University of Nevada, Reno the Impact of Geological Environment on the Lithium Concentration and Structural Composition of Hecto

University of Nevada, Reno

The Impact of Geological Environment on the Lithium Concentration and Structural Composition of Hectorite Clays

A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science in Hydrology

Claude Lamy Morissette

Dr. Lisa L. Stillings/Thesis Advisor

May, 2012

THE GRADUATE SCHOOL

We recommend that the thesis prepared under our supervision by

CLAUDE LAMY MORISSETTE

entitled

The Impact Of Geological Environment On The Lithium Concentration And Structural Composition Of Hectorite Clays

be accepted in partial fulfillment of the requirements for the degree of

MASTER OF SCIENCE

Lisa Stillings, Advisor

John McCormack, Committee Member

Jonathan Price, Committee Member

Mark Coolbaugh, Graduate School Representative

Marsha H. Read, Ph. D., Dean, Graduate School

May, 2012

Abstract

Hectorite is a Li-rich trioctahedral smectite with reported concentrations varying from

0.16% to 0.74% Li, where Li can occur both in the octahedral and the interlayer sites of

the mineral structure. It forms either authigenically or as an alteration product under both

low temperature and hydrothermal conditions. The objective of this research is to

characterize the Li concentration and structural composition of hectorites from 4 sites in

the western USA believed to have formed under different geological environments. The

hypotheses are: (1) the clay structure will be dependent on its formational origin, and the lithium content will be positively correlated with temperatures of formation; (2) the layer charge and cation exchange capacity will be proportional to the structural lithium content of the clay.

A suite of 18 samples was collected for this research: 6 samples from the Esmeralda

Formation in Clayton Valley NV, believed to have formed under low temperature conditions (<100°C); 1 sample from Fish Lake Valley NV, 1 sample from Hector CA and

9 samples from the McDermitt Caldera NV, believed to have formed under elevated temperature conditions (>100°C); and 1 sample of synthetic hectorite. All samples were cleaned using a 2-step method of size separation and carbonate dissolution to concentrate the clay fraction and remove the non-clay minerals. The samples were analyzed using X- ray diffraction (XRD) to determine their structure, major and minor element chemistry to determine their composition, cation exchange capacity (CEC) and layer charge to ii

evaluate the effect of lithium concentration and clay structure on both properties, and

scanning electron microscopy (SEM) to determine the morphological characteristics of

the clays. The rock samples were also examined under a petrographic microscope and

with the XRD to identify the associated minerals and their textural relationships.

Random XRD profiles indicate that the cleaning procedure was effective at removing

impurities from the samples. These profiles, along with basal-oriented XRD profiles (air-

dried and glycolated) show the majority of the clays to be hectorite, with a few of the

McDermitt samples having an illite signature consistent with the mineral tainiolite. The

Clayton Valley samples were a mixture of illite and smectite, with the smectite

component too small to be clearly identified. These results are consistent with the

chemistry and the formulas calculated for all samples. The Li concentration of the

purified clay samples varies from 0.1% Li in Clayton Valley to 1.2% Li in McDermitt.

Most samples, excluding Clayton Valley, are Mg rich (>10% Mg) and Al poor (<3% Al)

and have high fluorine concentrations (up to 6.5% F).

The high lithium and fluorine contents of the clay samples indicate the deposits from

Hector, McDermitt and Fish Lake Valley formed under hydrothermal conditions. Clays

at Hector formed through the alteration of volcanic ash by hydrothermal fluids, the degree of alteration being recognized by the purity of the clay and the absence of zeolites.

Clays in Fish Lake Valley most likely formed through direct precipitation from

hydrothermal fluids, given the close relationship with calcite in the groundmass. Clays at iii

McDermitt most likely formed through alteration of pre-existing sediments, given layering visible in all samples. Furthermore the presence of tainiolite could confirm the hydrothermal origin, since tainiolite has previously only been identified in pegmatites and in rocks that were hydrothermally altered. Clays from the Esmeralda Formation in

Clayton Valley most likely formed through direct precipitation from low temperature pore fluids, given the dioctahedral structure, low lithium and fluorine concentration, and close relationship between the clay and calcite in the groundmass. These results are consistent with the proposed model for lithium-rich clay deposits.

The 1st hypothesis is supported by the results of this work and we can conclude that clay structure and lithium content are dependent on the formational origin and positively

correlated with temperatures of formation. The 2nd hypothesis is partly supported by the

results, as a positive correlation can be determined between lithium content and

octahedral layer charge, but the relationship with the CEC is inconclusive, as the CEC is

dependent on the type and expandability of the clay.

Acknowledgements

This work would not have been possible without the support of the companies whose deposits are the subject of this thesis. Dennis Bryan from Western Lithium has provided samples, access to their Kings Valley lithium deposit in McDermitt and financial support as well as being a member of my thesis committee. Joyce Fitzerald from Elementis

Specialties and everyone at the Hector Mine have provided access to the mine and allowed us to collect samples from the mine. Melissa Jennings and Joe Dunn from

Chemetall Foote have provided access to Clayton Valley and allowed us to collect samples. Derek Amen from American Lithium Minerals has provided us with a sample from their Borate Hills property in Fish Lake Valley. Finally, Don Eisenhour from

American Colloid has provided a sample from their hectorite deposit in McDermitt.

Thanks to all of you for sharing information about your property and about the formation of the deposit.

Of course, I thank my advisor, Dr. Lisa Stillings, for suggesting lithium as a topic, allowing me to work up such an interesting project, and for the support, both moral and technical, as I went through the ups and downs of graduate school. The U.S. Geological

Survey, Mineral Resources Program has provided ample resources, both material and financial. This project is also financially supported by the Society of Economic

Geologists through a student research grant from the Hugh E. McKinstry Fund. Finally the Department of Geological Sciences and Engineering, the Graduate Program of v

Hydrological Sciences, both at the University of Nevada Reno, and the Desert Research

Institute have provided financial support through teaching and research assistantships.

The faculty members of my committee, Dr. Jonathan Price, Dr. Mark Coolbaugh and Dr.

John McCormack, have provided good advice throughout this process and have always been available when I needed help.

Last but certainly not least, my friends and family, for providing all the moral support I needed throughout this process. vi

Table of Content

Abstract...... i

Acknowledgements ...... iv

Table of Content ...... vi

List of Tables ...... ix

List of Figures ...... x

Introduction ...... 1 Conceptual Framework ...... 2 Objectives and Relevance of Research ...... 5 Geological Settings ...... 6 Hector, CA ...... 6 Clayton Valley, NV ...... 11 Fish Lake Valley, NV ...... 17 McDermitt, NV ...... 20 Methods...... 25 Sample Acquisition ...... 25 Cleaning Procedure ...... 26 Size Separation ...... 26 Removal of Carbonate Phases ...... 29 Chemistry ...... 30 X-Ray Diffraction ...... 30 Petrographic Analysis ...... 33 Scanning Electron Microscopy ...... 33 Cation Exchange Capacity ...... 34 Layer Charge ...... 35 Results ...... 38 Whole Rock Mineralogy ...... 38 vii

Clayton Valley ...... 38 McDermitt ...... 39 Hector ...... 40 Fish Lake Valley ...... 40 Whole Rock Chemistry ...... 41 Clay Mineralogy ...... 42 Clayton Valley ...... 45 McDermitt ...... 46 Hector ...... 47 Fish Lake Valley ...... 47 Synthetic hectorite ...... 48 Clay Chemistry ...... 48 Analytical ...... 48 CEC ...... 49 Layer Charge ...... 55 Discussion ...... 59 Clays ...... 59 Sample compositions ...... 59 Chemical Formulas ...... 62 Charge balance ...... 70 Mineral identification ...... 77 Geological Environment ...... 84 Chemistry ...... 84 Deposit formation...... 87 Conclusion ...... 91

References ...... 96

Appendix I – Sample description ...... 102

Appendix II – XRD patterns...... 107

Appendix III – Petrographic Analysis ...... 164

Appendix IV – Scanning Electron Microscopy ...... 196 viii

Appendix V – Analytical Chemistry Results ...... 214

Appendix VI – Layer Charge ...... 218

Appendix VII – Structural Formula Calculations ...... 226 ix

List of Tables

Table 1: Hectorite chemistry from various localities ...... 10

Table 2: Lithium concentration from bulk samples of the Esmeralda Formation, Clayton

Valley ...... 10

Table 3: List of samples analyzed for this work ...... 28

Table 4: Chemical analyses of the bulk samples...... 44

Table 5: Size fraction used for the detailed analyses of the clay samples ...... 45

Table 6: Mineralogy of bulk samples and cleaned clay samples...... 45

Table 7: Peak locations and reflection ID for all smectite samples ...... 51

Table 8: Peak locations and reflection ID for all illite samples ...... 51

Table 9: Chemical analyses of the clay concentrates. nd – not detected...... 52

Table 10: Results from the cation exchange capacity analyses ...... 53

Table 11: Results for the composition of the CEC wash solutions ...... 57

Table 12: Comparison of the cation concentrations recovered from the CEC solution with the clay chemistry ...... 57

Table 13: Results from the layer charge analysis ...... 58

Table 14: Summary of the normalized chemistry and structural formulas ...... 72

Table 15: Structural formulas for all samples ...... 73

Table 16: Summary of the clay mineralogy from each field site ...... 85 x

List of Figures

Figure 1: Chemical structure of smectites ...... 3

Figure 2: Location of field sites ...... 6

Figure 3: Idealized environment of the formation of the Hector hectorite deposit,

California ...... 9

Figure 4: Physiographic features around Clayton Valley ...... 12

Figure 5: Location of outcrops of the Esmeralda Formation ...... 15

Figure 6: Location of the lithium deposit in Fish Lake Valley relative to the Esmeralda

Formation in Clayton Valley ...... 18

Figure 7: General geology of McDermitt Caldera ...... 21

Figure 8: Generalized cross-section of McDermitt complex ...... 22

Figure 9: Alteration patterns in McDermitt caldera ...... 24

Figure 10: Random XRD scan showing the effect of cleaning procedure on the sample from Hector ...... 43

Figure 11: Calibration curves obtained from the ammonia electrode at specific concentrations of the standard ammonia solution ...... 50

Figure 12: Graph for the determination of the smectite:illite ratio ...... 63

Figure 13: Relationship between the degree of F substitution for OH with respect to the

060 reflection for all trioctahedral samples ...... 70

Figure 14: Comparison of the layer charge calculated from the structural formula and the layer charge calculated analytically with the alkylammonium method ...... 71 xi

Figure 15: Comparison of the layer charge calculated from the structural formula and the cation exchange capacity ...... 75

Figure 16: Comparison of the layer charge calculated from the structural formula and the lithium content for all samples ...... 76

Figure 17: Comparison of the octahedral charge calculated from the structural formula and the lithium content for all samples ...... 78

Figure 18: Comparison of the lithium and fluorine contents of all clay samples ...... 86

Introduction

Lithium has become a technologically important metal, being used more and more in

rechargeable batteries, electric vehicles and advanced technologies for its energy

efficiency. In 2009, the US Government invested $2.4 billion in the development of

batteries and electric-drive vehicles, 40% of which being dedicated to the development

and recycling of lithium batteries (USGS MRP, 2010). Most of the lithium being

consumed in the US currently comes from imports. The current known exploitable

sources of lithium are continental brines and pegmatites, which together represent 85% of

global Li reserves and resources (Evans, 2008). Hectorite, a lithium-rich smectite clay, is

the 3rd most important source of Li, representing 7% of global reserves (Evans, 2008).

The only active production of lithium in the United States is from a lithium brine deposit

in Clayton Valley, NV (Jaskula, 2010). Total production and reserves from Clayton

Valley were estimated at 90,000 tonnes Li in 1991, and an estimated 2 to 22 million

tonnes of Li may be present in the aquifer (Harrop, 2009). An alternative source of lithium for the United States may be hectorite clays. The only known major hectorite deposit to have been in production is the Hector deposit, in San Bernardino County, CA, though lithium was never extracted from the hectorite (AMEC, 2008). The hectorite deposit in McDermitt Caldera, NV, has the potential to become a source of lithium, with estimated resources at 2.4 million tonnes of contained Li (AMEC, 2008).

In order to evaluate the potential of hectorite clays as a source of lithium, it is important to understand how the origin and structure of the hectorite affects its lithium content.

Conceptual Framework

Hectorite is a phyllosilicate clay mineral of the smectite family. Phyllosilicates have

layer structures in which planes of oxygen atoms form “sheets”, with alternating

tetrahedral and octahedral cation coordination between adjacent sheets (Figure 1)

(Kloprogge et al., 1999). Tetrahedral sheets are composed of hexagonal rings of oxygen

tetrahedron linked by shared basal oxygen. The tetrahedra in a typical phyllosilicate contains Si, Al and/or Fe3+. The apical oxygen forming the tetrahedra also forms the base

of octahedral sheets. Octahedral sheets typically have brucite-like or gibbsite-like

structures and contain cations like Mg, Al, Li, Fe2+ and Fe3+. A layer consists of a regular

repeating assemblage of sheets.

Smectites are characterized by a 2:1 layer structure, where an octahedral sheet is found

between two tetrahedral sheets. This structure causes the apical oxygen of the tetrahedral

sheets to form hexagonal rings, thus allowing an oxygen from the octahedral sheet to be

located in the centre of the ring and form a structural hydroxyl. In half a unit cell having

10 oxygen atoms and 2 hydroxyls, there are four tetrahedral and three octahedral sites

(Kloprogge et al., 1999). A smectite will be considered dioctahedral if two of the octahedral sites are occupied, and trioctahedral when all sites are occupied. Isomorphic substitution is frequent in both the octahedral and tetrahedral sheets, and this process can 3

lead to a charge imbalance when the substituting cations have different valences

(Kloprogge et al., 1999). This imbalance is typically compensated by larger cations that coordinate to the surfaces of adjacent tetrahedral sheets between each 2:1 layer. These cations are referred to as interlayer or exchangeable cations.

Figure 1: Chemical structure of smectites (USGS, 2001).

Lithium can thus be found in two places in the structure of smectites: (1) in the structural octahedral site as a substitution for Mg2+ and (2) as an exchangeable cation in the

interlayer space (Vigier et al., 2008). Hectorite is characterized by the substitution of Li+ for Mg2+ in the octahedral structure and little to no substitution in the tetrahedral structure

(Decarreau, 1980). Its generic formula is (Granquist and Pollack, 1959; Kloprogge et al.,

1999):

M/MgLiSiAlOOHF ∙nHO (1) 4

It is classified as a trioctahedral smectite, since all of its octahedral sites are occupied by a divalent cation. The lithium content of natural hectorite varies from 0.16% to 0.74% Li

(Newman and Brown, 1987; Odom, 1992). Fluoride is commonly observed substituting for structural hydroxyls in hectorites.

Smectites are primarily thought to be detrital in origin – i.e. forming from the weathering of other silicates, such as micas or chlorites (Borchardt, 1989; Kloprogge et al., 1999).

However, some smectites are known to form authigenically – i.e. from alteration of a precursor mineral or direct precipitation from a solution (Calvo et al., 1999). Hectorite is one of the most common clay mineral to form authigenically (Kloprogge et al., 1999).

Different types of genesis have been suggested for the formation of hectorite (Orris &

Bliss, 1991): precipitation in alkaline lake deposits (Calvo et al. 1999; Starkey, 1982), incorporation of Li into pre-existing smectite, and alteration of volcanic glass under hydrothermal conditions or under low temperatures (Starkey, 1982; Kloprogge et al.,

1999).

It is often hard to distinguish between these three origins, as little is known about their effect on the structure of hectorite. Most studies have previously focused on synthesizing hectorite in the lab, without giving much information about its structure or its formation mechanisms (Kloprogge et al., 1999). Vigier et al. (2008) suggested that the crystallinity of synthetic hectorite increases at higher temperatures. They also suggest a positive correlation between structural lithium content and temperature of formation. 5

Objectives and Relevance of Research

The goal of this study is to characterize the structural composition of hectorites from

Clayton Valley NV, McDermitt NV, Fish Lake Valley NV and Hector CA, and correlate

their structure and lithium contents with the geology and formation mechanisms of each

deposit. We hypothesize that the structure of the hectorite and the amount of lithium it contains will be dependent on its formational origin. Given that the proposed formation

mechanism is expected to be different for each locality, the chemistry and lithium content

should reflect these differences (Vigier et al., 2008). For example, we expect the lithium

contents of hectorite from Clayton Valley to be lower than those of Hector, McDermitt

and Fish Lake Valley, given that hectorite from Clayton Valley most likely formed in a

low-temperature environment, while the others may have a hydrothermal origin.

Furthermore, the crystallinity of each sample may give some indication of temperature, as

it was suggested that crystallinity improves at higher temperature (Vigier et al., 2008).

We also hypothesize that the layer charge and the cation exchange capacity of each

hectorite will be proportional to its structural lithium content. Given that Li+ substitutes

for Mg2+ in the octahedral site, a higher lithium content will create a greater negative charge on the layers (eq.1). Furthermore, since the interlayer or exchangeable cations are responsible for neutralizing the layer charge, the cation exchange capacity should increase with a greater negative layer charge, effectively increasing at higher lithium concentrations.

This work is of great significance when considering hectorite as a source of lithium.

Understanding exactly where the lithium is located in the hectorite structure will help the mining industry in their search for a method to effectively extract lithium from hectorite.

Furthermore, being able to link lithium content with depositional environment will allow exploration geologists to focus their search for other economical hectorite deposits.

Geological Settings

McDermitt

Fish Lake Valley Clayton Valley

Figure 2: Location of field sites Hector (source: Google Earth, 2010).

Hector, CA

The Hector deposit is located in the Mojave Desert of California, approximately 188 km

Southwest of Las Vegas (Figure 2). It is the type locality for hectorite clays. Production

from the mine began in 1931, though it has never been exploited for lithium (Ames et al.,

1958; Moll, 2001). The hectorite has been mined for its swelling and gel properties and

is used in paints, cosmetics, cement and drilling mud, to name a few. The deposit is in 7

the southwestern part of the Basin and Range Province on the Mojave Block, which is bounded by the San Andreas Fault to the west and the Garlock Fault to the north

(Willette, 1995). The area is incised by numerous north to northwest trending faults, including the Pisgah Fault which ruptured in the vicinity of the mine during the October

16, 1999 magnitude 7.1 Hector Mine earthquake (Monroe, 2002; Willette, 1995).

The deposit is located within a major west-northwest trending structure, the Barstow-

Bristol trough (Ames et al., 1958). It is found within Pliocene lakebeds which overlay a green hypersthene, augite porphyritic andesite, thought to be part of the Red Mountain andesite series (Willette, 1995). The beds are composed of calcareous and tuffaceous bentonite clays with numerous zeolitic bands and are approximately 100-125 m in thickness. The hectorite is found associated with travertine and forms generally contiguous lenses within the lakebeds. The lenses range in thickness from 1.2 to 3.6 m, though thicknesses up to 12 m have been reported (Wright et al., 1953). The lakebeds are extensively deformed and are overlain by a 10-30 m thick olivine basalt, which originated from the nearby Mount Pisgah.

Typically the hectorite has a chalky-white colour and is found mixed with calcite. The pure hectorite from the deposit is a soft, very pale grey to bluish-gray translucent clay and resembles paraffin wax (Willette, 1995). It initially has a moisture content of approximately 40-50% its weight, but reduces to a moisture content of 8-10% when air dried. It can swell up to 6 times its dry volume when placed in water (Foshag and 8

Woodford, 1936). The hectorite itself is distinctly crystalline and appears to be made of tangled masses of small doubly-refracting grains and larger plates, with a poor basal cleavage. Typical chemical composition is shown in Table 1.

Most of the hectorite beds are sheared and plastically deformed (Willette, 1995).

Dogtooth spar and radiating calcite concretions are typically found in the nose of folds.

Travertine grains, pellets and occasional boulders are also commonly found within the hectorite beds. Quartz nodules of a black, blue-gray and purplish-blue colour are also locally found. The top of the beds are usually characterized by a laminar hectorite of an olive-green to grey colour, which is thoroughly mixed with the overlying bentonitic sediments.

Multiple origins have been suggested for the formation of the Hector deposit. The first hypothesis, proposed by Foshag and Woodford (1936), suggests that the deposit is associated with a small anticline, as the beds appear to be dipping away from the anticline. They assume the clay is the product of the alteration of a dacitic volcanic ash.

Kerr (1949) proposed that the hectorite was the product of the hydrothermal alteration of a basic volcanic ash or a lava flow. He suggested that the deformation and tight folding at some location allowed the hectorite to form thick beds.

Ames et al. (1958) propose that the hectorite formation is related to hot spring activity in a restricted lake environment (Figure 3). They suggest that hot spring activity along the 9

Northwest trending fault system caused the precipitation of a travertine ridge, which had previously been mistaken for an anticline. Tuff and volcanic ash that were deposited in the restricted alkaline lake while hot springs were active would initially alter to clinoptilolite, which would further alter to hectorite. The lithium and fluorine were supplied by the hot spring waters while the magnesium was provided by the lake waters.

When the springs were not active, the ash would alter to analcime.

Willette (1995) suggested that the travertine ridge allowed sediments to build up in the lake, thus forming a restrictive bar (Figure 3). A regulated flow developed between the marginal, lithium and fluorine-rich hot spring water from the lagoon and the magnesium- rich alkaline lake. The fine sediments from the bars were selectively transported into the lagoon and altered to hectorite clays. The high pH allowed the aluminum and silica to remain in solution and migrate out into the lake water.

Figure 3: Idealized environment of the formation of the Hector hectorite deposit, California (source: Willette, 1995). 10

Table 1: Hectorite chemistry from various localities Hector 1Hector 2Hector 3Hector 4McDermitt 5McDermitt 6McDermitt 7 Morrocco 8 wt%wt%wt%wt%wt%wt%wt%wt%

SiO2 53.68 51.26 55.17 55.86 58.70 58.80 57.30 55.02

Al2O3 0.60 0.36 0.33 0.13 0.58 0.70 0.92 1.12

TiO2 0.01 nd 0.05 0.07 0.21

Fe2O3 0.09 0.12 0.03 0.38 0.47 0.56 FeO tr 0.70 MnO trndndndnd CaO 0.52 2.60 0.90 tr 1.70 1.70 2.00 0.54 MgO 25.34 23.25 24.51 25.03 25.20 24.30 23.80 24.89

Na2O 3.003.472.202.680.210.260.280.94

K2O 0.070.100.080.100.060.050.040.43

Li2O 1.120.601.141.051.501.601.500.36

H2O+ 8.24 5.14 2.84 7.24 10.20 9.80 10.20 6.42

H2O‐ 7.28 11.56 8.93 9.90 ‐‐‐7.66 Cl 0.31 0.21 nd 0.06 0.09

CO2 1.35 0.63 nd nd nd 0.30 F none4.755.965.005.204.903.22

P2O5 0.05 nd 0.03 0.02 Total 100.16 99.84 101.87 102.98 103.61 103.04 101.80 101.60

Less O  F & Cl 2.04 2.51 2.06 2.15 2.05 1.36 Corrected Total 99.43 100.47 101.55 100.89 99.75 100.24

(1),(2) Foshag and Woodford, 1936 (3) Ames et al., 1958 (4),(8) Newman and Brown, 1987 (5),(6),(7) Odom, 1992

Table 2: Lithium concentration from bulk samples* of the Esmeralda Formation, Clayton Valley

Li (ppm) LiO2 (wt%) CV1 710 0.40 CV2 910 0.51 CV3 860 0.48 CV4 780 0.44 CV5 400 0.22 CV6 160 0.09 *Samples washed once with distilled water. (Kunasz, 1970) 11

Clayton Valley, NV

Clayton Valley is a closed basin in the Basin and Range Province, located in

southwestern Nevada, approximately 280 km northwest of Las Vegas (Figures 2 and 4).

The valley floor is about 100 km2, at an elevation of 1,300 m above sea level (Davis et

al., 1986). Most of the water contributing to the valley’s hydrologic inflow comes from

precipitation over a drainage area of approximately 1,420 km2 (Davis et al., 1986). Being

a closed basin, the outflow is entirely through evapotranspiration, resulting in the

formation of saline brines in the basin. The structural setting and stratigraphy of the

basin have allowed the accumulation of lithium-enriched brines in 6 different aquifers

(Zampirro, 2004). The deposit was discovered in the late 1950s and has been exploited

for lithium since 1966 (Davis et al., 1986). Total production from Clayton Valley was

estimated at 25,600 tonnes of Li in 1991, and reserves were estimated at 65,000 tonnes of

Li (Price et al., 2000). The total resource is estimated at approximately 2 to 22 million tonnes of Li, making the Clayton Valley deposit one of the world’s largest Li deposit

(Harrop, 2009). Lithium is extracted from the brine through solar evaporation in large ponds constructed on the playa. As the brine evaporates, halite and other phases

precipitate out of the solution, progressively concentrating Li up to 15 times the original

brine concentration (Davis et al., 1986; Price et al., 2000). 12

Figure 4: Physiographic features around Clayton Valley (source: Davis et al., 1986). 13

The valley consists primarily of Quaternary sediments made up of a mixture of clay minerals, halite and gypsum (Kunasz, 1974). It is surrounded by mountains on all sides: the Silver Peak Range on the west (2870 m), the Palmetto Mountains to the south (2810 m), the Montezuma Range to the east (2550 m) and the Weepah Hills to the north (2340 m) (Figure 4). The rocks that make up these mountains are varied, including Pre-

Cambrian carbonates, granites and lepidolite-bearing pegmatite on the western, eastern and northern margins of the valley. Jurassic age intrusives associated with the Sierra

Nevada Batholith are primarily found in the Palmetto Mountains, and a few outcrops are also observed in the Weepah Hills, the Silver Peak Range and the Montezuma Range.

The dominant sequence of rocks is the Upper Miocene to Pliocene sequence of tuffaceous sediments known as the Esmeralda Formation. It is exposed in the Silver Peak

Range, the Weepah Hills and in the low hills east of the playa (Davis, 1981). The formation was originally described as a 4500 m thick sequence of lacustrine sediments, including poorly sorted conglomerates and sandstones, limestone, mudstones and tuffaceous units (Kunasz, 1974). Davis (1981) separated the formation in three distinct members (Figure 5).

The lower member consists of approximately 275 m of orange conglomerate and sandstone and contains no volcanic detritus. The rocks are highly faulted, and their deposition may predate the beginning of Basin and Range faulting. The middle member consists of more than 1800 m of gray, yellow and orange conglomerate, sandstone, 14

siltstone, shale and limestone, and contains tuffaceous but non-pumiceous Miocene rocks. The unit becomes more tuffaceous moving up section. The thin beds and fine- grained nature of the sediments of the lower portion of this member, along with the presence of molluscs and fish fossils, suggest deposition in a freshwater lake. The upper portion of the middle member is more thickly bedded and coarser, and shows more variations in exposure. It may have been deposited in a braided stream environment or a distal alluvial fan-delta deposit.

The upper member consists of approximately 150 m of sediments and tuffs characterized by abundant pumice lapilli and obsidian. It lays unconformably on top of the middle member of the Formation. It is exposed in the Weepah Hills along the northern margin of the valley, and in the low hills east of the valley, on Angel Island (Figures 4 and 5).

The eastern exposure appears to be the most lithium rich and is made of a sequence of white, light gray and greenish gray mudstone and vitric tuff (~40 m thick), white to pale yellow sandstone and conglomerate (~10 m thick) and a section of interbedded greenish- gray mudstone, white tuff, diatomite and travertine (~50 m thick) locally capped by a conglomerate. The lower portion of this member may have been deposited in a lake or playa, while the middle section has more similarities to an alluvial fan environment and the upper section may be more lacustrine.

Figure 5: Location of outcrops of the Esmeralda Formation (source: Davis, 1981). 16

Hectorite has been identified both in the playa sediments and in the mudstone of the lower section of the upper member of the Esmeralda Formation (Table 2) (Davis, 1981;

Kunasz, 1970). The crystals identified consist of thin laths about 1 to 3 m in size, similar to those observed at Hector. It was found in association with clinoptilolite and phillipsite in the Esmeralda Formation. The lithium concentration of the clay sediments appear to be highest in proximity to a fault located on the eastern side of the playa, immediately adjacent to the Esmeralda Formation (Kunasz, 1974).

The origin of the hectorite is still controversial. It may be detrital in origin, coming from the clay fraction of the volcanic tuffs (Davis, 1981). This hypothetical origin is not favored, because the hectorite alteration on the tuff is not extensive enough to explain the high lithium concentrations observed in the Esmeralda Formation. Furthermore, there is no clear relationship between hectorite and the volcanic detritus in the sediment. The hectorite may have originated from the alteration of detrital volcanic glass (Davis, 1981).

This origin is similar to that proposed for the formation of the Hector deposit, but the lack of correlation between hectorite and the volcanic detritus argues against this option. A third hypothesis is that hectorite authigenically precipitated from lake waters or pore fluids (Davis, 1981). This appears to be the favored hypothesis, as the lithium content of the mudstone correlates with the carbonate content, suggesting hectorite formation may be related to calcite precipitation.

It has been suggested that the lithium present in Clayton Valley originates from the nearby rhyolitic volcanic rocks (Price et al., 2000). Price et al. (2000) argued that up to

20 billion kg of Li may have been leached from the ash-flow and tuffaceous sedimentary rocks of the Montezuma Range/Clayton Ridge area and from the rhyolite flow. It was also suggested that the lithium was introduced in the valley by hot springs located at the periphery of the playa, since the composition of the springs is proportionally the same as that of the brines (Kunasz, 1974). It is possible, however, that the springs have been contaminated by the brines through groundwater mixing and that only 10% of the spring composition may be attributed to hydrothermal water.

Fish Lake Valley, NV

Fish Lake Valley is located immediately west of Clayton Valley, the two being separated by the Silver Peak Mountains (Figure 6). It is a closed basin in the Basin and Range

Province, located approximately 300 km northwest of Las Vegas (Figure 2). The valley

is oriented north-south, with a length of 40 km, an average width of 13 km and a floor at

an elevation of 1,340 m above sea level. Water inflow primarily comes from

precipitation and from a single stream draining the White Mountains, located west of the

valley (Albers & Stewart, 1972). When present, outflow from the valley drains into

Columbus Marsh, immediately north of Fish Lake Valley. The valley is bounded to the

north by the Volcanic Hills, to the west and south by the White Mountains and to the east

by the Silver Peak Mountains (Figure 6). The southern part of the valley extends into

California and is immediately northwest of Death Valley. 18

Fish Lake Valley

Clayton Valley

Alluvium (Quaternary) Sedimentary rocks (Paleozoic – Generally unmetamorphosed) Volcanic and associated nonmarine sedimentary rocks (Quaternary and Tertiary) – Approximately Metamorphosed sedimentary rocks (Lower 6 Ma and younger Cambrian and Late Proterozoic) Weepah unit (Miocene) – Nonmarine sedimentary Granitic rocks (Mesozoic and Mesozoic?) rocks, approximately 7 Ma Esmeralda Formation (Miocene) Detachment fault – Hachures on upper plate Andesitic rocks, rhyolite tuff, and associated Normal fault – Bar and ball on downthrown side sedimentary rocks (Tertiary) – Approximately 15 Ma to 26 Ma Anticlinal axis

Figure 6: Location of the lithium deposit in Fish Lake Valley relative to the Esmeralda Formation in Clayton Valley (Source: Diamond, 1990).

Most of the rocks in the valley and the surrounding mountains are Tertiary in age and consist primarily of ash flows, andesitic breccia, tuffaceous sedimentary rocks and clastic sedimentary rocks. The valley floor is filled with Quaternary sediments, mainly playa deposits with some older alluvium on the west side of the valley. The valley is bounded 19

on its western side by the Death Valley-Furnace Creek fault zone, a large NW-SE strike- slip structure accounting for up to 30 km of right-lateral movement in the area.

Borate minerals were discovered in Fish Lake Valley in the late 1860s. Borate was already being extracted from the adjacent Columbus Marsh when borax was first produced from Fish Lake Valley in 1873. Borax was extracted from ulexite, and two processing plants were operating in the area (Albers & Stewart, 1972). Production in

Fish Lake Valley ended around 1930 (Castor & Ferdock, 2004). It is unknown how much borax was extracted from the area, but production is estimated at less than

$900,000 (Albers & Stewart, 1972).

More recently the Borate Hills, located on the eastern margin of Fish Lake Valley (Figure

6), were identified as having high grade boron and lithium mineralization (up to 0.27%

Li), with a grade and size comparable to other lithium deposits in the world (American

Lithium Minerals Inc., 2010). The deposit is located immediately north of the Silver

Peak caldera in a sedimentary basin filled with lake sediments. The basin is approximately 1.5 km in width and 5 km in length, with a thickness up to 400 m. A

North-Northwest / South-Southeast fault crosses the basin, as identified by the structural mapping done by American Lithium Minerals Inc. (Amen, personal comm.). Lithium concentrations appear higher along this fault, as observed from the geochemistry done on the core samples drilled by American Lithium Minerals Inc. (Amen, personal comm.).

The clay sediments form continuous beds within the basin and are thinly laminated with 20

calcareous material, suggesting they were deposited underwater in a shallow lake environment.

McDermitt, NV

The McDermitt caldera is a large oval-shaped complex, approximately 45 km in length

and 35 km in width (Rytuba and Glanzman, 1978) located on the Nevada-Oregon border,

nearly 330 km northeast of Reno, NV. The complex consists in 5 overlapping collapse

structures, each structure marked by a ring fracture and a resurgent dome. The complex

was formed in the Miocene when large volumes of rhyolitic and peralkaline ash-flow

tuffs were erupted from 17.9 to 15.8 million years ago (Rytuba and Glanzman, 1978).

Following the last major collapse and resurgence, tuffaceous sediments have accumulated

in a depression (moat) formed between the walls of the caldera and the resurgent dome

(Figure 7 and 8) (AMEC, 2008). Lakes later occupied this depression, which is evident

from the fossils found in the sediments (Glanzman et al., 1978).

Ore deposits with economic concentrations of mercury, uranium, lithium, and perhaps

gallium, are found within the caldera, reflecting the anomalous concentrations of these

elements in the rhyolites associated with the complex (Rytuba and Glanzman, 1978;

Rytuba et al., 2003). The lithium concentration in the volcanic rocks averages 230 ppm, which is almost 5 times higher than average rhyolitic rocks (Rytuba and Glanzman,

1978). The highest lithium concentrations are found in the clay fraction of the tuffaceous sediments found in the lacustrine beds of the moat, more precisely in the mineral 21

hectorite. Concentrations tend to increase southward, with values up to 0.1-0.2% Li in the Bretz area, 0.1-0.3% Li in the Opalite area and up to 0.1-0.6% Li in the Kings Valley area (Figures 7 & 9; Glanzman et al., 1978). The Li distribution appears to be closely related to the zeolite alteration associated with hydrothermal activity in the caldera

(Rytuba and Glanzman, 1978).

Bretz Placer Aurora

Disaster Peak McDermitt Hg Moat Sediments Intracaldera Rhyolite Tuffs Flows, Intrusions, Domes Outflow-facies Ash Flow Tuffs Kings Valley Precaldera Andesites Li Granitic Basement After Rytuba and Glanzman (1979)

After Glanzman et al (1978)

Figure 7: General geology of McDermitt Caldera (source: AMEC, 2008).

The clay is typically light- to dark-green or brown in color, depending on the degree of oxidation and mixing with volcanic sediments (Glanzman et al., 1978; Odom, 1992).

Bed thicknesses range from 4 m in the Disaster Peak area to more than 60 m in the PCD

Lens area near the southern end of the caldera (Odom, 1992; AMEC, 2008). The crystals are extremely fine and appear to be flake-shaped (Odom, 1992). Chemical analysis of the hectorite found in the Disaster Peak deposit can be found in Table 1. The clay contains various amounts of calcite as nodules, thin beds or powder (Glanzman et al., 1978).

Irregular amethyst-like quartz concretions are also found sporadically within the beds

(Odom, 1992).

Figure 8: Generalized cross-section of McDermitt complex (AMEC, 2008).

As previously noted, lithium mineralization is generally associated with zeolitization of the rock (Rytuba & Glanzman, 1978; Glanzman et al., 1978). Three zones of mineralogical association with the lithium-rich clays have been identified (Figure 9). The most lithium-poor association is in relatively unaltered glassy sediments, with lithium concentrations ranging from 0.07% to 0.34%. The clinoptilolite – K-feldspar zone has Li concentrations ranging from 0.1% to 0.4% and is intermediate in terms of lithium concentrations. The most enriched zone is associated with analcime – K-feldspar altered tuffaceous sediments and ranges in Li concentrations from 0.1% to 0.65%. This zonation is most likely due to sequences of increasing salinity and possible alkalinity of interstitial fluid during the zeolitization process (Glanzman et al., 1978).

Various formation mechanisms have been suggested for the genesis of the hectorite deposits in the McDermitt caldera. Since the rhyolitic rocks associated with the caldera are enriched with respect to lithium, leaching of the rocks may have been induced during low-temperature or hydrothermal alteration (Rytuba and Glanzman, 1978). Given that the caldera formed a closed basin, the lithium-rich solutions were able to accumulate in the depression and later be incorporated into lithium-bearing clays. Another hypothesis is related to the fact that the deposits are generally located over the ring fracture of the caldera (AMEC, 2008). It was suggested that intrusions came up along those fractures, which allowed the circulation of hydrothermal fluids up through the volcanic sections and into the moat sediments. These fluids extracted the lithium from the volcanic rocks and were later deposited in the lake environment of the moat. It was suggested that the 24

lithium-rich fluids were deposited into the moat where they formed a gel and precipitated as a massive layer of lithium-rich claystone (AMEC, 2008). Another proposition is that the lithium-bearing clays are the product of alteration of in-situ clay-rich beds. It is uncertain at this time whether alteration of the sediments to hectorite-bearing beds occurred simultaneously with deposition or after deposition of the tuffaceous sediments.

Glass

Glass and Clinoptilolite Erionite Clinoptilolite Clinoptilolite Mordenite Clinoptilolite Potassium feldspar Analcime Clinoptilolite Potassium feldspar Analcime Potassium feldspar Potassium feldspar Alluvium covered volcaniclastic sediments Caldera complex boundary (approximate)

Figure 9: Alteration patterns in McDermitt caldera (Glanzman & Rytuba, 1979).

Methods

Sample Acquisition

Clay samples were obtained from each locality. A sample from Hector, CA (SHCa;

Table 3) was purchased from the Clay Minerals Society (CMS) Source Clays. Since the

CMS sample was powdered, a rock sample was collected for petrographic analysis during a visit to the Hector Mine in August 2011.

Samples from Clayton Valley, NV (CV2010-01 to -07; Table 3) were obtained with permission from Chemetall Foote. The site was visited in August 2010, and 6 surface samples were collected from the Esmeralda Formation, which was exposed on Angel

Island, on the eastern side of the Valley (Figure 4). No sediment samples were collected from the playa.

One sample from Fish Lake Valley, NV was provided by American Lithium Minerals

Inc. from their South Borate Hills property (SBH-1; Table 3). It is an unconsolidated gravel and clay sample obtained through RC drilling.

Samples from McDermitt, NV were obtained with permission from Western Lithium

Corporation. Western Lithium’s Kings Valley property was visited in July 2010 and 8

samples were collected: 3 trench samples (WLT02D, F, I; Table 3) and 5 core samples 26

(WLC03-01 to -05; Table 3). In addition, a sample was provided by American Colloid from their McDermitt property (DP1; Table 3).

Finally, a sample of synthetic hectorite (SynH; Table 3) was obtained from the Clay

Mineral Society. The sample is an Optigel synthetic hectorite, made by United Catalysts

Inc.

Detailed sample descriptions can be found in Appendix I.

Cleaning Procedure

The samples were first air-dried before being gently crushed using an agate mortar and

pestle to reduce the grain size to a few millimeters. When gravel was present, the sample

was sieved using a 28 mesh sieve to remove the coarse size fraction.

Size Separation

Approximately 25 to 30 g of sample was weighed and placed in an industrial blender

with approximately 250 mL of distilled water. The sample was blended at full power for

2 minutes and transferred to a 500 mL HDPE container for an ultrasonic treatment of 3

minutes. The suspension was then transferred to 50 mL HDPE centrifuge tubes, filled up

to the 40 mL line, and centrifuged in a Fisher Scientific accuSpinTM centrifuge for 2

minutes at a speed of 1,000 rpm to separate the clay fraction (<2m) from the silt and 27

sand. Centrifuge time was calculated using Stoke’s law applied to centrifugal sedimentation (Lagaly, 2006):

ln (2)

-3 Where t is time (s),  is water viscosity (1.054 x 10 kg/m·s), ro is the initial distance of

the particle from the axis of rotation (m), r is the final distance of the particle from the

axis of rotation (m), d is the diameter of the particle (m),  is the angular velocity

3 (rpm/60s),  is the particle density (2,650 kg/m ) and o is the water density (998.49 kg/m3). Centrifuge time was calculated assuming a water temperature of 18ºC.

After centrifugation, the suspended clay fraction in the supernatant was transferred to a

2.8 L polypropylene container for about an hour to await further treatment. The sediment

plug remaining in the centrifuge bottles was re-suspended in 40 mL of distilled water,

ultrasonically treated for 3 minutes, centrifuged and decanted again, the supernatant being poured in the same plastic container. This process was repeated until the supernatant runs clear (free of clay particles). The sand and silt fraction remaining in the centrifuge bottles is transferred to a small dish to dry in the oven at 50ºC.

Table 3: List of samples analyzed for this work.

Sample Site location source sample type Comments CV2010‐01 Clayton Valley, NV Chemetall Foote surface Sample collected from the upper member of the Esmeralda Formation CV2010‐02 Clayton Valley, NV Chemetall Foote surface Sample collected from the upper member of the Esmeralda Formation CV2010‐04 Clayton Valley, NV Chemetall Foote surface Sample collected from the upper member of the Esmeralda Formation CV2010‐05 Clayton Valley, NV Chemetall Foote surface Sample collected from the upper member of the Esmeralda Formation CV2010‐06 Clayton Valley, NV Chemetall Foote surface Sample collected from the upper member of the Esmeralda Formation CV2010‐07 Clayton Valley, NV Chemetall Foote surface Sample collected from the upper member of the Esmeralda Formation WLC03‐01 McDermitt, NV Western Lithium Corporation core Hole WLC03, depth 100‐105ft WLC03‐02 McDermitt, NV Western Lithium Corporation core Hole WLC03, depth 135‐140ft WLC03‐03 McDermitt, NV Western Lithium Corporation core Hole WLC03, depth 190‐195ft WLC03‐04 McDermitt, NV Western Lithium Corporation core Hole WLC03, depth 195‐200ft WLC03‐05 McDermitt, NV Western Lithium Corporation core Hole WLC03, depth 205‐210ft WLT02D McDermitt, NV Western Lithium Corporation trench Trench #2, composite from pile D WLT02F McDermitt, NV Western Lithium Corporation trench Trench #2, composite from pile F WLT02I McDermitt, NV Western Lithium Corporation trench Trench #2, composite from pile I DP1 McDermitt, NV American Colloid pit Crude hectorite from pit. Rock fragments too small for thin section SHCa Hector, CA Clay Mineral Society pit Source Clay. Rock sample also obtained from Elementis Specialties for thin section SBH‐1Fish Lake Valley, NV American Lithium Minerals Inc. RC chip South Borate Hills property, hole SBH‐1, depth ~200ft SynH ‐ Clay Mineral Society synthetic Sample synthesized by United Catalysts Inc. 28

Removal of Carbonate Phases

Given the sensitivity of clays to strong acid, CO2 gas was used to dissolve the carbonates

present in the samples (Bain and Smith, 1994). The introduction of CO2 gas creates a

weak carbonic acid solution which dissolves carbonate minerals by converting carbonate

into water-soluble bicarbonate (Khoury et al., 1984). The clay suspension is treated with a stream of CO2 gas for approximately 3 hours. Following this treatment, the suspension

is placed in 50 mL HDPE centrifuge tubes filled up to 40 mL and centrifuged for 3

minutes at 8,500 rpm. The supernatant was discarded and the clay plug transferred to a

small dish to dry in the oven at 50ºC.

The dried clay concentrates were gently crushed again using an agate mortar and pestle

and scanned on the X-ray diffractometer (XRD). A random scan was done on the clay to

identify remaining impurities. If the sample had impurities remaining in the <2 m size

fraction, the concentrate was brought back into suspension following the same procedure

described above. The sample was centrifuged for 2 minutes at 2,000 rpm in 50 mL tubes

filled to the 40 mL line to separate the >1 m fraction, 2 minutes at 4,000 rpm in tubes

filled to the 40 mL line to separate the >0.5 m fraction, 3 minutes at 8,500 rpm in tubes filled to the 40 mL line to separate the >0.2 m fraction, and 25 minutes at 8,500 rpm in tubes filled to the 25 mL line to concentrate the remainder of the clay. Each fraction was scanned on the XRD again to identify the fractions that were pure clay.

Chemistry

All samples were sent for chemical analysis to the US Geological Survey analytical laboratory in Denver CO. Both the unprocessed rock samples and the clay concentrates were analyzed for their major and minor ion chemistry. The major elements were analyzed using X-ray fluorescence (XRF), while the minor elements were analyzed using a 4-acid digest ICP-AES-MS. They were also analyzed for their total carbon and total sulfur contents using combustion. The carbonate carbon was analyzed by coulometric titration. Finally, the clay concentrates were analyzed for essential and non-essential water by combustion, and chloride and fluoride by ion selective electrodes (Taggart,

2002).

X-Ray Diffraction

The samples were scanned on the XRD using both random and oriented mounts. The

diffractometer is a Philips automated XRD using CuK radiation, a scintillation detector

and a receiving slit of 0.2 mm. The data were acquired on a PC using MDI Datascan

software and processed using MDI Jade and ICDD PDF minerals data base. The XRD

was set at a voltage of 40 kV and a current of 30 mA. The machine is housed at the

Nevada Bureau of Mines and Geology in Reno, Nevada.

The random mounts were prepared using the back-loaded method (Moore and Reynolds,

1989). An aluminum holder was taped to a glass slide and the powdered sample was

packed in the opening. A spatula was used to evenly pack and press the powder in the cavity, making sure that no sample fell on the surface of the holder. A second glass slide was taped over the aluminum holder, covering the opening. The holder was then flipped over and the 1st glass slide was removed by cutting the tape with a razor blade, exposing

the “bottom” surface of the packed sample. The samples were scanned in the aluminum

holder between the angles of 2-65 °2 using steps of 0.02 °2 and a dwell time of 1s.

Both the bulk rock samples and the concentrated clay samples were scanned with the

random mount. The aluminum holder was used as a calibration standard.

The oriented mounts were prepared for the concentrated clays only, using the filter

transfer method (Moore and Reynolds, 1989). A vacuum filter apparatus was used with a

Millipore mixed cellulose easter filter (0.45m) or, for finer clays, a Millipore durapore®

membrane filter (0.1m). Approximately 1.8 g of sample is placed in 30 mL of distilled

water and brought in suspension. The suspension is poured in the funnel and allowed to

filter for 3 to 10 minutes, without drawing the entire solution. Samples with finer clay particles typically take more time to accumulate enough material on the filter. The

vacuum flask is then brought up to room pressure and drained of excess liquid. The filter

is gently removed from the glass frit with a metal spatula and carefully placed face-down

on a glass slide, making sure no air pockets are trapped. The glass slide is placed in the

oven at 50ºC for 2 to 8 minutes to allow the sample to dry a little bit, so that the clay will

stick to the slide when peeling off the filter. The sample is ready when the filter surface

shows opaque and translucent streaks. The filter is then gently peeled off, with the

sample remaining on the glass. This procedure is very temperamental, as filtering and drying times will vary depending on the sample, and multiple attempts were done on most samples. Two samples (SHCa and SynH) were prepared using the glass slide method, where the suspension is simply added to the surface of the slide and allowed to air-dry. These samples were prepared with this method because they form a thick gel when brought in suspension, making them virtually impossible to filter. The samples were placed in a desiccator to wait for X-ray measurement.

The air-dried oriented samples were scanned between the angles of 2-35 °2 using steps of 0.02 °2 and a dwell time of 1s. Each sample was scanned twice – the 1st time by itself and the 2nd time with a powdered quartz standard, which was simply added on top

of the slide. This 2-step scanning was done in order to calibrate the scan using the quartz

standard and to avoid interference between the quartz peak at 26.65 º2(3.34 Å) and the

003/005 illite/smectite clay reflection near 26.6 º2 (3.33 Å). The two scans were

superimposed to verify their similarity using MDI Jade, thus facilitating adjustment to the

quartz standard.

The final step was ethylene glycol solvation, to test for smectite minerals. The samples

were placed in a desiccator filled with ethylene glycol, heated at 50ºC for approximately

1 hour, then left at room temperature for 12 hours or more. They were scanned again

following the same method described above.

The spacing and peak location for each sample was calculated using Braggs’ Law:

2d sin  = n 3

Where d is the spacing,  is the diffraction angle, n is and integer related to the planes of spacing d, and  is the wavelength of the incident beam ( = 1.54 Å for Cu).

Petrographic Analysis

Thin sections were prepared for all rock samples except for DP1, because the rock

fragments were too small. The sections were prepared by Spectrum Petrographics and

are standard, vacuum embedded thin sections. They were examined with an Olympus

petrographic microscope to identify the associated minerals and describe their textural

relationship with the clay.

Scanning Electron Microscopy

All cleaned samples were examined with a Hitachi S-4700 II Scanning Electron

Microscope (SEM) to determine their morphological characteristics. The SEM was set at

a voltage of 20 kV and a current of 10 A. Pictures were taken for each sample at various magnifications.

Cation Exchange Capacity

The Cation Exchange Capacity (CEC) was determined following the procedure by

Busenberg and Clemency (1973) for the ammonia electrode. In this procedure, a

+ concentrated ammonium (NH4 ) is used to suspend the clay sample and saturate the

+ + exchange sites within the clay structure with NH4 . The NH4 -saturated clay is then

+ reacted with a strong base to convert NH4 to NH3, which is measured by the electrode.

Approximately 500 mg of sample was placed in a 50 mL HDPE centrifuge tube with 40

mL of a 1M solution of ammonium acetate at pH 7 and allowed to react overnight. The

pH was adjusted by adding either ammonium hydroxide (NH4OH) to increase the pH or

acetic acid (CH3COOH) to decrease it. The samples were decanted and placed in a fresh

ammonium acetate solution twice more, each time allowing the sample to react with the

solution overnight. The samples were then concentrated using a centrifuge and washed

five times with 20 mL of a 1M solution of ammonium acetate at pH 7, followed by four

washes with 20 mL of a 1M solution of ammonium chloride at pH 7 and one wash with

20 mL of a 0.25M solution of ammonium chloride at pH 7. The washing technique

involved re-suspending the sample in the centrifuge tube with the washing solution and

using the centrifuge to re-concentrate the clay. The samples were then rinsed with isopropyl alcohol until all chloride was removed as tested with a 0.1M silver nitrate solution. It took approximately 12-15 rinses to obtain a negative silver nitrate test, where no AgCl precipitated out of the solution. The solid samples were then air-dried. The wash solutions for each sample were retained and combined into an ammonium acetate

and ammonium chloride composite, which were concentrated by evaporation to 15 mL for analysis of exchangeable ion chemistry. They were sent to the US Geological Survey laboratory in Denver CO and analyzed for their major and minor elements composition using ICP-MS.

Before measurement of the NH3 can be made, a calibration curve needs to be created for

the ammonia electrode. The curve relates the ammonia potential in solution, measured

by the electrode, to the ammonia concentration. The calibration curve was created by

-2 -4 diluting a 0.1M solution of NH4Cl for ammonia concentrations of 10 M to 10 M.

The ammonia concentration in the clay samples is produced by reacting the ammonium-

saturated clay with a 10M sodium hydroxide (NaOH) solution at the time of

measurement. Approximately 100 mg of solid is placed in a beaker with 50 mL of

ammonia-free water and a Teflon-covered stirring bar. The electrode is immersed in the

solution and tapped firmly to remove air bubbles. The stir bar is started and 0.5 mL of

10M NaOH is added with a pipette. Millivolt readings from the electrode are recorded

every 30 seconds until a constant reading is obtained. The NH3 concentration is then read

from the calibration curve.

Layer Charge

Each sample was analyzed for its layer charge using the n-alkylammonium method. This

method involves the exchange of alkylammonium ions with the interlayer cations of clay

minerals. The samples were prepared following the procedure described by Ruehlicke and Kohler (1981). Approximately 100 mg of the clay samples were dispersed in small

9.5 mL Pyrex borosilicate glass tubes with a solution of alkylamine hydrochloride, with the alkylamine chain length varying from 6 to 18 carbon atoms. The solutions were prepared following the procedure by Lagaly (1994). For alkylamines with chain lengths of 6 to 10 C, 1 mL of solution was used for the suspension. Alkylamines with chain lengths of 11 to 15 C used 2 mL of solution, and those with chain lengths of 16 to 18 C used 4 mL of solution. The suspension is held overnight at 65ºC, then centrifuged to separate the solid, discarding the supernatant. The clay is washed once with 50% ethanol, dispersed in a fresh alkylamine solution and held again at 65ºC overnight. The suspension is centrifuged once again to separate the solid from the solution. The clay is then dispersed in 3-4 mL of ethanol 95% and held overnight at 65ºC. The clay is further washed 3 to 5 times consecutively with a fresh solution of 95% ethanol. Following the last wash, the clay is suspended one last time in 1 mL of 95% ethanol. The suspension is transferred on a standard microscope glass slide and allowed to dry. The slides are then placed in a desiccator until they are ready to be X-rayed.

The layer charge for each sample was calculated following the procedure from Lagaly

(1994). The alkylammonium ions will take a different disposition in the interlayer space depending on the chain length of the alkylammonium. For smaller chains, the ions will form a monolayer to create a structural d-spacing between 13.4 and 13.6 Å. Longer chains will transition to a bilayer arrangement, causing a shift in the d-spacing from 13.6

to 17.6 Å, with a spacing of 17.6 Å representing a typical bilayer arrangement. The layer charge calculation depends on the area of the half-unit cell of the clay, and is averaged from the values calculated for an alkylammonium chain that forms a tightly packed monolayer at 13.6 Å, representing the upper value of the calculated range of the layer charge, and the alkylammonium chain that forms a bilayer at 17.6 Å, representing the lower value.

Results

Whole Rock Mineralogy

For all samples, whole rock mineralogy was primarily determined through X-ray

diffraction (XRD) analysis (Appendix II). In addition, examination of thin sections from all samples provided supporting evidence for the presence of accessory minerals

(Appendix III), and some textural relationships could be identified.

Clayton Valley

All samples from Clayton Valley are characterized by having a matrix composed of clay and calcite and abundant grains of quartz, feldspar and micas, primarily muscovite and some biotite (Figures III-1 to III-12). Fragments of volcanic glass and glass shards are also observed in some samples (Figures III-4, III-5, III-6, III-11), and clays can be observed replacing glass fragments in Figure III-5. Though coarse grains of calcite are visible in some samples filling void spaces (Figures III-1, III-3), calcite is ubiquitous in the fine-grained matrix of all samples. The grains visible in all samples appear to have no preferred orientation. Sample CV2010-07 (Figure III-11 and III-12) appear different than the other samples, due to the greater size and abundance of glass fragments and accessory minerals.

The XRD patterns have identified quartz, feldspar, muscovite, calcite and halite in all samples (Figures II-1, II-5, II-9, II-13, II-17 and II-21). Kaolinite was also identified in a number of samples. No zeolites were identified in the Clayton Valley samples.

McDermitt

The samples from McDermitt are composed of abundant fragments (Figures III-13, -16, -

18, -23, -25 and -27), all of which have been altered to clays. The fragments are typically elongated and appear to be aligned parallel to bedding. Bedding is apparent on all samples, and the clays are generally oriented parallel to the bedding, which is visible from the parallel extinction of the minerals in crossed-polarized light. The fragments are similar in all samples, and those not fully altered to clay appear composed of very fine- grained glass and feldspars (Figure III-19 and -21). Carbonates are abundant in all samples, though its form varies. Some samples have carbonates finely disseminated within the clays (Figures III-15 and -27), others have large crystals of dolomite or calcite

(Figures III-16, -18, -20 and -24). In sample WLC03-02, the carbonates are found along preferred bedding, which seems to also contain abundant feldspar needles (Figures III-16 and -17). In sample WLC03-05, the carbonates appear to have slightly dissolved, visible from the gap with the clay groundmass and the rounded edge of the crystals (Figure III-

24).

The XRD patterns have identified abundant smectite in all samples except for WLC03-

03, -04 and -05, which are dominated by an illitic mineral (Figures II-25, II-29, II-33, II-

37, II-41, II-45, II-49, II-53 and II-57), based on the intensity of the peaks on the random patterns. The clays are typically accompanied by dolomite as their dominant carbonate phase, except for WLC03-03, -04 and -05, which are dominated by calcite. Quartz, feldspar and pyrite are also abundant accessory minerals. No zeolites were identified in the McDermitt samples.

Hector

The sample from Hector is primarily composed of clay and calcite (Figures III-28 to –

30). The clay appears to form irregular masses with an uneven surface (Figure III-29).

Calcite forms in large concretions and is found separated from the clay. Given the very soft nature of the clay, it can appear to flow between grains of calcite (Figure III-30).

Quartz, when present, is interstitial, found between fragments of clay and grains of calcite.

The XRD pattern confirms the presence of abundant calcite and clay, along with dolomite and quartz (Figure II-61). Though the fit with the hectorite standard is not perfect, the clay has an XRD pattern characteristic of smectite. No zeolites were identified in the

Hector sample.

Fish Lake Valley

The sample from Fish Lake Valley is characterized by abundant quartz fragments in a matrix of clay and calcite (Figures III-31 and –32). The quartz seems to form irregular

aggregates, with a size up to 200 m, and contains occasional inclusions of clays and calcite (Figure III-31). Other minerals such as muscovite and feldspar can also be observed in thin section. Calcite appears to be ubiquitous in the fine-grained matrix, mixed in with the clays. Occasional coarse-grained calcite can also be found in the sample (Figure III-32).

The XRD pattern has identified abundant calcite, along with quartz, dolomite and a smectite clay similar to hectorite (Figure II-65). No zeolites were identified in the Fish

Lake Valley sample.

Whole Rock Chemistry

A summary of the analytical results of the bulk samples is provided in Table 4. For a

complete dataset, refer to Appendix V. The oxide total includes the majors and the most

important minor elements, and the volatiles are expressed in terms of LOI, which is the

weight loss on ignition. The LOI includes all water and CO2 that was lost upon heating

the sample to 950ºC. The individual values for organic and carbonate carbon are also

given. The total oxide weight is at or near 100% for all samples. The low total weights

in some samples may be caused by an absence of fluorine concentrations, since it was not included in the bulk sample analysis.

Clay Mineralogy

The cleaning procedure was effective in removing accessory minerals from the samples,

leaving pure concentrated clays. The first cleaning step, centrifugation, removed most

impurities, but abundant carbonates remained in the clay size fraction (Figure 10). After

the second step, consisting in a CO2 treatment of approximately 2 hours, only minor amounts of carbonates remained in the sample. All samples were thus treated for 3 hours with a stream of CO2 gas, which removed most carbonates from the samples.

Most samples were free of accessory minerals with a simple CO2 treatment and the

concentration of the <2 m size fraction. However, some samples required further

separation of the 0.5 m size fraction, or the 0.2 m size fraction, as the very fine grained

feldspars found in some samples would remain in the <2 m fraction (Table 5). Since

smectites tend to concentrate in the finest fractions (<0.1 m) and illites concentrate in

the 0.1-0.5 m, these extra size separations were effective at removing impurities,

including accessory clays and detrital material (Brown and Brindley, 1980). Illite will be

defined here as a clay-size mica mineral, consistent with the definition by Grim et al.

(1937). While great care was taken in removing impurities, a small fraction remained in

some of the samples (Table 6, Appendix II).

All XRD patterns were adjusted using powdered quartz as a standard. The correction

averaged ±0.13 º2, with the largest correction applied to sample WLT02I at 0.27 º2.

The peak locations listed in Tables 7 and 8 were automatically selected by the computer

program JADE, and some uncertainty is most likely associated to the 2 value for each peak, with the exact value of uncertainty being undefined.

Figure 10: Random XRD scan showing the effect of cleaning procedure on the sample from Hector.

Table 4: Chemical analyses of the bulk samples. CV2010‐01 CV2010‐02 CV2010‐04 CV2010‐05 CV2010‐06 CV2010‐07 WLC03‐01 WLC03‐02 WLC03‐03 WLC03‐04 WLC03‐05 WLT02‐DWLT02‐FWLT02‐I DP1 SHCa SBH‐1SynH

Al2O3 (%) 14.10 14.90 11.00 12.30 11.70 12.50 4.44 6.10 5.22 4.73 6.06 4.83 4.25 4.93 2.06 0.84 0.99 0.13 CaO (%) 5.78 2.93 10.00 4.70 8.98 6.18 3.21 3.79 7.01 5.91 3.75 3.09 9.13 7.34 7.14 22.60 28.10 0.04

Fe2O3 (%) 4.76 4.86 3.64 4.13 3.99 3.34 1.98 2.88 2.70 1.92 2.59 2.01 1.82 1.92 1.01 0.32 0.30 nd

K2O (%) 3.91 4.19 6.24 7.47 6.70 5.00 1.43 3.55 6.02 6.36 5.44 1.35 2.21 2.42 0.42 0.17 0.63 nd MgO (%) 3.70 3.33 5.03 3.28 3.43 3.78 17.70 15.30 11.30 13.40 11.10 18.10 16.90 16.70 19.10 13.90 8.47 24.00 MnO (%) 0.06 0.09 0.07 0.06 0.08 0.09 0.02 0.05 0.09 0.11 0.05 0.02 0.05 0.15 0.04 0.01 0.05 nd

Na2O (%) 4.01 3.78 3.71 5.19 1.48 3.25 0.40 0.37 1.63 1.45 2.51 0.66 0.64 0.85 0.28 1.29 0.16 2.34

P2O5 (%) 0.09 0.16 0.09 0.10 0.09 0.11 0.01 0.02 nd nd nd 0.01 0.05 0.02 0.03 0.01 0.04 nd

SiO2 (%) 46.40 52.10 41.40 45.30 45.40 53.60 47.40 46.10 49.80 50.70 52.80 48.30 40.90 41.80 43.70 34.10 28.10 51.50

TiO2 (%) 0.55 0.51 0.43 0.46 0.45 0.47 0.18 0.16 0.45 0.37 0.41 0.20 0.23 0.13 0.22 0.04 0.03 0.01 LOI (%) 15.00 12.10 16.00 12.60 15.40 8.84 21.60 18.30 9.31 7.75 7.80 20.50 21.90 22.30 24.40 24.50 30.10 21.70

Li2O (%) 0.23 0.11 0.30 0.59 0.24 0.14 0.61 0.79 1.38 1.53 1.38 0.65 0.76 0.51 0.79 0.60 0.52 0.62 SrO (%) 0.08 0.03 0.16 0.11 0.09 0.23 0.03 0.04 0.04 0.04 0.02 0.03 0.09 0.05 0.05 0.17 1.04 0.00 BaO (%) 0.05 0.04 0.04 0.03 0.07 0.06 0.02 0.02 0.02 0.02 0.01 0.01 0.02 0.03 0.32 0.01 0.13 0.00

Rb2O (%) 0.04 0.03 0.03 0.05 0.04 0.03 0.02 0.04 0.10 0.11 0.09 0.02 0.04 0.03 0.00 0.00 0.00 0.00

As2O3 (%) 0.00 0.00 0.01 0.01 0.00 0.00 0.00 0.01 0.04 0.03 0.04 0.00 0.00 0.00 0.00 0.00 0.01 0.00

Cs2O (%) 0.01 0.00 0.00 0.01 0.01 0.00 0.02 0.03 0.04 0.04 0.04 0.01 0.02 0.01 0.00 0.00 0.00 0.00

SO2 (%) 0.14 0.20 0.24 0.90 0.16 0.62 1.56 2.98 3.00 1.92 3.00 0.54 0.24 0.18 0.28 0.18 0.36 0.18 Total 98.91 99.36 98.39 97.28 98.31 98.25 100.64 100.53 98.14 96.38 97.11 100.33 99.25 99.37 99.86 98.74 99.03 100.52

CV2010‐01 CV2010‐02 CV2010‐04 CV2010‐05 CV2010‐06 CV2010‐07 WLC03‐01 WLC03‐02 WLC03‐03 WLC03‐04 WLC03‐05 WLT02‐DWLT02‐FWLT02‐I DP1 SHCa SBH‐1SynH‐1 CRBNT_C (%) 0.83 0.11 2.24 0.91 1.61 1.11 0.73 1.18 1.40 1.18 0.81 0.62 2.28 2.43 1.86 4.86 6.60 0.10 OrgC (%) 0.22 0.44 0.19 0.09 0.09 0.17 0.98 0.71 0.96 0.65 0.60 0.13 0.03 0.01 0.00 0.01 0.02 0.01 TotC (%) 1.05 0.55 2.43 1.00 1.70 1.28 1.71 1.89 2.36 1.83 1.41 0.75 2.31 2.44 1.80 4.87 6.62 0.11 44

Table 5: Size fraction used (m) for the detailed analyses of the clay samples. Sample Size fraction Sample Size fraction Sample Size fraction used used used CV2010-01 <0.2 WLC03-01 <2 WLT02-F <2 CV2010-02 <0.5 WLC03-02 <2 WLT02-I <2 CV2010-04 <0.2 WLC03-03 <0.5 SBH-1 <0.5 CV2010-05 <0.2 WLC03-04 <0.5 DP1 <2 CV2010-06 <0.2 WLC03-05 <0.5 SHCa <2 CV2010-07 <0.2 WLT02-D <2 SynH -

Table 6: Mineralogy of bulk samples and cleaned clay samples. Sample Bulk Mineralogy Mineralogy after cleaning CV2010-01 quartz/calcite/halite/kaolinite/muscovite/feldspar/smectite/illite illite/smectite CV2010-02 quartz/calcite/halite/kaolinite/muscovite/feldspar/smectite/illite illite/smectite CV2010-04 quartz/calcite/halite/feldspar/muscovite/smectite/illite illite/smectite CV2010-05 quartz/calcite/halite/feldspar/muscovite/illite illite CV2010-06 quartz/calcite/halite/feldspar/muscovite/illite illite/smectite CV2010-07 quartz/calcite/halite/muscovite/dolomite/kaolinite/feldspar/illite illite/smectite WLC03-01 quartz/calcite/dolomite/feldspar/smectite/pyrite smectite/dolomite WLC03-02 quartz/calcite/dolomite/smectite/pyrite smectite WLC03-03 quartz/calcite/dolomite/illite/pyrite/feldspar illite WLC03-04 quartz/calcite/illite/pyrite/feldspar illite WLC03-05 quartz/calcite/dolomite/illite/pyrite/feldspar illite/albite WLT02-D dolomite/feldspar/smectite smectite/dolomite WLT02-F dolomite/feldspar/smectite smectite WLT02-I quartz/dolomite/feldspar/smectite smectite DP1 quartz/dolomite/calcite/feldspar/smectite smectite/dolomite SHCa quartz/dolomite/calcite/smectite smectite/calcite SBH-1 quartz/dolomite/calcite/smectite smectite SynH smectite

Clayton Valley

The samples in Clayton Valley typically show a mixture of smectite and illite (Appendix

II). Smectites are characterized by having a regular 00l basal spacing at 15 Å in oriented samples, which expands to 17 Å upon treatment with ethylene glycol, while illites have a

regular spacing at 10 Å in oriented samples and do not expand upon treatment with ethylene glycol (Brindley, 1980). Table 7 shows the location of the peaks characteristic of smectites and Table 8 those characteristic of illite. Since the illite’s 002 and 003 reflections occur at the same angle 2 as the smectite’s 003 and 005 reflections, the illite’s reflections are calculated from the peak positions of the glycolated samples, and the smectite’s reflections from the peak positions in the air-dried samples.

Morphologically, the clays vary in size from 0.1 m to about 2 m (see Appendix IV).

They form stubby plates, though seem to lack specific crystal structure.

McDermitt

The samples from McDermitt can be separated in two different groups. The majority of the samples (Type-1) have an XRD profile similar to smectites, with a sharp air-dried peak at approximately 5.9º 2 (15.0 Å) which moves to 5.24º – 5.16º 2 (16.8 – 17.1 Å) upon ethylene glycol treatment (Table 7, Appendix II). Morphologically, the clays appear wispy with a distinguishable flaky texture. No clear structure or crystal form can be discerned from the images.

The second group (Type-2), consisting of samples WLC03-03, -04 and -05, have an XRD profile more similar to illites, with peaks regularly spaced around 8.8º 2 (10 Å), 17.7º 2

(5.0 Å) and 26.7º 2 (3.3 Å) (Table 8, Appendix II). The small shift of the 001 reflection upon ethylene glycol treatment could be an indication of a minor smectite component,

though too small to show a distinguishable smectite peak. The 3 samples show a sharp

060 reflection around 61.3º 2 (1.51 Å). Morphologically, the clays appear to form elongated to stubby flakes, ranging in size from 0.5 m to 2 m. They are similar in shape and form to the Clayton Valley samples.

Hector

The sample from Hector has an XRD profile similar to that of a smectite (Appendix II), consistent to what has been observed for hectorite. It has a strong peak at 6.06º 2 (14.6

Å), which shifts to 5.22º 2 (16.9 Å) after ethylene glycol treatment (Table 7). The peaks are very broad, especially when compared to those observed for the McDermitt samples.

The random XRD profile indicates that a small percentage of calcite remained in the sample after CO2 treatment. It also shows a sharp 060 reflection at 60.91º 2 (1.52 Å).

Morphologically the clay appears wispy and flaky, similar to the other samples identified

as smectites. No definite crystal shape can be identified on the images.

Fish Lake Valley

The sample from Fish Lake Valley has an XRD profile similar to smectites (Appendix

II), with a strong peak at 5.88º 2 (15.0 Å) which moves to 5.18º 2 (17.0 Å) upon ethylene glycol treatment (Table 7). The peaks on both the oriented and random profiles

are fairly sharp, especially the 001 reflection at 5.88º 2 (15.0 Å) and the 060 reflection

at 61.16º 2 (1.51 Å).

Morphologically, the clay appears wispy and flaky, with no clear structure identifiable. It is very similar to the primary group of clays identified at McDermitt.

Synthetic hectorite

The synthetic sample has an XRD profile similar to that of a smectite (Appendix II), with a strong peak at 6.87º 2 (12.8 Å), which shifts to 5.37º 2 (16.5 Å) after ethylene glycol treatment (Table 7). The peaks are very broad, broader than those observed for the

Hector sample. The random profile indicates the 060 peak to be at 60.61º 2 (1.53 Å).

Morphologically, the sample appears somewhat stubby in shape, and no crystal structure could be defined from the image. While it seems to have a bit of a platy texture, it lacks the wispy features commonly identified in the other smectite samples.

Clay Chemistry

Analytical

A summary of the chemical analyses is provided in Table 9. For a complete dataset, refer

to Appendix V. The oxide total includes the majors and the most important minor

- elements, along with all volatiles in the form of H2O and CO2. The H2O result represents

the non-essential water which evaporates upon drying the sample for 2 hours at 105ºC.

+ The H2O result represents essential water which is released from the mineral structure

upon heating the sample to 950ºC. The CO2 result represents total carbon, both organic

and carbonate. The individual values for organic and carbonate carbon is also given.

Fluorine is expressed in percent, and the total analysis is corrected to account for the

excess oxygen recorded. Since one excess oxygen atom is recorded for each two atoms

of fluorine, the oxygen equivalent is calculated by subtracting F (%) from F2O (%) (Deer et al., 1966). The weight equivalent (O≡F) is then subtracted from the total.

The total weight oxide is at or near 100% for all samples, within a margin of ±4%. This margin of error is caused by the volatiles present in the samples, which include CO2 and

H2O. When the weight oxide total is calculated with the Loss on Ignition (LOI) instead

of the individual volatile components, the weight sum is 100 ±2% in all cases (Table 9).

It is fairly difficult to recalculate the LOI from individual analysis of the volatiles,

especially on high fluorine samples, as fluorine interferes with detection.

CEC

Results from the cation exchange capacity are shown in Table 10. Calibration standards

for the NH3 analysis were measured 4 times during the analysis – at the beginning, after 6

and 12 samples, and at the end – in order to correct for drift in electrode readings (Figure

11). Given the slight drift in the curve, the ammonia concentration for each sample was

calculated depending on its proximity in time to a given calibration measurement: in each

set of 6 samples, the first 2 samples were calculated using the initial calibration curve, the last 2 samples using the 2nd or final curve of the set, and the 2 samples in the middle were

calculated using an average of both curves. Table 10 identifies the curve used for each

sample.

The CEC is calculated as (Busenberg and Clemency, 1973):

(4)

where c is the concentration of ammonia (in mol/L) as calculated from the calibration

curve, v is the volume of water added (in mL), w is the weight of the sample (in mg) and

10-5 is a conversion factor.

Figure 11: Calibration curves obtained from the ammonia electrode at specific concentrations of the standard ammonia solution. Curve 1 was measured before any samples, curve 2 after 6 samples, curve 3 afte r 12 samples and curve 4 at the end, after 18 samples.

Table 7: Peak locations and reflection ID for all smectite samples. Basal spacing calculated with the oriented air-dried 003 reflection, using Bragg’s Law. “-“ indicates not measured. Oriented air dried Oriented glycolated Randomly oriented 001 003 004 005 001 002 003 004 005 006 001 003 02,11 005 13,20 04,22 15,24,31 06,33 basal spacing sample ID º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 ÅÅ CV2010‐01 6.23 14.16 17.75 4.99‐ ‐ 5.22 16.92 9.85 8.97 16.20 5.46 19.95 4.45 26.72 3.33 31.96 2.79 6.35 13.92 17.69 5.01 19.59 4.53 26.79 3.32 34.75 2.58‐ 53.52 1.71 61.42 1.51 15.8 CV2010‐02‐ 17.75 4.99‐ ‐ 5.27 16.75‐ 16.20 5.46‐ ‐ ‐ ‐ 17.70 5.00 19.63 4.52 26.54 3.35 34.74 2.58‐ 53.86 1.70 61.55 1.50 15.8 CV2010‐04 6.05 14.59 17.73 5.00‐ ‐ 5.28 16.74 9.85 8.97 15.90 5.57 20.15 4.40 26.72 3.33 31.70 2.82 6.03 14.64 17.69 5.01 19.63 4.52 26.90 3.31 34.74 2.58‐ 53.51 1.71 61.56 1.50 15.8 CV2010‐06 6.46 13.67 17.74 5.00‐ ‐ 5.24 16.87‐ 16.36 5.41‐ 26.74 3.33 31.95 2.80 7.15 12.35 17.78 4.98 19.62 4.52 26.84 3.32 34.58 2.59‐ 53.72 1.70 61.54 1.50 15.8 CV2010‐07 5.98 14.78 17.64 5.02‐ ‐ 5.18 17.05‐ 16.01 5.53‐ 26.74 3.33 31.71 2.82 5.85 15.10 17.84 4.97 19.55 4.54 26.77 3.33 34.69 2.58‐ 53.72 1.70 61.29 1.51 15.9 WLC03‐01 5.96 14.83 17.85 4.96 23.70 3.75 29.84 2.99 5.14 17.18 10.34 8.55 15.84 5.59‐ 26.52 3.36 31.92 2.80 6.13 14.41 17.93 4.94 19.51 4.55‐ 34.61 2.59 39.87 2.26 53.42 1.71 61.01 1.52 14.9 WLC03‐02 5.87 15.04 17.69 5.01 24.11 3.69 29.63 3.01 5.25 16.82 10.43 8.48 15.99 5.54 ‐ 26.67 3.34 31.99 2.80 6.04 14.63 18.07 4.90 19.59 4.53 27.07 3.29 34.50 2.60 39.76 2.26 53.30 1.72 61.07 1.52 15.0 WLT02D 5.89 15.00 17.77 4.99 24.11 3.69 29.75 3.00 5.40 16.35 10.49 8.43 15.96 5.55 ‐ 26.56 3.35 31.92 2.80 6.02 14.66 17.88 4.96 19.58 4.53 29.75 3.00 34.60 2.59 39.61 2.27 53.26 1.72 60.97 1.52 15.0 WLT02F 5.86 15.08 17.64 5.02 ‐ 29.34 3.04 5.26 16.80 10.35 8.54 15.95 5.55 ‐ 26.60 3.35 31.90 2.80 6.00 14.71 17.82 4.97 19.62 4.52 27.44 3.25 37.06 2.42 39.70 2.27 53.32 1.72 61.18 1.51 15.1 WLT02I 5.73 15.42 17.61 5.03 ‐ 27.72 3.22 5.22 16.92 9.85 8.97 16.18 5.47 ‐ 26.52 3.36 32.08 2.79 5.99 14.75 17.70 5.01 19.50 4.55 26.73 3.33 34.20 2.62 39.52 2.28 53.19 1.72 60.92 1.52 15.6 DP1 5.88 15.03 17.82 4.97 24.20 3.67 29.72 3.00 5.28 16.72 10.48 8.43 15.90 5.57 20.92 4.24 26.58 3.35 31.94 2.80 6.14 14.38 18.06 4.91 19.54 4.54 26.58 3.62 34.64 2.59 ‐ 53.30 1.72 61.04 1.52 15.0 SHCa 6.06 14.57 17.76 4.99 ‐ 28.86 3.09 5.22 16.92 10.24 8.63 15.84 5.59 20.54 4.32 26.50 3.36 31.60 2.83 6.65 13.28 18.00 4.92 19.47 4.56 27.85 3.20 34.69 2.58 ‐ 53.19 1.72 60.91 1.52 15.2 SBH‐1 5.88 15.03 17.72 5.00 23.88 3.72 29.65 3.01 5.18 17.05 10.34 8.55 15.72 5.63 20.80 4.27 26.40 3.37 31.74 2.81 6.35 13.90 ‐ 19.66 4.51 26.68 3.34 34.64 2.59 ‐ 53.36 1.71 61.16 1.51 15.0 SynH 6.87 12.84 16.81 5.27 ‐ 28.12 3.17 5.37 16.46 9.57 9.24 15.83 5.59 19.58 4.53 26.58 3.35 31.14 2.87 6.08 14.53 ‐ 19.53 4.54 27.71 3.22 35.07 2.56 ‐ 53.10 1.72 60.61 1.53 15.8

Table 8: Peak locations and reflection ID for all illite samples. Basal spacing calculated with the oriented glycolated 002 reflection, using Bragg’s Law. “-“ indicates not measured.

Oriented air dried Oriented glycolated Randomly oriented 001 002 003 001 002 003 001 002 02,11 003 13,20201 04,22 133 005 15,31 204 06,33 basal spacing sample ID º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 Å º2 ÅÅ CV2010‐01 8.69 10.18 17.75 4.99 26.82 3.32 8.68 10.17 17.78 4.98 26.72 3.33 8.71 10.14 17.69 5.01 19.59 4.53 26.79 3.32 34.75 2.58 36.95 2.43 39.82 2.26 42.28 2.14 45.35 2.00 53.52 1.71 55.47 1.65 61.42 1.51 10.0 CV2010‐02 8.77 10.08 17.75 4.99 26.80 3.32 8.85 9.98 17.71 5.00 26.73 3.33 8.57 10.31 17.70 5.00 19.63 4.52 26.54 3.35 34.74 2.58 36.51 2.45 39.98 2.25 42.41 2.13 45.27 2.00 53.86 1.70 55.56 1.65 61.55 1.50 10.0 CV2010‐04 8.69 10.17 17.73 5.00 26.89 3.31 8.84 10.00 17.69 5.01 26.72 3.33 8.66 10.21 17.69 5.01 19.63 4.52 26.90 3.31 34.74 2.58 37.10 2.42 39.98 2.25 42.34 2.13 45.42 1.99 53.51 1.71 54.95 1.67 61.56 1.50 10.0 CV2010‐05 8.66 10.20 17.66 5.02 26.80 3.33 8.77 10.08 17.77 4.99 26.75 3.33 8.85 9.98 17.70 5.01 19.71 4.50 26.87 3.31 34.83 2.57 37.20 2.41 39.89 2.26 42.47 2.12 45.56 1.99 53.76 1.70 55.35 1.65 61.55 1.50 10.0 CV2010‐06 8.61 10.26 17.74 5.00 26.88 3.32 8.82 10.02 17.63 5.02 26.74 3.33 8.53 10.35 17.78 4.98 19.62 4.52 26.84 3.32 34.58 2.59 36.77 2.44 39.97 2.25 42.67 2.12 45.50 1.99 53.72 1.70 55.88 1.64 61.54 1.50 10.0 CV2010‐07 8.58 10.30 17.64 5.02 26.74 3.33 8.82 10.02 17.72 5.00 26.74 3.33 8.76 10.09 17.84 4.97 19.55 4.54 26.77 3.33 34.69 2.58 36.80 2.44 39.99 2.25‐ 45.31 2.00 53.72 1.70 55.60 1.65 61.29 1.51 10.0 WLC03‐03 8.51 10.39 17.60 5.04 26.69 3.34 8.87 9.97 17.63 5.03 26.77 3.33 8.45 10.46 17.69 5.01 19.47 4.56 26.59 3.35 34.35 2.61 37.15 2.42 39.73 2.27 41.76 2.16 45.34 2.00 53.64 1.71 55.26 1.66 61.25 1.51 10.0 WLC03‐04 8.51 10.38 17.77 4.99 26.81 3.33 8.85 9.98 17.51 5.06 26.71 3.33 8.39 10.53 17.43 5.08 19.55 4.54 26.72 3.33 34.38 2.61 37.25 2.41 39.80 2.26 41.73 2.16 45.41 2.00 53.57 1.71 55.00 1.67 61.22 1.51 10.0 WLC03‐05 8.35 10.59 17.84 4.97 26.65 3.34 8.69 10.17 17.57 5.04 26.57 3.35 8.42 10.49 17.78 4.98 19.64 4.52 26.63 3.34 34.48 2.60 37.07 2.42 39.75 2.27 41.69 2.16 45.32 2.00 53.48 1.71 55.35 1.66 61.34 1.51 10.0

Table 9: Chemical analyses of the clay concentrates. nd – not detected. CV2010‐01 CV2010‐02 CV2010‐04 CV2010‐05 CV2010‐06 CV2010‐07 WLC03‐01 WLC03‐02 WLC03‐03 WLC03‐04 WLC03‐05 WLT02D WLT02F WLT02I DP1 SHCa SBH‐1SynH

Al2O3 (%) 9.94 16.80 10.00 12.60 10.50 9.79 4.45 3.77 1.54 1.62 2.33 3.69 4.73 5.21 1.60 0.75 0.51 0.16 CaO (%) 0.86 0.97 1.41 0.61 1.08 1.10 1.35 1.13 0.30 0.40 0.11 1.79 1.32 1.26 1.92 1.89 1.92 0.02

Cr2O3 (%) 0.01 0.01 nd 0.01 0.01 0.01 nd nd nd nd nd nd nd nd nd nd nd nd

Fe2O3 (%) 7.55 6.38 6.93 8.07 8.47 6.82 1.59 0.97 1.40 1.04 1.91 1.47 2.09 2.14 0.81 0.24 0.21 nd

K2O (%) 3.74 4.20 3.51 5.93 4.53 3.77 1.27 1.85 7.29 7.22 7.33 0.80 2.33 2.72 0.13 0.12 0.12 nd MgO (%) 8.06 4.81 9.98 6.68 7.10 10.60 18.60 19.20 18.90 19.40 17.20 20.00 17.20 16.90 21.80 23.10 21.70 23.80 MnO (%) 0.09 0.09 0.09 0.13 0.12 0.14 0.02 0.01 0.05 0.05 0.03 0.01 nd 0.02 0.01 nd 0.02 nd

Na2O (%) 0.29 0.40 0.18 0.24 0.10 0.24 0.28 0.13 0.15 0.17 0.48 0.31 0.21 0.30 0.14 0.60 nd 2.36

P2O5 (%) 0.04 0.13 0.10 0.07 0.07 0.10 nd nd nd nd nd nd 0.01 nd nd nd 0.03 nd

SiO2 (%) 51.10 50.60 49.90 52.30 50.30 50.10 49.00 49.50 54.20 54.00 54.40 47.90 51.20 50.70 48.70 52.00 49.70 50.40

TiO2 (%) 0.34 0.38 0.44 0.54 0.53 0.41 0.46 0.12 0.49 0.43 0.56 0.22 0.30 0.24 0.23 0.03 0.04 0.02

Li2O (%) 1.07 0.25 0.72 0.77 0.93 0.70 0.90 1.28 2.54 2.58 2.67 0.84 1.23 1.10 1.19 1.23 1.46 0.79 SrO (%) 0.02 0.01 0.03 0.01 0.02 0.06 0.01 0.02 0.00 0.01 0.00 0.02 0.01 0.01 0.02 0.06 0.19 0.00

Rb2O (%) 0.06 0.04 0.04 0.08 0.06 0.06 0.03 0.04 0.06 0.11 0.10 0.02 0.04 0.05 0.00 0.00 0.00 0.00

Cs2O (%) 0.02 0.00 0.01 0.01 0.01 0.01 0.02 0.03 0.06 0.05 0.07 0.01 0.02 0.02 0.00 0.00 0.00 0.00 ‐ H2O (%) 9.30 6.60 9.20 5.80 8.90 8.20 9.70 8.70 4.60 3.80 4.00 10.60 8.60 7.90 11.20 10.10 14.10 12.00 + H2O (%) 5.80 6.80 6.50 5.80 6.00 6.60 6.60 8.20 4.10 4.40 3.50 6.00 6.30 6.20 8.80 6.90 7.00 8.60

CO2 (%) 0.18 0.26 0.62 0.22 0.22 0.44 3.37 3.30 3.63 2.82 2.64 0.73 0.51 0.77 0.84 0.84 2.05 0.48

SO2 (%) nd nd nd nd nd nd 0.32 0.32 0.12 0.14 0.56 0.28 0.26 0.28 0.26 0.30 nd 0.22 F (%) 1.46 0.185 0.75 0.741 1.03 0.538 3.36 4.44 6.48 6.52 6.52 3.59 4.08 4.28 3.18 4.29 2.81 0.014 Total 99.93 98.91 100.42 100.61 99.98 99.69 101.35 103.00 105.91 104.77 104.41 98.28 100.44 100.10 100.83 102.46 101.86 98.86 less O≡F 0.61 0.08 0.32 0.31 0.43 0.23 1.41 1.87 2.73 2.74 2.74 1.51 1.72 1.80 1.34 1.81 1.18 0.01 New total 99.32 98.83 100.10 100.30 99.55 99.47 99.93 101.13 103.18 102.02 101.67 96.77 98.73 98.30 99.49 100.65 100.68 98.85

LOI (%) 16.00 14.20 16.50 12.00 15.40 15.50 20.70 19.70 9.22 9.13 8.21 20.80 17.80 17.20 22.50 19.40 23.50 22.60 Total 100.03 99.38 100.28 100.48 99.83 99.73 100.96 100.63 100.07 100.13 99.74 100.24 101.11 100.63 101.15 102.21 101.03 100.38

CO2 (%) represents total carbon (carbonate and organic) as oxide

CV2010‐01 CV2010‐02 CV2010‐04 CV2010‐05 CV2010‐06 CV2010‐07 WLC03‐01 WLC03‐02 WLC03‐03 WLC03‐04 WLC03‐05 WLT02D WLT02F WLT02I DP1 SHCa SBH‐1SynH CRBNT_C (%) 0.02 0.02 0.07 0.04 0.02 0.04 0.06 0.02 0.01 0.01 0.01 0.09 0.02 0.03 0.15 0.14 0.02 0.11 OrgC (%) 0.03 0.05 0.1 0.02 0.04 0.08 0.86 0.88 0.98 0.76 0.71 0.11 0.12 0.18 0.08 0.09 0.54 0.02 TotC (%) 0.05 0.07 0.17 0.06 0.06 0.12 0.92 0.9 0.99 0.77 0.72 0.2 0.14 0.21 0.23 0.23 0.56 0.13 52

Table 10: Results from the cation exchange capacity analyses. NH3 results calculated from the calibration curves measured from the ammonia electrode.

sample weight volume reading NH3 conc. CEC calibration (mg) (mL) (mV) (mol/L) meq/100g curve used CV2010‐01 104 50 22.5 1.04E‐03 50.04 1,2 CV2010‐02 106 50 16.9 1.11E‐03 52.14 3,4 CV2010‐04 100 50 17.7 1.01E‐03 50.29 4 CV2010‐05 99 50 31.4 6.34E‐04 32.00 3 CV2010‐06 101 50 21.8 9.51E‐04 47.06 3 CV2010‐07 103 50 28.9 7.99E‐04 38.77 1,2 WLC03‐01 106 50 8.6 1.71E‐03 80.65 2,3 WLC03‐02 102 50 9.8 1.58E‐03 77.36 3 WLC03‐03 103 50 42.9 4.28E‐04 20.76 2 WLC03‐04 106 50 33.1 5.90E‐04 27.82 3 WLC03‐05 107 50 38.7 5.09E‐04 23.77 2 WLT02D 106 50 ‐1.6 2.34E‐03 110.51 4 WLT02F 103 50 11 1.55E‐03 75.09 2,3 WLT02I 102 50 9.7 1.51E‐03 73.84 3,4 DP1 105 50 7.7 2.01E‐03 95.94 1 SBH‐1 105 50 8.1 1.80E‐03 85.51 2 SHCa 105 50 13 1.47E‐03 69.87 2 SynH 105 50 42.8 4.69E‐04 22.34 1

The results indicate the smectite samples from McDermitt, Fish Lake Valley and Hector have the highest CEC, with values ranging between 70 and 110 meq/100g. The samples from Clayton Valley have smaller CEC values, ranging between 32 and 52 meq/100g.

The 3 illite samples from McDermitt have some of the lowest CEC, with values ranging between 21 and 28 meq/100g. Finally, the synthetic hectorite sample also has a low

CEC, with a value of 22 meq/100g.

The analytical results for composition of the wash solutions can be found in Appendix V

(Table V-5), with a summary provided in Table 11. The solutions NH4Cl and NH4- acetate matrices were too concentrated for analysis by ICP-MS and were diluted 100x by

54 the lab. This significantly increased the detection limit, and most of the elements were reported as below detection. Furthermore, a few samples had a gel-like consistency and could not be analyzed. The data is thus very incomplete, but some Li was recovered for some of the samples.

In order to compare with the clay chemistry, the results were converted from a mg/L concentration to a mg/kg concentration (Table 11). The data from the lab was first adjusted for the dilution and concentration. The corrected results (in mg/L) were then multiplied by the wash solution volume (in L) and divided by the initial sample weight

(in kg) to obtain the concentration in mg/kg. The elements Mg and Na were also converted to g/kg (equivalent to percent), for comparison purposes. Table 12 compares the results between the CEC wash solutions chemistry and the clay concentrates chemistry.

The results indicate that only a small proportion (<5%) of Li is found in the interlayer space. The synthetic sample appears to be an exception, with approximately 17% of the lithium found as an exchangeable cation. The results for Mg are similar, with a proportion of about 5% Mg found in the interlayer space, up to 10% in the synthetic sample. The trace elements Cs and Rb are also found in very small concentration in the interlayer (<25%). Finally, the elements Na, Ba and Sr are found in much higher proportions when compared to the concentrates chemistry (65-100%), suggesting they are primarily found in the interlayer site.

Layer Charge

The layer spacing of each sample for each individual alkylamine chain is shown in Table

13. The 17-C chain was not commercially available and was not used in this analysis.

Samples CV2010-05, WLC03-03, -04, -05 and SynH did not produce conclusive results and could not be interpreted. While illites and micas can have a high layer charge, they need a much longer reaction time to displace the potassium ions from the interlayer space

(Lagaly, 1994), so the results for the illite samples above show no shift in the 001 peak.

The synthetic sample SynH did not react properly with the alkylammonium ions, as the

001 peak shift does not show a regular transition with increasing chain length between

13.6 and 17.6 Å, so the data cannot be interpreted.

The layer charge is calculated as (Lagaly, 1994):

(5) 5.6714

Where a and b are unit cell parameters, n(I) is the number of carbon atoms in a chain,

and the layer charge (n) has units of eq/O20(OH)4. Given that all samples have low

aluminum and high magnesium and lithium, the unit cell parameters of hectorite (a = 5.25

Å, b = 9.18 Å (Brindley, 1980)) were used for all calculations. The upper limit of the

layer charge is achieved when the alkylammonium ions are tightly packed in a monolayer

and the layer spacing is between 13.4-13.6 Å. In this case, the value of n(I) is taken as

the longest chain length that yields a d-spacing equal or less than 13.6 Å. The lower limit

of the layer charge is achieved when the alkylammonium ions form a bilayer and the

layer spacing is 17.6 Å. In this case, the value of n(I) is taken as the shortest chain length

56 that yields a d-spacing equal or greater than 17.7 Å (Mermut & Lagaly, 2001). The respective values for each sample are highlighted in Table 13.

The simple mean is calculated as an average between the upper and lower limits of the layer charge. The distributive mean takes into consideration the non-uniform charge distribution characteristic of most 2:1 clay minerals (Lagaly, 1994) and is calculated from the variations in interlayer cation densities in the transition range from 13.6 Å to 17.7 Å.

Each alkylammonium ion of a given chain length has a specific cation density, and the d- spacing in the transition range depends on the fraction of alkylammonium ions that take a bilayer arrangement. A relationship between d-spacing and fraction of alkylammonium ions in a bilayer arrangement was developed by Lagaly (1994) and is shown in Appendix

VI (Table VI-1). The proportion of bilayers (Xn) can be determined from the d-spacing

and interpolated from the data in Table VI-1, and the cation density can be calculated by

multiplying the proportion difference (Xi = (Xn+Xn+1)/2) and average cation density (I

= (n+n+1)/2) between the results of two alkylammonium chain length analyses. The final mean is the sum of the distributive mean from each interval (∑ ∗∆. The distributive mean calculations for all samples can be seen in Appendix VI.

Table 11: Results for the composition of the CEC wash solutions. “-“ represents values below detection limit. as received correction for initial Sample Ba Cs Li Mg Na Rb Sr concentration/ Ba Cs Li Mg Na Rb Sr volume Ba Cs Li Mg Na Rb Sr initial weight Ba Cs Li Mg Na Rb Sr mg/L mg/L mg/L mg/L mg/L mg/L mg/L dilution mg/L mg/L mg/L mg/L mg/L mg/L mg/L L mg mg mg mg mg mg mg kg mg/kg mg/kg mg/kg mg/kg g/kg mg/kg g/kg mg/kg mg/kg CV2010‐01 ‐ 0.016 ‐‐‐0.019 ‐ x 100 / 10.94 = ‐ 0.14 ‐‐‐0.17 ‐ x 0.180 = ‐ 0.026 ‐‐‐0.031 ‐ /5.09E‐04 = ‐ 51 ‐ ‐‐‐‐62 ‐ CV2010‐02 ‐‐‐‐‐0.009 ‐ x 100 / 11.67 = ‐‐‐‐‐0.08 ‐ x 0.185 = ‐‐‐‐‐0.014 ‐ /5.04E‐04 = ‐ ‐ ‐ ‐‐‐‐29 ‐ CV2010‐04 ‐ 0.003 0.019 ‐‐0.007 0.063 x 100 / 11.82 = ‐ 0.02 0.16 ‐‐0.06 0.53 x 0.186 = ‐ 0.004 0.029 ‐‐0.011 0.099 / 5.27E‐04 = ‐ 756‐‐‐‐22 188 CV2010‐05 ‐ 0.004 0.043 ‐‐0.011 ‐ x 100 / 11.12 = ‐ 0.03 0.39 ‐‐0.10 ‐ x 0.184 = ‐ 0.006 0.071 ‐‐0.019 ‐ /5.23E‐04 = ‐ 12 135 ‐‐‐‐36 ‐ CV2010‐06 ‐ 0.002 ‐‐‐0.009 ‐ x 100 / 10.41 = ‐ 0.02 ‐‐‐0.08 ‐ x 0.188 = ‐ 0.004 ‐‐‐0.016 ‐ /5.30E‐04 = ‐ 8 ‐ ‐‐‐‐29 ‐ CV2010‐07 ‐ 0.003 0.019 ‐‐0.013 0.143 x 100 / 11.33 = ‐ 0.02 0.17 ‐‐0.11 1.26 x 0.188 = ‐ 0.004 0.031 ‐‐0.021 0.238 / 5.12E‐04 = ‐ 961‐‐‐‐41 464 WLC03‐02 ‐ 0.018 ‐ 1.900 ‐ 0.006 ‐ x 100 / 11.66 = ‐ 0.15 ‐ 16.29 ‐ 0.05 ‐ x 0.191 = ‐ 0.029 ‐ 3.109 ‐ 0.010 ‐ /5.42E‐04 = ‐ 54 ‐ 5736 0.57 ‐‐19 ‐ WLC03‐03 ‐ 0.008 0.016 ‐‐0.007 ‐ x 100 / 10.49 = ‐ 0.07 0.15 ‐‐0.06 ‐ x 0.183 = ‐ 0.013 0.028 ‐‐0.011 ‐ /5.00E‐04 = ‐ 27 55 ‐‐‐‐23 ‐ WLC03‐04 ‐ 0.009 0.014 ‐‐0.007 ‐ x 100 / 11.25 = ‐ 0.08 0.12 ‐‐0.06 ‐ x 0.182 = ‐ 0.014 0.022 ‐‐0.011 ‐ /5.22E‐04 = ‐ 28 42 ‐‐‐‐20 ‐ WLT02F ‐ 0.003 ‐‐‐0.004 ‐ x 100 / 10.82 = ‐ 0.02 ‐‐‐0.03 ‐ x 0.192 = ‐ 0.005 ‐‐‐0.006 ‐ /5.38E‐04 = ‐ 9 ‐ ‐‐‐‐12 ‐ SHCa ‐‐0.019 1.200 1.300 0.001 0.186 x 100 / 11.73 = ‐‐0.16 10.23 11.09 0.01 1.59 x 0.185 = ‐‐0.030 1.891 2.048 0.002 0.293 / 5.32E‐04 = ‐‐56 3554 0.36 3850 0.38 4 551 SynH ‐‐0.208 4.900 5.700 ‐‐x 100 / 11.74 = ‐‐1.77 41.72 48.53 ‐‐x 0.184 = ‐‐0.326 7.672 8.925 ‐‐/5.22E‐04 = ‐‐624 14698 1.47 17098 1.71 ‐‐ DP1 0.055 ‐‐2.100 ‐ 0.002 ‐ x 100 / 12.65 = 0.44 ‐‐16.60 ‐ 0.02 ‐ x 0.196 = 0.086 ‐‐3.258 ‐ 0.003 ‐ /5.17E‐04 = 166 ‐‐6301 0.63 ‐‐6 ‐

Table 12: Comparison of the cation concentrations recovered from the CEC solution with the clay chemistry from Table V-3. Ba (mg/kg) Cs (mg/kg) Li (mg/kg) Mg (g/kg) Na (g/kg) Rb (mg/kg) Sr (mg/kg) Sample CEC chem CEC chem CEC chem CEC chem CEC chem CEC chem CEC chem CV2010‐01 ‐‐51 223 ‐‐‐‐‐‐62 573 ‐‐ CV2010‐02 ‐‐‐‐‐‐‐‐‐‐29 322 ‐‐ CV2010‐04 ‐‐785563340‐‐‐‐22 388 188 279 CV2010‐05 ‐‐12 106 135 3570 ‐‐‐‐36 732 ‐‐ CV2010‐06 ‐‐8106‐‐‐‐‐‐29 553 ‐‐ CV2010‐07 ‐‐9 106 61 3260 ‐‐‐‐41 545 464 533 WLC03‐02 ‐‐54 293 ‐‐0.57 12.1 ‐‐19 324 ‐‐ WLC03‐03 ‐‐27 548 55 11800 ‐‐‐‐23 544 ‐‐ WLC03‐04 ‐‐28 495 42 12000 ‐‐‐‐20 1030 ‐‐ WLT02F ‐‐9180‐‐‐‐‐‐12 389 ‐‐ SHCa ‐‐‐‐56 5710 0.36 14.4 0.38 0.50 4 24 551 519 SynH ‐‐‐‐624 3660 1.47 15 1.71 1.95 ‐‐‐‐ DP1 166 161 ‐‐‐‐0.63 13.7 ‐‐626‐‐ 57

Table 13: Results from the layer charge analysis, including d-spacing (Å) for each alkylammonium ion and calculated value of the layer charge. Values in boxes represent the spacing characteristic of tightly packed monolayers (orange) and bilayers (green), and the corresponding chain length for which the upper and lower limits of the layer charge were calculated. See Appendix VI for details on the calculations of the distributive mean. CV2010‐01 CV2010‐02 CV2010‐04 CV2010‐05 CV2010‐06 CV2010‐07 WLC03‐01 WLC03‐02 WLC03‐03 WLC03‐04 WLC03‐05 WLT02D WLT02F WLT02I DP1 SHCa SBH‐1SynH C6 13.0 13.0 13.4 10.2 12.1 13.4 13.6 13.4 10.4 10.6 10.6 13.4 13.3 13.3 13.5 13.5 13.4 13.8 C7 13.5 13.2 13.5 10.3 13.0 13.6 13.4 13.5 10.4 10.6 10.5 13.6 13.4 13.4 13.6 13.5 13.6 14.4 C8 13.5 13.4 13.6 10.2 13.4 13.4 14.0 13.9 10.4 10.5 10.4 13.9 13.7 13.7 13.7 13.8 13.7 14.3 C9 13.6 14.0 13.8 10.2 13.5 13.6 14.9 15.4 10.2 10.4 10.3 15.2 14.9 15.2 14.8 13.5 13.8 14.2 C10 14.515.613.810.314.813.615.815.810.110.310.216.015.915.915.413.614.614.8 C11 14.815.613.810.115.614.016.116.410.110.110.116.416.516.415.913.614.913.9 C12 16.116.614.310.116.714.617.317.910.110.010.017.417.317.317.414.515.914.4 C13 16.418.115.610.117.315.617.517.810.110.010.117.417.417.417.615.215.915.2 C14 17.517.716.810.117.316.317.617.810.010.010.017.817.717.817.615.716.815.0 C15 17.818.317.510.117.717.617.817.710.110.110.118.017.818.117.915.917.314.3 C16 18.218.417.810.118.617.918.118.510.210.210.118.818.418.418.016.917.614.3 C18 19.220.018.310.120.418.519.720.010.210.210.220.319.420.018.917.618.115.9

layer charge (eq/O20(OH,F)4)) upper limit 0.741 0.812 0.812 0.741 0.682 0.898 0.898 0.898 0.898 0.898 0.898 0.631 0.898 lower limit 0.487 0.549 0.460 0.487 0.460 0.487 0.587 0.516 0.516 0.516 0.487 0.415 0.460 simple mean 0.614 0.681 0.636 0.614 0.571 0.692 0.743 0.707 0.707 0.707 0.692 0.523 0.679 distributive mean 0.597 0.644 0.553 0.617 0.549 0.676 0.693 0.682 0.672 0.674 0.665 0.485 0.588 58

Discussion

Clays

Sample compositions

Clay minerals can often have layers of a second component in their structure. These

clays are called mixed-layered, or interstratified (Moore & Reynolds, 1989). The layers

can be stacked in a regular or a random sequence. A clay mineral having a regular

stratification of illite (I) and smectite (S) would have the layer arrangement ISISISIS, or a

similarly ordered stratification. Perfectly regular stratification will produce a 001

reflection at a greater spacing than expected for smectite, which is equal to the sum of the

thickness of each component (Wilson, 1987). This will yield a rational series of higher- order reflections in which the 00l reflections will be evenly spaced. For example, a regular 50:50 mixture of illite and smectite would have a 001 reflection close to 26 Å

(3.4º 2), comprised of the illite d-spacing at 10 Å and the smectite d-spacing at 16 Å.

A clay mineral having a random stratification of illite and smectite would show no order

in the layering of the two components. These minerals produce an XRD pattern in which

the basal spacing is intermediate between illite and smectite (Wilson, 1987). They are

characterized by having irrational higher-order reflections, where the 00l reflections are

not evenly spaced.

Interstratified illite/smectite clay minerals typically show an XRD pattern most similar to smectite, though the exact pattern depends on the degree of randomness and the proportions of illite and smectite. The proportions of illite and smectite can be determined graphically by comparing the peak location of the reflections at 15.4º to 17.7º

2 (5.75 Å to 5.00 Å; 002 reflection for illite, 003 for smectite) with the ones at 26º to 27º

2 (3.42 Å to 3.30 Å; 003 reflection for for illite, 005 for smectite) measured from the glycolated samples (Figure 12) (Środoń, 1980). For a pure illite, the 002 peak is located at 17.7º 2(5.00 Å) and the 003 peak at 26.7º 2(3.33 Å), giving a 10 Å spacing characteristic of illite. For a pure smectite treated with ethylene glycol, the 003 peak is located at 15.7º 2(5.64 Å) and the 005 peak at 26.3º 2 (3.38 Å), giving a spacing of

16.9 Å (Moore & Reynolds, 1989). A randomly stratified clay will thus have a peak position intermediate between 15.7º 2 and 17.7º 2 (5.64 Å to 5.00 Å) for the 002/003 peak and 26.3º 2 and 26.7º 2 (3.38 Å to 3.33 Å) for the 003/005 peak, the exact location depending on the proportion of illite and smectite layers.

These reflections, however, can be strongly affected by the ethylene glycol-smectite layer thickness, the manner of interstratification and the domain size (Środoń, 1980). Domain size refers to the volume of a structure that scatters X-rays coherently. Smaller domain sizes produce reflections that are distinctly broader with a lower intensity than larger domain sizes. Smaller domain sizes can also shift peak positions from their normal place, especially in the region between 7º and 10º 2 (12.6 Å and 8.8 Å; Reynolds & Hower,

1970). The positions of the peaks in the regions at 15.4º to 17.7º 2 (5.75 Å to 5.00 Å)

61 and at 26º to 27º 2 (3.42 Å to 3.30 Å) are only slightly affected by domain size, but their position is greatly affected by the thickness of the ethylene glycol complex in the interlayer space (Środoń, 1980). The ethylene glycol complex can vary in thickness from

16.86 Å to 17.1 Å (5.24º to 5.16º 2), which can account for an error up to 30% in the estimation of the illite/smectite component ratio, especially when the concentration of smectite is greater than that of illite.

Since none of the samples have an air-dried 001 reflection greater than 16 Å (5.52º 2;

Table 7), it is assumed that any interstratified clay, if present, will have a random interstratification. The XRD profiles from most of the Clayton Valley glycolated samples showed two distinct peaks in the 15.7º to 17.7º 2 (5.64 Å to 5.00 Å) region

(Table 7), suggesting two different clay minerals may be present. Both peaks are plotted in Figure 12, with the peak at the highest angle 2 in blue and the one at the lowest angle shown in red. For most samples, the peak at the lower 2 angle is not very distinct, so its value was determined by subtracting the air-dried profile from the glycolated profile

(Appendix II). This is appropriate because subtraction will remove the illite peak from the scan, as it does not move upon glycolation, and enhance the weak smectite peak.

With the exception of CV2010-05, results from Figure 12 indicate the Clayton Valley samples contain 2 minerals: an illite clay represented by the blue points, and a smectite- rich, interstratified clay represented by the red points. The smectite rich component of samples CV2010-04, and -07 is considered to be pure smectite, because it plots at ≥80%

62 smectite. The other samples of CV2010-01, -02, and -06 appear to have an interstratified smectite/illite component of 50 – 65% smectite. The exact proportion of each component was not determined for the Clayton Valley samples. The samples from Fish Lake Valley,

Hector and McDermitt plot at ≥80% smectite. Samples that plot in this area of the diagram are assumed to be pure smectite, because of the 30% error mentioned above.

This assumption is supported by the rational series of the higher-order reflections on all samples that plot in this range, and by the lack of illite d-spacings, as observed on their cleaned XRD patterns (Appendix II). Samples SBH-1, SHCa, SynH, WLCO3-01, DP1,

WLT02D, WLT02F, and WLCO3-02 are thus classified as pure smectite. Sample

WLT02I is an interstratified clay with a smectite component of 50%.

Chemical Formulas

Since the unit cell parameters were not calculated for any of the samples, the structural formulas were calculated on the assumption that the anionic charge is that of an ideal anionic composition of O20(OH,F)4, with a charge of -44 (Newman & Brown, 1987).

This anionic composition is valid for both illites and smectites. Minor amounts of

impurities were identified from the XRD patterns and the chemical analysis. When the

impurities could be quantified with certainty, they were removed from the chemical

analysis. All samples were thus corrected for their carbon and sulfur contents. The mass

of calcite or dolomite was deducted from the chemistry of the samples based upon the

mass of carbonate carbon. If neither calcite nor dolomite could be identified from the

cleaned XRD pattern, the bulk pattern was examined to identify the dominant carbonate

mineral phase present.

Figure 12: Graph for the determination of the smectite:illite ratio. After Środoń (1980).

An example calculation is given for sample SHCa. Remaining calcite can be identified from the cleaned XRD pattern on Figure II-62. The carbon analysis from Table 9 identified the concentration of carbonate carbon to be 0.14%. Since the ideal composition of calcite is CaCO3, we know that Ca and CO3 will be present in a 1:1 ratio.

The concentration of carbon was thus converted to CO3 by dividing the concentration of

carbonate carbon by its proportion in CO3:

0.14% 0.70% 0.20/

We then know the concentration of Ca in calcite must be 0.70%. Following the same

procedure as above, we can calculate the weight of Ca as CaO to deduct from the

chemical analysis:

0.70% 0.98% 0.71/

Since carbon is given in terms of CO2 in the oxide total, the concentration of carbonate

carbon can be converted to CO2:

0.14% 0.51% 0.27/

The results give a total concentration for calcite of 1.49%. The remaining carbon present

in the analysis represents organic carbon and is simply deducted from the analysis. A

similar procedure was followed when dolomite was identified. When sulfur is present in

the analysis, it is assumed to be under the form of pyrite (FeS2) for all samples except

SHCa (Hector) SynH (synthetic hectorite). No sulfur-containing mineral species were

identified for these samples and sulfur is simply considered an impurity and deducted as

is. Other impurities such as Cr2O3, P2O5, SrO, Rb2O, Cs2O, MnO and TiO2 were deducted from the analysis if their concentration was less than 0.2%.

Sample WLC03-05 was found to have albite (NaAlSi3O8) as an impurity (Figure II-43).

WLC03-05 is similar structurally to WLC03-03 and -04 and its chemistry shows a

slightly greater concentration in Na2O and Al2O3 than both WLC03-03 and -04 (Table 9).

The amount of albite present in the sample was estimated from the Na2O concentration

above the average value calculated from samples WLC03-03 and -04. A procedure

similar to the one described for calcite was used to calculate the concentration of albite in

the sample (Table VII-11). The amount of elemental Na was determined, which allowed

the calculation of elemental Al and Si associated in the sample, given the ratio Na:Al:Si

of 1:1:3. All were then converted back to oxides and deducted from the chemical

analysis. This method estimated that 2.92% of albite was present as impurities in the

samples.

Overall, no more than 5% of impurities were present in the samples, except for WLC03-

05, which had a total of 6.17% impurities. This is considered satisfactory for the

calculation of a structural formula (Bain & Smith, 1994). The corrections for the

chemical analyses can be observed in Appendix VII.

Following corrections, the chemistry was normalized to a total of 100%, and the values

obtained after normalization were used to calculate the structural formula (Newman &

Brown, 1987). The calculations can be seen in Appendix VII, and a summary of the data is provided in Tables 14 and 15.

The normalized weight oxides are converted to equivalent cations by dividing each by their molecular weight, then multiplied by the number of cations present in the oxide, giving the fraction of cations in the oxide. The fraction is then multiplied by the charge of the cation to obtain the equivalent percentage. For example, Al is present under the oxide form Al2O3, having a molecular weight of 101.96 g/mol, 2 cations per oxide and a

charge of +3. After the equivalent percentage is calculated for each cation, their sum is used to calculated the proportion of cations per unit formula, assuming a formula basis of

O20(OH, F)4 with a total charge of 44. The fraction of cations calculated previously is

then multiplied by the proportionality factor to obtain the number of cations per unit cell,

which is used in the structural formula. A similar procedure is used for the anions OH

and F, with the exception that the proportionality factor calculated for the cations is used

to calculate the number of anions per unit cell.

In all cases, the structural formula was calculated using the following assumptions:

1. All Si goes in the tetrahedral site

2. If space is still available in the tetrahedral site, it will be filled with Al3+ first and

Fe3+ second, up to a maximum of 8 cations

3. The remaining Al3+ and Fe3+ goes in the octahedral site

4. All Fe is assumed to be Fe3+

5. The remainder of the octahedral site is filled with Mg2+, up to 4 cations for

dioctahedral samples and 6 cations for trioctahedral samples

6. If the mineral is trioctahedral, Li+ is assumed to be structural and goes in the

octahedral site; for dioctahedral minerals, Li+ is assumed to be found in the

interlayer space

7. If space is still available in the octahedral site, it is filled with Ti4+, when present

8. All Ca2+, Na+ and K+ are placed in the interlayer space. Any element remaining

(Mg2+, Ti4+) is also placed in the interlayer site

9. All F- was assumed to substitute for OH-, up to a maximum of 4 anions.

The calculations were made assuming an anionic composition of O20(OH,F)4, suggesting the structural water content is unknown, which isn’t necessarily true for our analysis,

+ since essential water content (H2O ) was analyzed (Table 9). According to Newman and

Brown (1987), the formula can be calculated assuming a total of 24 anions when the structural water content is known. This method was evaluated in this work and it resulted in a negative anionic charge smaller than 44, due to an excess of structural water, giving an oxygen content smaller than 20 ions per unit cell. By assuming an anionic composition of O20(OH,F)4, we can fix the anionic charge to -44, which will accurately balance the cationic charge to +44, and the excess water can be assigned to the interlayer space.

All analyses showed an excess of structural water content (see Appendix VII). Structural

+ water (H2O in Table 9) is estimated by the weight difference obtained from drying the sample at 105ºC for 1 hour, removing hygroscopic water, and from heating the sample to

950ºC. This method is not necessarily satisfactory for clays, since many types of clay are

still highly hydrated beyond 105ºC (Newman & Brown, 1987). Since structural water is calculated by a weight difference, any hygroscopic water remaining on the sample after heating to 105ºC would be considered structural, effectively making the amount of structural water greater than it actually is. For this reason, it is assumed that excess structural water is in fact hygroscopic and the structural site is first filled with F, then

- with OH. While the results for H2O were used to calculate the normalized chemistry, they were not used in the calculations of the formula.

The assumption that all Fe is present in the form of Fe3+ may not be true for all samples,

since some of the samples are green and pyrite was found associated with the illite

samples from McDermitt. This assumption was made because the Fe speciation was not

determined in the chemical analysis. An attempt was made on some samples to calculate

the formula using Fe2+. The results showed that using Fe2+ instead of Fe3+ didn’t cause a

big change on the layer charge, and the Fe occupies the octahedral site in both cases.

Since speciation was not determined, the assumption that all Fe is present in the form of

Fe3+ is acceptable.

From the calculations of the structural formulas, all samples are trioctahedral, except for

the Clayton Valley samples, which are dioctahedral (Tables 14 and 15). The Clayton

Valley samples all have Al filling the octahedral site, taking up to 2 of the 6 available sites. Furthermore, none have enough Mg to fill all of the 6 available octahedral sites.

Therefore, only 4 of the 6 sites available are filled for the Clayton Valley samples, making them dioctahedral. All other samples have Al in less than 1 site and Mg taking at least 4 sites, making them trioctahedral. This includes all smectite samples and the 3 illite samples from McDermitt (WLC03-03, -04 and -05). None of the samples from

McDermitt, except for DP1, have enough cations to fill 6 octahedral sites, leaving a small vacancy in the structure (Table 14).

The distinction between dioctahedral and trioctahedral structures is not as easily determined from XRD data. Typically, minerals having a dioctahedral form will have a

060 reflection between 1.49 Å and 1.52 Å (62.05º and 60.70º 2), while trioctahedral samples have a 060 reflection between 1.52 Å and 1.53 Å (60.70º and 60.25º 2; Środoń,

2006). The data summarized in Table 7 shows most of the samples have a 060 reflection in the range between 1.50 Å and 1.52 Å (61.56º and 60.91º 2), except for the synthetic sample with a 1.53 Å (60.61º 2) reflection (Tables 7 and 8). The 060 peak is a reflection caused by the b spacing of the mineral structure (Brown & Brindley, 1980) and is affected by the composition of the octahedral sheet, the amount of Al in tetrahedral coordination and the degree of tetrahedral tilt (Moore & Reynolds, 1989). Furthermore,

Robert et al. (1993) have shown that a greater substitution of F for OH in the structure of micas can have the effect of reducing the dimension of the b parameter. Their experiment on a synthetic Mg-rich trioctahedral mica showed the b parameter can be reduced to a minimum dimension of 9.06 Å, equivalent to a 060 reflection of 1.51 Å

70 around 61.3º 2 (9.06 Å ÷ 6 = 1.51 Å). Figure 13 shows a similar relationship for the trioctahedral samples analyzed in this study.

Figure 13: Relationship between the degree of F substitution for OH with respect to the 060 reflection for all trioctahedral samples.

Charge balance

A layer charge was calculated for the tetrahedral layer and the octahedral layer based on

the cation distribution in the structural formulas. All samples have a small negative

charge on the tetrahedral layer, caused by the substitution of Al3+ for Si4+, and a relatively larger negative charge on the octahedral layer (Table 14). In all cases, the sum of the layer charge calculated from the structural formula is balanced by the calculated interlayer charge, within a range of ±0.04 eq/O20(OH,F)4.

The layer charge calculated with the alkylammonium method can be compared to the

charge of the structural formula only to a certain extent. The alkylammonium method

71 was only effective for the true smectite samples, as illites and micas don’t exchange their interlayer cations as easily as smectites do. Figure 14 compares the layer charge calculated with both methods for all smectite samples, which includes the type-1

McDermitt samples and the samples from Hector and Fish Lake Valley. The relationship is close to 1:1, though the formula method seems to slightly overestimate the charge, which is consistent with the results from Laird et al (1989). Given the positive relationship between the two methods, the layer charge calculated with the formula method will be used here, as it provides information for all samples.

Figure 14: Comparison of the layer charge calculated from the structural formula and the layer charge calculated analytically with the alkylammonium method.

Table 14: Summary of the normalized chemistry and structural formulas calculated for all samples. Calculation details are found in Appendix VII. CV2010‐01 CV2010‐02 CV2010‐04 CV2010‐05 CV2010‐06 CV2010‐07 WLC03‐01 WLC03‐02 WLC03‐03 WLC03‐04 WLC03‐05 WLT02D WLT02F WLT02I DP1 SHCa SBH‐1SynH

Al2O3 (%) 10.07 17.12 10.13 12.66 10.62 9.95 4.66 3.89 1.55 1.64 1.97 3.89 4.85 5.38 1.65 0.76 0.52 0.16 CaO (%) 0.73 0.85 0.93 0.33 0.95 0.83 1.19 1.09 0.23 0.33 0.04 1.56 1.28 1.19 1.45 0.93 1.81 0.02

Fe2O3 (%) 7.65 6.50 7.02 8.11 8.56 6.93 1.43 0.76 1.32 0.95 1.58 1.34 1.95 2.00 0.64 0.24 0.21 ‐

K2O (%) 3.79 4.28 3.56 5.96 4.58 3.83 1.33 1.91 7.36 7.32 7.68 0.84 2.39 2.81 0.13 0.12 0.12 ‐ MgO (%) 8.16 4.90 10.11 6.71 7.18 10.78 19.22 19.79 19.07 19.66 18.01 20.70 17.55 17.45 21.88 23.47 22.10 24.25

Na2O (%) 0.29 0.41 0.18 0.24 0.10 0.24 0.29 0.13 0.15 0.17 0.17 0.33 0.22 0.31 0.14 0.61 ‐ 2.40

SiO2 (%) 51.74 51.55 50.55 52.57 50.86 50.93 51.33 51.03 54.69 54.73 55.37 50.52 52.50 52.35 50.31 52.83 50.61 51.36

Li2O (%) 1.08 0.25 0.73 0.77 0.94 0.71 0.94 1.32 2.56 2.62 2.80 0.89 1.26 1.14 1.23 1.25 1.48 0.80

TiO2 (%) 0.34 0.39 0.45 0.54 0.54 0.42 0.48 ‐ 0.49 0.44 0.59 0.23 0.31 0.25 ‐‐‐‐ ‐ H2O (%) 9.42 6.72 9.32 5.83 9.00 8.34 10.16 8.97 4.64 3.85 4.19 11.18 8.82 8.16 11.57 10.26 14.36 12.23 + H2O (%) 5.87 6.93 6.58 5.83 6.07 6.71 6.91 8.45 4.14 4.46 3.66 6.33 6.46 6.40 9.09 7.01 7.13 8.76 F (%) 1.48 0.19 0.76 0.74 1.04 0.55 3.52 4.58 6.54 6.61 6.83 3.79 4.18 4.42 3.29 4.36 2.86 0.01 Total 100.62 100.08 100.32 100.31 100.44 100.23 101.48 101.93 102.75 102.77 102.87 101.60 101.76 101.86 101.39 101.83 101.20 100.00

less O≡F 0.62 0.08 0.32 0.31 0.44 0.23 1.48 1.93 2.75 2.77 2.87 1.60 1.76 1.86 1.39 1.83 1.20 0.00 Total corrected 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00

Number of cations on the basis O20(OH,F)4 Si 7.68 7.40 7.54 7.54 7.58 7.52 7.72 7.77 7.86 7.83 7.89 7.67 7.80 7.75 7.84 7.94 7.94 7.89 Al 0.32 0.60 0.46 0.46 0.42 0.48 0.28 0.23 0.14 0.17 0.11 0.33 0.20 0.25 0.16 0.06 0.06 0.03  tet. 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 7.92

Al 1.44 2.29 1.32 1.68 1.45 1.25 0.55 0.47 0.12 0.11 0.22 0.37 0.65 0.69 0.14 0.07 0.04 Mg 1.81 1.05 1.89 1.44 1.60 1.98 4.31 4.49 4.09 4.19 3.82 4.68 3.89 3.85 5.08 5.26 5.16 5.56 Li 0.57 0.81 1.48 1.50 1.60 0.54 0.75 0.68 0.77 0.75 0.93 0.49 Fe 0.85 0.70 0.79 0.88 0.96 0.77 0.16 0.09 0.14 0.10 0.17 0.15 0.22 0.22 0.08 0.03 0.03 Ti 0.05 0.05 0.05 0.06 0.03 0.03 0.03  oct. 4.10 4.04 4.00 4.00 4.01 4.00 5.64 5.86 5.88 5.95 5.87 5.77 5.54 5.47 6.07 6.11 6.16 6.05

Ca 0.12 0.13 0.15 0.05 0.15 0.13 0.19 0.18 0.04 0.05 0.01 0.25 0.20 0.19 0.24 0.15 0.30 Mg 0.36 0.39 Li 0.64 0.14 0.44 0.45 0.56 0.42 Na 0.08 0.18 0.05 0.07 0.03 0.07 0.09 0.04 0.04 0.05 0.05 0.10 0.06 0.09 0.04 0.18 0.72 K 0.72 0.78 0.68 1.09 0.87 0.72 0.26 0.37 1.35 1.33 1.39 0.16 0.45 0.53 0.03 0.02 0.02 Ti 0.04 0.04 0.05 0.06 0.06 0.05  interl. 1.60 1.27 1.73 1.72 1.67 1.78 0.54 0.59 1.43 1.43 1.45 0.51 0.71 0.81 0.31 0.35 0.32 0.72

F 0.69 0.09 0.36 0.34 0.49 0.26 1.67 2.20 2.97 2.99 3.08 1.82 1.97 2.07 1.62 2.07 1.42 0.01 OH 3.31 3.91 3.64 3.66 3.51 3.74 2.33 1.80 1.03 1.01 0.92 2.18 2.03 1.93 2.83 1.93 2.58 3.99

eq/O20(OH,F)4 Tetrahedral charge ‐0.32 ‐0.60 ‐0.46 ‐0.46 ‐0.42 ‐0.48 ‐0.28 ‐0.23 ‐0.14 ‐0.17 ‐0.11 ‐0.33 ‐0.20 ‐0.25 ‐0.16 ‐0.06 ‐0.06 ‐0.35 Octahedral charge ‐1.51 ‐0.93 ‐1.89 ‐1.44 ‐1.57 ‐1.98 ‐0.48 ‐0.53 ‐1.36 ‐1.29 ‐1.35 ‐0.42 ‐0.74 ‐0.77 ‐0.41 ‐0.43 ‐0.54 ‐0.39 Layer charge ‐1.83 ‐1.53 ‐2.35 ‐1.90 ‐1.99 ‐2.46 ‐0.76 ‐0.76 ‐1.50 ‐1.46 ‐1.46 ‐0.75 ‐0.94 ‐1.02 ‐0.57 ‐0.49 ‐0.60 ‐0.74 72 Interlayer charge 1.84 1.52 2.39 1.95 2.00 2.45 0.73 0.77 1.47 1.48 1.46 0.76 0.91 1.00 0.55 0.50 0.62 0.72

Table 15: Structural formulas for all samples Sample Structural formula Clay type Structural type

CV2010-01 K0.72Na0.08Ca0.12Li0.64Ti0.04(Al1.44Mg1.81Fe0.85)(Si7.68Al0.32)O20(OH3.31F0.69)∙2.5H2O illite/smectite dioctahedral

CV2010-02 K0.78Na0.18Ca0.13Li0.44Ti0.04(Al2.29Mg1.05Fe0.70)(Si7.40Al0.60)O20(OH3.91F0.09)∙2.7H2O illite/smectite dioctahedral

CV2010-04 K0.68Na0.05Ca0.15Mg0.36Li0.44Ti0.05(Al1.32Mg1.89Fe0.79)(Si7.54Al0.46)O20(OH3.64F0.36)∙2.9H2O illite/smectite dioctahedral

CV2010-05 K1.09Na0.07Ca0.05Li0.45Ti0.06(Al1.68Mg1.44Fe0.88)(Si7.54Al0.46)O20(OH3.66F0.34)∙1.9H2O illite dioctahedral

CV2010-06 K0.87Na0.03Ca0.15Li0.56Ti0.06(Al1.45Mg1.60Fe0.96)(Si7.58Al0.42)O20(OH3.51F0.49)∙2.5H2O illite/smectite dioctahedral

CV2010-07 K0.72Na0.07Ca0.13Li0.42Ti0.05(Al1.25Mg1.98Fe0.77)(Si7.52Al0.48)O20(OH3.74F0.26)∙2.9H2O illite/smectite dioctahedral

WLC03-01 K0.26Na0.09Ca0.19(Al0.55Mg4.31Li0.57Fe0.16Ti0.05)(Si7.72Al0.28)O20(OH2.33F1.67)∙4.6H2O smectite trioctahedral

WLC03-02 K0.37Na0.04Ca0.18(Al0.47Mg4.49Li0.81Fe0.09)(Si7.77Al0.23)O20(OH1.80F2.20)∙6.8H2O smectite trioctahedral

WLC03-03 K1.35Na0.04Ca0.04(Al0.12Mg4.09Li1.48Fe0.14Ti0.05)(Si7.86Al0.14)O20(OH1.03F2.97)∙2.9H2O illite trioctahedral

WLC03-04 K1.33Na0.05Ca0.05(Al0.11Mg4.19Li1.50Fe0.10Ti0.05)(Si7.83Al0.17)O20(OH1.01F2.99)∙3.2H2O illite trioctahedral

WLC03-05 K1.39Na0.05Ca0.01(Al0.22Mg3.82Li1.60Fe0.17Ti0.06)(Si7.89Al0.11)O20(OH0.92F3.08)∙2.6H2O illite trioctahedral

WLT02-D K0.16Na0.10Ca0.25(Al0.37Mg4.68Li0.54Fe0.15Ti0.03)(Si7.67Al0.33)O20(OH2.18F1.82)∙4.2H2O smectite trioctahedral

WLT02-F K0.45Na0.06Ca0.20(Al0.65Mg3.89Li0.75Fe0.22Ti0.03)(Si7.80Al0.20)O20(OH2.03F1.97)∙4.4H2O smectite trioctahedral

WLT02-I K0.53Na0.09Ca0.19(Al0.69Mg3.85Li0.68Fe0.22Ti0.03)(Si7.75Al0.25)O20(OH1.93F2.07)∙4.4H2O smectite trioctahedral

DP1 K0.03Na0.04Ca0.24(Al0.14Mg5.08Li0.77Fe0.08)(Si7.84Al0.16)O20(OH2.38F1.62)∙7.1H2O smectite trioctahedral

SHCa K0.02Na0.18Ca0.15(Al0.07Mg5.26Li0.75Fe0.03)(Si7.94Al0.06)O20(OH1.93F2.07)∙5.1H2O smectite trioctahedral

SBH-1 K0.02Ca0.30(Al0.04Mg5.16Li0.93Fe0.03)(Si7.94Al0.06)O20(OH2.58F1.42)∙4.9H2O smectite trioctahedral

SynH Na0.72(Mg5.56Li0.49)(Si7.89Al0.03)O20(OH3.99F0.01)∙5H2O smectite trioctahedral 73

The results from Table 14 show the illite/smectite samples from Clayton Valley have the highest layer charge, the majority having a negative charge near -2 eq/O20(OH,F)4. The

illites from McDermitt also have a large negative layer charge, at an average of -1.5

eq/O20(OH,F)4. Finally, the smectite samples have a smaller negative layer charge, with

the Hector sample having the lowest value at -0.4 eq/O20(OH,F)4, consistent with hectorite which tends to have a smaller layer charge than most smectites (Newman &

Brown, 1987). The layer charge of hectorite is expected to vary between -0.40 and -0.50 eq/O20(OH,F)4 (Lagaly, 1994).

Because the clay mineral must have a net neutral charge, the layer charge is neutralized

by the charge of the inner layer cations. The cation exchange capacity (CEC) is an

indication of how much exchange can take place in the interlayer space of the samples

and is equal to the total layer charge of the clay particle (Van Olphen, 1987). The layer

charge and CEC should be positively correlated, however they appear to be negatively

correlated, with the CEC being greater for samples that have a small negative layer

charge and lower for samples with a larger negative layer charge (Figure 15). Most illites

and micas are non-expandable minerals, and little to no exchange occurs with the

interlayer cations (Środoń & Eberl, 1984). In contrast, smectites are characterized by

their expandability, which could be explained by their small layer charge (Moore and

Reynolds, 1989). It was suggested that their small layer charge could cause the interlayer

cations to be less attracted to the layer charge than to the water in the environment, which

would allow the expansion of the interlayer and high CEC values. This would explain

the negative relationship observed in Figure 15. Since the CEC considers all exchangeable sites on the clay, including interlayer and surface sites, the surface exchange could be responsible for the plateau in CEC observed around 20-30 meq/100g for the samples with a negative layer charge greater than -1.5 eq/O20(OH,F)4.

Furthermore, the samples from Clayton Valley were determined to have a smectite component, which would explain their intermediate CEC values. The results obtained are consistent with known CEC values of illites and smectites.

A comparison of the layer charge with the lithium content of the clays is seen in Figure

16. No clear relationship can be determined, though a weak trend may be present for the smectite and dioctahedral samples, where lithium contents appear to decrease with a greater negative layer charge.

Figure 15: Comparison of the layer charge calculated from the structural formula and the cation exchange capacity.

Since it is assumed that all the lithium is found in the octahedral site of the trioctahedral clays, a comparison between lithium content and octahedral charge may be more appropriate (Figure 17). Two distinct trends can be observed, which appear related to the octahedral state of the samples. All samples show a positive correlation between lithium content and octahedral layer charge. The trioctahedral samples plot along a trend of 2:1 lithium oxide per negative charge, while the dioctahedral samples plot along a trend of

1:2 lithium oxide per negative charge. The reasons for this are unclear, but it may be due to the fact that more cations are allowed in a trioctahedral structure, or that lithium typically goes in the interlayer space of dioctahedral clays (Asher-Bolinder, 1982) and that dioctahedral clays generally carry less lithium than trioctahedral clays (Glanzman et al., 1978).

Figure 16: Comparison of the layer charge calculated from the structural formula and the lithium content for all samples.

Mineral identification

McDermitt

The type-1 samples from McDermitt, which include WLC03-01, -02, WLT02D,

WLT02F, WLT02I and DP1, have a structure characteristic of smectite clays. They are

characterized by a basal spacing of 15 Å under ambient conditions, which expands to 17

Å upon treatment with ethylene glycol. Their chemistry is somewhat intermediate

+ + between hectorite (M [Mg6-yLiy]Si8O20[OH,F]4), stevensite (M [Mg6-yy]Si8O20[OH,F]4)

+ 3+ and saponite (M [Mg6-yM y][Si8-xAlx]O20[OH,F]4). Saponite is characterized by having

a negative tetrahedral charge from the substitution of Si4+ by Al3+, balanced by a positive octahedral charge from the substitution of Mg2+ by trivalent cations, such as Al3+ and

Fe3+ (Newman & Brown, 1987). Stevensite is characterized by having a deficiency of

octahedral cations, creating a negative charge on the octahedral layer, and no substitution

in the tetrahedral layer (Brindley, 1980). Hectorite is characterized by the substitution of

Li+ for Mg2+ in the octahedral layer, creating a negative charge on the octahedral layer,

and little to no Al3+ for Si4+ substitution in the tetrahedral layer.

All of the McDermitt samples from the first group have a small amount of Al substitution

in the tetrahedral site, causing a small negative charge on the tetrahedral layer. All of

them also have a small amount of Al and Fe substitution in the octahedral site, but this

substitution is not large enough to create a positive charge on the octahedral layer.

Furthermore, the large substitution of Mg2+ by Li+ in all samples has the effect of

reducing the charge on the octahedral layer, creating a negative octahedral layer charge

(Table 14). Finally, all samples have a small vacancy in the octahedral layer, except for

DP1. Therefore, the type-1 McDermitt samples are most similar to hectorite.

Structurally, the peak locations from the XRD analysis (Figures II-26, II-30, II-46, II-50,

II-54 and II-58) are most similar to hectorite, as identified from the PDF minerals data

base (Table 16).

Figure 17: Comparison of the octahedral charge calculated from the structural formula and the lithium content for all samples.

These mineral identifications are consistent with previous research on the McDermitt

clays (Rytuba & Glanzman, 1978; Glanzman et al., 1978; Odom, 1992). They identified

a sequence of clay, ranging from dioctahedral at the bottom to trioctahedral at the top,

and found the lithium concentration to be proportional to the amount of trioctahedral

clay. They described this clay as a white and light green to dark green and brown, flake-

shaped crystals, and they identified it as hectorite. This description is similar to the observations from this study, with colors varying from whitish gray to greenish gray

(Appendix I) and a flaky texture (Appendix IV).

Reported lithium concentration in McDermitt rocks varies between 0.22% Li2O up to

1.60% Li2O (Glanzman et al., 1978; Odom, 1992), similar to the range observed in this

work (0.51-0.79% Li2O for bulk rocks (Table 4), 0.84-1.28% Li2O for clay concentrates

(Table 9)). Odom (1992) identified Ca as the predominant exchangeable cation in the

McDermitt hectorite, which is different from the results in this research (Table 14), where

Ca dominates in only two samples (WLT02D and DP1) and K dominates in the

remaining four samples (WLC03-01, -02, WLT02F and WLT02I).

The type-2 samples from McDermitt, which include WLC03-03, -04 and -05, have a structure similar to illite. They are characterized by a 10 Å basal spacing and do not swell upon treatment with ethylene glycol. Chemically, they are characterized by having

almost no Al3+ in either the tetrahedral or the octahedral sites. They also have a large

amount of substitution of Li+ for Mg2+ in the octahedral site, have all 3 octahedral sites

occupied, making them trioctahedral, and have K+ as the dominant cation in the interlayer

space. Their lack of Al and high Mg and Li content makes them most similar to tainiolite

(K2[Mg4Li2]Si8O20(OH,F)4) (Table 16).

Tainiolite has not previously been identified in McDermitt. It is a rare and unusual lithium-magnesium trioctahedral mica characterized by the absence of aluminum in the structure (Miser & Stevens, 1938). It is generally described as greenish brown, colorless or silvery, forming pseudohexagonal crystals up to 5 cm in diameter (Deer et al., 1978;

Anthony et al., 2001). It was first described in a nepheline syenite pegmatite from

Greenland and is usually found in alkaline and peralkaline rocks, particularly in syenites, or in associated alkaline metasomatites (Cooper et al., 1995), which are rocks that have been chemically altered by hydrothermal fluids (Raymond, 2002). Given the chemical similarities between tainiolite and hectorite, it is possible that the presence of tainiolite in

McDermitt is the result of the diagenetic smectite-to-illite conversion in a hydrothermal environment. The smectite-to-illite conversion is a well-known diagenetic process where smectite will naturally convert to illite with increasing depth and temperature (Velde,

1985). Given that the illite samples from McDermitt were all located at a greater depth

(see Appendix I for details on sample collection), the smectite-to-illite conversion could be represented at McDermitt by a hectorite to tainiolite conversion.

Hector & Fish Lake Valley

The sample from Hector, SHCa, and the one from Fish Lake Valley, SBH-1, are similar

to the McDermitt samples from the first group in that they have a structure similar to

smectite, characterized by having a basal spacing of 15 Å under ambient conditions that

expands to 17 Å after treatment with ethylene glycol. Chemically, they are characterized

by having very little Al3+ substitution for Si4+ in the tetrahedral site, virtually no Al in the

octahedral site, and significant substitution of Li+ for Mg2+ in the octahedral site, with no

deficiencies, and have all 3 octahedral sites occupied. Both have the structure and

chemistry expected for hectorite (Table 16).

The results obtained for the Hector sample are consistent with the data available in the

literature. The lithium concentrations (0.60% Li2O bulk sample (Table 4), 1.23% Li2O clay concentrate (Table 9)) are within the range previously reported (Table 1). The peaks identified on the XRD pattern, though not exactly at the position as the ones from the

PDF minerals data base (Figure II-62 and II-64), are consistent with the ones identified in the Clay Mineral Society (CMS) Source Clays baseline analysis for sample SHCa

(Chipera & Bish, 2001). The same is also true for the CEC and layer charge analyses, where the CMS determined the CEC to be 66 ±4 meq/100g (Borden & Giese, 2001) compared to 69.9 meq/100g for this work (Table 9), and the layer charge at 0.46 eq/O20(OH)4 (Mermut & Lagaly, 2001) compared to 0.48 eq/O20(OH)4 for this work

(Table 13). The hectorite clay from Hector was previously described as white to pale- brown, with an earthy to semi-waxy luster, and swells up to 5 or 6 times in water (Foshag

& Woodford, 1936). It has also been described as forming small plates or flakes, 3 to 15

m in length, and to be made of tangled masses of grains and plates. This is consistent to

what was observed in this work, where the clay was described as forming small flakes

from the SEM images (Figures IV-31 and IV-32) and irregular masses in thin section

(Figures III-28, -29 and -30).

No information could be found in the literature for the clays from Fish Lake Valley.

However they appear very similar to the Hector sample on a morphological, structural and chemical basis. The Fish Lake Valley sample was described as forming small flakes from the SEM image (Figures IV-33 and IV-34) and has an X-ray diffraction pattern similar to the Hector sample, with the peak located more closely to the ones identified in the PDF minerals data base (Figure II-66). The lithium concentration of the bulk sample

(0.52% Li2O, Table 4) is within the range previously reported for the Hector sample

(Table 1), but the concentrated clay sample has a higher lithium content than the ones

previously reported for Hector (1.46% Li2O, Table 9). The Fish Lake Valley sample has

the highest lithium content reported in this work for a smectite. The clay was abundant in

thin section (Figure III-31 and III-32), but didn’t form irregular masses like the Hector

sample.

Clayton Valley

The Clayton Valley samples were discussed earlier and determined to be a mixture of

illite and smectite (Table 16). No attempt was made to quantify the amount of illite and

smectite in the sample, and the structural formula was calculated with the assumption that

the samples have an anionic basis of O20(OH,F)4, which is valid for both illite and

smectite.

These results are different from those previously published for Clayton Valley (Davis,

1981; Kunasz, 1974). Previous work identified hectorite as the lithium-rich phase in the

Esmeralda Formation of Clayton Valley. However hectorite could not be clearly identified in this work. The results from this work suggest that a dioctahedral clay is present in the samples, and dioctahedral clays typically carry Li in the interlayer space, unlike trioctahedral clays which carry Li in the octahedral structure (Asher-Bolinder,

1982). The CEC analysis was inconclusive in confirming whether Li was indeed found primarily in the interlayer space, as Li was only recovered in small concentrations in 2 samples (CV2010-04, -05; Tables 11 and 12). This could be related to the large negative layer charge of the clays, which may help retain the cations in the interlayer space of the mineral (Moore & Reynolds, 1989). Furthermore, it was shown at McDermitt that dioctahedral clays typically carry less lithium than trioctahedral clays (Glanzman et al.,

1978). This result cannot be confirmed for the McDermitt clays analyzed in this study, as none were determined to be dioctahedral, but it is consistent with the overall results of this work, since the Clayton Valley samples have the lowest lithium concentration and are the only dioctahedral clays recovered.

Synthetic

The synthetic sample, SynH, has a structure similar to smectite. Its basal spacing under

ambient conditions is 13 Å, which is smaller than expected, but its interlayer space is

saturated with Na+, which gives a characteristic 12.5 Å spacing under ambient conditions

(Wilson, 1987). The basal spacing expands to 16.5 Å after treatment with ethylene

glycol. Chemically, it has virtually no Al3+ substitution in the tetrahedral site and some

Li+ substitution in the octahedral site, which is typical for hectorite (Table 16). The peak

location from the XRD pattern (Figure II-71) is also consistent with the PDF minerals data base for synthetic hectorite.

Geological Environment

Chemistry

The degree of substitution of F- for OH- in clay minerals and micas tend to be a function

of the temperature, concentration of fluorine in the environment and the cation population

of the octahedral sheet (Munoz, 1984). Fluorine substitution in micas and clays is greatly

influenced by their octahedral state. In a trioctahedral structure, the OH group does not

have too much interaction with the tetrahedral oxygen, so exchange with F can easily

occur (Robert et al, 1993). The same is not true for a dioctahedral structure, where OH

can interact with the tetrahedral oxygen, and F replacement is more difficult. The low F

concentration observed in the Clayton Valley samples could be explained by the fact that

all samples are dioctahedral rather than trioctahedral, limiting the exchange of F- for OH-.

Fluorine is fairly abundant in nature, though found in low concentrations in seawater

(1.2-1.4 ppm) and major rivers (0.1-0.2 ppm). Fluorine can be found in high

concentrations in hydrothermal fluids and some saline lakes, and clays formed under

these conditions would necessarily have unusually high fluorine content (Thomas et al,

1977). This would suggest that the samples from Hector, McDermitt and Fish Lake

Valley were formed in an environment which was rich in fluorine. Since the Clayton

Valley samples are dioctahedral and don’t allow as much F substitution, the environment

in which they formed may have been enriched in fluorine, but it is not observed in the samples.

Table 16: Summary of the clay mineralogy from each field site. Clay type Mineral name Mineral structure Average Li%

Clayton Valley Illite/Smectite Illite/Smectite dioctahedral 0.34 McDermitt Smectite Hectorite trioctahedral 0.51 Illite Tainiolite trioctahedral 1.21 Hector Smectite Hectorite trioctahedral 0.57 Fish Lake Valley Smectite Hectorite trioctahedral 0.68 Synthetic Smectite Hectorite trioctahedral 0.37

Both Foster (1960) and Starkey (1984) have shown a positive linear relationship between

Li and F contents in micas and trioctahedral smectites. A similar comparison can be drawn from the samples in this study (Figure 18). Starkey (1984) suggested that the linear relationship observed between Li and F in minerals from different environments may be an indication that the structure or chemistry of the mineral has a greater influence on the concentration of these elements in the mineral than the environment of formation.

However, studies of lepidolite (K(Li,Al)6(Si,Al)8O20(F,OH)4) formation in Yellowstone

(Bargar et al, 1973) have suggested that, even though the hydrothermal waters from

which lepidolite was forming were fairly diluted, they were anomalously rich in F and Li

when compared to other groundwaters. While the relative concentration of F and Li in micas and smectites may be structurally controlled, both elements need to be present in anomalous concentrations for Li- and F-rich minerals to crystallize. Furthermore, Barth

(1947) reported that alkaline hot spring water has fluorine concentrations in the same range as that observed in regular river waters, and that the fluorine is lost before reaching the surface. The fluorine content of acidic hot springs, however, can be extremely high, up to hundreds and thousands of ppm (Nordstrom & Jenne, 1977). Given that both F and

Li need to be found in anomalously high concentration in order to crystallize Li-rich smectites and micas, it follows that the depositional environment in all locations would have to be hydrothermal.

Figure 18: Comparison of the lithium and fluorine contents of all clay samples.

Deposit formation

Previous work suggested that the lithium mineralization in the McDermitt caldera is associated with the zeolite alteration zones in the lake beds within the tuffaceous sediments (Rytuba & Glanzman, 1978). The rocks had lithium removed in the alteration zones of erionite, clinoptilolite and mordenite, and it was concentrated in the alteration zones of analcime and K-feldspar. The zeolite alteration zones are related to diagenesis and hydrothermal activity. The highest concentrations of lithium are usually found in the analcime zone, which has been further converted to feldspar from hydrothermal fluids generated from the emplacement of the intrusive bodies along the ring fracture. The current work did not identify any zeolite in the rock samples, either through petrographic analysis or X-ray diffraction, but abundant feldspars were identified. The presence of both feldspars and carbonates found together in some samples (Figure III-17) also supports the hypothesis of alteration by hydrothermal fluid, as carbonates are frequently found in such fluids (Asher-Bolinder, 1982). Finally, the presence of tainiolite, which has been reported only found in rocks altered by hydrothermal, alkali-rich fluids, suggests a hydrothermal alteration of the sediments.

Previous work also determined the hectorite from McDermitt to be associated with volcanic sediments, limestones (CaCO3) and dolomites (CaMg(CO3)2) (Odom, 1992).

Abundant volcanic sediments were identified in thin section, most of which are altered to

clays. The visible bedding and apparent alignment of the clay minerals to bedding

suggests the clays didn’t precipitate authigenically but may be an alteration product of the pre-existing sediments.

A clear distinction can be made between the samples from McDermitt and those from

Clayton Valley, Fish Lake Valley and Hector. While bedding is prominent at McDermitt, no bedding is observed in the samples from other locations. Petrographic analysis showed the clay minerals at Clayton Valley and Fish Lake Valley are randomly oriented and closely related to fine-grained calcite, where they both form a fine-grained matrix.

This is consistent with the results from Davis (1981) who suggested that the close correlation between carbonate and lithium content in the mudstones of the Esmeralda

Formation was an indication of authigenic formation of the clay minerals directly from pore fluids. The coarse calcite identified filling void spaces is most likely secondary, not related to clay precipitation.

Volcanic glass is visible in some samples from Clayton Valley, and evidence of clay replacement suggests that some of the clays in Clayton Valley may be the result of alteration of volcanic glass. Kunasz (1974) suggested that the clays from the Esmeralda

Formation consisted of smectite, illite, kaolinite and chlorite, and that most of the lithium was found in the smectite phase hectorite. All the samples collected in Clayton Valley originated from the Esmeralda Formation, but while a smectite component was found in the clay fraction, pure hectorite could not be separated from the samples. Kunasz (1974) recognized an areal zonation in lithium content in Clayton Valley, with the highest

concentrations found near a fault zone immediately adjacent to the Esmeralda Formation.

He suggested that the fault zone may have acted as a conduit for lithium-bearing solutions. No smectites could be separated from the rocks collected in this research from the Esmeralda Formation in Clayton Valley, even though they were collected next to the fault zone previously identified. However, the lithium concentrations obtained in the clay concentrates from this research are in the same range as to the ones obtained by Kunasz

(1974) for samples collected in the Esmeralda Formation. It is thus possible that the lithium identified in the Clayton Valley samples is found in the smectite fraction of the samples, which could not be separated. The dioctahedral structure calculated from the structural formula of these samples suggests, however, that the clays formed in a low- temperature environment (Asher-Bolinder, 1982).

The sample from Hector shows no particular relationship with calcite, which could indicate that calcite is secondary to clay formation. The calcite identified in thin section

(Figures III-28 to III-30) forms small pockets or nodules, suggesting it crystallized after the formation of the hectorite. No volcanic glass was identified from the thin section, similarly to Fish Lake Valley, so it is unknown whether the clay could have formed through alteration of volcanic glass. Hectorite from the Hector deposit is typically found associated with calcite, quartz and zeolites (Ames et al., 1958). Both quartz and calcite were identified in this work (Figure II-61) but no zeolites could be found in thin section or on the XRD pattern. It was suggested that the hectorite formed from the hydrothermal

alteration of volcanic ash and zeolites and that the absence of both suggests a more complete alteration (Ames et al., 1958).

The results obtained in this research are consistent with the model proposed for lithium- rich smectite deposits (Asher-Bolinder, 1982; Orris & Bliss, 1991). It is suggested that lithium-enriched clays can form in closed basin filled with volcanic ash, where hydrothermal- or ground-water can provide the elements and conditions necessary for clay formation, either through leaching of the surrounding silicic and peralkaline rocks or from fluids derived from intrusive alkaline magmas. An arid environment could be necessary to concentrate the lithium-rich fluids in the basin.

All samples in this research were collected in closed basin associated with silicic peralkaline volcanic rocks. Hydrothermal fluids appear to have been the main driver for the formation of the lithium-rich trioctahedral clay in all cases, except for Clayton Valley where dioctahedral clays were precipitated instead (Asher-Bolinder, 1982). It was suggested that the reactive chemistry of ashes and the hydrothermal leaching of another silicic body, along with evaporative conditions, are required to produce lithium-rich clays with Li concentrations as high as 1% Li2O (Brenner-Tourtelot & Glanzman, 1978).

Conclusion

Hectorite is a lithium-rich clay found in various locations in the Basin and Range

geological province. It is characterized by the substitution of Li for Mg in the octahedral

site of the clay structure, the lack of Al substitution for Si in the tetrahedral structural site

and the substitution of F for OH. Clay samples were obtained from four different areas:

Clayton Valley NV, Fish Lake Valley NV, McDermitt NV and Hector CA.

Hector is the type locality for hectorite. The deposit is believed to have formed from the alteration of volcanic ash by hydrothermal fluids in a lake environment. McDermitt is the location of a large caldera where hectorite was identified in moat sediments found along the ring fracture, between the wall of the caldera and the resurgent dome. The deposit is believed to have formed from the alteration of the volcaniclastic sediments by lithium-rich fluids, most likely in a hydrothermal environment. Clayton Valley is the location of a lithium-rich aquifer, the only current production of Li in the United States.

Hectorite was identified in the valley and it is believed to have formed authigenically, through direct precipitation from lake waters or pore fluids. Fish Lake Valley is adjacent to Clayton Valley, and hectorite was identified in a small basin on the eastern margin of the valley, south of the Silver Peak Mountains. It is believed the basin was filled with volcaniclastic lake sediments and altered by Li-rich fluids, most likely of hydrothermal origin.

The goal of this study is to characterize the structural composition of hectorites from

Clayton Valley NV, McDermitt NV, Fish Lake Valley NV and Hector CA, and correlate their structure and lithium contents with the geology and formation mechanisms of each deposit. The hypotheses are: (1) the clay structure and lithium content will be dependent on its formational origin and positively correlated with temperatures of formation; (2) the layer charge and cation exchange capacity will be proportional to the structural lithium content of the clay.

The presence of the mineral hectorite was confirmed in all locations except for Clayton

Valley, where an illite was identified as the primary phase and hectorite, if present, could not be separated from the sample. Detailed chemistry, X-ray diffraction, cation exchange capacity and layer charge analyses were used to confirm the presence of hectorite.

Lithium concentrations ranged from 0.84% Li2O to 1.46% Li2O for hectorite from all

locations, with the lowest concentration found at McDermitt and the highest at Fish Lake

Valley.

In addition to hectorite, the mineral tainiolite was identified at McDermitt. Tainiolite is a

rare and unusual mica typically found associated in rocks that have been hydrothermally

altered by alkaline intrusions. Its lithium concentration at McDermitt averages 1.60%

Li2O, the highest concentration recorded for all the samples. Its presence could be related

to the smectite-to-illite conversion typically observed during diagenesis, and it could

confirm the hydrothermal origin of the Li-rich clays found at McDermitt.

In addition to clay chemistry and mineralogy, a petrographic analysis was done on the rock samples to identify textural relationships between the clays and the associated minerals to help in relating the clay formation to the geological environment. In all cases carbonate minerals were abundant. The close relationship between calcite and the clays for both Clayton Valley and Fish Lake Valley, where the clays are forming a very fine grained matrix with the calcite, suggests co-precipitation of the two minerals, an indication that the clay formed directly from pore fluids. A similar relationship is observed for McDermitt, though it seems less consistent. The presence of carbonates forming beds parallel to bedding and closely related to feldspar laths at McDermitt suggests co-precipitation of these two minerals, which would happen in hydrothermal systems. The strong bedding visible in all McDermitt samples suggests the clays may be the result of hydrothermal alteration of the sediments, as oppose to authigenic precipitation like the other deposits.

In all cases, a positive relationship could be determined between the lithium and fluorine content of the samples. Both elements need to be present in anomalous concentration for the formation of trioctahedral, lithium-rich clay minerals, including both hectorite and tainiolite. Hydrothermal fluids and saline lakes are the two known environments for which anomalous concentrations of lithium and fluorine can occur.

The results obtained in this research are consistent with the model proposed for lithium- rich smectite deposits, since all samples were collected in closed basin in arid

environments associated with silicic volcanics. The results also suggest all samples, except for the ones from Clayton Valley, were formed by hydrothermal fluids, either through direct precipitation like Fish Lake Valley and Hector, or by alteration of existing sediments, like McDermitt. The low lithium content at Clayton Valley and the presence of a dioctahedral illite instead of a trioctahedral smectite suggest the clays were formed by low-temperature authigenic precipitation from pore fluids.

From hypothesis 1, we can conclude that clay structure and lithium content are dependent on the formational origin and positively correlated with temperatures of formation. A low temperature environment will produce a dioctahedral clay, which will host lithium in the interlayer space, as observed in Clayton Valley. A hydrothermal environment will produce a trioctahedral clay which hosts lithium in the octahedral site, as observed in

Hector, McDermitt and Fish Lake Valley. The amount of lithium present in the clay will depend on the concentration of lithium in the fluid.

From hypothesis 2, we can conclude that the relationship between lithium content and total layer charge is not very clear, but a positive correlation can be determined between lithium content and octahedral layer charge. For clays with a trioctahedral structure, the relationship is 2:1 lithium to octahedral charge equivalent, while clays with a dioctahedral structure have a relationship of 1:2 lithium to octahedral charge equivalent.

The relationship with the CEC is inconclusive, as the CEC is dependent on the type and expandability of the clay.

More work is necessary to understand the presence of tainiolite at McDermitt, as it has not been identified previously in volcaniclastic sediments. A detailed study sampling clay minerals with depth could be done in the McDermitt deposit, which could confirm the smectite-to-illite diagenetic conversion suggested here and could provide information on the kinetics governing the reaction. A study of lithium isotopes could also provide some information on the source of the lithium in all cases, as it might help distinguish between hydrothermal lithium and lithium derived from leaching of silicic rocks.

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USGS (2001) A Laboratory Manual for X‐Ray Powder Diffraction. U. S. Geological Survey Open‐ File Report 01‐041. http://pubs.usgs.gov/of/2001/of01‐041/htmldocs/clays/smc.htm, accessed May 2010.

USGS MRP (2010) http://minerals.usgs.gov/minerals/pubs/commodity/lithium/mcs‐2010‐ lithi.pdf, accessed March 2010.

Van Olphen, H. (1987) Dispersion and flocculation. In Newman, A.C.D. (Ed) Chemistry of Clays and Clay Minerals. Mineralogical Society Monograph No.6. John Wiley and Sons, New York NY: 203‐224.

Velde, B. (1985) Clay minerals: A physic‐chemical explanation of their occurrence. Elsevier, Amsterdam: 426p.

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Willette, R.D. (1995) Geology of the Hector Mine deposit. In Tabilio, M. and D.L. Dupras (Eds.) 29th Forum on the Geology of Industrial Minerals: Proceedings; California Department of Conservation, Division of Mines and Geology Special Publication. 110: 189‐194.

Wilson, M.J. (1987) X‐ray powder diffraction methods. In Wilson, M.J. (Ed) A Handbook of Determinative Methods in Clay Mineralogy. Blackie & Son Limited, London UK: 26‐98.

Wright, L.A., R.M. Stewart, T.E. Gay and G.C. Hazenbush (1953) Mines and mineral deposits of San Bernardino County, California. California Journal of Mines and Geology. 49: 157‐160.

Zampirro, D. (2004) Hydrogeology of Clayton Valley brine deposits, Esmeralda County, Nevada. Nevada Bureau of Mines and Geology Special Publication. 33: 271‐280.

102

Appendix I – Sample description

Clayton Valley, NV

All samples from Clayton Valley were collected from the upper member of the

Esmeralda Formation, exposed at Angel Island on the eastern side of the playa.

CV2010-01

Sample is a claystone, light grayish tan color, located on a small ridge on the North side of Silverpeak Road, immediately north of Angel Island. Ridge is approximately 30m wide and 2m high, dipping SSE. Exposed surface shows a puffy, popcorn-like weathering surface characteristic of swelling clays. Sample is dry.

Located 37º47.375N, 117º28.936W

CV2010-02

Sample is a claystone, orangey tan in color, located on the west side of Angel Island.

Section is approximately 3m high, with a conglomerate on top. Weathered surface shows clay swelling. Sample is dry.

Located 37º45.113N, 117º33.599W

CV2010-04

Sample is a claystone, dark greenish gray in color with occasional tan layers, located on the west side of Angel Island. Section is below a conglomerate unit. Surface is 103 weathering to a brownish tan color and doesn’t show too much swelling. Sample is fairly moist.

Located 37º45.494N, 117º33.682W

CV2010-05

Sample is a claystone, light greenish gray in color, located on the west side of Angel

Island. It is found below a conglomerate unit. The weathered surface shows the characteristic clay swelling texture. Some oxidation can also be observed near the surface. Sample is dry.

Located 37º44.550N, 117º33.268W

CV2010-06

Sample is an isolated claystone mound on the south side of Angel Island, greenish gray in color. The conglomerate normally seen on the section above is not observed here.

Weathered surface shows the characteristic clay swelling. Sample is semi-dry.

Located 37º44.166N, 117º33.044W

CV2010-07

Sample represents surface weathering of an ash fall, light gray in color, located on the northeast side of Angel Island. Clay content in sample is approximately 10-20%.

Surface shows the characteristic clay swelling texture. Sample is dry.

Located 37º46.714N, 117º31.531W 104

McDermitt, NV

All samples from McDermitt were collected within the McDermitt Caldera, in Nevada.

All samples were provided by Western Lithium Corporation, except for DP1, which was

provided by American Colloid.

WLC03-01

Core sample from drillhole WLC03, collected at a depth of 100-105 ft. Sample is a

whitish tan claystone with some calcite crystals. Interval is laminated with ash, but none

were sampled. Sample is dry.

WLC03-02

Core sample from drillhole WLC03, collected at a depth of 135-140 ft. Sample is a tan-

gray claystone with the occasional pyrite cube visible. Sample has a waxy texture. Some

ash beds are present in the interval. Sample is dry.

WLC03-03

Core sample from drillhole WLC03, collected at a depth of 190-195 ft. Sample is a

greenish-gray clay with a dull luster. Some calcite crystals and pyrite cubes are present.

Sample shows some green layering. Sample is dry.

WLC03-04

Core sample from drillhole WLC03, collected at a depth of 195-200 ft. Sample is a

greenish-gray clay with a dull luster. Some calcite crystals and pyrite cubes are present.

Sample shows some green layering. Sample is dry. 105

WLC03-05

Core sample from drillhole WLC03, collected at a depth of 205-210 ft. Sample is a layered dark greenish-gray clay. Abundant calcite crystals are present. Sample is dry.

WLT02-D

Sample was collected from trench #2 in pile D. It is a grayish-tan clay with a waxy texture. Sample is wet.

WLT02-F

Sample was collected from trench #2 in pile F. It is a grayish-tan clay with a waxy texture. Sample is wet.

WLT02-I

Sample was collected from trench #2 in pile I. It is a grayish-tan clay with a waxy texture. Sample is wet.

DP1

Sample was obtained from American Colloid. It consists in crushed hectorite ore. The sample is a grayish-white clay with a waxy texture. Calcite crystals can be visible. The sample is moist.

106

Hector, CA

SHCa

Sample was purchased from the Clay Mineral Society and is one of their Source Clays. It

is a powdered white clay. A rock sample was obtained from the Hector mine, operated

by Elementis Specialties, for spectrographic analysis. The sample was collected in

drying yard 8 and represent hectorite ore. It consists in white clay with calcite mixed in.

The sample is very dry.

Fish Lake Valley, NV

SBH-1

Sample was obtained from American Lithium Minerals Inc. It is a medium gray, clay-

rich gravel. Sample was collected from drill cuttings at a depth of approximately 200 ft

downhole. It contains approximately 20% coarse sand, 5% gravel and 75% silt and clay.

Synthetic

SynH

The sample is an Optigel synthetic hectorite, made by United Catalists Inc. and purchased

from the Clay Mineral Society. It is a powdered white clay.

107

Appendix II – XRD patterns

Four profiles are shown for each pattern:

- A random scan of the bulk whole rock, identifying associated minerals. The peaks at 38.5 º2 and 44.7º2 represent the Aluminum holder, used as a standard (PDF#04-0787)

- A random scan of the clay concentrate, identifying remaining impurities and possible clay phase present

- A random scan of the clay concentrate, identifying the different peaks and their position

- An oriented scan of the clay concentrate in both the air-dried and glycolated state, identifying the different peaks and their position

Some of the peaks from the Clayton Valley samples in the glycolated state were too weak to determine from the oriented scans. The air-dried scan was thus subtracted from the glycolated scan to determine their position, and these residual profiles are shown in

Figures II-72 to II-76.

The key for sample ID is found in Table 3 (p.26).

108

Figure II‐1: Random XRD pattern for the unprocessed sample CV2010‐01, identifying accessory minerals.

109 Figure II‐2: Random XRD pattern for the cleaned sample CV2010‐01, identifying phases present.

110

Figure II‐3: Random XRD pattern for the cleaned sample CV2010‐01.

Figure II‐4: Oriented XRD pattern for the cleaned sample CV2010‐01.

111 Figure II‐5: Random XRD pattern for the unprocessed sample CV2010‐02, identifying accessory minerals.

Figure II‐6: Random XRD pattern for the cleaned sample CV2010‐02, identifying phases present. 112

113

Figure II‐7: Random XRD pattern for cleaned sample CV2010‐02.

Figure II‐8: Oriented XRD pattern for cleaned sample CV2010‐02.

114 Figure II‐9: Random XRD pattern for the unprocessed sample CV2010‐04, identifying accessory minerals.

115 Figure II‐10: Random XRD pattern for the cleaned sample CV2010‐04, identifying phases present.

116

Figure II‐11: Random XRD pattern for cleaned sample CV2010‐04.

Figure II‐12: Oriented XRD pattern for cleaned sample CV2010‐04.

117 Figure II‐13: Random XRD pattern for the unprocessed sample CV2010‐05, identifying accessory minerals.

118 Figure II‐14: Random XRD pattern for the cleaned sample CV2010‐05, identifying phases present.

119

Figure II‐15: Random XRD pattern for cleaned sample CV2010‐05.

Figure II‐16: Oriented XRD pattern for cleaned sample CV2010‐05.

120 Figure II‐17: Random XRD pattern for the unprocessed sample CV2010‐06, identifying accessory minerals.

121 Figure II‐18: Random XRD pattern for the cleaned sample CV2010‐06, identifying phases present.

122

Figure II‐19: Random XRD pattern for cleaned sample CV2010‐06.

Figure II‐20: Oriented XRD pattern for cleaned sample CV2010‐06.

123 Figure II‐21: Random XRD pattern for the unprocessed sample CV2010‐07, identifying accessory minerals.

124 Figure II‐22: Random XRD pattern for the cleaned sample CV2010‐07, identifying phases present.

125

Figure II‐23: Random XRD pattern for cleaned sample CV2010‐07.

Figure II‐24: Oriented XRD pattern for cleaned sample CV2010‐07.

126

Figure II‐25: Random XRD pattern for the unprocessed sample WLC03‐01, identifying accessory minerals.

127 Figure II‐26: Random XRD pattern for the cleaned sample WLC03‐01, identifying phases present.

128

Figure II‐27: Random XRD pattern for cleaned sample WLC03‐01.

Figure II‐28: Oriented XRD pattern for cleaned sample WLC03‐01.

129 Figure II‐29: Random XRD pattern for the unprocessed sample WLC03‐02, identifying accessory minerals.

130 Figure II‐30: Random XRD pattern for the cleaned sample WLC03‐02, identifying phases present.

131

Figure II‐31: Random XRD pattern for cleaned sample WLC03‐02.

Figure II‐32: Oriented XRD pattern for cleaned sample WLC03‐02.

132 Figure II‐33: Random XRD pattern for the unprocessed sample WLC03‐03, identifying accessory minerals.

133 Figure II‐34: Random XRD pattern for the cleaned sample WLC03‐03, identifying phases present.

134

Figure II‐35: Random XRD pattern for cleaned sample WLC03‐03.

Figure II‐36: Oriented XRD pattern for cleaned sample WLC03‐03.

135 Figure II‐37: Random XRD pattern for the unprocessed sample WLC03‐04, identifying accessory minerals.

136 Figure II‐38: Random XRD pattern for the cleaned sample WLC03‐04, identifying phases present.

137

Figure II‐39: Random XRD pattern for cleaned sample WLC03‐04.

Figure II‐40: Oriented XRD pattern for cleaned sample WLC03‐04.

138

Figure II‐41: Random XRD pattern for the unprocessed sample WLC03‐05, identifying accessory minerals.

139 Figure II‐42: Random XRD pattern for the cleaned sample WLC03‐05, identifying phases present.

140

Figure II‐43: Random XRD pattern for cleaned sample WLC03‐05.

Figure II‐44: Oriented XRD pattern for cleaned sample WLC03‐05.

141 Figure II‐45: Random XRD pattern for the unprocessed sample WLT02D, identifying accessory minerals.

142 Figure II‐46: Random XRD pattern for the cleaned sample WLT02D, identifying phases present.

143

Figure II‐47: Random XRD pattern for cleaned sample WLT02D.

Figure II‐48: Oriented XRD pattern for cleaned sample WLT02D.

144 Figure II‐49: Random XRD pattern for the unprocessed sample WLT02F, identifying accessory minerals.

145 Figure II‐50: Random XRD pattern for the cleaned sample WLT02F, identifying phases present.

146

Figure II‐51: Random XRD pattern for cleaned sample WLT02F.

Figure II‐52: Oriented XRD pattern for cleaned sample WLT02F.

147

Figure II‐53: Random XRD pattern for the unprocessed sample WLT02I, identifying accessory minerals.

148 Figure II‐54: Random XRD pattern for the cleaned sample WLT02I, identifying phases present.

149

Figure II‐55: Random XRD pattern for cleaned sample WLT02I.

Figure II‐56: Oriented XRD pattern for cleaned sample WLT02I.

150 Figure II‐57: Random XRD pattern for the unprocessed sample DP1, identifying accessory minerals.

151 Figure II‐58: Random XRD pattern for the cleaned sample DP1, identifying phases present.

152

Figure II‐59: Random XRD pattern for cleaned sample DP1.

Figure II‐60: Oriented XRD pattern for cleaned sample DP1.

153 Figure II‐61: Random XRD pattern for the unprocessed sample SHCa, identifying accessory minerals.

154

Figure II‐62: Random XRD pattern for the cleaned sample SHCa, identifying phases present.

155

Figure II‐63: Random XRD pattern for cleaned sample SHCa.

Figure II‐64: Oriented XRD pattern for cleaned sample SHCa.

156 Figure II‐65: Random XRD pattern for the unprocessed sample SBH‐1, identifying accessory minerals.

157 Figure II‐66: Random XRD pattern for the cleaned sample SBH‐1, identifying phases present.

158

Figure II‐67: Random XRD pattern for cleaned sample SBH‐1.

Figure II‐68: Oriented XRD pattern for cleaned sample SBH‐1.

159 Figure II‐69: Random XRD pattern for the cleaned sample SynH, identifying phases present.

160

Figure II‐70: Random XRD pattern for sample SynH.

Figure II‐71: Oriented XRD pattern for sample SynH.

161

Subtracted profiles

Figure II‐72: Residual of the glycolated XRD pattern after subtraction of the air‐dried

pattern for sample CV2010‐01.

Figure II‐73: Residual of the glycolated XRD pattern after subtraction of the air‐dried pattern for sample CV2010‐02.

162

Figure II‐74: Residual of the glycolated XRD pattern after subtraction of the air‐dried pattern for sample CV2010‐04.

Figure II‐75: Residual of the glycolated XRD pattern after subtraction of the air‐dried pattern for sample CV2010‐06.

163

Figure II‐76: Residual of the glycolated XRD pattern after subtraction of the air‐dried pattern for sample CV2010‐07.

164

Appendix III – Petrographic Analysis

CV2010-01

100 m

Figure III-1: Calcite crystals filling void space. A – plane light; B – crossed

polars. 165

CV2010-01

50 m

Figure III-2: Groundmass of clay and muscovite. Grains are randomly

oriented. A – plane light; B – crossed polars.

166

CV2010-01

50 m

B Mv

Fsp

Cc 50 m

Figure III-3: Calcite (Cc) seen filling void spaces. All other grains randomly oriented in clay groundmass. A – plane light; B – crossed polars.

167

CV2010-02

50 m

Glass

50 m

Figure III-4: Glass shards in matrix of clays, micas and calcite. A – plane light; B – crossed polars.

168

CV2010-02

50 m

Glass

50 m

Figure III-5: Glass fragments in matrix of clay, micas and calcite, being replaced by clays. A – plane light; B – crossed polars.

169

CV2010-02

100 m

B Glass

Qtz Fsp

100 m

Figure III-6: Detrital grains of quartz (Qtz) and feldspar (Fsp) with abundant glass fragments in matrix of clay and calcite. Grains in the matrix are randomly oriented. A – plane light; B – crossed polars.

170

CV2010-04

100 m

Fsp Qtz 100 m

Figure III-7: Detrital grains of quartz (Qtz) and feldspar (Fsp) in matrix of clay and calcite. A – plane light; B – crossed polars.

171

CV2010-05

50 m

Qtz

50 m

Figure III-8: Detrital grains of quartz (Qtz) in matrix of clay and calcite. A – plane light; B – crossed polars.

172

CV2010-06

50 m

Figure III-9: Matrix of clay and calcite, with occasional coarser grains of calcite. A – plane light; B – crossed polars.

173

CV2010-06

100 m

Figure III-10: Matrix of clay and calcite, with occasional detrital grains of quartz, feldspar and mica. A – plane light; B – crossed polars.

174

CV2010-07

100 m

Qtz

Glass

100 m

Figure III-11: Abundant glass shards and quartz (Qtz) fragments in a matrix of clay and calcite. A – plane light; B – crossed polars.

175

CV2010-07

100 m

Mica Qtz

Glass

100 m

Figure III-12: Abundant glass shards, quartz (Qtz) and mica fragments in a matrix of clay and calcite. A – plane light; B – crossed polars.

176

WLC03-01

100 m

Figure III-13: Apparent lithic fragments in clay matrix. A – plane light; B – crossed polars.

177

WLC03-01

500 m

Figure III-14: Bedding apparent in thin section. Clay extinction in crossed polarized light is parallel to bedding. A – plane light; B – crossed polars.

178

WLC03-01

100 m

Glass

100 m

Figure III-15: Glass fragments visible in thin section. Abundant fine-grained carbonate present in clay groundmass. A – plane light; B – crossed polars.

179

WLC03-02

500 m

B Cc

500 m

Figure III-16: Abundant lithic fragments, carbonate alteration (Cc) follows bedding. A – plane light; B – crossed polars.

180

WLC03-02

100 m

Fsp

100 m

Figure III-17: Carbonate-rich (Cc) beds have abundant feldspar (Fsp) laths. A – plane light; B – crossed polars. 181

WLC03-03

Figure III‐19

500 m

B Cc

500 m

Figure III-18: Apparent alignment of clays with bedding. Large calcite (Cc) crystals and other lithic fragments present. A – plane light; B – crossed polars.

182

WLC03-03

100 m

Fsp

100 m

Figure III-19: Lithic fragment primarily composed of fine-grained feldspar (Fsp) and other fine-grained material. A – plane light; B – crossed polars.

183

WLC03-04

500 m

Figure III‐21

500 m

Figure III-20: Large isotropic fragments in fine-grained clay matrix. Large calcite (Cc) crystals present. A – plane light; B – crossed polars.

184

WLC03-04

100 m

Figure III-21: Fragment composed of very fine-grained feldspar and other fine-grained isotropic material (glass?). No clear distinction visible from image (A). Clays are surrounding the fragment. A – plane light; B – crossed polars. 185

WLC03-04

500 m

Figure III-22: Visible layering. Clay oriented parallel to layering, due to

parallel extinction in cross-polarized light. A – plane light; B – crossed polars.

186

WLC03-05

500 m

Figure III-23: Abundant fragments in clay matrix. A – plane light; B – crossed polars.

187

WLC03-05

50 m

Figure III-24: Dissolution features on calcite crystals. A – plane light; B – crossed polars.

188

WLT02D

500 m

Figure III-25: Fragments visible in clay groundmass. A – plane light; B – crossed polars.

189

WLT02F

100 m

Figure III-26: Color variations in clay groundmass. A – plane light; B – crossed polars.

190

WLT02I

500 m

Figure III-27: Fragments all parallel to bedding. Abundant fine-grained disseminated carbonate. A – plane light; B – crossed polars. 191

SHCa

100 m

B Cc

Clay

100 m

Figure III-28: Fragments of clay with irregular calcite (Cc) crystals. Interstitial quartz may be present between clay and calcite. A – plane light; B – crossed polars.

192

SHCa

50 m

Clay

Cc 50 m

Figure III-29: Fragments of clay, showing irregular surface. Calcite (Cc)

crystals seen surrounding the clay. A – plane light; B – crossed polars.

193

SHCa

50 m

Clay

50 m

Figure III-30: Clay fragment separated by 2 large irregular calcite (Cc) grains. A – plane light; B – crossed polars. 194

SBH-1

100 m

B Qtz Mica

100 m

Figure III-31: Irregular quartz (Qtz) grain and occasional micas in a matrix of fine-grained clay and calcite. A – plane light; B – crossed polars.

195

SBH-1

100 m

Qtz Cc

100 m

Figure III-32: Quartz (Qtz) and muscovite (Mv) (?) crystals in a matrix of clay and calcite. Some larger calcite (Cc) crystals also present. A – plane light; B – crossed polars.

196

Appendix IV – Scanning Electron Microscopy

Clayton Valley, NV

Figure IV-1: SEM image of sample CV2010-01 at 10,000x magnification.

Figure IV-2: SEM image of sample CV2010-01 at 20,000x magnification. 197

Figure IV-3: SEM image of sample CV2010-02 at 10,000x magnification.

Figure IV-4: SEM image of sample CV2010-02 at 30,000x magnification.

198

Figure IV-5: SEM image of sample CV2010-04 at 5,000x magnification.

Figure IV-6: SEM image of sample CV2010-04 at 20,000x magnification.

199

Figure IV-7: SEM image of sample CV2010-05 at 10,000x magnification.

Figure IV-8: SEM image of sample CV2010-05 at 30,000x magnification.

200

Figure IV-9: SEM image of sample CV2010-06 at 10,000x magnification.

Figure IV-10: SEM image of sample CV2010-06 at 20,000x magnification.

201

Figure IV-11: SEM image of sample CV2010-07 at 5,000x magnification.

Figure IV-12: SEM image of sample CV2010-07 at 25,000x magnification.

202

McDermitt, NV

Figure IV-13: SEM image of sample WLC03-01 at 10,000x magnification.

Figure IV-14: SEM image of sample WLC03-01 at 20,000x magnification. 203

Figure IV-15: SEM image of sample WLC03-02 at 5,000x magnification.

Figure IV-16: SEM image of sample WLC03-02 at 20,000x magnification.

204

Figure IV-17: SEM image of sample WLC03-03 at 10,000x magnification.

Figure IV-18: SEM image of sample WLC03-03 at 20,000x magnification.

205

Figure IV-19: SEM image of sample WLC03-04 at 10,000x magnification.

Figure IV-20: SEM image of sample WLC03-04 at 30,000x magnification.

206

Figure IV-21: SEM image of sample WLC03-05 at 10,000x magnification.

Figure IV-22: SEM image of sample WLC03-05 at 30,000x magnification. 207

Figure IV-23: SEM image of sample WLT02D at 10,000x magnification.

Figure IV-24: SEM image of sample WLT02D at 30,000x magnification.

208

Figure IV-25: SEM image of sample WLT02F at 10,000x magnification.

Figure IV-26: SEM image of sample WLT02F at 20,000x magnification.

209

Figure IV-27: SEM image of sample WLT02I at 10,000x magnification.

Figure IV-28: SEM image of sample WLT02I at 30,000x magnification.

210

Figure IV-29: SEM image of sample DP1 at 2,000x magnification.

Figure IV-30: SEM image of sample DP1 at 10,000x magnification.

211

Hector, CA

Figure IV-31: SEM image of sample SHCa at 10,000x magnification.

Figure IV-32: SEM image of sample SHCa at 20,000x magnification. 212

Fish Lake Valley, NV

Figure IV-33: SEM image of sample SBH-1 at 10,000x magnification.

Figure IV-34: SEM image of sample SBH-1 at 20,000x magnification. 213

Synthetic hectorite

Figure IV-35: SEM image of sample SynH at 10,000x magnification.

Figure IV-36: SEM image of sample SynH at 20,000x magnification. 214

Appendix V – Analytical Chemistry Results

Table V-1: Trace elements chemistry for the bulk samples. ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP Field No. Al Ca Fe K Mg Na S Ti Ag As Ba Be Bi Cd Ce Co Cr Cs Cu Ga In La Li Mn Mo Nb Ni P Pb Rb Sb Sc Sn Sr Te Th Tl U V W Y Zn % % % % % % % % ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm CV2010-01 7.15 3.98 3.16 3.21 2.07 2.79 0.04 0.23 <1 10 472 2.3 0.19 <0.1 53.5 15.7 42 87 20.8 24.7 0.06 26.2 1080 450 0.73 13.5 23.8 340 19.4 336 1.25 10.6 2.0 650 <0.1 8.2 1.2 4.1 79 22.3 10.9 70 CV2010-02 7.62 2.08 3.37 3.33 1.85 2.62 0.08 0.30 <1 30 361 3.1 0.40 0.2 80.9 15.7 28 21 21.7 27.1 0.07 38.9 496 592 2.55 23.8 25.7 670 22.5 278 3.23 10.3 2.5 242 <0.1 16.4 0.8 3.8 82 7.5 23.0 92 CV2010-04 5.49 7.28 2.39 4.91 2.79 2.50 0.16 0.22 <1 45 340 2.1 0.22 0.2 57.3 9.9 24 43 17.1 18.7 0.05 26.0 1400 523 4.19 15.0 15.2 400 13.4 304 2.18 8.7 1.8 1330 <0.1 14.2 0.8 7.9 66 3.4 20.5 60 CV2010-05 5.98 3.15 2.69 5.83 1.80 3.52 0.59 0.26 <1 60 257 2.3 0.27 0.3 62.0 10.1 21 55 21.7 20.8 0.06 30.1 2740 500 58.60 18.3 17.9 410 13.2 440 1.92 8.6 2.0 892 <0.1 11.2 1.1 4.1 76 10.7 16.6 69 CV2010-06 5.79 5.74 2.55 5.08 1.85 0.96 0.03 0.24 <1 24 664 2.3 0.26 0.1 59.2 11.9 25 50 19.5 20.2 0.06 29.4 1110 535 3.27 17.3 18.5 410 14.6 345 2.25 8.5 1.9 758 <0.1 14.2 0.8 3.6 81 20.8 18.1 65 CV2010-07 6.56 4.28 2.33 4.20 2.16 2.36 0.35 0.25 <1 33 558 2.4 0.25 0.3 63.9 10.4 22 34 16.8 20.8 0.04 32.1 669 575 79.60 17.9 15.0 510 18.5 279 2.21 7.5 1.8 1910 <0.1 12.3 0.8 5.7 64 3.9 19.5 59 WLC03-01 2.30 2.23 1.39 1.20 10.80 0.28 0.72 0.12 <1 37 135 8.8 0.13 0.3 11.2 5.7 4 228 11.5 9.1 0.04 4.8 2850 178 31.80 8.9 3.3 60 6.4 208 6.21 1.8 1.1 237 <0.1 1.6 0.9 2.5 32 0.6 10.7 41 WLC03-02 3.25 2.71 1.98 2.97 9.40 0.27 1.80 0.10 <1 64 222 7.7 0.30 0.5 23.8 5.8 4 245 13.6 12.1 0.07 11.5 3690 347 55.70 5.8 3.2 90 7.6 394 7.70 2.7 1.2 305 <0.1 2.7 0.8 1.3 39 0.9 20.6 48 WLC03-03 2.77 4.94 1.87 4.96 6.79 1.20 1.80 0.27 <1 269 202 9.2 0.32 0.7 49.6 4.5 5 348 11.4 14.5 0.07 22.6 6410 617 221.00 20.0 4.4 <50 10.4 932 21.20 5.9 2.5 335 <0.1 6.3 1.2 8.4 41 3.1 66.0 60 WLC03-04 2.51 4.10 1.29 5.26 8.23 1.08 1.10 0.22 <1 208 166 7.7 0.21 0.6 33.5 2.9 4 352 7.8 12.1 0.06 15.6 7110 776 174.00 14.9 2.2 <50 8.5 990 17.10 3.9 1.7 314 <0.1 4.4 1.2 6.7 32 1.5 39.4 51 WLC03-05 3.06 2.52 1.75 4.35 6.56 1.77 1.78 0.24 <1 332 121 5.9 0.20 0.5 32.4 5.6 4 416 11.7 13.4 0.06 15.2 6420 419 148.00 12.2 2.8 <50 7.6 843 23.60 3.4 1.5 198 <0.1 3.0 0.9 6.3 45 16.7 23.5 52 WLT02-D 2.51 2.14 1.26 1.13 11.00 0.47 0.02 0.03 <1 7 67 11.0 0.26 <0.1 19.2 3.3 3 135 11.4 9.6 0.07 9.2 3000 190 2.88 6.3 2.3 70 4.4 198 2.03 1.8 0.9 219 <0.1 2.4 0.3 0.8 27 1.6 10.0 34 WLT02-F 2.31 6.45 1.17 1.92 10.50 0.47 0.02 0.14 <1 7 169 7.1 0.15 <0.1 22.3 4.3 4 151 10.0 9.0 0.04 10.2 3520 454 4.00 8.5 2.3 250 4.4 366 2.31 2.8 1.0 783 <0.1 2.2 0.2 2.5 41 1.5 39.2 29 WLT02-I 2.59 4.98 1.29 2.02 10.00 0.62 0.01 0.08 <1 4 243 5.7 0.25 0.2 25.0 8.9 3 100 11.5 10.8 0.04 9.2 2370 1020 3.37 6.3 3.2 90 9.4 269 3.34 2.8 1.1 403 <0.1 3.6 1.0 1.2 39 3.1 20.5 38 DP1 1.03 4.96 0.65 0.36 11.70 0.19 0.11 0.14 <1 15 2890 5.5 0.06 <0.1 12.9 2.0 3 17 5.7 9.4 <0.02 6.4 3690 297 0.83 4.4 3.0 130 2.8 40.4 1.96 6.5 0.5 438 <0.1 2.7 0.3 1.1 31 1.0 10.9 13 SBH-1 0.53 19.20 0.22 0.56 5.15 0.15 0.23 0.02 <1 102 1150 1.8 <0.04 <0.1 6.0 0.7 9 7 17.5 1.3 <0.02 3.3 2400 359 18.30 1.8 7.0 200 2.0 26.4 13.50 0.3 0.3 8780 <0.1 1.5 3.0 6.5 9 2.2 1.6 35 SHCa 0.44 >15 0.22 0.16 8.44 0.99 0.01 0.03 <1 3 48 2.6 <0.04 <0.1 14.7 2.0 3 <5 3.1 1.6 <0.02 1.7 2800 81 0.71 1.4 2.9 60 2.9 11.4 0.11 0.8 0.2 1410 <0.1 2.8 0.1 0.250.22.18 SynH 0.06 0.02 <0.01 0.01 14.80 1.68 0.03 0.01 <1 1 20 <0.1 <0.04 <0.1 2.6 0.7 2 <5 1.3 0.5 <0.02 1.3 2880 <5 <0.05 0.6 1.8 <50 2.3 0.2 0.06 0.1 0.1 5.8 <0.1 0.5 <0.1 <0.1 <1 <0.1 1.1 2

Table V-2: Major elements chemistry for the bulk samples.

WDXRF WDXRF WDXRF WDXRF WDXRF WDXRF WDXRF WDXRF WDXRF WDXRF WDXRF WDXRF CO2 C CO2 C Org C Tot C Tot S Field No. Al2O3 CaO Cr2O3 Fe2O3 K2O LOI MgO MnO Na2O P2O5 SiO2 TiO2 CO2 CRBNT_C Organic_C C S %%%%%%%%%%%% % % % %% CV2010-01 14.10 5.78 <0.01 4.76 3.91 15.00 3.70 0.06 4.01 0.09 46.40 0.55 3.03 0.83 0.22 1.05 0.07 CV2010-02 14.90 2.93 <0.01 4.86 4.19 12.10 3.33 0.09 3.78 0.16 52.10 0.51 0.41 0.11 0.44 0.55 0.10 CV2010-04 11.00 10.00 <0.01 3.64 6.24 16.00 5.03 0.07 3.71 0.09 41.40 0.43 8.20 2.24 0.19 2.43 0.12 CV2010-05 12.30 4.70 <0.01 4.13 7.47 12.60 3.28 0.06 5.19 0.10 45.30 0.46 3.34 0.91 0.09 1.00 0.45 CV2010-06 11.70 8.98 <0.01 3.99 6.70 15.40 3.43 0.08 1.48 0.09 45.40 0.45 5.91 1.61 0.09 1.70 0.08 CV2010-07 12.50 6.18 <0.01 3.34 5.00 8.84 3.78 0.09 3.25 0.11 53.60 0.47 4.06 1.11 0.17 1.28 0.31 WLC03-01 4.44 3.21 <0.01 1.98 1.43 21.60 17.70 0.02 0.40 0.01 47.40 0.18 2.67 0.73 0.98 1.71 0.78 WLC03-02 6.10 3.79 <0.01 2.88 3.55 18.30 15.30 0.05 0.37 0.02 46.10 0.16 4.33 1.18 0.71 1.89 1.49 WLC03-03 5.22 7.01 <0.01 2.70 6.02 9.31 11.30 0.09 1.63 <0.01 49.80 0.45 5.12 1.40 0.96 2.36 1.50 WLC03-04 4.73 5.91 <0.01 1.92 6.36 7.75 13.40 0.11 1.45 <0.01 50.70 0.37 4.33 1.18 0.65 1.83 0.96 WLC03-05 6.06 3.75 <0.01 2.59 5.44 7.80 11.10 0.05 2.51 <0.01 52.80 0.41 2.97 0.81 0.60 1.41 1.50 WLT02-D 4.83 3.09 <0.01 2.01 1.35 20.50 18.10 0.02 0.66 0.01 48.30 0.20 2.26 0.62 0.13 0.75 0.27 WLT02-F 4.25 9.13 <0.01 1.82 2.21 21.90 16.90 0.05 0.64 0.05 40.90 0.23 8.37 2.28 0.03 2.31 0.12 WLT02-I 4.93 7.34 <0.01 1.92 2.42 22.30 16.70 0.15 0.85 0.02 41.80 0.13 8.91 2.43 0.01 2.44 0.09 DP1 2.06 7.14 <0.01 1.01 0.42 24.40 19.10 0.04 0.28 0.03 43.70 0.22 6.81 1.86 -0.06 1.80 0.14 SBH-1 0.99 28.10 <0.01 0.30 0.63 30.10 8.47 0.05 0.16 0.04 28.10 0.03 24.20 6.60 0.02 6.62 0.18 SHCa 0.84 22.60 <0.01 0.32 0.17 24.50 13.90 0.01 1.29 0.01 34.10 0.04 17.80 4.86 0.01 4.87 0.09 SynH 0.13 0.04 <0.01 <0.01 <0.01 21.70 24.00 <0.01 2.34 <0.01 51.50 0.01 0.36 0.10 0.01 0.11 0.09

215

Table V-3: Trace elements chemistry for the clay concentrates. ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP ICP Field No. Al Ca Fe K Mg Na S Ti Ag As Ba Be Bi Cd Ce Co Cr Cs Cu Ga In La Li Mn Mo Nb Ni P Pb Rb Sb Sc Sn Sr Te Th Tl U V W Y Zn % % % % % % % % ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm CV2010-01 5.08 0.58 4.91 3.12 4.74 0.23 <0.01 0.20 <1 9 59 3.0 0.25 <0.1 32.4 22.2 40 223 48.8 15.9 0.10 18.6 4950 608 1.05 11.4 42.2 160 21.3 573 2.92 10.5 2.5 136 0.4 8.6 1.0 5.7 135 58.5 7.4 110 CV2010-02 8.74 0.67 4.24 3.48 2.85 0.32 0.02 0.23 <1 28 175 4.1 0.48 0.2 88.6 17.4 41 24 35.7 22.8 0.10 41.5 1140 685 1.96 18.0 45.9 570 22.4 322 4.51 13.7 3.3 125 <0.1 21.7 0.8 4.5 95 8.4 25.7 120 CV2010-04 5.03 0.93 4.43 2.86 5.80 0.15 0.01 0.26 <1 50 100 3.8 0.37 0.2 50.4 13.5 31 85 38.9 16.8 0.08 22.1 3340 604 1.70 15.2 26.0 380 15.2 388 4.40 12.6 3.1 276 <0.1 20.4 0.9 10.6 110 5.3 15.2 115 CV2010-05 6.42 0.41 5.24 4.97 3.92 0.20 <0.01 0.29 <1 76 81 4.5 0.59 0.2 71.5 15.2 33 106 47.7 20.3 0.12 34.1 3570 908 19.70 7.0 35.2 300 20.6 732 1.32 15.9 3.5 98.8 <0.1 13.4 1.4 6.2 130 8.2 13.2 135 CV2010-06 5.30 0.73 5.48 3.76 4.14 0.09 <0.01 0.30 <1 20 108 4.5 0.50 0.1 51.6 15.7 33 106 48.6 17.3 0.12 30.1 4320 822 4.20 18.8 41.6 290 18.8 553 4.71 15.2 3.8 167 <0.1 17.0 1.0 4.2 141 80.2 13.2 137 CV2010-07 4.80 0.71 4.30 3.01 6.00 0.17 0.01 0.23 <1 41 109 3.6 0.47 0.4 46.1 14.9 24 106 45.2 15.3 0.09 22.3 3260 928 68.40 14.8 34.9 430 21.1 545 4.11 12.1 3.4 533 <0.1 17.0 0.9 7.7 92 8.2 14.1 123 WLC03-01 2.39 0.94 1.14 1.30 11.40 0.24 0.03 0.24 <1 2 80 12.0 0.12 0.2 6.5 2.3 21 225 5.9 7.6 0.06 2.5 4190 128 8.05 15.2 5.5 <50 4.7 318 3.24 2.0 1.6 123 <0.1 2.3 0.1 2.7 38 1.0 7.3 57 WLC03-02 2.06 0.81 0.72 1.85 12.10 0.12 0.03 0.08 <1 2 81 10.7 0.15 0.2 4.2 3.0 16 293 4.3 6.9 0.05 1.8 5940 87 18.80 3.9 3.0 <50 3.3 324 1.81 1.4 1.2 139 <0.1 0.7 <0.1 0.9 31 0.3 5.0 45 WLC03-03 0.82 0.22 0.98 6.80 11.50 0.13 0.03 0.28 <1 27 55 14.6 0.16 0.4 10.2 3.3 18 548 1.3 8.7 0.11 4.4 11800 340 62.30 14.8 4.3 <50 4.4 544 13.00 4.0 3.3 38.0 <0.1 1.6 0.4 4.0 61 1.8 7.9 87 WLC03-04 0.86 0.28 0.75 7.00 11.90 0.15 0.03 0.24 <1 33 55 11.1 0.15 0.4 16.0 2.5 18 495 5.3 7.4 0.08 8.1 12000 379 101.00 10.8 3.0 <50 5.6 1030 14.90 3.2 2.2 47.6 <0.1 1.9 0.3 4.1 46 1.4 9.7 70 WLC03-05 1.21 0.09 1.33 5.59 10.60 0.39 0.30 0.34 <1 349 52 9.7 0.21 0.3 12.7 1.9 34 664 4.0 7.6 0.06 6.0 12400 240 176.00 12.7 16.0 <50 3.4 933 26.50 3.9 2.2 19.4 <0.1 1.5 0.7 4.3 79 31.1 9.7 40 WLT02-D 1.97 1.19 1.04 0.79 12.00 0.27 0.02 0.14 <1 3 33 12.8 0.15 <0.1 2.9 1.5 10 93 10.3 6.6 0.04 1.2 3920 76 0.19 7.2 2.6 <50 8.0 161 1.26 2.2 0.9 143 <0.1 0.7 0.1 0.4 28 0.9 3.1 36 WLT02-F 2.52 0.92 1.49 2.24 10.60 0.18 0.01 0.18 <1 5 37 9.0 0.37 <0.1 7.3 3.2 18 180 13.2 6.3 0.11 2.9 5700 61 1.61 8.3 4.0 <50 6.8 389 2.64 1.8 1.3 114 <0.1 1.5 0.1 0.7 31 1.1 9.2 54 WLT02-I 2.75 0.87 1.51 2.62 10.30 0.25 0.01 0.15 <1 5 33 8.8 0.18 <0.1 8.0 3.0 17 187 17.4 7.0 0.06 2.9 5110 110 2.44 7.0 3.8 <50 7.4 455 4.18 1.8 1.5 102 <0.1 1.5 0.20.7331.29.062 DP1 0.89 1.35 0.58 0.16 13.70 0.12 0.01 0.14 <1 9 161 5.1 0.08 <0.1 4.0 1.0 8 13 4.0 7.2 <0.02 1.7 5510 81 0.47 2.6 2.8 <50 2.5 26.1 1.22 4.2 0.7 138 <0.1 1.1 0.1 0.3330.72.314 SBH-1 0.27 1.34 0.16 0.11 13.60 <0.01 0.08 0.02 <1 54 136 2.7 <0.04 <0.1 2.3 0.8 6 11 11.9 1.6 <0.02 1.1 6770 160 2.61 2.2 10.6 150 1.1 19.7 5.66 0.2 0.7 1590 <0. 11.10.53.8211.70.624 SHCa 0.40 1.31 0.19 0.20 14.40 0.50 0.02 0.02 <1 6 18 3.4 0.13 <0.1 6.1 1.4 9 11 2.9 1.2 <0.02 0.9 5710 46 1.77 1.0 3.9 <50 2.7 24.2 0.45 0.8 0.4 519 <0.1 1.2 <0.1 0.150.30.810 SynH 0.07 0.03 <0.01 0.01 15.00 1.95 0.04 0.01 <1 <1 21 <0.1 <0.04 <0.1 2.4 0.2 3 <5 <0.5 0.2 <0.02 1.2 3660 <5 0.09 0.6 1.6 <50 2.9 0.5 0.08 <0.1 0.2 7.2 <0.1 0.4 <0.1 <0.1 <1 <0.1 1.0 1

Table V-4: Major elements chemistry, including essential and non-essential water, chlorine and fluorine, for the clay concentrates.

WDXRF WDXRF WDXRF WDXRF WDXRF WDXRF WDXRF WDXRF WDXRF WDXRF WDXRF WDXRF CO2 C CO2 C Org C Tot C Tot S Tot H2O Tot H2O Tot H2O Cl_ISE F_ISE Field No. Al2O3 CaO Cr2O3 Fe2O3 K2O LOI MgO MnO Na2O P2O5 SiO2 TiO2 CO2 CRBNT_C Organic_C C S H2O_Minus H2O_Plus Total_H2O Cl F %%%%%%%%%%%%%% % %%% % %ppmppm CV2010-01 9.94 0.86 0.01 7.55 3.74 16.00 8.06 0.09 0.29 0.04 51.10 0.34 0.08 0.02 0.03 0.05 <0.05 9.3 5.8 15.1 150 14600 CV2010-02 16.80 0.97 0.01 6.38 4.20 14.20 4.81 0.09 0.40 0.13 50.60 0.38 0.06 0.02 0.05 0.07 <0.05 6.6 6.8 13.4 70 1850 CV2010-04 10.00 1.41 <0.01 6.93 3.51 16.50 9.98 0.09 0.18 0.10 49.90 0.44 0.24 0.07 0.10 0.17 <0.05 9.2 6.5 15.7 100 7500 CV2010-05 12.60 0.61 0.01 8.07 5.93 12.00 6.68 0.13 0.24 0.07 52.30 0.54 0.14 0.04 0.02 0.06 <0.05 5.8 5.8 11.6 100 7410 CV2010-06 10.50 1.08 0.01 8.47 4.53 15.40 7.10 0.12 0.10 0.07 50.30 0.53 0.06 0.02 0.04 0.06 <0.05 8.9 6.0 14.9 80 10300 CV2010-07 9.79 1.10 0.01 6.82 3.77 15.50 10.60 0.14 0.24 0.10 50.10 0.41 0.16 0.04 0.08 0.12 <0.05 8.2 6.6 14.8 70 5380 WLC03-01 4.45 1.35 <0.01 1.59 1.27 20.70 18.60 0.02 0.28 <0.01 49.00 0.46 0.22 0.06 0.86 0.92 0.16 9.7 6.6 16.3 <50 33600 WLC03-02 3.77 1.13 <0.01 0.97 1.85 19.70 19.20 0.01 0.13 <0.01 49.50 0.12 0.08 0.02 0.88 0.90 0.16 8.7 8.2 16.9 <50 44400 WLC03-03 1.54 0.30 <0.01 1.40 7.29 9.22 18.90 0.05 0.15 <0.01 54.20 0.49 0.04 0.01 0.98 0.99 0.06 4.6 4.1 8.7 <50 64800 WLC03-04 1.62 0.40 <0.01 1.04 7.22 9.13 19.40 0.05 0.17 <0.01 54.00 0.43 0.04 0.01 0.76 0.77 0.07 3.8 4.4 8.2 <50 65200 WLC03-05 2.33 0.11 <0.01 1.91 7.33 8.21 17.20 0.03 0.48 <0.01 54.40 0.56 0.04 0.01 0.71 0.72 0.28 4.0 3.5 7.5 60 65200 WLT02-D 3.69 1.79 <0.01 1.47 0.80 20.80 20.00 0.01 0.31 <0.01 47.90 0.22 0.34 0.09 0.11 0.20 0.14 10.6 6.0 16.6 <50 35900 WLT02-F 4.73 1.32 <0.01 2.09 2.33 17.80 17.20 <0.01 0.21 0.01 51.20 0.30 0.06 0.02 0.12 0.14 0.13 8.6 6.3 14.9 <50 40800 WLT02-I 5.21 1.26 <0.01 2.14 2.72 17.20 16.90 0.02 0.30 <0.01 50.70 0.24 0.10 0.03 0.18 0.21 0.14 7.9 6.2 14.1 <50 42800 DP1 1.60 1.92 <0.01 0.81 0.13 22.50 21.80 0.01 0.14 <0.01 48.70 0.23 0.55 0.15 0.08 0.23 0.13 11.2 8.8 20.0 <50 31800 SBH-1 0.51 1.92 <0.01 0.21 0.12 23.50 21.70 0.02 <0.01 0.03 49.70 0.04 0.06 0.02 0.54 0.56 <0.05 14.1 7.0 21.1 50 28100 SHCa 0.75 1.89 <0.01 0.24 0.12 19.40 23.10 <0.01 0.60 <0.01 52.00 0.03 0.53 0.14 0.09 0.23 0.15 10.1 6.9 17.0 80 42900 SynH 0.16 0.02 <0.01 <0.01 <0.01 22.60 23.80 <0.01 2.36 <0.01 50.40 0.02 0.39 0.11 0.02 0.13 0.11 12.0 8.6 20.6 <50 140

216

Table V-5: Chemistry from the CEC wash solutions. nr = not recovered.

Field No. Ag Al As Ba Be Bi Ca Cd Ce Co Cr Cs Cu Fe Ga K La Li Mg Mn Mo Na Nb Ni P Pb Rb Sb Sc Se SiO2 SO4 Sr Th Ti Tl U V Y Zn ug/L ug/L ug/L ug/L ug/L ug/L mg/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L mg/L ug/L ug/L mg/L ug/L ug/L mg/L ug/L ug/L mg/L ug/L ug/L ug/L ug/L ug/L mg/L mg/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L CV2010‐01 <100 <200 <100 <20 <5 < 20 <20 <2 < 1 <2 <100 15.7 <50 <5000 < 5<3< 10 < 10 <1 <20 < 200 <1 < 20 <40 < 1<519<30< 60 < 100 < 20 < 200 < 50 < 20 < 50 <10 < 10 <50 < 1 <300 CV2010‐02 <100 <200 <100 <20 <5 < 20 <20 <2 < 1 <2 <100 < 2 <50 <5000 < 5<3< 10 < 10 <1 <20 < 200 <1 < 20 <40 < 1<59.1<30< 60 < 100 < 20 < 200 < 50 < 20 < 50 <10 < 10 <50 1.4 <300 CV2010‐04 <100 <200 <100 <20 <5 < 20 <20 <2 < 1 <2 <100 2.5 <50 <5000 < 5<3< 10 18.6 <1 <20 < 200 <1 < 20 <40 < 1<57.2<30< 60 < 100 < 20 < 200 62.9 < 20 < 50 <10 < 10 <50 < 1 <300 CV2010‐05 <100 <200 <100 <20 <5 < 20 <20 <2 < 1 <2 <100 3.7 <50 <5000 < 5<3< 10 42.8 <1 <20 < 200 <1 < 20 <40 < 1 <5 11.4 <30 < 60 < 100 < 20 < 200 < 50 < 20 < 50 <10 < 10 <50 < 1 <300 CV2010‐06 <100 <200 <100 <20 <5 < 20 <20 <2 < 1 <2 <100 2.2 <50 <5000 < 5<3< 10 < 10 <1 <20 < 200 <1 < 20 <40 < 1<58.6<30< 60 < 100 < 20 < 200 < 50 < 20 < 50 <10 < 10 <50 < 1 <300 CV2010‐07 <100 <200 <100 <20 <5 < 20 <20 <2 < 1 <2 <100 2.7 <50 <5000 < 5<3< 10 18.7 <1 <20 < 200 <1 < 20 <40 < 1 <5 12.7 <30 < 60 < 100 < 20 < 200 143 < 20 < 50 <10 < 10 <50 < 1 <300 DP1 <100 <200 <100 55.3 <5 < 20 <20 <2 < 1 <2 <100 < 2 <50 <5000 < 5<3< 1< 10 2.1 <20 < 200 <1 < 20 <40 < 1<51.9<30< 60 < 100 < 20 < 200 < 50 < 20 < 50 <10 < 10 <50 < 1 <300 SBH‐1 nrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnrnr SHCa <100 <200 <100 <20 <5 < 20 <20 <2 < 1 <2 <100 < 2 <50 <5000 < 5<3< 1 18.9 1.2 <20 < 200 1.3 < 20 <40 < 1<51.4<30< 60 < 100 < 20 < 200 186 < 20 < 50 <10 < 10 <50 < 1 <300 WLC03‐01 nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr WLC03‐02 <100 <200 <100 <20 <5 < 20 <20 <2 < 1 <2 <100 17.9 <50 <5000 < 5<3< 1< 10 1.9 <20 < 200 <1 < 20 <40 < 1<56.3<30< 60 < 100 < 20 < 200 < 50 < 20 < 50 <10 < 10 <50 < 1 <300 WLC03‐03 <100 <200 <100 <20 <5 < 20 <20 <2 < 1 <2 <100 7.7 <50 <5000 < 5<3< 10 15.8 <1 <20 < 200 <1 < 20 <40 < 1<56.5<30< 60 < 100 < 20 < 200 < 50 < 20 < 50 <10 < 10 <50 < 1 <300 WLC03‐04 <100 <200 <100 <20 <5 < 20 <20 <2 < 1 <2 <100 8.9 <50 <5000 < 5<3< 10 13.6 <1 <20 < 200 <1 < 20 <40 < 1<56.5<30< 60 < 100 < 20 < 200 < 50 < 20 < 50 <10 < 10 <50 < 1 <300 WLC03‐05 nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr WLT02D nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr WLT02F <100 <200 <100 <20 <5 < 20 <20 <2 < 1 <2 <100 2.7 <50 <5000 < 5<3< 1< 10 <1 <20 < 200 <1 < 20 <40 < 1<53.6<30< 60 < 100 < 20 < 200 < 50 < 20 < 50 <10 < 10 <50 < 1 <300 WLT02I nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr nr SynH <100 <200 <100 <20 <5 < 20 <20 <2 < 1 <2 <100 < 2 <50 <5000 < 5<3< 1 208 4.9 <20 < 200 5.7 < 20 <40 < 1<5< 1<30< 60 < 100 < 20 < 200 < 50 < 20 < 50 <10 < 10 <50 < 1 <300 217

218

Appendix VI – Layer Charge

Table VI‐1: Peak migration curve for the evaluation of the charge distribution. Xi represents the fraction of interlayer spaces occupied by bilayers of alkylammonium ions (Lagaly, 1994).

d(001) Xi d(001) Xi 13.6 0.00 16.0 0.49 14.0 0.13 16.5 0.58 14.5 0.24 17.0 0.70 15.0 0.33 17.3 0.80 15.5 0.40 17.7 1.00

Table VI‐2: Charge distribution for sample CV2010‐01. I is cation density (eq/ O10(OH)2); d(001) is layer spacing (Å).

ξi Xi n ξn d(001) Xn ξi*Xi (ξn + ξn+1)/2 (Xn + Xn+1)/2 9 0.371 13.6 0.000 0.356 0.240 0.085 10 0.341 14.5 0.240 0.328 0.036 0.012 11 0.316 14.8 0.276 0.305 0.232 0.071 12 0.294 16.1 0.508 0.284 0.054 0.015 13 0.275 16.4 0.562 0.266 0.338 0.090 14 0.258 17.5 0.900 0.251 0.100 0.025 15 0.243 17.8 1.000  0.298 eq/O10(OH)2

219

Table VI‐3: Charge distribution for sample CV2010‐02. I is cation density (eq/ O10(OH)2); d(001) is layer spacing (Å).

ξi Xi n ξn d(001) Xn ξi*Xi (ξn + ξn+1)/2 (Xn + Xn+1)/2 8 0.406 13.4 0.000 0.388 0.130 0.050 9 0.371 14.0 0.130 0.356 0.288 0.102 10 0.341 15.6 0.418 0.328 0.000 0.000 11 0.316 15.6 0.418 0.305 0.186 0.057 12 0.294 16.6 0.604 0.284 0.396 0.113 13 0.275 18.1 1.000  0.322 eq/O10(OH)2

Table VI‐4: Charge distribution for sample CV2010‐04. I is cation density (eq/ O10(OH)2); d(001) is layer spacing (Å).

ξi Xi n ξn d(001) Xn ξi*Xi (ξn + ξn+1)/2 (Xn + Xn+1)/2 8 0.406 13.6 0.000 0.388 0.065 0.025 9 0.371 13.8 0.065 0.356 0.000 0.000 10 0.341 13.8 0.065 0.328 0.000 0.000 11 0.316 13.8 0.065 0.305 0.131 0.040 12 0.294 14.3 0.196 0.284 0.222 0.063 13 0.275 15.6 0.418 0.266 0.234 0.062 14 0.258 16.8 0.652 0.251 0.248 0.062 15 0.243 17.5 0.900 0.237 0.100 0.024 16 0.230 17.8 1.000  0.276 eq/O10(OH)2

220

Table VI‐5: Charge distribution for sample CV2010‐06. I is cation density (eq/ O10(OH)2); d(001) is layer spacing (Å).

ξi Xi n ξn d(001) Xn ξi*Xi (ξn + ξn+1)/2 (Xn + Xn+1)/2 9 0.371 13.5 0.000 0.356 0.294 0.105 10 0.341 14.8 0.294 0.328 0.124 0.041 11 0.316 15.6 0.418 0.305 0.210 0.064 12 0.294 16.7 0.628 0.284 0.172 0.049 13 0.275 17.3 0.800 0.266 0.000 0.000 14 0.258 17.3 0.800 0.251 0.200 0.050 15 0.243 17.7 1.000  0.308 eq/O10(OH)2

Table VI‐6: Charge distribution for sample CV2010‐07. I is cation density (eq/ O10(OH)2); d(001) is layer spacing (Å).

ξi Xi n ξn d(001) Xn ξi*Xi (ξn + ξn+1)/2 (Xn + Xn+1)/2 10 0.341 13.6 0.000 0.328 0.130 0.043 11 0.316 14.0 0.130 0.305 0.128 0.039 12 0.294 14.6 0.258 0.284 0.160 0.045 13 0.275 15.6 0.418 0.266 0.126 0.034 14 0.258 16.3 0.544 0.251 0.406 0.102 15 0.243 17.6 0.950 0.237 0.050 0.012 16 0.230 17.9 1.000  0.274 eq/O10(OH)2

221

Table VI‐7: Charge distribution for sample WLC03‐01. I is cation density (eq/ O10(OH)2); d(001) is layer spacing (Å).

ξi Xi n ξn d(001) Xn ξi*Xi (ξn + ξn+1)/2 (Xn + Xn+1)/2 7 0.449 13.4 0.000 0.427 0.130 0.056 8 0.406 14.0 0.130 0.388 0.182 0.071 9 0.371 14.9 0.312 0.356 0.142 0.051 10 0.341 15.8 0.454 0.328 0.054 0.018 11 0.316 16.1 0.508 0.305 0.292 0.089 12 0.294 17.3 0.800 0.284 0.100 0.028 13 0.275 17.5 0.900 0.266 0.050 0.013 14 0.258 17.6 0.950 0.251 0.050 0.013 15 0.243 17.8 1.000  0.338 eq/O10(OH)2

Table VI‐8: Charge distribution for sample WLC03‐02. I is cation density (eq/ O10(OH)2); d(001) is layer spacing (Å).

ξi Xi n ξn d(001) Xn ξi*Xi (ξn + ξn+1)/2 (Xn + Xn+1)/2 7 0.449 13.5 0.000 0.427 0.098 0.042 8 0.406 13.9 0.098 0.388 0.289 0.112 9 0.371 15.4 0.386 0.356 0.068 0.024 10 0.341 15.8 0.454 0.328 0.108 0.035 11 0.316 16.4 0.562 0.305 0.438 0.133 12 0.294 17.9 1.000  0.347 eq/O10(OH)2

222

Table VI‐9: Charge distribution for sample WLT02D. I is cation density (eq/ O10(OH)2); d(001) is layer spacing (Å).

ξi Xi n ξn d(001) Xn ξi*Xi (ξn + ξn+1)/2 (Xn + Xn+1)/2 7 0.449 13.6 0.000 0.427 0.098 0.042 8 0.406 13.9 0.098 0.388 0.261 0.101 9 0.371 15.2 0.358 0.356 0.132 0.047 10 0.341 16.0 0.490 0.328 0.072 0.024 11 0.316 16.4 0.562 0.305 0.288 0.088 12 0.294 17.4 0.850 0.284 0.000 0.000 13 0.275 17.4 0.850 0.266 0.150 0.040 14 0.258 17.8 1.000  0.341 eq/O10(OH)2

Table VI‐10: Charge distribution for sample WLT02F. I is cation density (eq/ O10(OH)2); d(001) is layer spacing (Å).

ξi Xi n ξn d(001) Xn ξi*Xi (ξn + ξn+1)/2 (Xn + Xn+1)/2 7 0.449 13.4 0.000 0.427 0.033 0.014 8 0.406 13.7 0.033 0.388 0.280 0.109 9 0.371 14.9 0.312 0.356 0.160 0.057 10 0.341 15.9 0.472 0.328 0.108 0.035 11 0.316 16.5 0.580 0.305 0.220 0.067 12 0.294 17.3 0.800 0.284 0.050 0.014 13 0.275 17.4 0.850 0.266 0.150 0.040 14 0.258 17.7 1.000  0.336 eq/O10(OH)2 223

Table VI‐11: Charge distribution for sample WLT02I. I is cation density (eq/ O10(OH)2); d(001) is layer spacing (Å).

ξi Xi n ξn d(001) Xn ξi*Xi (ξn + ξn+1)/2 (Xn + Xn+1)/2 7 0.449 13.4 0.000 0.427 0.033 0.014 8 0.406 13.7 0.033 0.388 0.326 0.126 9 0.371 15.2 0.358 0.356 0.114 0.041 10 0.341 15.9 0.472 0.328 0.090 0.030 11 0.316 16.4 0.562 0.305 0.238 0.073 12 0.294 17.3 0.800 0.284 0.050 0.014 13 0.275 17.4 0.850 0.266 0.150 0.040 14 0.258 17.8 1.000  0.337 eq/O10(OH)2

224

Table VI‐12: Charge distribution for sample DP1. I is cation density (eq/ O10(OH)2); d(001) is layer spacing (Å).

ξi Xi n ξn d(001) Xn ξi*Xi (ξn + ξn+1)/2 (Xn + Xn+1)/2 7 0.449 13.6 0.000 0.427 0.033 0.014 8 0.406 13.7 0.033 0.388 0.262 0.102 9 0.371 14.8 0.294 0.356 0.092 0.033 10 0.341 15.4 0.386 0.328 0.086 0.028 11 0.316 15.9 0.472 0.305 0.378 0.115 12 0.294 17.4 0.850 0.284 0.100 0.028 13 0.275 17.6 0.950 0.266 0.000 0.000 14 0.258 17.6 0.950 0.251 0.050 0.013 15 0.243 17.9 1.000  0.332 eq/O10(OH)2

Table VI‐13: Charge distribution for sample SHCa. I is cation density (eq/ O10(OH)2); d(001) is layer spacing (Å).

ξi Xi n ξn d(001) Xn ξi*Xi (ξn + ξn+1)/2 (Xn + Xn+1)/2 11 0.316 13.6 0.000 0.305 0.240 0.073 12 0.294 14.5 0.240 0.284 0.028 0.008 13 0.275 15.2 0.268 0.266 0.168 0.045 14 0.258 15.7 0.436 0.251 0.036 0.009 15 0.243 15.9 0.472 0.237 0.156 0.037 16 0.230 16.9 0.628 0.219 0.322 0.070 18 0.208 17.6 0.950  0.242 eq/O10(OH)2

225

Table VI‐14: Charge distribution for sample SBH‐1. I is cation density (eq/ O10(OH)2); d(001) is layer spacing (Å).

ξi Xi n ξn d(001) Xn ξi*Xi (ξn + ξn+1)/2 (Xn + Xn+1)/2 7 0.449 13.6 0.000 0.427 0.033 0.014 8 0.406 13.7 0.033 0.388 0.033 0.013 9 0.371 13.8 0.065 0.356 0.193 0.069 10 0.341 14.6 0.258 0.328 0.054 0.018 11 0.316 14.9 0.312 0.305 0.160 0.049 12 0.294 15.9 0.472 0.284 0.000 0.000 13 0.275 15.9 0.472 0.266 0.180 0.048 14 0.258 16.8 0.652 0.251 0.148 0.037 15 0.243 17.3 0.800 0.237 0.200 0.047 16 0.230 1.000  0.294 eq/O10(OH)2 226

Appendix VII – Structural Formula Calculations 227

CV2010-01

Table VII‐1: Calculation of the structural formula for sample CV2010‐01. (a) correction for impurities; (b) calculations. Lab Corrections (wt%) Corrected Normalized

(a) analysis (wt%) Calcite (CaCO3)OtherSumanalysis (wt%) analysis (wt%)

Al2O3 9.94 9.94 10.07 CaO 0.86 0.14 0.14 0.72 0.73

Cr2O3 0.01 0.01 0.01 0.00 0.00

Fe2O3 7.55 7.55 7.65

K2O 3.74 3.74 3.79 MgO 8.06 8.06 8.16 MnO 0.09 0.09 0.09 0.00 0.00

Na2O 0.29 0.29 0.29

P2O5 0.04 0.04 0.04 0.00 0.00

SiO2 51.10 51.10 51.74

TiO2 0.34 0.34 0.34

Li2O 1.07 1.07 1.08 SrO 0.02 0.02 0.02 0.00 0.00

Rb2O 0.06 0.06 0.06 0.00 0.00

Cs2O 0.02 0.02 0.02 0.00 0.00 ‐ H2O 9.30 9.30 9.42 + H2O 5.80 5.80 5.87

CO2 0.18 0.07 0.11 0.18 0.00 0.00 F 1.46 1.46 1.48 less O≡F 0.61 0.61 0.62 Total 99.32 0.21 0.35 0.56 98.75 100.00

Normalized Molecular # cations % cationscharge equivalent (%) Proportionality Cations (b) analysis (wt%) weight (g/mol) factor (44/4.9347) per unit cell

Al2O3 10.07 / 101.96 x 2 = 0.1974 x 3 = 0.5923 x 8.9164 = 1.76 CaO 0.73 / 56.08 x 1 = 0.0130 x 2 = 0.0260 x 8.9164 = 0.12

Fe2O3 7.65 / 159.69 x 2 = 0.0958 x 3 = 0.2873 x 8.9164 = 0.85

K2O 3.79 / 94.20 x 2 = 0.0804 x 1 = 0.0804 x 8.9164 = 0.72 MgO 8.16 / 40.30 x 1 = 0.2025 x 2 = 0.4050 x 8.9164 = 1.81

Na2O 0.29 / 61.98 x 2 = 0.0095 x 1 = 0.0095 x 8.9164 = 0.08

SiO2 51.74 / 60.08 x 1 = 0.8612 x 4 = 3.4448 x 8.9164 = 7.68

Li2O 1.08 / 29.88 x 2 = 0.0722 x 1 = 0.0722 x 8.9164 = 0.64

TiO2 0.34 / 79.90 x 1 = 0.0043 x 4 = 0.0172 x 8.9164 = 0.04  4.9347

+ H2O 5.87 / 18.0152 x 2 = 0.6520 x 1 = 0.6520 x 8.9164 = 5.81 F 1.48 / 18.9984 x 1 = 0.0778 x 1 = 0.0778 x 8.9164 = 0.69

............ ∙2.5 228

CV2010-02

Table VII‐2: Calculation of the structural formula for sample CV2010‐02. (a) correction for impurities; (b) calculations. Lab Corrections (wt%) Corrected Normalized

(a) analysis (wt%) Calcite (CaCO3)OtherSumanalysis (wt%) analysis (wt%)

Al2O3 16.80 16.80 17.12 CaO 0.97 0.14 0.14 0.83 0.85

Cr2O3 0.01 0.01 0.01 0.00 0.00

Fe2O3 6.38 6.38 6.50

K2O 4.20 4.20 4.28 MgO 4.81 4.81 4.90 MnO 0.09 0.09 0.09 0.00 0.00

Na2O 0.40 0.40 0.41

P2O5 0.13 0.13 0.13 0.00 0.00

SiO2 50.60 50.60 51.55

TiO2 0.38 0.38 0.39

Li2O 0.25 0.25 0.25 SrO 0.01 0.01 0.01 0.00 0.00

Rb2O 0.04 0.04 0.04 0.00 0.00 ‐ H2O 6.60 6.60 6.72 + H2O 6.80 6.80 6.93

CO2 0.26 0.07 0.18 0.26 0.00 0.00 F 0.185 0.19 0.19 less O≡F 0.08 0.08 0.08 Total 98.83 0.21 0.46 0.68 98.15 100.00

Normalized Molecular # cations% cations charge equivalent (%) Proportionality Cations (b) analysis (wt%) weight (g/mol) factor (44/5.1047) per unit cell

Al2O3 17.12 / 101.96 x 2 = 0.3357 x 3 = 1.0072 x 8.6196 = 2.89 CaO 0.85 / 56.08 x 1 = 0.0151 x 2 = 0.0302 x 8.6196 = 0.13

Fe2O3 6.50 / 159.69 x 2 = 0.0814 x 3 = 0.2442 x 8.6196 = 0.70

K2O 4.28 / 94.20 x 2 = 0.0909 x 1 = 0.0909 x 8.6196 = 0.78 MgO 4.90 / 40.30 x 1 = 0.1216 x 2 = 0.2432 x 8.6196 = 1.05

Na2O 0.41 / 38.99 x 2 = 0.0209 x 1 = 0.0209 x 8.6196 = 0.18

SiO2 51.55 / 60.08 x 1 = 0.8580 x 4 = 3.4320 x 8.6196 = 7.40

Li2O 0.25 / 29.88 x 2 = 0.0167 x 1 = 0.0167 x 8.6196 = 0.14

TiO2 0.39 / 79.90 x 1 = 0.0048 x 4 = 0.0194 x 8.6196 = 0.04  5.1047

+ H2O 6.93 / 18.0152 x 2 = 0.7691 x 1 = 0.7691 8.6196 = 6.63 F 0.19 / 18.9984 x 1 = 0.0099 x 1 = 0.0099 8.6196 = 0.09

............ ∙2.7 229

CV2010-04

Table VII‐3: Calculation of the structural formula for sample CV2010‐04. (a) correction for impurities; (b) calculations. Lab Corrections (wt%) Corrected Normalized

(a) analysis (wt%) Calcite (CaCO3)OtherSumanalysis (wt%) analysis (wt%)

Al2O3 10.00 10.00 10.13 CaO 1.41 0.49 0.49 0.92 0.93

Fe2O3 6.93 6.93 7.02

K2O 3.51 3.51 3.56 MgO 9.98 9.98 10.11 MnO 0.09 0.09 0.09 0.00 0.00

Na2O 0.18 0.18 0.18

P2O5 0.10 0.10 0.10 0.00 0.00

SiO2 49.90 49.90 50.55

TiO2 0.44 0.44 0.45

Li2O 0.72 0.72 0.73 SrO 0.03 0.03 0.03 0.00 0.00

Rb2O 0.04 0.04 0.04 0.00 0.00

Cs2O 0.01 0.01 0.01 0.00 0.00 ‐ H2O 9.20 9.20 9.32 + H2O 6.50 6.50 6.58

CO2 0.62 0.26 0.37 0.62 0.00 0.00 F 0.75 0.75 0.76 less O≡F 0.32 0.32 0.32 Total 100.10 0.75 0.64 1.38 98.72 100.00

Normalized Molecular # cations % cationscharge equivalent (%) Proportionality Cations (b) analysis (wt%) weight (g/mol) factor (44/4.9124) per unit cell

Al2O3 10.13 / 101.96 x 2 = 0.1987 x 3 = 0.5961 x 8.9570 = 1.78 CaO 0.93 / 56.08 x 1 = 0.0166 x 2 = 0.0333 x 8.9570 = 0.15

Fe2O3 7.02 / 159.69 x 2 = 0.0879 x 3 = 0.2638 x 8.9570 = 0.79

K2O 3.56 / 94.20 x 2 = 0.0755 x 1 = 0.0755 x 8.9570 = 0.68 MgO 10.11 / 40.30 x 1 = 0.2508 x 2 = 0.5017 x 8.9570 = 2.25

Na2O 0.18 / 61.98 x 2 = 0.0059 x 1 = 0.0059 x 8.9570 = 0.05

SiO2 50.55 / 60.08 x 1 = 0.8413 x 4 = 3.3651 x 8.9570 = 7.54

Li2O 0.73 / 29.88 x 2 = 0.0488 x 1 = 0.0488 x 8.9570 = 0.44

TiO2 0.45 / 79.90 x 1 0.0056 x 4 = 0.0223 x 8.9570 = 0.05  4.9124

+ H2O 6.58 / 18.0152 x 2 = 0.7310 x 1 = 0.7310 x 8.9570 = 6.55 F 0.76 / 18.9984 x 1 = 0.0400 x 1 = 0.0400 x 8.9570 = 0.36

............. ∙2.9 230

CV2010-05

Table VII‐4: Calculation of the structural formula for sample CV2010‐05. (a) correction for impurities; (b) calculations. Lab Corrections (wt%) Corrected Normalized

(a) analysis (wt%) Calcite (CaCO3)OtherSumanalysis (wt%) analysis (wt%)

Al2O3 12.60 12.60 12.66 CaO 0.61 0.28 0.28 0.33 0.33

Cr2O3 0.01 0.01 0.01 0.00 0.00

Fe2O3 8.07 8.07 8.11

K2O 5.93 5.93 5.96 MgO 6.68 6.68 6.71 MnO 0.13 0.13 0.13 0.00 0.00

Na2O 0.24 0.24 0.24

P2O5 0.07 0.07 0.07 0.00 0.00

SiO2 52.30 52.30 52.57

TiO2 0.54 0.54 0.54

Li2O 0.77 0.77 0.77 SrO 0.01 0.01 0.01 0.00 0.00

Rb2O 0.08 0.08 0.08 0.00 0.00

Cs2O 0.01 0.01 0.01 0.00 0.00 ‐ H2O 5.80 5.80 5.83 + H2O 5.80 5.80 5.83

CO2 0.22 0.15 0.07 0.22 0.00 0.00 F 0.741 0.74 0.74 less O≡F 0.31 0.31 0.31 Total 100.30 0.43 0.38 0.81 99.49 100.00

Normalized Molecular # cations% cations charge equivalent (%) Proportionality Cations (b) analysis (wt%) weight (g/mol) factor (44/5.1079) per unit cell

Al2O3 12.66 / 101.96 x 2 = 0.2484 x 3 = 0.7453 x 8.6141 = 2.14 CaO 0.33 / 56.08 x 1 = 0.0059 x 2 = 0.0118 x 8.6141 = 0.05

Fe2O3 8.11 / 159.69 x 2 = 0.1016 x 3 = 0.3048 x 8.6141 = 0.88

K2O 5.96 / 94.20 x 2 = 0.1266 x 1 = 0.1266 x 8.6141 = 1.09 MgO 6.71 / 40.30 x 1 = 0.1666 x 2 = 0.3332 x 8.6141 = 1.44

Na2O 0.24 / 61.98 x 2 = 0.0078 x 1 = 0.0078 x 8.6141 = 0.07

SiO2 52.57 / 60.08 x 1 = 0.8749 x 4 = 3.4996 x 8.6141 = 7.54

Li2O 0.77 / 29.88 x 2 = 0.0517 x 1 = 0.0517 x 8.6141 = 0.45

TiO2 0.54 / 79.90 x 1 = 0.0068 x 4 = 0.0272 x 8.6141 = 0.06  5.1079

+ H2O 5.83 / 18.0152 x 2 = 0.6472 x 1 = 0.6472 x 8.6141 = 5.58 F 0.74 / 18.9984 x 1 = 0.0392 x 1 = 0.0392 x 8.6141 = 0.34

............ ∙1.9 231

CV2010-06

Table VII‐5: Calculation of the structural formula for sample CV2010‐06. (a) correction for impurities; (b) calculations. Lab Corrections (wt%) Corrected Normalized

(a) analysis (wt%) Calcite (CaCO3)OtherSumanalysis (wt%) analysis (wt%)

Al2O3 10.50 10.50 10.62 CaO 1.08 0.14 0.14 0.94 0.95

Cr2O3 0.01 0.01 0.01 0.00 0.00

Fe2O3 8.47 8.47 8.56

K2O 4.53 4.53 4.58 MgO 7.10 7.10 7.18 MnO 0.12 0.12 0.12 0.00 0.00

Na2O 0.10 0.10 0.10

P2O5 0.07 0.07 0.07 0.00 0.00

SiO2 50.30 50.30 50.86

TiO2 0.53 0.53 0.54

Li2O 0.93 0.93 0.94 SrO 0.02 0.02 0.02 0.00 0.00

Rb2O 0.06 0.06 0.06 0.00 0.00

Cs2O 0.01 0.01 0.01 0.00 0.00 ‐ H2O 8.90 8.90 9.00 + H2O 6.00 6.00 6.07

CO2 0.22 0.07 0.15 0.22 0.00 0.00 F 1.03 1.03 1.04 less O≡F 0.43 0.43 0.44 Total 99.55 0.21 0.44 0.65 98.90 100.00

Normalized Molecular # cations % cationscharge equivalent (%) Proportionality Cations (b) analysis (wt%) weight (g/mol) factor (44/4.9130) per unit cell

Al2O3 10.62 / 101.96 x 2 = 0.2083 x 3 = 0.6248 x 8.9558 = 1.87 CaO 0.95 / 56.08 x 1 = 0.0170 x 2 = 0.0339 x 8.9558 = 0.15

Fe2O3 8.56 / 159.69 x 2 = 0.1073 x 3 = 0.3218 x 8.9558 = 0.96

K2O 4.58 / 94.20 x 2 = 0.0973 x 1 = 0.0973 x 8.9558 = 0.87 MgO 7.18 / 40.30 x 1 = 0.1781 x 2 = 0.3562 x 8.9558 = 1.60

Na2O 0.10 / 61.98 x 2 = 0.0033 x 1 = 0.0033 x 8.9558 = 0.03

SiO2 50.86 / 60.08 x 1 = 0.8465 x 4 = 3.3860 x 8.9558 = 7.58

Li2O 0.94 / 29.88 x 2 = 0.0629 x 1 = 0.0629 x 8.9558 = 0.56

TiO2 0.54 / 79.90 x 1 = 0.0067 x 4 = 0.0268 x 8.9558 = 0.06  4.9130

+ H2O 6.07 / 18.0152 x 2 = 0.6735 x 1 = 0.6735 x 8.9558 = 6.03 F 1.04 / 18.9984 x 1 = 0.0548 x 1 = 0.0548 x 8.9558 = 0.49

............ ∙2.5 232

CV2010-07

Table VII‐6: Calculation of the structural formula for sample CV2010‐07. (a) correction for impurities; (b) calculations. Lab Corrections (wt%) Corrected Normalized

(a) analysis (wt%) Calcite (CaCO3)OtherSumanalysis (wt%) analysis (wt%)

Al2O3 9.79 9.79 9.95 CaO 1.10 0.28 0.28 0.82 0.83

Cr2O3 0.01 0.01 0.01 0.00 0.00

Fe2O3 6.82 6.82 6.93

K2O 3.77 3.77 3.83 MgO 10.60 10.60 10.78 MnO 0.14 0.14 0.14 0.00 0.00

Na2O 0.24 0.24 0.24

P2O5 0.10 0.10 0.10 0.00 0.00

SiO2 50.10 50.10 50.93

TiO2 0.41 0.41 0.42

Li2O 0.70 0.70 0.71 SrO 0.06 0.06 0.06 0.00 0.00

Rb2O 0.06 0.06 0.06 0.00 0.00

Cs2O 0.01 0.01 0.01 0.00 0.00 ‐ H2O 8.20 8.20 8.34 + H2O 6.60 6.60 6.71

CO2 0.44 0.15 0.29 0.44 0.00 0.00 F 0.538 0.54 0.55 less O≡F 0.23 0.23 0.23 Total 99.47 0.43 0.67 1.10 98.37 100.00

Normalized Molecular # cations% cations charge equivalent (%) Proportionality Cations (b) analysis (wt%) weight (g/mol) factor (44/4.9592) per unit cell

Al2O3 9.95 / 101.96 x 2 = 0.1952 x 3 = 0.5857 x 8.8725 = 1.73 CaO 0.83 / 56.08 x 1 = 0.0149 x 2 = 0.0297 x 8.8725 = 0.13

Fe2O3 6.93 / 159.69 x 2 = 0.0868 x 3 = 0.2605 x 8.8725 = 0.77

K2O 3.83 / 94.20 x 2 = 0.0814 x 1 = 0.0814 x 8.8725 = 0.72 MgO 10.78 / 40.30 x 1 = 0.2674 x 2 = 0.5347 x 8.8725 = 2.37

Na2O 0.24 / 61.98 x 2 = 0.0079 x 1 = 0.0079 x 8.8725 = 0.07

SiO2 50.93 / 60.08 x 1 = 0.8477 x 4 = 3.3907 x 8.8725 = 7.52

Li2O 0.71 / 29.88 x 2 = 0.0478 x 1 = 0.0478 x 8.8725 = 0.42

TiO2 0.42 / 79.90 x 1 = 0.0052 x 4 = 0.0209 x 8.8725 = 0.05  4.9592

+ H2O 6.71 / 18.0152 x 2 = 0.7449 x 1 = 0.7449 x 8.8725 = 6.61 F 0.55 / 18.9984 x 1 = 0.0288 x 1 = 0.0288 x 8.8725 = 0.26

............. ∙2.9 233

WLC03-01

Table VII‐7: Calculation of the structural formula for sample WLC03‐01. (a) correction for impurities; (b) calculations. Lab Corrections (wt%) Corrected Normalized

(a) analysis (wt%) Dolomite (CaMg(CO3)2)Pyrite (FeS2)OtherSumanalysis (wt%) analysis (wt%)

Al2O3 4.45 4.45 4.66 CaO 1.35 0.21 0.21 1.14 1.19

Fe2O3 1.59 0.23 0.23 1.36 1.43

K2O 1.27 1.27 1.33 MgO 18.60 0.25 0.25 18.35 19.22 MnO 0.02 0.02 0.02 0.00 0.00

Na2O 0.28 0.28 0.29

SiO2 49.00 49.00 51.33

TiO2 0.46 0.46 0.48

Li2O 0.90 0.90 0.94 SrO 0.01 0.01 0.01 0.00 0.00

Rb2O 0.03 0.03 0.03 0.00 0.00

Cs2O 0.02 0.02 0.02 0.00 0.00 ‐ H2O 9.70 9.70 10.16 + H2O 6.60 6.60 6.91

CO2 3.37 0.22 3.15 3.37 0.00 0.00

SO2 0.32 0.32 0.32 0.00 0.00 F 3.36 3.36 3.52 less O≡F 1.41 1.41 1.48 Total 99.93 0.68 0.55 3.24 4.47 95.46 100.00

Normalized Molecular # cations% cations charge equivalent (%) Proportionality Cations (b) analysis (wt%) weight (g/mol) factor (44/4.8667) per unit cell

Al2O3 4.66 / 101.96 x 2 = 0.0914 x 3 = 0.2743 x 9.0410 = 0.83 CaO 1.19 / 56.08 x 1 = 0.0213 x 2 = 0.0426 x 9.0410 = 0.19

Fe2O3 1.43 / 159.69 x 2 = 0.0179 x 3 = 0.0536 x 9.0410 = 0.16

K2O 1.33 / 94.20 x 2 = 0.0282 x 1 = 0.0282 x 9.0410 = 0.26 MgO 19.22 / 40.30 x 1 = 0.4770 x 2 = 0.9539 x 9.0410 = 4.31

Na2O 0.29 / 61.98 x 2 = 0.0095 x 1 = 0.0095 x 9.0410 = 0.09

SiO2 51.33 / 60.08 x 1 = 0.8543 x 4 = 3.4172 x 9.0410 = 7.72

Li2O 0.94 / 29.88 x 2 = 0.0632 x 1 = 0.0632 x 9.0410 = 0.57

TiO2 0.48 / 79.90 x 1 = 0.0060 x 4 = 0.0241 x 9.0410 = 0.05  4.8667

+ H2O 6.91 / 18.0152 x 2 = 0.7676 x 1 = 0.7676 x 9.0410 = 6.94 F 3.52 / 18.9984 x 1 = 0.1853 x 1 = 0.1853 x 9.0410 = 1.67

............ ∙4.6

234

WLC03-02

Table VII‐8: Calculation of the structural formula for sample WLC03‐02. (a) correction for impurities; (b) calculations. Lab Corrections (wt%) Corrected Normalized

(a) analysis (wt%) Dolomite (CaMg(CO3)2)Pyrite (FeS2)OtherSumanalysis (wt%) analysis (wt%)

Al2O3 3.77 3.77 3.89 CaO 1.13 0.07 0.07 1.06 1.09

Fe2O3 0.97 0.23 0.23 0.74 0.76

K2O 1.85 1.85 1.91 MgO 19.20 19.20 19.79 MnO 0.01 0.01 0.01 0.00 0.00

Na2O 0.13 0.13 0.13

SiO2 49.50 49.50 51.03

TiO2 0.12 0.12 0.12 0.00 0.00

Li2O 1.28 1.28 1.32 SrO 0.02 0.02 0.02 0.00 0.00

Rb2O 0.04 0.04 0.04 0.00 0.00

Cs2O 0.03 0.03 0.03 0.00 0.00 ‐ H2O 8.70 8.70 8.97 + H2O 8.20 8.20 8.45

CO2 3.30 0.07 3.22 3.30 0.00 0.00

SO2 0.32 0.32 0.32 0.00 0.00 F 4.44 4.44 4.58 less O≡F 1.87 1.87 1.93 Total 101.13 0.14 0.55 3.44 4.13 97.00 100.00

Normalized Molecular # cations % cationscharge equivalent (%) Proportionality Cations (b) analysis (wt%) weight (g/mol) factor (44/4.8089) per unit cell

Al2O3 3.89 / 101.96 x 2 = 0.0762 x 3 = 0.2287 x 9.1497 = 0.70 CaO 1.09 / 56.08 x 1 = 0.0195 x 2 = 0.0390 x 9.1497 = 0.18

Fe2O3 0.76 / 159.69 x 2 = 0.0096 x 3 = 0.0287 x 9.1497 = 0.09

K2O 1.91 / 94.20 x 2 = 0.0405 x 1 = 0.0405 x 9.1497 = 0.37 MgO 19.79 / 40.30 x 1 = 0.4911 x 2 = 0.9822 x 9.1497 = 4.49

Na2O 0.13 / 61.98 x 2 = 0.0043 x 1 = 0.0043 x 9.1497 = 0.04

SiO2 51.03 / 60.08 x 1 = 0.8493 x 4 = 3.3972 x 9.1497 = 7.77

Li2O 1.32 / 29.88 x 2 = 0.0882 x 1 = 0.0882 x 9.1497 = 0.81  4.8089

+ H2O 8.45 / 18.0152 x 2 = 0.9385 x 1 = 0.9385 x 9.1497 = 8.59 F 4.58 / 18.9984 x 1 = 0.2409 x 1 = 0.2409 x 9.1497 = 2.20

........... ∙6.8

235

WLC03-03

Table VII‐9: Calculation of the structural formula for sample WLC03‐03. (a) correction for impurities; (b) calculations. Lab Corrections (wt%) Corrected Normalized

(a) analysis (wt%) Calcite (CaCO3)Pyrite (FeS2)OtherSumanalysis (wt%) analysis (wt%)

Al2O3 1.54 1.54 1.55 CaO 0.30 0.07 0.07 0.23 0.23

Fe2O3 1.40 0.09 0.09 1.31 1.32

K2O 7.29 7.29 7.36 MgO 18.90 18.90 19.07 MnO 0.05 0.05 0.05 0.00 0.00

Na2O 0.15 0.15 0.15

SiO2 54.20 54.20 54.69

TiO2 0.49 0.49 0.49

Li2O 2.54 2.54 2.56

Rb2O 0.06 0.06 0.06 0.00 0.00

Cs2O 0.06 0.06 0.06 0.00 0.00 ‐ H2O 4.60 4.60 4.64 + H2O 4.10 4.10 4.14

CO2 3.63 0.04 3.59 3.63 0.00 0.00

SO2 0.12 0.12 0.12 0.00 0.00 F 6.48 6.48 6.54 less O≡F 2.73 2.73 2.75 Total 103.18 0.11 0.21 3.76 4.08 99.10 100.00

Normalized Molecular # cations% cations charge equivalent (%) Proportionality Cations (b) analysis (wt%) weight (g/mol) factor (44/5.0942) per unit cell

Al2O3 1.55 / 101.96 x 2 = 0.0305 x 3 = 0.0914 x 8.6373 = 0.26 CaO 0.23 / 56.08 x 1 = 0.0041 x 2 = 0.0083 x 8.6373 = 0.04

Fe2O3 1.32 / 159.69 x 2 = 0.0166 x 3 = 0.0497 x 8.6373 = 0.14

K2O 7.36 / 94.20 x 2 = 0.1562 x 1 = 0.1562 x 8.6373 = 1.35 MgO 19.07 / 40.30 x 1 = 0.4732 x 2 = 0.9464 x 8.6373 = 4.09

Na2O 0.15 / 61.98 x 2 = 0.0049 x 1 = 0.0049 x 8.6373 = 0.04

SiO2 54.69 / 60.08 x 1 = 0.9103 x 4 = 3.6410 x 8.6373 = 7.86

Li2O 2.56 / 29.88 x 2 = 0.1716 x 1 = 0.1716 x 8.6373 = 1.48

TiO2 0.49 / 79.90 x 1 = 0.0062 x 4 = 0.0248 x 8.6373 = 0.05  5.0942

+ H2O 4.14 / 18.0152 x 2 = 0.4593 x 1 = 0.4593 x 8.6373 = 3.97 F 6.54 / 18.9984 x 1 = 0.3442 x 1 = 0.3442 x 8.6373 = 2.97

............ ∙2.9

236

WLC03-04

Table VII‐10: Calculation of the structural formula for sample WLC03‐04. (a) correction for impurities; (b) calculations. Lab Corrections (wt%) Corrected Normalized

(a) analysis (wt%) Calcite (CaCO3)Pyrite (FeS2)OtherSumanalysis (wt%) analysis (wt%)

Al2O3 1.62 1.62 1.64 CaO 0.40 0.07 0.07 0.33 0.33

Fe2O3 1.04 0.10 0.10 0.94 0.95

K2O 7.22 7.22 7.32 MgO 19.40 19.40 19.66 MnO 0.05 0.05 0.05 0.00 0.00

Na2O 0.17 0.17 0.17

SiO2 54.00 54.00 54.73

TiO2 0.43 0.43 0.44

Li2O 2.58 2.58 2.62 SrO 0.01 0.01 0.01 0.00 0.00

Rb2O 0.11 0.11 0.11 0.00 0.00

Cs2O 0.05 0.05 0.05 0.00 0.00 ‐ H2O 3.80 3.80 3.85 + H2O 4.40 4.40 4.46

CO2 2.82 0.04 2.78 2.82 0.00 0.00

SO2 0.14 0.14 0.14 0.00 0.00 F 6.52 6.52 6.61 less O≡F 2.74 2.74 2.78 Total 102.02 0.11 0.24 3.00 3.35 98.67 100.00

Normalized Molecular # cations % cationscharge equivalent (%) Proportionality Cations (b) analysis (wt%) weight (g/mol) factor (44/5.1210) per unit cell

Al2O3 1.64 / 101.96 x 2 = 0.0322 x 3 = 0.0965 x 8.5921 = 0.28 CaO 0.33 / 56.08 x 1 = 0.0060 x 2 = 0.0119 x 8.5921 = 0.05

Fe2O3 0.95 / 159.69 x 2 = 0.0119 x 3 = 0.0358 x 8.5921 = 0.10

K2O 7.32 / 94.20 x 2 = 0.1554 x 1 = 0.1554 x 8.5921 = 1.33 MgO 19.66 / 40.30 x 1 = 0.4878 x 2 = 0.9757 x 8.5921 = 4.19

Na2O 0.17 / 61.98 x 2 = 0.0056 x 1 = 0.0056 x 8.5921 = 0.05

SiO2 54.73 / 60.08 x 1 = 0.9109 x 4 = 3.6434 x 8.5921 = 7.83

Li2O 2.62 / 29.88 x 2 = 0.1750 x 1 = 0.1750 x 8.5921 = 1.50

TiO2 0.44 / 79.90 x 1 = 0.0054 x 4 = 0.0218 x 8.5921 = 0.05  5.1210

+ H2O 4.46 / 18.0152 x 2 = 0.4951 x 1 = 0.4951 x 8.5921 = 4.25 F 6.61 / 18.9984 x 1 = 0.3478 x 1 = 0.3478 x 8.5921 = 2.99

............ ∙3.2

237

WLC03-05

Table VII‐11: Calculation of the structural formula for sample WLC03‐05. (a) correction for impurities; (b) calculations. Lab Corrections (wt%) Corrected Normalized

(a) analysis (wt%) Calcite (CaCO3)Pyrite (FeS2) Albite (NaAlSi3O8)OtherSumanalysis (wt%) analysis (wt%)

Al2O3 2.33 0.45 0.45 1.88 1.97 CaO 0.11 0.07 0.07 0.04 0.04

Fe2O3 1.91 0.40 0.40 1.51 1.58

K2O7.33 7.33 7.68 MgO 17.20 17.20 18.01 MnO 0.03 0.03 0.03 0.00 0.00

Na2O 0.48 0.32 0.32 0.16 0.17

SiO2 54.40 1.52 1.52 52.88 55.37

TiO2 0.56 0.56 0.59

Li2O2.67 2.67 2.80

Rb2O 0.10 0.10 0.10 0.00 0.00

Cs2O 0.07 0.07 0.07 0.00 0.00 ‐ H2O 4.00 4.00 4.19 + H2O 3.50 3.50 3.66

CO2 2.64 0.04 2.60 2.64 0.00 0.00

SO2 0.56 0.56 0.56 0.00 0.00 F6.52 6.52 6.83 less O≡F2.74 2.74 2.87 Total 101.67 0.11 0.96 2.29 2.80 6.16 95.50 100.00

Normalized Molecular # cations % cationscharge equivalent (%) Proportionality Cations (b) analysis (wt%) weight (g/mol) factor (44/5.1412) per unit cell

Al2O3 1.97 / 101.96 x 2 = 0.0386 x 3 = 0.1159 x 8.5582 = 0.33 CaO 0.04 / 56.08 x 1 = 0.0007 x 2 = 0.0015 x 8.5582 = 0.01

Fe2O3 1.58 / 159.69 x 2 = 0.0198 x 3 = 0.0594 x 8.5582 = 0.17

K2O 7.68 / 94.20 x 2 = 0.1630 x 1 = 0.1630 x 8.5582 = 1.39 MgO 18.01 / 40.30 x 1 = 0.4468 x 2 = 0.8937 x 8.5582 = 3.82

Na2O 0.17 / 61.98 x 2 = 0.0054 x 1 = 0.0054 x 8.5582 = 0.05

SiO2 55.37 / 60.08 x 1 = 0.9215 x 4 = 3.6859 x 8.5582 = 7.89

Li2O 2.80 / 29.88 x 2 = 0.1871 x 1 = 0.1871 x 8.5582 = 1.60

TiO2 0.59 / 79.90 x 1 = 0.0073 x 4 = 0.0294 x 8.5582 = 0.06  5.1412

+ H2O 3.66 / 18.0152 x 2 = 0.4069 x 1 = 0.4069 x 8.5582 = 3.48 F 6.83 / 18.9984 x 1 = 0.3593 x 1 = 0.3593 x 8.5582 = 3.08

............ ∙2.6

238

WLT02D

Table VII‐12: Calculation of the structural formula for sample WLT02D. (a) correction for impurities; (b) calculations. Lab Corrections (wt%) Corrected Normalized

(a) analysis (wt%) Dolomite (CaMg(CO3)2)Pyrite (FeS2)OtherSumanalysis (wt%) analysis (wt%)

Al2O3 3.69 3.69 3.89 CaO 1.79 0.31 0.31 1.48 1.56

Fe2O3 1.47 0.20 0.20 1.27 1.34

K2O 0.80 0.80 0.84 MgO 20.00 0.37 0.37 19.63 20.70 MnO 0.01 0.01 0.01 0.00 0.00

Na2O 0.31 0.31 0.33

SiO2 47.90 47.90 50.52

TiO2 0.22 0.22 0.23

Li2O 0.84 0.84 0.89 SrO 0.02 0.02 0.02 0.00 0.00

Rb2O 0.02 0.02 0.02 0.00 0.00

Cs2O 0.01 0.01 0.01 0.00 0.00 ‐ H2O 10.60 10.60 11.18 + H2O 6.00 6.00 6.33

CO2 0.73 0.33 0.40 0.73 0.00 0.00

SO2 0.28 0.28 0.28 0.00 0.00 F 3.59 3.59 3.79 less O≡F 1.51 1.51 1.59 Total 96.77 1.02 0.48 0.46 1.96 94.81 100.00

Normalized Molecular # cations % cationscharge equivalent (%) Proportionality Cations (b) analysis (wt%) weight (g/mol) factor (44/4.8252) per unit cell

Al2O3 3.89 / 101.96 x 2 = 0.0763 x 3 = 0.2290 x 9.1188 = 0.70 CaO 1.56 / 56.08 x 1 = 0.0277 x 2 = 0.0555 x 9.1188 = 0.25

Fe2O3 1.34 / 159.69 x 2 = 0.0168 x 3 = 0.0503 x 9.1188 = 0.15

K2O 0.84 / 94.20 x 2 = 0.0179 x 1 = 0.0179 x 9.1188 = 0.16 MgO 20.70 / 40.30 x 1 = 0.5136 x 2 = 1.0273 x 9.1188 = 4.68

Na2O 0.33 / 61.98 x 2 = 0.0106 x 1 = 0.0106 x 9.1188 = 0.10

SiO2 50.52 / 60.08 x 1 = 0.8409 x 4 = 3.3634 x 9.1188 = 7.67

Li2O 0.89 / 29.88 x 2 = 0.0596 x 1 = 0.0596 x 9.1188 = 0.54

TiO2 0.23 / 79.90 x 1 0.0029 x 4 = 0.0116 x 9.1188 = 0.03  4.8252

+ H2O 6.33 / 18.0152 x 2 = 0.7026 x 1 = 0.7026 x 9.1188 = 6.41 F 3.79 / 18.9984 x 1 = 0.1993 x 1 = 0.1993 x 9.1188 = 1.82

............ ∙4.2

239

WLT02F

Table VII‐13: Calculation of the structural formula for sample WLT02F. (a) correction for impurities; (b) calculations. Lab Corrections (wt%) Corrected Normalized

(a) analysis (wt%) Dolomite (CaMg(CO3)2)Pyrite (FeS2)OtherSumanalysis (wt%) analysis (wt%)

Al2O3 4.73 4.73 4.85 CaO 1.32 0.07 0.07 1.25 1.28

Fe2O3 2.09 0.19 0.19 1.90 1.95

K2O 2.33 2.33 2.39 MgO 17.20 0.08 0.08 17.12 17.55

Na2O 0.21 0.21 0.22

P2O5 0.01 0.01 0.01 0.00 0.00

SiO2 51.20 51.20 52.50

TiO2 0.30 0.30 0.31

Li2O 1.23 1.23 1.26 SrO 0.01 0.01 0.01 0.00 0.00

Rb2O 0.04 0.04 0.04 0.00 0.00

Cs2O 0.02 0.02 0.02 0.00 0.00 ‐ H2O 8.60 8.60 8.82 + H2O 6.30 6.30 6.46

CO2 0.51 0.07 0.44 0.51 0.00 0.00

SO2 0.26 0.26 0.26 0.00 0.00 F 4.08 4.08 4.18 less O≡F 1.72 1.72 1.76 Total 98.73 0.23 0.45 0.52 1.20 97.53 100.00

Normalized Molecular # cations% cations charge equivalent (%) Proportionality Cations (b) analysis (wt%) weight (g/mol) factor (44/4.9275) per unit cell

Al2O3 4.85 / 101.96 x 2 = 0.0951 x 3 = 0.2854 x 8.9296 = 0.85 CaO 1.28 / 56.08 x 1 = 0.0229 x 2 = 0.0457 x 8.9296 = 0.20

Fe2O3 1.95 / 159.69 x 2 = 0.0245 x 3 = 0.0734 x 8.9296 = 0.22

K2O 2.39 / 94.20 x 2 = 0.0507 x 1 = 0.0507 x 8.9296 = 0.45 MgO 17.55 / 40.30 x 1 = 0.4354 x 2 = 0.8709 x 8.9296 = 3.89

Na2O 0.22 / 61.98 x 2 = 0.0069 x 1 = 0.0069 x 8.9296 = 0.06

SiO2 52.50 / 60.08 x 1 = 0.8737 x 4 = 3.4948 x 8.9296 = 7.80

Li2O 1.26 / 29.88 x 2 = 0.0842 x 1 = 0.0842 x 8.9296 = 0.75

TiO2 0.31 / 79.90 x 1 = 0.0038 x 4 = 0.0154 x 8.9296 = 0.03  4.9275

+ H2O 6.46 / 18.0152 x 2 = 0.7171 x 1 = 0.7171 x 8.9296 = 6.40 F 4.18 / 18.9984 x 1 = 0.2202 x 1 = 0.2202 x 8.9296 = 1.97

............ ∙4.4

240

WLT02I

Table VII‐14: Calculation of the structural formula for sample WLT02I. (a) correction for impurities; (b) calculations. Lab Corrections (wt%) Corrected Normalized

(a) analysis (wt%) Dolomite (CaMg(CO3)2)Pyrite (FeS2)OtherSumanalysis (wt%) analysis (wt%)

Al2O3 5.21 5.21 5.38 CaO 1.26 0.10 0.10 1.16 1.19

Fe2O3 2.14 0.20 0.20 1.94 2.00

K2O 2.72 2.72 2.81 MgO 16.90 16.90 17.45 MnO 0.02 0.02 0.02 0.00 0.00

Na2O 0.30 0.30 0.31

SiO2 50.70 50.70 52.35

TiO2 0.24 0.24 0.25

Li2O 1.10 1.10 1.14 SrO 0.01 0.01 0.01 0.00 0.00

Rb2O 0.05 0.05 0.05 0.00 0.00

Cs2O 0.02 0.02 0.02 0.00 0.00 ‐ H2O 7.90 7.90 8.16 + H2O 6.20 6.20 6.40

CO2 0.77 0.11 0.66 0.77 0.00 0.00

SO2 0.28 0.28 0.28 0.00 0.00 F 4.28 4.28 4.42 less O≡F 1.80 1.80 1.86 Total 98.30 0.21 0.48 0.76 1.46 96.84 100.00

Normalized Molecular # cations % cationscharge equivalent (%) Proportionality Cations (b) analysis (wt%) weight (g/mol) factor (44/4.9437) per unit cell

Al2O3 5.38 / 101.96 x 2 = 0.1055 x 3 = 0.3166 x 8.9003 = 0.94 CaO 1.19 / 56.08 x 1 = 0.0213 x 2 = 0.0425 x 8.9003 = 0.19

Fe2O3 2.00 / 159.69 x 2 = 0.0251 x 3 = 0.0753 x 8.9003 = 0.22

K2O 2.81 / 94.20 x 2 = 0.0596 x 1 = 0.0596 x 8.9003 = 0.53 MgO 17.45 / 40.30 x 1 = 0.4330 x 2 = 0.8660 x 8.9003 = 3.85

Na2O 0.31 / 61.98 x 2 = 0.0100 x 1 = 0.0100 x 8.9003 = 0.09

SiO2 52.35 / 60.08 x 1 = 0.8713 x 4 = 3.4853 x 8.9003 = 7.75

Li2O 1.14 / 29.88 x 2 = 0.0760 x 1 = 0.0760 x 8.9003 = 0.68

TiO2 0.25 / 79.90 x 1 = 0.0031 x 4 = 0.0124 x 8.9003 = 0.03  4.9437

+ H2O 6.40 / 18.0152 x 2 = 0.7107 x 1 = 0.7107 x 8.9003 = 6.33 F 4.42 / 18.9984 x 1 = 0.2326 x 1 = 0.2326 x 8.9003 = 2.07

............ ∙4.4

241

DP1

Table VII‐15: Calculation of the structural formula for sample DP1. (a) correction for impurities; (b) calculations. Lab Corrections (wt%) Corrected Normalized

(a) analysis (wt%) Dolomite (CaMg(CO3)2)Pyrite (FeS2)OtherSumanalysis (wt%) analysis (wt%)

Al2O3 1.60 1.60 1.65 CaO 1.92 0.52 0.52 1.40 1.45

Fe2O3 0.81 0.19 0.19 0.62 0.64

K2O 0.13 0.13 0.13 MgO 21.80 0.62 0.62 21.18 21.88 MnO 0.01 0.01 0.01 0.00 0.00

Na2O 0.14 0.14 0.14

SiO2 48.70 48.70 50.31

TiO2 0.23 0.23 0.23 0.00 0.00

Li2O 1.19 1.19 1.23 SrO 0.02 0.02 0.02 0.00 0.00 ‐ H2O 11.20 11.20 11.57 + H2O 8.80 8.80 9.09

CO2 0.84 0.55 0.29 0.84 0.00 0.00

SO2 0.26 0.26 0.26 0.00 0.00 F 3.18 3.18 3.29 less O≡F 1.34 1.34 1.38 Total 99.49 1.69 0.45 0.55 2.69 96.79 100.00

Normalized Molecular # cations% cations charge equivalent (%) Proportionality Cations (b) analysis (wt%) weight (g/mol) factor (44/4.6978) per unit cell

Al2O3 1.65 / 101.96 x 2 = 0.0324 x 3 = 0.0973 x 9.3661 = 0.30 CaO 1.45 / 56.08 x 1 = 0.0258 x 2 = 0.0516 x 9.3661 = 0.24

Fe2O3 0.64 / 159.69 x 2 = 0.0080 x 3 = 0.0241 x 9.3661 = 0.08

K2O 0.13 / 94.20 x 2 = 0.0029 x 1 = 0.0029 x 9.3661 = 0.03 MgO 21.88 / 40.30 x 1 = 0.5429 x 2 = 1.0858 x 9.3661 = 5.08

Na2O 0.14 / 61.98 x 2 = 0.0047 x 1 = 0.0047 x 9.3661 = 0.04

SiO2 50.31 / 60.08 x 1 = 0.8374 x 4 = 3.3495 x 9.3661 = 7.84

Li2O 1.23 / 29.88 x 2 = 0.0820 x 1 = 0.0820 x 9.3661 = 0.77  4.6978

+ H2O 9.09 / 18.0152 x 2 = 1.0093 x 1 = 1.0093 x 9.3661 = 9.45 F 3.29 / 18.9984 x 1 = 0.1729 x 1 = 0.1729 x 9.3661 = 1.62

........... ∙7.1

242

SHCa

Table VII‐16: Calculation of the structural formula for sample SHCa. (a) correction for impurities; (b) calculations. Lab Corrections (wt%) Corrected Normalized

(a) analysis (wt%) Calcite (CaCO3)OtherSumanalysis (wt%) analysis (wt%)

Al2O3 0.75 0.75 0.76 CaO 1.89 0.98 0.98 0.91 0.93

Fe2O3 0.24 0.24 0.24

K2O 0.12 0.12 0.12 MgO 23.10 23.10 23.47

Na2O 0.60 0.60 0.61

SiO2 52.00 52.00 52.83

TiO2 0.03 0.03 0.03 0.00 0.00

Li2O 1.23 1.23 1.25 SrO 0.06 0.06 0.06 0.00 0.00 ‐ H2O 10.10 10.10 10.26 + H2O 6.90 6.90 7.01

CO2 0.84 0.51 0.33 0.84 0.00 0.00

SO2 0.30 0.30 0.30 0.00 0.00 F 4.29 4.29 4.36 less O≡F 1.81 1.81 1.83 Total 100.65 1.49 0.72 2.21 98.44 100.00

Normalized Molecular # cations% cations charge equivalent (%) Proportionality Cations (b) analysis (wt%) weight (g/mol) factor (44/4.8741) per unit cell

Al2O3 0.76 / 101.96 x 2 = 0.0149 x 3 = 0.0448 x 9.0272 = 0.13 CaO 0.93 / 56.08 x 1 = 0.0165 x 2 = 0.0330 x 9.0272 = 0.15

Fe2O3 0.24 / 159.69 x 2 = 0.0031 x 3 = 0.0092 x 9.0272 = 0.03

K2O 0.12 / 94.20 x 2 = 0.0026 x 1 = 0.0026 x 9.0272 = 0.02 MgO 23.47 / 40.30 x 1 = 0.5822 x 2 = 1.1645 x 9.0272 = 5.26

Na2O 0.61 / 61.98 x 2 = 0.0197 x 1 = 0.0197 x 9.0272 = 0.18

SiO2 52.83 / 60.08 x 1 = 0.8792 x 4 = 3.5168 x 9.0272 = 7.94

Li2O 1.25 / 29.88 x 2 = 0.0836 x 1 = 0.0836 x 9.0272 = 0.75  4.8741

+ H2O 7.01 / 18.0152 x 2 = 0.7782 x 1 = 0.7782 x 9.0272 = 7.02 F 4.36 / 18.9984 x 1 = 0.2294 x 1 = 0.2294 x 9.0272 = 2.07

........... ∙5.1

243

SBH-1

Table VII‐17: Calculation of the structural formula for sample SBH‐1. (a) correction for impurities; (b) calculations. Lab Corrections (wt%) Corrected Normalized

(a) analysis (wt%) Calcite (CaCO3)OthersSumanalysis (wt%) analysis (wt%)

Al2O3 0.51 0.51 0.52 CaO 1.92 0.14 0.14 1.78 1.81

Fe2O3 0.21 0.21 0.21

K2O 0.12 0.12 0.12 MgO 21.70 21.70 22.10 MnO 0.02 0.02 0.02 0.00 0.00

Na2O 0.03 0.03 0.03 0.00 0.00

SiO2 49.70 49.70 50.61

TiO2 0.04 0.04 0.04 0.00 0.00

Li2O 1.46 1.46 1.48 SrO 0.19 0.19 0.19 0.00 0.00 ‐ H2O 14.10 14.10 14.36 + H2O 7.00 7.00 7.13

CO2 2.05 0.07 1.98 2.05 0.00 0.00 F 2.81 2.81 2.86 less O≡F 1.18 1.18 1.20 Total 100.67 0.21 2.26 2.47 98.20 100.00

Normalized Molecular # cations % cationscharge equivalent (%) Proportionality Cations (b) analysis (wt%) weight (g/mol) factor (44/4.6705) per unit cell

Al2O3 0.52 / 101.96 x 2 = 0.0102 x 3 = 0.0305 x 9.4208 = 0.10 CaO 1.81 / 56.08 x 1 = 0.0323 x 2 = 0.0645 x 9.4208 = 0.30

Fe2O3 0.21 / 159.69 x 2 = 0.0027 x 3 = 0.0080 x 9.4208 = 0.03

K2O 0.12 / 94.20 x 2 = 0.0026 x 1 = 0.0026 x 9.4208 = 0.02 MgO 22.10 / 40.30 x 1 = 0.5483 x 2 = 1.0965 x 9.4208 = 5.16

SiO2 50.61 / 60.08 x 1 = 0.8423 x 4 = 3.3692 x 9.4208 = 7.94

Li2O 1.48 / 29.88 x 2 = 0.0991 x 1 = 0.0991 x 9.4208 = 0.93  4.6705

+ H2O 7.13 / 18.0152 x 2 = 0.7913 x 1 = 0.7913 x 9.4208 = 7.46 F 2.86 / 18.9984 x 1 = 0.1506 x 1 = 0.1506 x 9.4208 = 1.42

.......... ∙4.9

244

SynH

Table VII‐18: Calculation of the structural formula for sample SynH. (a) correction for impurities; (b) calculations. Lab Corrections Corrected Normalized (a) analysis (wt%) (wt%) analysis (wt%) analysis (wt%)

Al2O3 0.16 0.16 0.16 CaO 0.02 0.02 0.02 MgO 23.80 23.80 24.25

Na2O 2.36 2.36 2.40

SiO2 50.40 50.40 51.36

TiO2 0.02 0.02 0.00 0.00

Li2O 0.79 0.79 0.80 ‐ H2O 12.00 12.00 12.23 + H2O 8.60 8.60 8.76

CO2 0.48 0.48 0.00 0.00

SO3 0.22 0.22 0.00 0.00 F 0.014 0.01 0.01 less O≡F 0.01 0.01 0.01 Total 98.85 0.72 98.13 100.00

Normalized Molecular # cations % cationscharge equivalent (%) Proportionality Cations (b) analysis (wt%) weight (g/mol) factor (44/4.7639) per unit cell

Al2O3 0.16 / 101.96 x 2 = 0.0032 x 3 = 0.0096 x 9.2362 = 0.03 CaO 0.02 / 56.08 x 1 = 0.0004 x 2 = 0.0007 x 9.2362 = 0.00 MgO 24.25 / 40.30 x 1 = 0.6017 x 2 = 1.2034 x 9.2362 = 5.56

Na2O 2.40 / 61.98 x 2 = 0.0776 x 1 = 0.0776 x 9.2362 = 0.72

SiO2 51.36 / 60.08 x 1 = 0.8547 x 4 = 3.4190 x 9.2362 = 7.89

Li2O 0.80 / 29.88 x 2 = 0.0535 x 1 = 0.0535 x 9.2362 = 0.49  4.7639

+ H2O 8.76 / 18.0152 x 2 = 0.9729 x 1 = 0.9729 x 9.2362 = 8.99 F 0.01 / 18.9984 x 1 0.0008 x 1 = 0.0008 x 9.2362 = 0.01

....... ∙5