiency of hydroseparation with heavy liquid separation.

103

Figure A.1: Schematic cross section (not to scale) of the HS-11 hydroseparator GST. The slurry

of water and minerals is introduced into the top of the GST, and then a water flow and pulse rate

is set to separate heavy minerals into the bottom elbow of the GST while light minerals flow out

of the top.

104

HS-11 Heavy Mineral Concentrate Reproducibility Results

<20 µm 20-45 µm 45-63 µm

Mineral - Sample WL008 (A) WL008(B) WL008 RSD WL008 (A) WL008(B) WL008 RSD WL008 (A) WL008(B) WL008 RSD

Amphibole 0.44% 0.51% 10.42% 0.66% 0.76% 9.96% 0.68% 0.65% 3.19%

Apatite 0.00% 0.01% 141.42% 0.05% 0.01% 94.28% 0.03% 0.04% 20.20%

Aluminosilicates 0.39% 0.17% 55.56% 0.37% 0.09% 86.08% 0.28% 0.23% 13.86%

Epidote 0.23% 0.26% 8.66% 0.24% 0.30% 15.71% 0.26% 0.25% 2.77%

Garnet 0.21% 0.28% 20.20% 0.66% 1.11% 35.95% 1.20% 1.25% 2.89%

Hematite 0.48% 0.44% 6.15% 1.14% 1.73% 29.07% 2.23% 2.06% 5.60%

Ilmenite 0.79% 0.73% 5.58% 1.20% 1.52% 16.64% 1.48% 1.61% 5.95%

K-Feldspar 3.00% 2.85% 3.63% 1.78% 1.70% 3.25% 1.16% 1.17% 0.61%

Mica 0.06% 0.06% 0.00% 0.06% 0.05% 12.86% 0.03% 0.03% 0.00%

Monazite 0.03% 0.03% 0.00% 0.02% 0.02% 0.00% 0.04% 0.05% 15.71%

Olivine 0.02% 0.02% 0.00% 0.02% 0.04% 47.14% 0.02% 0.02% 0.00%

Plagioclase 2.97% 3.11% 3.26% 2.65% 2.67% 0.53% 2.17% 2.17% 0.00%

Pyrite 0.03% 0.13% 88.39% 0.06% 0.08% 20.20% 0.02% 0.03% 28.28%

Pyroxene 0.07% 0.08% 9.43% 0.14% 0.18% 17.68% 0.16% 0.18% 8.32%

Quartz 89.98% 89.76% 0.17% 87.97% 85.39% 2.10% 85.62% 85.33% 0.24%

Rutile 0.66% 0.59% 7.92% 0.86% 1.20% 23.34% 0.95% 0.93% 1.50%

Titanite 0.03% 0.02% 28.28% 0.04% 0.05% 15.71% 0.04% 0.04% 0.00%

Unknown 0.14% 0.53% 82.32% 0.42% 0.71% 36.29% 0.45% 0.66% 26.76%

Zircon 0.47% 0.43% 6.29% 1.65% 2.38% 25.62% 3.16% 3.29% 2.85%

Notes: HS-11 heavy mineral concentrate abundances determined by MLA. Relative standard deviations of each mineral (Standard

deviation of abundances divided by the mean) between two concentrates from two splits of the same original sample.

105

HS-11 Settings, Final Concentrate, and Final Concentrate Tailings (FCT) Weights <20µm

Sample # Setting LGST-SGST Flow Rate (ml/min) (LGST)-(SGST) Conc Weight (mg) FCT Weight (mg)

WL008 1.3-1.2 (50-55)-(50-55) 64 493

WL038 1.3-1.2 (50-55)-(50-55) 16 82

WL060 1.3-1.2 (50-55)-(50-55) 12 246

WL066 1.3-1.2 (50-55)-(50-55) 9 81

WL087 1.3-1.2 (50-55)-(50-55) 7 133

WL106 1.3-1.2 (50-55)-(50-55) 11 15

WL134 1.3-1.2 (50-55)-(50-55) 9 8

WL229 1.3-1.2 (50-55)-(50-55) 98 159

WL313 1.3-1.2 (50-55)-(50-55) 11 45

WL154 1.3-1.2 (50-55)-(20-25) 46 – mostly clay 133

WL302 1.3-1.3 (50-55)-(20-25) 16 880

WL305 1.3-1.3 (50-55)-(20-25) 8 1485

WL338 1.3-1.3 (50-55)-(20-25) 14 303

WL509 1.3-1.3 (50-55)-(20-25) 37 3.5

WL518 1.3-1.3 (50-55)-(20-25) 0 350

106

HS-11 Settings, Final Concentrate, and Final Concentrate Tailings (FCT) Weights 20-45µm


WL008 1.3-1.2 (70-75)-(70-75) 19 224

WL038 1.3-1.2 (70-75)-(70-75) 60 435

WL060 1.3-1.2 (70-75)-(70-75) 56 174

WL066 1.3-1.2 (70-75)-(70-75) 59 568

WL087 1.3-1.2 (70-75)-(70-75) 60 139

WL106 1.3-1.2 (70-75)-(70-75) 58 268

WL134 1.3-1.2 (70-75)-(70-75) 20 74

WL229 1.3-1.2 (70-75)-(70-75) 118 322

WL313 1.3-1.2 (70-75)-(70-75) 17 78

WL154 1.3-1.2 (70-75)-(40-45) 4 61

WL302 1.3-1.3 (70-75)-(40-45) 17 570

WL305 1.3-1.3 (70-75)-(40-45) 19 398

WL338 1.3-1.3 (70-75)-(40-45) 7 110

WL509 1.3-1.3 (70-75)-(40-45) 34 422

WL518 1.3-1.3 (70-75)-(40-45) 11 1250

107

HS-11 Settings, Final Concentrate, and Final Concentrate Tailings (FCT) Weights 45-63µm


WL008 1.3-1.2 (90-95)-(90-95) 37 423

WL038 1.3-1.2 (90-95)-(90-95) 70 793

WL060 1.3-1.2 (90-95)-(90-95) 75 279

WL066 1.3-1.2 (90-95)-(90-95) 31 589

WL087 1.3-1.2 (90-95)-(90-95) 117 506

WL106 1.3-1.2 (90-95)-(90-95) 114 547

WL134 1.3-1.2 (90-95)-(90-95) 24 282

WL229 1.3-1.2 (90-95)-(90-95) 147 1512

WL313 1.3-1.2 (90-95)-(90-95) 8 27

WL154 1.3-1.2 (90-95)-(90-95) Lost 19

WL302 1.3-1.3 (90-95)-(90-95) 74 1025

WL305 1.3-1.3 (90-95)-(90-95) 40 1640

WL338 1.3-1.3 (90-95)-(90-95) 30 375

WL509 1.3-1.3 (90-95)-(90-95) 9 352

WL518 1.3-1.3 (90-95)-(90-95) 20 602

108

Concentration factors with heavy liquid separation were significantly higher in some

samples than with the hydroseparator; however, the efficiency of concentration was more

variable than the hydroseparator. Figure A.2 shows a comparison of zircon concentration factors

for heavy liquid to concentration factors for hydroseparation. Some heavy liquid concentration

factors were up to an order of magnitude higher than that of hydroseparation (e.g. zircon,

monazite), but there was a range heavy mineral concentration factors from 1 to 204. HMCs made

from methylene iodide contained many “unknown” minerals indicating that there likely was

contamination in these concentrates.

Heavy mineral concentration using hydroseparation is typically a pre-concentration method

before using heavy liquid separation (Stendal and Theobald, 1994; Towie and Seet, 1995; McClenaghan,

2011). Samples in this study were not pre-concentrated before heavy liquid separation. Pre-concentration

is important because although some heavy liquid concentrates had substantially higher concentration

factors than HS-11, other heavy liquid concentrates appeared to have no effective concentration of heavy

minerals. There were also many minerals in heavy liquid concentrates that were identified by MLA as

“unknown”. All of the minerals in the samples and HS-11 concentrates had already been identified on

MLA with <1% unknowns suggesting that contamination occurred during heavy liquid separation.

Heavy liquids are expensive and toxic, so they are commonly filtered and recycled (Towie and Seet,

1995). It is likely that new heavy mineral concentrates can contain minerals from previous heavy liquid

separations contaminating the HMC. Thousands of grains are counted on MLA and rapid scans may be

performed to identify specified minerals (Fandrich et al., 2007). Although the heavy minerals are not

concentrated as much with hydroseparation alone, MLA can still count several hundred heavy mineral

grains per 10-20mg HMC mount. Therefore, the HS-11 hydroseparation combined with mono-layer grain

mounting and MLA may be used an alternative to multistep heavy mineral concentration processes, but

further investigation of this is required.

109

Figure A.2: Comparison of concertation factors from hydroseparation versus concentration factors from

heavy liquid separation.

0

20

40

60

80

100

120

140

0.00 5.00 10.00 15.00 20.00 25.00 30.00

He

avy

Liq

uid

Se

par

atio

n (

<63

μm

)

Hydroseparation (45-63 μm)

Heavy Mineral Concentration factors for Heavy Liquid Separation Vs. Hydroseparation

WL038

WL087

WL229

WL313

110

Heavy Liquid Separation Results WL038 WL087 WL229 WL313

Mineral Original

Wt.% Conc. Wt.% Factor

Original Wt.%

Conc. Wt.% Factor

Original Wt.%

Conc. Wt.% Factor

Original Wt.%

Conc. Wt.% Factor

Amphibole 1.27% 1.61% 1.27 1.24% 1.01% 0.82 1.48% 0.49% 0.33 4.31% 5.20% 1.20

Apatite 0.00% 0.00% 0.00 0.00% 0.00% 0.00 0.01% 0.00% 0.30 0.09% 0.23% 2.65

Aluminosilicates 1.62% 0.26% 0.16 4.49% 1.13% 0.25 3.56% 0.07% 0.02 3.21% 2.50% 0.78

Epidote 0.23% 1.37% 6.04 0.26% 0.12% 0.46 0.28% 0.51% 1.83 0.46% 1.00% 2.18

Garnet 0.35% 27.78% 79.37 0.73% 3.45% 4.76 0.52% 14.18% 27.10 1.23% 0.79% 0.64

Hematite 0.06% 1.26% 21.60 1.74% 34.38% 19.78 0.84% 32.62% 39.07 0.76% 1.00% 1.31

Ilmenite 0.15% 17.68% 115.30 0.94% 12.28% 13.11 0.45% 15.94% 35.41 0.51% 0.74% 1.45

K-Feldspar 5.67% 0.75% 0.13 5.64% 3.16% 0.56 6.04% 0.24% 0.04 8.17% 6.22% 0.76

Mica 0.08% 0.03% 0.38 0.10% 0.13% 1.32 0.08% 0.02% 0.26 0.17% 0.10% 0.58

Monazite 0.00% 0.34% 204.00 0.02% 0.30% 13.85 0.02% 0.32% 21.17 0.01% 0.02% 4.00

Olivine 0.03% 0.02% 0.60 0.02% 0.07% 3.23 0.02% 0.02% 1.13 0.03% 0.05% 1.69

Plagioclase 8.26% 0.29% 0.04 7.15% 3.07% 0.43 7.52% 0.18% 0.02 12.73% 10.62% 0.83

Pyrite 0.02% 0.04% 1.85 0.03% 0.19% 6.00 0.05% 0.03% 0.59 0.05% 0.03% 0.58

Pyroxene 0.20% 2.76% 13.80 0.20% 0.31% 1.58 0.21% 0.88% 4.13 0.47% 0.84% 1.76

Quartz 81.23% 2.02% 0.02 75.58% 17.49% 0.23 77.63% 1.71% 0.02 66.66% 68.90% 1.03

Rutile 0.24% 9.13% 38.58 0.43% 1.97% 4.64 0.45% 5.73% 12.69 0.32% 0.61% 1.90

Titanite 0.04% 0.43% 11.73 0.06% 0.01% 0.17 0.06% 0.24% 4.41 0.11% 0.20% 1.72

Unknown 0.30% 1.32% 4.40 0.20% 3.52% 17.31 0.19% 0.58% 3.08 0.37% 0.54% 1.47

Zircon 0.26% 32.89% 128.14 1.19% 17.41% 14.67 0.61% 26.25% 42.92 0.36% 0.45% 1.27

Notes: Heavy Liquid (methylene iodide) heavy mineral concentrate mineral abundances determined by MLA.

111

Appendix D

LA-ICPMS Results from 168 Zircon Grains

Sample ID Repetition Rate 206Pb (ppm) 207Pb (ppm) 208Pb (ppm) U (ppm)

008_1 50 Hz 79.541 11.767 21.017 531.658

008_2 50 Hz 54.976 9.092 17.819 286.624

008_3 50 Hz 30.911 3.744 9.291 135.571

008_4 50 Hz 41.840 4.748 12.152 158.964

008_5 50 Hz 26.096 3.444 8.299 102.716

008_6 5 Hz 33.428 4.264 6.156 117.888

008_7 5 Hz 113.143 23.098 13.988 598.073

008_8 5 Hz 32.259 4.199 7.130 102.594

008_9 5 Hz 96.645 14.114 26.190 1152.282

008_10 5 Hz 34.338 4.872 12.077 146.660

008_11 10 Hz 43.080 5.557 9.745 299.290

008_12 10 Hz 26.725 3.514 8.858 203.695

008_13 10 Hz 40.099 7.932 7.650 94.445

008_14 10 Hz 36.138 7.560 8.280 87.863

008_15 10 Hz 164.222 28.356 2.944 432.714

008_16 20 Hz 19.408 2.726 2.271 108.151

008_17 20 Hz 52.093 9.420 9.138 135.244

008_18 20 Hz 70.534 10.586 10.940 212.730

008_19 20 Hz 29.447 3.919 10.329 118.091

008_20 20 Hz 29.081 3.683 4.378 182.186 008_21 5 Hz 21.696 2.263 7.065 82.286

008_22 5 Hz 104.310 19.365 23.383 238.664

008_23 5 Hz 94.708 11.889 9.240 405.441

008_24 5 Hz 114.333 26.245 53.900 1598.935

008_25 5 Hz 82.649 22.131 41.502 1511.716

008_26 5 Hz 906.843 94.990 48.276 4363.304

008_27 5 Hz 68.777 15.368 36.192 625.442

008_28 5 Hz 362.988 63.981 24.901 873.802

008_29 5 Hz 60.900 7.839 18.394 321.277

008_30 5 Hz 66.016 7.579 4.355 248.097

112


038_1 5 Hz 440.107 58.376 50.567 1214.492

038_2 5 Hz 62.342 6.869 9.296 192.542

038_3 5 Hz 527.085 81.345 23.802 1221.337

038_4 5 Hz 71.285 13.489 16.363 169.222

038_5 5 Hz 7.062 0.876 3.418 23.227

038_6 5 Hz 48.781 5.190 13.874 171.413

038_7 5 Hz 304.611 51.667 23.690 670.388

038_8 5 Hz 23.107 2.600 7.726 83.894

038_9 5 Hz 74.040 13.176 21.430 167.566

038_10 5 Hz 45.423 5.514 21.323 273.113

060_1 5 Hz 91.965 11.414 10.988 542.285

060_2 5 Hz 94.136 13.824 16.564 1216.771

060_3 5 Hz 19.269 2.028 3.938 62.571

060_4 5 Hz 66.082 8.862 15.660 1179.558

060_5 5 Hz 364.880 51.571 25.515 1301.648

060_6 5 Hz 19.567 2.437 7.913 71.523

060_7 5 Hz 51.387 8.090 7.626 131.785

060_8 5 Hz 22.756 2.561 8.055 175.343

060_9 5 Hz 63.102 7.783 26.113 1006.288

060_10 5 Hz 50.692 6.144 8.094 212.168

066_1 50 Hz 33.677 3.492 5.752 241.270

066_2 50 Hz 33.592 3.170 10.694 231.337

066_3 50 Hz 54.478 8.103 6.981 341.204

066_4 50 Hz 35.526 4.626 6.059 294.087

066_5 50 Hz 61.254 7.643 12.985 268.614

066_6 50 Hz 45.524 5.155 5.988 158.875

066_7 50 Hz 28.135 3.646 3.368 137.806

066_8 50 Hz 36.168 5.172 10.098 166.962

113


087_1 5 Hz 36.628 4.048 6.720 149.485

087_2 5 Hz 100.009 17.418 17.378 619.583

087_3 5 Hz 62.123 6.940 19.739 293.687

087_4 5 Hz 52.654 6.114 5.449 177.208

087_5 5 Hz 35.368 3.850 11.361 126.515

087_6 5 Hz 29.851 3.910 10.239 113.778

087_7 5 Hz 54.524 8.030 6.880 140.377

087_8 5 Hz 49.568 5.083 7.435 172.083

087_9 5 Hz 36.498 3.562 9.207 148.806

087_10 5 Hz 44.077 8.821 7.617 97.613

087_11 5 Hz 47.869 4.742 10.110 206.882

087_12 5 Hz 61.638 6.219 22.656 236.847

087_13 5 Hz 46.151 4.514 10.276 182.879

087_14 5 Hz 61.779 18.773 56.044 62.741

087_15 5 Hz 65.327 9.104 19.027 690.822

087_16 5 Hz 66.444 10.634 9.955 171.904

106_1 5 Hz 39.371 3.859 9.696 173.005

106_2 5 Hz 126.286 19.232 22.478 301.354

106_3 5 Hz 75.883 10.117 13.445 688.017

106_4 5 Hz 23.867 2.593 3.409 78.242

106_5 5 Hz 80.696 14.387 12.739 158.812

106_6 5 Hz 80.397 10.155 10.856 396.082

106_7 5 Hz 74.909 10.080 11.623 770.907

106_8 5 Hz 43.283 4.452 6.561 147.971

106_9 5 Hz 90.013 11.460 16.963 293.204

106_10 5 Hz 22.081 2.892 6.445 72.768

134_1 5 Hz 26.420 3.198 3.650 57.094

134_2 5 Hz 43.187 4.453 14.148 128.898

134_3 5 Hz 21.991 3.008 4.442 58.843

134_4 5 Hz 50.205 6.477 16.369 323.679

134_5 5 Hz 34.263 3.469 12.140 168.798

134_6 5 Hz 48.151 5.093 9.959 254.446

134_7 5 Hz 83.881 12.727 13.970 814.204

134_8 5 Hz 77.194 13.721 16.912 655.633

134_9 5 Hz 82.940 9.434 13.854 382.995

134_10 5 Hz 89.767 11.289 19.081 777.827

114


229_1 50 Hz 22.382 2.452 3.496 74.206

229_2 50 Hz 17.710 1.860 6.274 79.657

229_3 50 Hz 32.658 3.441 9.719 140.837

229_4 50 Hz 23.161 2.426 5.581 98.006

229_5 50 Hz 40.678 5.023 2.424 141.749

229_6 50 Hz 26.809 4.928 4.697 118.600

229_7 50 Hz 60.628 10.051 6.709 150.090

229_8 50 Hz 27.710 3.399 4.435 113.457

229_9 50 Hz 25.652 2.659 6.987 120.593

302_1 5 Hz 61.601 6.815 3.530 219.204

302_2 5 Hz 69.227 8.095 7.827 564.244

302_3 5 Hz 29.499 3.627 11.602 175.236

302_4 5 Hz 89.102 13.903 26.726 1324.481

302_5 5 Hz 161.335 16.642 20.883 493.976

302_6 5 Hz 62.527 6.737 4.683 189.634

302_7 5 Hz 33.814 3.700 5.444 99.049

302_8 5 Hz 42.004 5.628 7.466 225.079

302_9 5 Hz 22.206 2.314 6.998 79.772

302_10 5 Hz 19.221 1.964 4.420 61.086

305_1⁺ 5 Hz 40.618 4.830 12.021 235.122

305_2⁺ 5 Hz 43.950 4.893 10.948 457.916

305_3⁺ 5 Hz 129.211 16.756 9.641 344.951

305_4⁺ 5 Hz 88.004 13.837 17.733 978.034

305_5⁺ 5 Hz 68.140 5.975 6.150 278.673

305_6⁺ 5 Hz 33.902 2.952 10.209 140.604

305_7⁺ 5 Hz 37.360 3.974 11.109 160.484

305_8⁺ 5 Hz 60.197 6.249 16.205 392.526

305_9⁺ 5 Hz 97.084 16.522 19.911 1245.783

Notes: ⁺Samples run on Xseries mass spectrometer rather than Element 2

115


313_1 50 Hz 16.835 3.154 9.486 331.745

313_2 50 Hz 15.621 1.742 5.244 58.468

313_3 50 Hz 65.849 9.934 5.752 333.058

313_4 5 Hz 52.992 7.243 8.831 535.504

313_5 5 Hz 20.682 2.573 4.153 80.974

313_6 5 Hz 27.990 3.342 10.186 102.947

313_7 5 Hz 43.435 5.993 9.685 179.104

313_8 5 Hz 253.393 42.718 61.859 707.382

313_9 10 Hz 37.395 7.626 7.768 158.855

313_10 10 Hz 7.924 1.082 3.870 31.095

313_11 10 Hz 40.479 5.578 8.997 212.676

313_12 10 Hz 156.002 20.470 32.069 552.143

313_13 10 Hz 33.887 4.076 8.617 169.955

313_14 20 Hz 60.966 8.037 12.303 198.827

313_15 20 Hz 33.727 4.196 4.880 133.496

313_16 20 Hz 30.485 4.422 8.538 232.562

313_17 20 Hz 29.078 2.919 9.014 118.674

338_1 5 Hz 127.944 18.003 14.150 301.182

338_2 5 Hz 69.980 7.479 10.391 215.422

338_3 5 Hz 40.195 4.178 8.818 198.495

338_4 5 Hz 31.149 3.125 6.970 129.999

338_5 5 Hz 102.759 23.451 38.289 1477.795

338_6 5 Hz 43.057 5.596 5.448 144.117

338_7 5 Hz 60.230 7.980 10.450 1101.221

338_8 5 Hz 385.673 63.192 5.991 732.070

338_9 5 Hz 39.859 5.260 7.244 111.726

338_10 5 Hz 40.141 5.356 14.974 301.932

509_1 5 Hz 55.948 7.518 10.972 251.844

509_2 5 Hz 21.959 2.557 1.788 54.491

509_3 5 Hz 78.931 16.748 34.364 2138.672

509_4 5 Hz 42.410 4.825 12.898 183.164

509_5 5 Hz 41.771 5.202 4.326 151.107

509_6 5 Hz 58.253 9.755 16.338 2158.795

509_7 5 Hz 25.632 3.109 9.296 98.894

509_8 5 Hz 23.497 2.354 6.341 74.664

509_9 5 Hz 56.675 6.449 13.650 211.049

509_10 5 Hz 37.806 2.732 3.805 939.444

116


518_1⁺ 5 Hz 35.422 3.428 6.571 149.049

518_2⁺ 5 Hz 29.620 3.033 5.715 119.189

518_3⁺ 5 Hz 9.404 1.082 2.394 64.919

518_4⁺ 5 Hz 34.690 3.731 5.401 201.838

518_5⁺ 5 Hz 453.970 28.190 9.619 1580.489

518_6⁺ 5 Hz 597.192 58.644 18.641 1431.004

518_7⁺ 5 Hz 41.653 3.675 10.464 471.732

518_8⁺ 5 Hz 612.099 71.778 42.878 1465.766

518_9⁺ 5 Hz 94.450 4.805 23.433 600.313

Notes: ⁺Samples run on Xseries mass spectrometer rather than Element 2

117

Appendix E

Clay Fraction Chemistry for Samples from 2013 Uravan Survey at Centennial (Nad 83 Zone 13) Sample

ID East North 207Pb/206Pb Ratio U

(ppm)

206Pb (ppm) 207Pb (ppm)

WL001 344521.2 6385494 0.714 2.948 2.06 1.47

WL002 344710.3 6385427 0.723 1.906 5.59 4.04

WL003 344897 6385357 0.809 1.081 4.77 3.86

WL004 345077.3 6385283 0.764 2.604 1.82 1.39

WL005 345266.7 6385227 0.749 1.958 3.67 2.75

WL006 345458.7 6385169 0.715 2.076 2.81 2.01

WL007 345651.2 6385078 0.826 0.601 3.57 2.95

WL008 345829.7 6385007 0.776 1.337 8.03 6.23

WL009 346022.1 6384947 0.722 1.551 11.31 8.17

WL011 344494.7 6385718 0.756 2.79 3.12 2.36

WL012 344678.9 6385651 0.820 1.029 10.45 8.57

WL013 344866 6385582 0.724 0.921 5.95 4.31

WL014 344957.9 6385543 0.731 1.315 6.32 4.62

WL016 345145.2 6385478 0.748 1.351 6.55 4.9

WL017 345252 6385468 0.748 2.049 4.25 3.18

WL018 345339.6 6385409 0.704 2.532 3.61 2.54

WL019 345434.3 6385374 0.694 2.889 2.42 1.68

WL020 345526.1 6385338 0.658 2.582 3.07 2.02

WL023 345816.2 6385236 0.761 1.771 4.73 3.6

WL024 345909.9 6385201 0.895 1.021 7.89 7.06

WL025 346000.8 6385166 0.722 0.583 8.01 5.78

WL026 346183.9 6385097 0.725 2.51 6.8 4.93

WL027 344951.5 6385654 0.676 0.86 3.61 2.44

WL028 345046 6385619 0.734 1.5 7.07 5.19

WL029 345135.1 6385585 0.719 0.475 3.42 2.46

WL031 345327.9 6385513 0.757 2.456 4.04 3.06

WL032 345421.5 6385480 0.713 1.019 6.91 4.93

WL033 345510.3 6385448 0.653 2.567 2.68 1.75

WL034 345606.4 6385412 0.738 1.533 5.08 3.75

WL035 345703.9 6385379 0.667 2.245 2.67 1.78

WL036 345790.1 6385343 0.625 4.65 2.61 1.63

WL037 345894.5 6385314 0.765 2.855 5.61 4.29

WL038 344656.2 6385872 0.760 2.154 2.54 1.93

WL039 344847.5 6385807 0.713 3.391 2.65 1.89

WL040 344923.5 6385776 0.634 1.726 5.22 3.31

WL042 345124 6385705 0.761 0.487 3.89 2.96

WL043 345208.9 6385673 0.754 1.318 10.39 7.83

WL044 345296.3 6385639 0.674 0.568 1.32 0.89

WL045 345416.9 6385570 0.664 1.544 3.18 2.11

WL046 345504.6 6385556 0.708 3.374 4.69 3.32

WL047 345599.1 6385525 0.616 2.892 3.2 1.97

WL048 345691.2 6385489 0.720 2.257 2.68 1.93

WL049 345786.2 6385457 0.669 1.848 4.29 2.87

WL051 345968.9 6385390 0.720 4.002 2.79 2.01

118

Sample


(ppm)


WL052 346160.1 6385315 0.698 1.562 11.64 8.13

WL053 346340.9 6385246 0.712 2.559 5.77 4.11

WL054 339577.8 6387843 0.697 1.801 2.97 2.07

WL055 340048.8 6387669 0.832 1.101 6.6 5.49

WL056 340515.6 6387499 0.612 3.021 2.73 1.67

WL057 340980 6387288 0.689 1.407 4.92 3.39

WL058 341542.6 6387164 0.687 1.304 4.12 2.83

WL059 341922.6 6386981 0.588 1.825 4.9 2.88

WL060 342394.6 6386807 0.644 2.24 2.7 1.74

WL061 342863.8 6386633 0.711 1.576 5.02 3.57

WL062 343325.2 6386462 0.774 2.035 3.59 2.78

WL063 343798.6 6386291 0.787 0.845 8.9 7

WL064 344273.6 6386111 0.796 2.279 5.04 4.01

WL065 345028 6385840 0.637 2.453 3.42 2.18

WL066 345112.2 6385800 0.678 2.031 4.54 3.08

WL068 345264.7 6385759 0.739 1.172 7.02 5.19

WL069 345296.6 6385733 0.809 2.395 3.19 2.58

WL071 345393.3 6385721 0.783 1.112 5.39 4.22

WL072 345440.8 6385688 0.642 1.534 1.2 0.77

WL074 345534.8 6385651 0.689 2.108 2.51 1.73

WL076 345631.3 6385614 0.654 2.283 4.36 2.85

WL077 345681.5 6385602 0.677 2.173 2.48 1.68

WL078 345725.1 6385588 0.705 2.088 1.76 1.24

WL079 345774.9 6385561 0.812 1.826 5.81 4.72

WL080 345856.8 6385531 0.673 2.311 2.84 1.91

WL081 345958.4 6385502 0.679 1.822 5.95 4.04

WL082 346612.5 6385240 0.742 2.939 3.68 2.73

WL083 347083 6385090 0.611 2.52 5.09 3.11

WL084 347553.7 6384916 0.639 2.033 6.85 4.38

WL085 348026 6384738 0.628 2.21 6.58 4.13

WL086 348491.9 6384635 0.569 3.007 4.89 2.78

WL087 348931.1 6384414 0.841 0.838 10.27 8.64

WL088 349419.8 6384220 0.716 2.131 4.54 3.25

WL089 349906.7 6384049 0.737 2.351 5.48 4.04

WL091 350839.7 6383702 0.680 1.891 3.75 2.55

WL092 351309.1 6383535 0.746 2.61 3.23 2.41

WL093 345201.5 6385827 0.763 1.466 7.09 5.41

WL095 345298.4 6385800 0.827 1.602 7.05 5.83

WL096 345346.7 6385778 0.715 2.135 4.32 3.09

WL097 345392.6 6385762 0.739 1.326 8.76 6.47

WL099 345483 6385730 0.753 0.362 1.58 1.19

WL100 345532.9 6385711 0.750 0.375 0.56 0.42

WL101 345571.5 6385683 0.772 2.264 3.16 2.44

WL102 345626.1 6385679 0.697 2.888 5.84 4.07

WL103 345673.3 6385659 0.704 2.297 4.25 2.99

WL104 345715 6385641 0.725 2.72 3.6 2.61

WL105 344633.6 6386099 0.650 3.283 3.34 2.17

119

Sample


(ppm)


WL106 344823.7 6386026 0.608 2.49 3.67 2.23

WL107 345049.1 6385954 0.619 2.995 4.23 2.62

WL108 345097.9 6385920 0.749 1.253 5.73 4.29

WL111 345288.3 6385850 0.660 2.493 4.65 3.07

WL112 345332.7 6385831 0.714 2.401 2.31 1.65

WL113 345388.4 6385824 0.719 1.722 6.69 4.81

WL114 345433.6 6385803 0.707 3.043 2.46 1.74

WL115 345481.2 6385781 0.626 2.308 2.81 1.76

WL116 345524.3 6385766 0.650 1.037 7.23 4.7

WL117 345592.1 6385741 0.611 1.761 3.19 1.95

WL118 345623.3 6385719 0.745 2.161 2.74 2.04

WL119 345671.8 6385708 0.736 1.874 9.53 7.01

WL120 345715.7 6385696 0.698 1.158 7.91 5.52

WL121 345762.8 6385679 0.720 1.816 6.1 4.39

WL122 345849.2 6385638 0.720 1.754 7.47 5.38

WL123 345950.5 6385610 0.689 2.669 6.08 4.19

WL124 346041.7 6385574 0.686 1.614 2.8 1.92

WL125 346133.2 6385540 0.630 3.43 2.38 1.5

WL126 346325.7 6385469 0.709 2.63 3.47 2.46

WL127 345233.6 6385928 0.772 1.652 9.71 7.5

WL129 345338.6 6385900 0.639 3.464 2.66 1.7

WL131 345421.7 6385849 0.659 0.99 11.72 7.72

WL132 345469.2 6385835 0.733 2.571 4.01 2.94

WL134 345571.6 6385795 0.613 1.499 3.67 2.25

WL135 345609.2 6385783 0.604 2.318 3.91 2.36

WL136 345659 6385769 0.652 2.16 4.14 2.7

WL137 345703.1 6385753 0.710 1.154 6.13 4.35

WL138 345763.7 6385730 0.699 1.326 6.72 4.7

WL139 345094.1 6386033 0.639 1.977 4.15 2.65

WL140 345178.7 6385993 0.599 2.417 3.22 1.93

WL140 345178.7 6385993 0.629 2.813 2.91 1.83

WL141 345287.8 6385960 0.751 1.389 4.41 3.31

WL142 345321.4 6385951 0.787 2.633 3.29 2.59

WL143 345378 6385925 0.778 1.648 9.01 7.01

WL144 345415.2 6385909 0.781 1.304 7.61 5.94

WL145 345518.9 6385866 0.808 2.393 2.34 1.89

WL146 345559.8 6385863 0.745 1.69 9.39 7

WL147 345614.6 6385844 0.647 0.964 9.69 6.27

WL148 345657.3 6385833 0.623 1.908 4.96 3.09

WL149 345702 6385805 0.674 2.531 2.98 2.01

WL151 345798.7 6385773 0.622 1.26 8.28 5.15

WL152 345843.3 6385753 0.676 1.66 6.57 4.44

WL153 345934.6 6385722 0.681 1.164 3.07 2.09

WL154 346028.8 6385686 0.516 1.354 3.74 1.93

WL155 345266.1 6386018 0.733 2.819 5.44 3.99

WL156 345319.3 6386004 0.615 1.261 9.32 5.73

120

Sample


(ppm)


WL158 345414.9 6385967 0.756 1.193 7.62 5.76

WL159 345459.9 6385949 0.776 1.607 5.5 4.27

WL160 345509.9 6385929 0.821 1.089 10.51 8.63

WL161 345556 6385916 0.689 2.871 4.38 3.02

WL163 345647 6385879 0.603 1.559 4.06 2.45

WL164 345691.2 6385863 0.668 2.426 3.4 2.27

WL165 345742.3 6385844 0.681 3.359 2.32 1.58

WL166 345787.3 6385832 0.635 1.724 3.29 2.09

WL167 344798.3 6386243 0.717 2.282 4.17 2.99

WL168 344978.9 6386169 0.665 3.191 2.39 1.59

WL171 345267.1 6386077 0.694 2.909 5.13 3.56

WL172 345313.1 6386058 0.660 3.241 2.82 1.86

WL173 345359.1 6386038 0.729 3.326 2.91 2.12

WL174 345407.3 6386020 0.570 2.108 4.53 2.58

WL175 345451.1 6386006 0.672 2.883 5.49 3.69

WL176 345490.5 6385994 0.756 1.908 6.6 4.99

WL177 345532.3 6385980 0.835 1.465 8.72 7.28

WL178 345593.2 6385953 0.693 2.475 3.65 2.53

WL180 345688.1 6385916 0.617 2.733 3.5 2.16

WL182 345787 6385874 0.783 1.209 7.75 6.07

WL183 345826.8 6385864 0.632 2.245 2.66 1.68

WL184 345920.4 6385831 0.754 1.155 8.3 6.26

WL185 346014.7 6385798 0.754 1.922 6.62 4.99

WL186 346103.1 6385752 0.744 0.329 5.44 4.05

WL187 346292.8 6385691 0.690 3.508 2.68 1.85

WL188 346485.5 6385623 0.721 2.196 3.33 2.4

WL189 345306.7 6386110 0.705 2.049 4.38 3.09

WL191 345400.6 6386077 0.715 2.415 5.75 4.11

WL192 345447.8 6386063 0.787 2.074 4.65 3.66

WL193 345482.1 6386043 0.795 1.266 9.85 7.83

WL194 345546.3 6386024 0.702 2.1 3.83 2.69

WL195 345606.2 6386002 0.723 2.936 3.25 2.35

WL196 345636.1 6385995 0.736 1.835 4.05 2.98

WL197 345693 6385969 0.708 1.048 5.1 3.61

WL198 345746.6 6385947 0.629 2.708 2.64 1.66

WL199 345776.1 6385940 0.828 0.916 10.12 8.38

WL199 345776.1 6385940 0.827 1.321 15.02 12.42

WL200 345824.9 6385934 0.665 2.853 2.63 1.75

WL201 345157.9 6386218 0.698 3.285 2.78 1.94

WL202 345250.8 6386186 0.631 2.091 3.77 2.38

WL203 345360.5 6386175 0.770 1.935 4.48 3.45

WL204 345391.9 6386134 0.847 1.356 5.49 4.65

WL206 345490.4 6386097 0.857 1.547 6.15 5.27

WL207 345535.9 6386082 0.765 2.636 5.19 3.97

WL208 345632 6386054 0.725 2.504 4.48 3.25

121

Sample ID East North 207Pb/206Pb Ratio U (ppm) 206Pb (ppm) 207Pb (ppm)

WL209 345669.9 6386028 0.794 0.591 5.43 4.31

WL211 345773 6385998 0.728 1.791 3.9 2.84

WL212 345804.4 6385978 0.754 2.562 6.66 5.02

WL213 345853.6 6385966 0.777 1.957 5.57 4.33

WL214 345910.7 6385936 0.620 3.102 2.76 1.71

WL216 346095.8 6385872 0.649 3.501 3.59 2.33

WL217 345363.8 6386198 0.706 2.859 2.65 1.87

WL218 345387.8 6386188 0.742 1.597 6.56 4.87

WL219 345434.8 6386179 0.828 1.33 7.74 6.41

WL220 345481.7 6386150 0.721 2.14 5.37 3.87

WL221 345527 6386140 0.756 2.56 5.17 3.91

WL222 345570.7 6386114 0.678 2.541 3.7 2.51

WL224 345729.1 6386062 0.765 0.392 5.91 4.52

WL225 345772.2 6386053 0.810 0.401 5.85 4.74

WL226 345810 6386029 0.717 1.83 2.33 1.67

WL227 345887 6386012 0.766 2.438 6.41 4.91

WL228 344767.8 6386469 0.624 2.847 4.82 3.01

WL229 344958.3 6386394 0.684 3.575 3.83 2.62

WL231 345297.8 6386277 0.755 0.828 8.2 6.19

WL233 345426.1 6386224 0.831 1.874 5.08 4.22

WL234 345475.2 6386213 0.783 1.914 6.09 4.77

WL235 345522 6386195 0.740 2.248 6.34 4.69

WL236 345567 6386173 0.709 2.168 7.18 5.09

WL237 345664.6 6386138 0.626 2.156 3.58 2.24

WL238 345730.7 6386113 0.776 0.591 5.59 4.34

WL239 345763.7 6386107 0.719 0.738 5.08 3.65

WL240 345802.5 6386083 0.830 1.424 6.23 5.17

WL241 345853.1 6386073 0.704 2.428 4.53 3.19

WL242 345898.9 6386055 0.794 0.667 5.63 4.47

WL243 345970 6385983 0.694 1.146 9.77 6.78

WL244 346088.9 6385996 0.738 2.015 3.32 2.45

WL245 346177.5 6385951 0.658 2.1 5.12 3.37

WL246 346274.1 6385916 0.636 2.411 3.05 1.94

WL247 346458 6385843 0.692 1.674 3.08 2.13

WL248 345415.2 6386278 0.624 2.361 3.14 1.96

WL249 345468.3 6386261 0.768 1.501 8.23 6.32

WL251 345565.8 6386229 0.666 2.935 3.38 2.25

WL252 345609.5 6386216 0.730 1.873 6.12 4.47

WL253 345656.6 6386203 0.746 2.739 7.68 5.73

WL254 345704.3 6386176 0.623 2.326 3.93 2.45

WL255 345747.3 6386167 0.666 4.9 4.49 2.99

WL256 345783.9 6386170 0.730 1 6.88 5.02

WL257 345853.9 6386142 0.778 0.6 4.32 3.36

WL260 345455.2 6386326 0.625 3.175 3.23 2.02

WL261 345505.8 6386305 0.747 2.378 4.87 3.64

122


WL262 345553.9 6386288 0.712 2.721 3.51 2.5

WL263 345605.4 6386269 0.673 3.551 4.49 3.02

WL264 345634.9 6386243 0.697 2.611 2.97 2.07

WL265 345691.7 6386243 0.755 1.918 4.12 3.11

WL266 345745.9 6386215 0.632 3.5 3.29 2.08

WL267 345792.2 6386196 0.659 2.367 2.49 1.64

WL268 345837.5 6386185 0.735 1.2 8.97 6.59

WL269 345884.8 6386163 0.713 2.053 2.09 1.49

WL271 345976.6 6386132 0.805 0.939 8.48 6.83

WL272 346071.8 6386095 0.692 2.101 3.54 2.45

WL273 346164 6386063 0.831 1.066 7.18 5.97

WL274 346727.9 6385852 0.749 1.936 2.87 2.15

WL275 346916.6 6385783 0.664 1.745 7.89 5.24

WL276 347110.6 6385714 0.770 2.209 7.95 6.12

WL277 347294.1 6385645 0.741 1.474 6.29 4.66

WL278 347484.5 6385585 0.802 1.634 6.37 5.11

WL279 347674.4 6385506 0.595 2.319 4.94 2.94

WL280 347858.9 6385440 0.618 2.654 3.56 2.2

WL281 348044.3 6385368 0.555 2.141 3.8 2.11

WL282 348232.2 6385299 0.566 3.714 3.39 1.92

WL283 348423.7 6385236 0.676 1.393 7.03 4.75

WL284 348611.8 6385163 0.765 1.314 6.25 4.78

WL285 348796.9 6385096 0.790 0.474 3.72 2.94

WL286 348982.2 6385028 0.683 0.984 7.93 5.42

WL287 349177.1 6384953 0.750 1.778 5.6 4.2

WL288 349365.6 6384887 0.582 2.074 4.86 2.83

WL289 349550.2 6384814 0.639 1.424 7.29 4.66

WL291 349922.9 6384687 0.688 1.547 5.68 3.91

WL292 350111.1 6384607 0.627 2.483 4.58 2.87

WL293 350299.2 6384551 0.536 2.613 5.35 2.87

WL294 350484.9 6384472 0.655 0.795 6.21 4.07

WL295 350676.6 6384397 0.817 1.031 8.64 7.06

WL296 350868.7 6384343 0.728 2.23 6.17 4.49

WL297 351049.7 6384267 0.608 2.218 5.92 3.6

WL299 351433.2 6384128 0.765 0.379 3.45 2.64

WL302 345503.1 6386363 0.541 1.986 1.81 0.98

WL303 345551 6386344 0.663 2.167 2.7 1.79

WL304 345595.4 6386330 0.660 2.079 2.88 1.9

WL305 345642.5 6386304 0.591 1.826 2.25 1.33

WL306 345693.5 6386295 0.716 2.598 4.62 3.31

WL307 345734.2 6386275 0.654 2.541 2.54 1.66

WL308 345786 6386254 0.666 1.9 3.5 2.33

WL309 345832.3 6386237 0.772 1.884 7.34 5.67

WL311 345122.5 6386552 0.653 3.569 4.55 2.97

WL313 345400.8 6386451 0.736 2.379 3.11 2.29

123


WL314 345449.5 6386429 0.625 2.4 6.98 4.36

WL315 345491.9 6386409 0.599 4.395 2.92 1.75

WL319 345677.4 6386355 0.682 2.27 1.73 1.18

WL319 345677.4 6386355 0.622 2.538 1.96 1.22

WL321 345777.7 6386308 0.677 2.528 3.87 2.62

WL322 345827.6 6386292 0.610 3.936 3.08 1.88

WL323 345870 6386277 0.636 1.4 3.05 1.94

WL324 346061.7 6386209 0.696 2.271 2.86 1.99

WL324 346061.7 6386209 0.706 2.348 3.16 2.23

WL325 346165.5 6386166 0.660 2.101 3.09 2.04

WL326 346248 6386139 0.723 2.128 4.15 3

WL327 346466.5 6386075 0.806 1.806 3.91 3.15

WL330 345492.1 6386471 0.688 2.285 2.92 2.01

WL331 345543.5 6386463 0.665 1.484 2.48 1.65

WL332 345581.6 6386436 0.693 3.1 3.06 2.12

WL333 345633.3 6386419 0.620 4.7 2.87 1.78

WL335 345722.6 6386384 0.773 0.966 12.67 9.79

WL336 345778.3 6386373 0.670 3.706 1.85 1.24

WL337 345820.7 6386349 0.676 2.725 3.06 2.07

WL338 345869.1 6386332 0.574 2.082 2.77 1.59

WL340 345297.1 6386595 0.693 1.578 2.61 1.81

WL341 345481.8 6386523 0.796 0.862 6.14 4.89

WL342 345534.8 6386510 0.750 1.128 5.49 4.12

WL343 345582.4 6386491 0.739 3.1 3.94 2.91

WL344 345627.5 6386476 0.646 2.5 4.04 2.61

WL347 345767.1 6386419 0.577 4.729 3.9 2.25

WL349 345861.6 6386393 0.598 2.003 3.41 2.04

WL351 345954 6386351 0.676 2.188 3.09 2.09

WL352 346004.4 6386334 0.645 2.529 3.38 2.18

WL353 346046.8 6386317 0.663 1.398 4.42 2.93

WL354 346144.5 6386285 0.580 2.075 5.07 2.94

WL355 346260.9 6386255 0.586 2.399 2.61 1.53

WL356 345476.3 6386578 0.722 2.2 3.88 2.8

WL357 345511.4 6386557 0.662 4.337 2.6 1.72

WL359 345619.1 6386527 0.622 4.5 2.83 1.76

WL361 345711.5 6386492 0.645 6.4 3.04 1.96

WL362 345759.6 6386477 0.669 1.5 2.39 1.6

WL363 345806.6 6386460 0.653 2.2 1.96 1.28

WL364 345842 6386452 0.661 2.371 2.74 1.81

WL365 345900.2 6386434 0.807 1.902 5.09 4.11

WL366 345947 6386410 0.582 3.775 3.66 2.13

WL367 345994.6 6386392 0.590 2.63 3.1 1.83

WL368 344915 6386843 0.767 1.812 6.18 4.74

WL369 345096.2 6386773 0.682 3.646 3.58 2.44

WL371 345473 6386639 0.639 3.2 3.99 2.55

124


WL372 345516.4 6386621 0.655 2.3 2.96 1.94

WL373 345567.3 6386603 0.690 2.5 3.55 2.45

WL374 345615.6 6386586 0.591 2.209 3.94 2.33

WL376 345703.6 6386540 0.634 3.2 1.86 1.18

WL378 345801.8 6386516 0.704 2.6 5.17 3.64

WL379 345848 6386499 0.680 1.8 1.75 1.19

WL380 345895.4 6386482 0.712 2.3 4.37 3.11

WL381 345941.5 6386464 0.772 1.6 7.69 5.94

WL381 345941.5 6386464 0.649 2.579 8.47 5.5

WL382 345989.9 6386448 0.601 2.957 2.43 1.46

WL383 346036.6 6386430 0.588 2.88 3.96 2.33

WL384 346129.5 6386394 0.590 2.667 3.24 1.91

WL385 346224 6386359 0.634 3.591 4.89 3.1

WL386 346318.1 6386321 0.592 2.613 3.73 2.21

WL387 346651.1 6386223 0.687 2.2 2.27 1.56

WL388 345513.3 6386671 0.683 2 3.53 2.41

WL389 345561 6386656 0.707 1 4.3 3.04

WL391 345643 6386617 0.759 1.3 5.06 3.84

WL393 345745.9 6386590 0.646 2.4 2.43 1.57

WL394 345791 6386575 0.723 2.9 5.2 3.76

WL395 345841.5 6386550 0.759 2.3 5.86 4.45

WL398 345986.5 6386504 0.649 3.2 3.05 1.98

WL399 346031 6386485 0.631 2.382 4.04 2.55

WL400 339925.6 6388784 0.679 2.863 3.05 2.07

WL401 340331.7 6388645 0.668 3.086 5.81 3.88

WL402 340860.7 6388436 0.668 2.811 2.44 1.63

WL403 341326.8 6388264 0.659 3.462 2.52 1.66

WL404 341799.8 6388062 0.767 1.46 4.5 3.45

WL405 342274.2 6387923 0.609 2.742 3.63 2.21

WL406 342740.7 6387750 0.649 2.364 5.56 3.61

WL407 343209.9 6387573 0.719 1.569 6.2 4.46

WL408 343676.4 6387404 0.701 1.371 5.08 3.56

WL409 344150.2 6387230 0.826 0.528 6.09 5.03

WL411 345368.5 6386782 0.639 4.377 2.77 1.77

WL412 345552.3 6386713 0.684 2.5 4.69 3.21

WL413 345648.3 6386677 0.682 2 3.65 2.49

WL415 345842.5 6386606 0.770 1.7 10.72 8.25

WL416 345925.7 6386578 0.680 2.4 3.69 2.51

WL417 346022.8 6386544 0.706 1.9 4.69 3.31

WL418 346118.2 6386507 0.616 2.283 3.07 1.89

WL419 346208.8 6386476 0.610 3.104 2.18 1.33

WL421 345077.3 6386991 0.748 2.682 7.79 5.83

WL422 345265.5 6386928 0.735 2.26 7.06 5.19

WL423 345353.7 6386893 0.627 2.172 4.56 2.86

WL424 345632.8 6386789 0.624 2.3 2.82 1.76

125


WL425 345727.4 6386753 0.711 1.7 4.19 2.98

WL426 345819.4 6386723 0.704 2.6 4.26 3

WL431 346294.9 6386550 0.630 3.046 2.65 1.67

WL432 346384.7 6386517 0.620 1.816 3.63 2.25

WL434 346764 6386374 0.714 1.824 2.41 1.72

WL435 345434.4 6386971 0.677 1.301 1.98 1.34

WL436 345623 6386903 0.755 2.3 4.85 3.66

WL437 345714.1 6386874 0.647 1.6 3.4 2.2

WL438 345811.8 6386826 0.704 1.9 5.7 4.01

WL439 345903.6 6386798 0.650 2.9 4.74 3.08

WL440 345994.3 6386776 0.627 3.7 4.15 2.6

WL441 346087 6386732 0.799 1.6 8.05 6.43

WL442 346184.4 6386692 0.723 2.3 4.7 3.4

WL443 346280.5 6386659 0.627 2.079 3.24 2.03

WL444 346371.4 6386623 0.630 2.388 2.65 1.67

WL445 345046.3 6387219 0.735 1.733 4.64 3.41

WL446 345234.3 6387151 0.597 1.491 3.15 1.88

WL447 345412.7 6387080 0.783 1.187 5.45 4.27

WL448 345706.3 6386977 0.696 1.7 3.98 2.77

WL448 345706.3 6386977 0.628 1.77 5.21 3.27

WL449 345797 6386940 0.703 1.2 4.62 3.25

WL451 345990 6386874 0.715 1.312 5.54 3.96

WL453 346171.6 6386801 0.819 1.5 9.78 8.01

WL454 346265.6 6386769 0.704 2 3.21 2.26

WL455 346361.2 6386735 0.685 2.4 2.98 2.04

WL455 346361.2 6386735 0.644 2.873 3.06 1.97

WL456 346457.5 6386703 0.637 2.5 2.45 1.56

WL457 346549.6 6386668 0.708 2.3 2.71 1.92

WL458 346737.5 6386597 0.643 2.911 3.64 2.34

WL459 345214 6387376 0.811 0.901 6.63 5.38

WL460 345406.4 6387308 0.803 1.838 6.69 5.37

WL461 345588.1 6387236 0.689 5.299 5.72 3.94

WL463 345961.4 6387101 0.662 1.6 4.53 3

WL464 346145 6387032 0.647 3.8 4.7 3.04

WL465 346323.9 6386960 0.648 3.4 3.18 2.06

WL467 346731.4 6386845 0.746 1.8 6.42 4.79

WL468 346901.4 6386751 0.630 2.697 3.81 2.4

WL469 345186.8 6387593 0.710 2.3 4.82 3.42

WL471 345561.5 6387457 0.625 1.627 4.11 2.57

WL472 345747.9 6387388 0.683 1.552 5.14 3.51

WL473 345935.1 6387318 0.703 1.951 4.78 3.36

WL473 345935.1 6387318 0.693 2.5 3.97 2.75

WL474 346121.1 6387253 0.778 0.7 6.79 5.28

WL475 346287.4 6387189 0.813 2.403 6.57 5.34

WL476 346500.3 6387106 0.680 2 4.5 3.06

126


WL477 346696.5 6387045 0.620 2.4 3.76 2.33

WL477 346696.5 6387045 0.628 2.857 4.52 2.84

WL478 346874.8 6386980 0.669 1.8 3.56 2.38

WL492 347076.4 6386893 0.671 3.112 4.56 3.06

WL494 346098.1 6387469 0.612 2.951 2.91 1.78

WL495 346284.9 6387402 0.689 1.069 10.07 6.94

WL496 346478 6387336 0.685 2.544 2.98 2.04

WL497 346663.2 6387261 0.616 3.262 2.94 1.81

WL498 346808.6 6387208 0.633 1.592 5.53 3.5

WL499 347037.5 6387127 0.601 2.13 3.28 1.97

WL500 347230.5 6387060 0.636 2.24 4.62 2.94

WL502 346261.5 6387626 0.601 2.282 4.74 2.85

WL503 346451.3 6387556 0.724 1.295 5.61 4.06

WL504 346644 6387486 0.688 2.155 4.58 3.15

WL505 346823.2 6387419 0.678 2.819 3.85 2.61

WL506 347011.1 6387353 0.654 2.657 4.33 2.83

WL507 347188.3 6387289 0.594 1.878 4.34 2.58

WL508 347392.6 6387210 0.592 2.064 5.07 3

WL509 346425.2 6387778 0.561 2.11 5.35 3

WL512 346987.9 6387572 0.751 2.161 3.94 2.96

WL513 347183 6387502 0.651 2.966 4.3 2.8

WL514 347369.5 6387436 0.661 3.253 4.22 2.79

WL515 347552 6387366 0.550 3.562 3.4 1.87

WL516 346407.6 6387992 0.640 2.204 3.78 2.42

WL517 346582 6387934 0.617 3.359 3.99 2.46

WL518 346780.8 6387860 0.568 3.132 3.89 2.21

WL519 346961.5 6387793 0.658 2.394 4.01 2.64

WL520 347144.3 6387730 0.601 2.804 4.54 2.73

WL521 347325.1 6387664 0.656 2.4 6.08 3.99

WL522 347526.6 6387586 0.640 4.311 4.19 2.68

WL523 346577.5 6388140 0.795 1.681 4.38 3.48

WL524 346751.3 6388086 0.659 1.681 5.13 3.38

WL525 346938.9 6388015 0.657 2.875 2.65 1.74

WL526 347125.5 6387947 0.800 0.421 6.3 5.04

WL527 347289.9 6387894 0.634 4.002 4.15 2.63

WL528 347501.8 6387808 0.584 3.644 5.75 3.36

WL529 347701.8 6387732 0.632 2.289 5.63 3.56

WL531 346921.6 6388242 0.753 1.773 7.73 5.82

WL532 347115 6388172 0.629 3.251 5.47 3.44

WL533 347298.8 6388100 0.804 1.976 5.88 4.73

WL534 347470.8 6388017 0.538 3.86 2.77 1.49

WL535 347665.9 6387960 0.667 2.975 4.32 2.88

127

Appendix F

Notes: Correlations (negative or positive) >0.5 are shaded green and correlations >0.75 are shaded red. Labels are also shaded red.

Amphibole Apatite Aluminosilicates Epidote Garnet Hematite Ilmenite K-Feldspar Mica Monazite Olivine Plagioclase Pyrite Pyroxene Quartz Rutile Titanite Unknown Zircon

Amphibole 1

Apatite 0.2183 1.0000

Aluminosilicates -0.3898 0.1151 1.0000

Epidote 0.1735 0.1291 -0.0045 1.0000

Garnet 0.3062 0.1007 -0.2372 -0.3372 1.0000

Hematite -0.0383 0.2614 -0.2178 -0.3865 0.8176 1.0000

Ilmenite 0.4234 -0.2203 -0.4638 0.1458 0.2495 0.2023 1.0000

K-Feldspar 0.0224 0.0831 -0.4126 0.1372 0.6119 0.7234 0.2880 1.0000

Mica -0.0785 -0.3443 -0.2609 -0.2599 -0.1876 -0.3171 0.1937 -0.4595 1.0000

Monazite -0.2435 -0.4681 -0.1312 -0.0294 -0.0619 -0.1568 0.2619 -0.2553 0.7461 1.0000

Olivine -0.0100 -0.0761 -0.0349 0.6558 -0.2724 -0.4635 0.0054 0.0388 0.1854 0.2066 1.0000

Plagioclase 0.1846 -0.1643 -0.3429 0.8021 -0.0904 -0.1819 0.4332 0.4841 -0.1276 0.0245 0.6881 1.0000

Pyrite -0.2238 0.4073 0.3867 0.2314 -0.1254 -0.1624 -0.4938 -0.1441 0.0796 -0.0134 0.4139 0.0068 1.0000

Pyroxene 0.5881 -0.0847 -0.3820 0.5625 0.1363 -0.1758 0.4730 0.3587 -0.1613 -0.1115 0.5437 0.7778 -0.0326 1.0000

Quartz 0.3288 -0.1290 -0.9144 -0.2685 0.1235 0.1207 0.3091 0.0909 0.4387 0.2058 -0.1685 -0.0185 -0.4086 0.0954 1.0000

Rutile -0.1730 0.2108 -0.2449 -0.2115 0.7066 0.9001 0.0190 0.8509 -0.4697 -0.2508 -0.3047 0.0093 -0.0982 -0.0425 0.0770 1.0000

Titanite 0.3387 0.3453 -0.3771 0.7576 -0.2907 -0.2021 0.2876 0.2672 -0.2673 -0.2917 0.3707 0.7059 -0.0260 0.5544 0.1438 -0.0282 1.0000

Unknown -0.2418 0.3394 -0.1429 0.5863 -0.0771 0.0189 -0.1706 0.3619 -0.1141 -0.0038 0.5792 0.5276 0.6229 0.2920 -0.0766 0.2437 0.4726 1.0000

Zircon 0.0894 0.0686 -0.4513 -0.3364 0.8044 0.8105 0.3149 0.7169 -0.1955 -0.0596 -0.2174 0.0155 -0.2354 0.2080 0.3235 0.8292 -0.0716 0.0989 1

<20µm Mineral-Mineral Correlation Matrix

128

Notes: Correlations (negative or positive) >0.5 are shaded green and labels are shaded red.

Amphibole Apatite Aluminosilicates Epidote Garnet Hematite Ilmenite K-Feldspar Mica Monazite Olivine Plagioclase Pyrite Pyroxene Quartz Rutile Titanite Unknown Zircon207Pb/206Pb -0.0815 -0.0656 -0.3878 -0.2752 -0.4637 -0.3874 -0.2380 -0.2668 -0.1252 0.0568 0.0107 -0.1430 -0.0054 -0.1221 0.5608 -0.2984 0.0173 0.0184 -0.2463

U ppm 0.5545 0.0246 -0.3513 0.0488 0.3635 0.1425 0.5118 0.1154 -0.0155 0.2774 -0.0284 0.1174 -0.5765 0.3002 0.3099 -0.0007 0.1263 -0.3020 0.2525

Th ppm 0.3537 -0.3857 -0.3817 -0.4516 0.5063 0.3061 0.6820 0.2032 0.1308 0.2071 -0.2333 -0.0129 -0.5557 0.1929 0.3812 0.1027 -0.2047 -0.5634 0.4505

La ppm 0.1568 -0.2350 0.0312 -0.2251 0.4387 0.2144 0.1675 0.1372 -0.3810 -0.1202 -0.4393 -0.1365 -0.4541 -0.1263 -0.0219 0.1567 -0.1767 -0.3646 0.1616

Ce ppm 0.5064 -0.1738 -0.1416 -0.3609 0.5847 0.2038 0.3403 0.1589 -0.3648 -0.1619 -0.3752 -0.1084 -0.4632 0.1468 0.1460 0.0653 -0.1883 -0.4971 0.2657

Pr ppm 0.4323 -0.0556 -0.1579 -0.2590 0.4400 0.1101 0.1459 0.1080 -0.4324 -0.3072 -0.2898 -0.1038 -0.3732 0.1159 0.1765 0.0698 -0.0225 -0.3075 0.2366

Nd ppm 0.4842 0.0808 -0.2458 -0.1828 0.5533 0.2664 0.1843 0.2597 -0.3635 -0.3439 -0.3295 -0.0489 -0.3290 0.1710 0.2184 0.2361 0.0953 -0.1846 0.3707

Sm ppm 0.5099 -0.0610 -0.2834 -0.0747 0.5777 0.1945 0.4051 0.2463 -0.3015 -0.0283 -0.1436 0.1028 -0.3744 0.3300 0.2159 0.1548 0.1102 -0.1766 0.4049

Eu ppm 0.5595 0.0337 -0.2572 -0.1070 0.5924 0.1905 0.3578 0.2145 -0.3739 -0.0899 -0.1523 0.0555 -0.2702 0.3398 0.2039 0.1185 0.0751 -0.1310 0.3887

Gd ppm 0.4988 0.1853 -0.2317 0.0640 0.4539 0.2779 0.2109 0.2596 -0.2551 -0.3326 -0.3161 0.0272 -0.2535 0.3164 0.1686 0.3123 0.2927 -0.0215 0.4403

Tb ppm 0.3401 0.0782 -0.0296 0.0453 0.6789 0.3261 0.2566 0.3729 -0.2411 -0.0783 -0.0266 0.1454 -0.1775 0.3070 -0.1112 0.3086 0.0438 0.0203 0.4486

Dy ppm 0.4513 0.0453 -0.2423 0.0536 0.6578 0.2786 0.3629 0.3554 -0.2214 0.0281 0.0023 0.1916 -0.2566 0.3753 0.1156 0.2570 0.1358 0.0120 0.4703

Y ppm 0.4034 0.2153 -0.1944 -0.1021 0.7061 0.4646 0.1942 0.4340 -0.1455 -0.2562 -0.2319 0.0350 -0.1517 0.2651 0.0895 0.4496 0.1173 0.0038 0.5825

Ho ppm 0.4184 0.0593 -0.0484 -0.0242 0.6356 0.2528 0.2603 0.3482 -0.2592 -0.1156 -0.0285 0.1656 -0.0598 0.4319 -0.0909 0.2361 0.0492 -0.0140 0.4484

Er ppm 0.2463 0.1087 -0.2287 -0.0580 0.6220 0.4553 0.3175 0.4949 -0.1040 -0.1135 -0.1929 0.1256 -0.2615 0.3445 0.0968 0.5146 0.1820 0.0611 0.6854

Tm ppm 0.3885 -0.1151 -0.2969 -0.0358 0.4986 0.1869 0.5141 0.2378 -0.0165 0.2822 0.0173 0.2116 -0.3191 0.3001 0.2034 0.1115 0.1322 -0.1943 0.3782

Yb ppm 0.4033 0.0918 -0.3355 -0.0714 0.6477 0.3645 0.4413 0.4399 -0.1512 0.0359 -0.1088 0.1872 -0.2035 0.3747 0.2076 0.3370 0.1804 0.0178 0.5649

Lu ppm 0.5093 0.1763 -0.3754 -0.0750 0.6302 0.3132 0.3851 0.3775 -0.0868 -0.0220 -0.0132 0.1664 -0.1556 0.4598 0.2644 0.2894 0.2064 0.0239 0.5827

Hf ppm 0.5066 -0.4778 -0.5017 -0.2402 0.4332 0.1064 0.7357 0.1802 -0.0205 0.2895 -0.1044 0.1622 -0.5097 0.4422 0.4660 -0.0158 -0.0533 -0.4328 0.3814

Zr ppm 0.2800 -0.5757 -0.3827 -0.2278 0.3094 0.0590 0.6802 0.0951 0.0442 0.4200 -0.0987 0.1353 -0.5716 0.2579 0.3690 -0.0339 -0.0728 -0.4819 0.3071

LREE 0.4693 -0.0999 -0.1619 -0.2707 0.5751 0.2320 0.2813 0.1984 -0.3855 -0.2168 -0.3746 -0.0839 -0.4355 0.1346 0.1520 0.1455 -0.0754 -0.3720 0.3074

HREE 0.4115 0.1696 -0.2172 -0.0712 0.7080 0.4336 0.2626 0.4377 -0.1617 -0.1751 -0.1797 0.0866 -0.1854 0.3124 0.0999 0.4213 0.1319 0.0088 0.5859204Pb ppm -0.4683 -0.4013 -0.1327 -0.2932 -0.5475 -0.3346 -0.1756 -0.3198 -0.0226 0.2727 -0.0745 -0.1751 -0.0234 -0.4808 0.3130 -0.3263 -0.2254 -0.1064 -0.4302206Pb ppm -0.4561 -0.4439 -0.0658 -0.2310 -0.5537 -0.3528 -0.0986 -0.3175 -0.0650 0.2763 -0.0528 -0.1205 -0.0384 -0.4689 0.2216 -0.3747 -0.2207 -0.1372 -0.4914207Pb ppm -0.4392 -0.3744 -0.1232 -0.2839 -0.5489 -0.3389 -0.1974 -0.3091 -0.0386 0.2049 -0.0796 -0.1721 -0.0286 -0.4722 0.2986 -0.3250 -0.2050 -0.1177 -0.4472208Pb ppm -0.4444 -0.4134 -0.0926 -0.2862 -0.5348 -0.3249 -0.1770 -0.2875 -0.0477 0.1837 -0.1192 -0.1669 -0.0674 -0.4680 0.2592 -0.3048 -0.2140 -0.1608 -0.4418

<20 μm Mineral-Element Correlation Matrix

129

Appendix G

Project Cost Analysis

Sample Prep/Analysis Hrs/Days/Samples Cost Per Day/Hr/Sample Total

ESEM Hrs 200 Hrs $35 $7,000

LA-ICPMS Days 5 days $1,468 $7,340

Polished Grain Mounts 130 samples $40 $5,200

EPMA 1 day $700 $700

Total

$20,240

Salary (Research/Teaching Assistantship, Scholarships, International Tuition Award)

Year

Funding

2013-2014

$26,000

2014-2015

$26,000

Total

$52,000

Overall Total

$72,240

Heavy Minerals in Soils from the Athabasca Basin and the ...

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