The Measurement of the Se/S Ratios in Sulphide Minerals and Their Application to Ore Deposit Studies

The measurement of the Se/S ratios in sulphide minerals and their application to ore deposit studies

By Alexander John Fitzpatrick

A thesis submitted to the Department of Geological Sciences and Geological Engineering in conformity with the requirements for the degree of Doctor of Philosophy

Queen’s University Kingston, Ontario, Canada February, 2008

Abstract

New analytical techniques have been developed for the determination of selenium

concentrations in sulphide minerals to assess the utility of the Se/S concentration ratios in tracing fluids associated with ore deposit formation. This has been accomplished via a new hydride generation (HG) sample introduction method for the determination of selenium contents in sulphide minerals, development of solid calibration standards by a sol-gel process, and the establishment of protocols for the measurement of selenium/sulphur ratios in sulphides using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS).

The low concentrations of selenium in sulphides require the use of hydride generation, which also requires the removal of metals to be effective. A process for the determination of selenium in sulphide minerals (~ 50 mg sample weight) wherein metals are removed by precipitation under alkaline conditions, followed by further removal by chelating resin, was developed. Determinations by HG-ICPMS on reference materials showed quantitative recoveries (100±5 %). Precision is 10 % relative standard deviation and the detection limit is 4 g g-1 in a sulphide mineral.

A sol-gel method for the fabrication of multi-element calibration standards, suitable

for laser ablation, was developed. The addition of selenium and sulphur to a normal sol-gel

method does not introduce detectable heterogeneity. Xerogel heterogeneity is less than that

of the NIST glass standards. Calculated sulphur contents in the NIST glass SRMs are

comparable to published data. Xerogels are potentially useful as standards in studies of

glasses, minerals, and other materials.

ii The development of a laser ablation technique allowed measurement of Se/S ratios in sulphide minerals. Sulphide minerals were sampled from volcanic hosted massive sulphide

(VHMS) (Flin Flon area, Canada), high-sulphidation epithermal (Pierina, Peru), and iron oxide copper gold (IOCG) (Mantoverde, Chile) deposits. Thermodynamic data, mineral assemblages, and isotopic compositions are used to define depositional conditions and Se/S ratios of ore generating fluids. Although the elements can fractionate from each other, high

Se/S ratios and low 34S values generally reflect magmatic fluids, typical of VHMS and epithermal deposits, whereas the opposite is true for basinal or evaporitic sources, such as recorded by sulphides at the Mantoverde deposits. The Se/S ratios aid in the identification of ore generating fluid sources and can indicate mixing of fluids.

iii Acknowledgments

This project would not have been possible without the help of many people from

whom I received support, intellectual and otherwise. First, I would like to thank my

supervisor Dr. Kurt Kyser for his infinite patience and positive reinforcement. Dr. Diane

Beauchemin is thanked for her particular support on the development of the xerogel

technique. The staff of the Queen’s Facility for Isotope Research are thanked for their support in the development of analytical techniques and particularly Dr. Don Chipley for his instruction in the mystical art of tuning and operating the high resolution ICPMS and Kerry

Klassen for instruction in sulphur isotope ratio determinations. Discussions with Dr. Dan

Layton-Matthews proved particularly useful in clarifying some of the mysteries of selenium thermodynamic data interpretation. Dr. Stephen Wilson of the U.S.G.S. is thanked for providing the PS-1 provisional reference material. This research project benefited tremendously from discussions with and assistance from my fellow graduate students and other colleagues. In particular, Paul Polito, Amelia Rainbow, and Jorge Benavides took time from their own research to provide samples, isotope data, and useful discussions on the deposits they were studying.

Peter Jones and Lew Ling of Carleton University are gratefully acknowledged for their assistance with microprobe and SEM analyses. The staff at the Centre for Neutron

Activation at McMaster University is thanked for rapid turnaround on samples.

Finally, I would like to thank my family for their continued support throughout this and all my academic endeavours.

iv Statement of Originality

The major contributions of this study are based on the author’s development of

analytical techniques, and interpretation of data obtained from determinations utilizing the

created techniques. However, through discussions with academic supervisors and colleagues, the author received constructive criticism and insightful observations, both of which were beneficial to the project. The project has two main components: analytical method development, and exploration of the utility of sulphide Se/S ratios in ore deposit studies, in

particular the identification of mineralizing fluids and their sources.

Selenium measurement in sulphides has received prior attention, but analytical

difficulties such as spectral and isobaric interferences have generally limited wide-scale

studies. The availability of analytical facilities at Queen’s University prompted the

development of techniques for the measurement of selenium in sulphides, selenium being an

element of geochemical interest with limited knowledge of its occurrence and behaviour on

an ore deposit scale.

The need for a method to allow more precise and accurate selenium determinations in

sulphides prompted development of an autochthonous precipitation and column separation

technique for the preparation of sulphides for hydride generation inductively coupled plasma

mass spectrometry. Precipitation as a technique to concentrate selenium has been used before

(Plotnikov 1960), while column separation is a widely employed technique. However, the

present technique is the first time, to the author’s knowledge, that autochthonous

precipitation and column separation have been combined in a manner suitable to prepare

sulphides for hydride generation techniques.

v The acquisition of a new laser ablation system over the course of this study prompted

an investigation of the possibilities of using laser ablation ICPMS as an analytical method for

selenium determination in sulphides. Preliminary investigations indicated that there were an inadequate number of suitable sulphide reference standards. Consequently, sulphides measured in the first part of this study were adopted as provisional calibration standards.

These were combined with two reference materials and a synthetic galena-clausthalite series

to form the basis of a calibration suite. Compositional gaps in this suite prompted

investigations into methods for additional solid calibration standards. The use of a sol-gel

process to produce a solid calibration standard suitable for laser ablation was suggested by

Dr. Diane Beauchemin and this study is the first attempt, to the author’s knowledge, to

produce a selenium calibration standard by this method.

The utility of Se/S ratios in conjunction with sulphur isotope data in ore deposit

studies has been investigated previously for VHMS (Yamamoto 1976; Yamamoto et al.

1983; Yamamoto et al. 1984; Huston et al. 1995) and magmatic nickel deposits (Eckstrand et

al. 1989). Samples collected by others provide the working materials used for the Se/S

determinations performed by the author. Others have performed the sulphur isotope

determinations. To the author’s knowledge, this is the first assessment of the utility of Se/S

ratios in combination with 34S value for the study of ore deposits other than VHMS and

magmatic nickel and PGE deposits.

vi Table of Contents

Abstract ...... ii

Acknowledgments ...... iv

Statement of Originality ...... v

Table of Contents...... vii

List Of Figures ...... xii

List of Tables...... xiv

Chapter 1. Introduction...... 1

1.01 Selenium Determination...... 2

1.02 Selenium and Ore Deposits ...... 4

1.03 Scope of Investigations ...... 6

1.04 The Scientific Contributions of this Study...... 7

1.04.1 GEOCHEMICAL ANALYSIS ...... 8

1.04.2 ORE DEPOSIT STUDIES ...... 8

1.05 Structure of Thesis...... 9

vii Chapter 2. Selenium Measurement in Sulphides by Hydride Generation

High-Resolution Inductively Coupled Plasma Mass Spectrometry ...... 11

2.01 Abstract...... 11

2.02 Introduction...... 12

2.03 Experimental Section...... 16

2.03.1 REAGENTS...... 16

2.03.2 CHELATING RESIN COLUMNS...... 17

2.03.3 REFERENCE MATERIALS ...... 18

2.03.4 SAMPLE PREPARATION ...... 18

2.03.5 INSTRUMENTATION ...... 20

2.04 Results and Discussion...... 24

2.04.1 THE EFFECTS OF PH ADJUSTMENT, CO-PRECIPITATION, AND TOLERANCE LEVELS ...... 24

2.04.2 CALIBRATIONS, DETECTION LIMITS AND METHOD BLANK...... 28

2.04.3 ANALYSIS OF STANDARDS AND REFERENCE MATERIALS ...... 29

2.04.4 ANALYSIS OF NATURAL SULPHIDES ...... 31

2.05 Conclusions...... 33

Chapter 3. Fabrication of Solid Calibration Standards by a Sol-Gel Process and Use in Laser Ablation ICPMS...... 34

3.01 Abstract...... 34

3.02 Introduction...... 35

3.03 Experimental Section...... 38

3.03.1 PREPARATION OF XEROGELS...... 38

viii 3.03.2 CALIBRATION STANDARDS...... 40

3.03.3 INSTRUMENTATION AND MEASUREMENT ...... 44

3.03.3.1 Bulk Chemical Composition and Sulphur Isotope Ratios of Xerogels ...... 44

3.03.3.2 Scanning Electron Microscopy and Electron Microprobe Analysis...... 45

3.03.3.3 LA-ICPMS Instrumentation and Parameters ...... 45

3.03.4 DATA TREATMENT AND CALIBRATION ...... 48

3.04 Results and Discussion...... 49

3.04.1 FORMATION AND PHYSICAL ASPECTS OF THE XEROGELS ...... 49

3.04.1.1 Bulk Composition of Xerogels...... 51

3.04.1.2 Physical Effects of Ablation...... 52

3.04.2 DETECTION LIMITS, ERROR, AND VARIATION ...... 53

3.04.3 SIGNAL RESPONSE...... 57

3.04.4 SULPHUR CONTENT OF NIST SRMS 610 AND 612 ...... 58

3.04.5 MULTI-ELEMENT XEROGEL STANDARDS AND FURTHER PROSPECTS ...... 59

3.05 Conclusions...... 61

Chapter 4. Selenium/Sulphur Ratios in Sulphide Minerals and Their

Significance for Ore Deposits...... 63

4.01 Abstract...... 63

4.02 Introduction...... 64

4.03 Analytical Techniques ...... 65

4.04 Geology...... 69

4.04.1 VHMS DEPOSITS AND BARREN SULPHIDE MINERAL BODIES IN THE FLIN FLON AREA,

CANADA ...... 69

ix 4.04.2 HIGH-SULPHIDATION EPITHERMAL AU-AG DEPOSITS: PIERINA AU-AG DEPOSIT...... 72

4.04.3 IOCG DEPOSITS OF THE MANTOVERDE DISTRICT ...... 75

4.05 Results...... 78

4.05.1 VHMS DEPOSITS: FLIN FLON AREA ...... 78

4.05.2 HIGH-SULPHIDATION EPITHERMAL AU-AG DEPOSITS: PIERINA ...... 82

4.05.3 IOCG DEPOSITS: MANTOVERDE DISTRICT DEPOSITS...... 84

4.06 Discussion...... 87

4.06.1 VHMS DEPOSITS...... 98

4.06.1.1 Trout Lake and Harmin VHMS deposits...... 99

4.06.1.2 Hargrave River Barren Sulphide Mineral Bodies...... 106

4.06.2 HIGH-SULPHIDATION EPITHERMAL AU-AG DEPOSITS ...... 107

4.06.3 IOCG DEPOSITS ...... 110

4.06.4 UTILITY OF SULPHIDE MINERAL SE/S RATIOS IN DEPOSIT STUDIES...... 113

4.07 Conclusions...... 115

Chapter 5. Conclusions and Recommendations...... 117

5.01 Scientific Results...... 118

5.01.1 ANALYTICAL ...... 118

5.01.2 ORE DEPOSIT STUDIES ...... 119

5.02 Recommendations...... 120

5.02.2 ANALYTICAL ...... 120

5.02.3 GEOCHEMICAL...... 121

References ...... 123

x Appendix A. Trout Lake Data...... 160

Appendix B. Harmin Data...... 162

Appendix C. Hargrave River Data ...... 163

Appendix D. Pierina, Santa Fe, and Santo Toribio Data...... 164

Appendix E. Mantoverde District Data ...... 165

Appendix F. Se/S Ratios in Sulphide Minerals Calculated From Published

Se Concentration Data...... 166

Pyrite ...... 166

Chalcopyrite...... 176

Sphalerite ...... 180

Galena...... 183

Pyrrhotite ...... 187

xi List Of Figures

Figure 2-1. Sketch of LI-2 Hydride Generation System ...... 22

Figure 2-2. Effect of pH on sorption of selenium and copper ionic species and solubility of

copper and iron hydroxides...... 27

Figure 3-1. Intact xerogel (SG10A) evaporated under partial atmospheric isolation– sealed

mould. Scale is centimeters...... 49

Figure 3-2. Drying of xerogel with varying atmospheric isolation...... 50

Figure 3-3 (A). SEM image of ablation crater in xerogel. (B) Showing spalling...... 52

Figure 3-4. Electron backscatter images of xerogels at smaller (A) and larger (B) scales. ....54

Figure 3-5. Calibration standard results and derived calibrations ...... 57

Figure 3-6. Electron backscatter image of series 5 xerogel (SG5A) with selenium, sulphur

and metal rich inclusions [bright spots] (A), with close-up of inclusions (B)...... 60

Figure 4-2. (a) Regional map of South America showing location of Pierina high-

sulphidation epithermal Au Ag deposit, and (b) regional geology of Pierina area...... 74

Figure 4-3. (a) Location map of Mantoverde District in Chile and (b) deposits/sulphide

mineral bodies within Mantoverde district...... 77

Figure 4-4. Relationship between Se/S ratios and 34S values for sulphide minerals from

VHMS deposits and barren Fe sulphide mineral bodies at (a) Trout Lake, (b) Harmin,

Figure 4-5. Relationship between Se/S ratios and 34S values for sulphide minerals from

Pierina high-sulphidation epithermal Ag-Au deposit...... 83

Figure 4-7. Relationship between Se/S ratios and 34S values for (a) pyrite, (b) chalcopyrite

from deposits in the Mantoverde area of Chile...... 86

xii Figure 4-8. Distribution of Se/S ratios in sulphide minerals from ore deposits and other

occurrences from published data and the present study...... 90

Figure 4-9. Distribution of Se/S ratios in sulphide minerals from VHMS deposits from the

literature and present study ...... 92

Figure 4-10. Speciation of S and Se, Fe mineral predominance, and variation of Se-2/S-2. 96

xiii List of Tables

Table 2.1. Column Scheme (Chelex™ 100)...... 19

Table 2.2. Typical Operating Conditions of HG-ICP-MS...... 23

Table 2.3. Selenium isotopes and potential interferences ...... 24

Table 2.4. Selenium recovery from selenium and copper standards...... 29

Table 2.5. Determination of selenium in five measurements of reference material CCU1-c .30

Table 2.6. Concentrations of selenium in sulphides from the Horne and other ore deposits..32

Table 3.1. Concentrations of sulphur and selenium in natural and reference sulphide materials

...... 41

Table 3.2. Available sulphur and selenium concentrations for NIST SRM glasses ...... 43

Table 3.3. Laser and mass spectrometer conditions...... 46

Table 3.4. Analyte contents, Se/S concentration ratios and 34S values of xerogels...... 52

Table 3.5. Typical relative standard deviations of the 77Se/32S signal ratio from multiple

ablation spots and combined concentration uncertainty...... 53

Table 3.6. Electron microprobe analysis of xerogels and NIST SRM 610; with analysis of

inclusion and matrix in SG5A and comparison to bulk composition...... 55

Table 3.7. Sulphur contents (g g-1) of NIST SRM glasses as determined with xerogel

calibration...... 59

Table 4.1. Laser and mass spectrometer settings used for LA-ICPMS analysis of sulphide

minerals...... 66

Table 4.2. Bulk Se/S, Cu/(Cu+Zn+Pb) ratios and gangue mineral composition of Trout Lake

ore types (Healy and Petruk 1988)...... 70

xiv Table 4.3. Selenium contents of Harmin sulphide minerals determined with electron

microprobe ...... 71

Table 4.4. Se/S ratios and 34S values of sulphide minerals, and calculated fluid Se/S

ratios from the Trout Lake and Harmin VHMS deposits and barren sulphide mineral

bodies at Hargrave River...... 79

Table 4.5. Se/S ratios and 34S values of stage II sulphide minerals and calculated fluid

Se/S ratios from Pierina...... 82

Table 4.6. Se/S ratios and 34S values of sulphide minerals and calculated fluid Se/S ratios

from Mantoverde district deposits...... 84

Table 4.7. The Se/S ratios of sulphide minerals from various ore deposits and other

occurrences determined from published Se concentration data...... 88

Table 4.8. The Se/S ratios of sulphide minerals from VHMS deposits determined from

published data...... 91

Table 4.9. Equilibrium constants for Se incorporation reactions at various temperatures...... 94

Chapter 1. Introduction

The presence of any element in an ore deposit that is not itself a primary economic commodity can, in addition to altering the economic feasibility of a deposit, lend itself towards understanding the genesis of the ore deposit. Thus, knowledge about the behaviour of the element can be used to alter further exploration and deposit development. Selenium fulfils this role for, although an element of wide industrial utility, it is nowhere exploited as a primary product of an ore deposit.

Despite its potential utility in ore deposit studies, selenium has not received the same attention as many other elements of geochemical interest, primarily due to analytical difficulties. Selenium is typically measured by neutron activation analysis, but non-routinely.

However, continued development of analytical instrumentation and techniques and both environmental and medical concerns has prompted a resurgence of interest in selenium and, consequently, its measurement for geochemical purposes.

The availability of new instrumentation, such as a inductively coupled plasma high resolution mass spectrometer and a 213 nm laser ablation system, in addition to ongoing studies of particular ore deposits, has prompted investigation into analytical techniques for selenium. Furthermore, the utility of sulphide Se/S concentration ratios in ore deposit studies has been investigated. In the present study, measurements are undertaken by high-resolution inductively coupled plasma mass spectrometry (ICPHRMS) with sample introduction by laser ablation (LA-ICP(HR)MS) and hydride generation (HG-ICP(HR)MS). This required the development of new analytical techniques to measure Se concentrations that were used to assess the utility of the Se/S ratio in the identification of mineralizing fluid and possible sources for various ore types.

1.01 Selenium Determination

Selenium concentrations in sulphides have been an area of interest for a considerable

period. Indeed, selenium was first discovered in sulphide ores (Berzelius 1818). From its

isolation and discovery in the early 19th Century to the present, selenium determination has remained a challenge. The early, labour intensive methods of separation, isolation and gravimetric determination shifted to indirect fluorimeteric measurement in the early part of

the 20th century with gradual improvements in analytical performance (Clennell 1906; Franke

et al. 1936). Although instrumental methods increasingly became the preferred method of

measurement for most elements in the 1950s, selenium determination remained a classical fluorimeric technique as late as the 1980s (Association of Official Analytical Chemists

1990). Greater access to neutron activation analysis (Gladney and Knab 1981; Heft and

Koszykowski 1982) resulted in a greater number of selenium determinations, but selenium is still not considered part of the normal suite of geochemical data.

Analytical difficulty is a result of low concentrations and interferences acting on selenium during measurement. Interferences may occur at various stages of sample preparation and measurement depending on the analytical technique and sample matrix. As

an example, measurement of Se by atomic absorption spectrometry results in overlap of

peaks in the absorbance spectrum of Se with those of other common elements such as Fe and

P (as phosphate) in the matrix (Ddina and Tsalev 1995). Interferences such as these have

lead to the development of hydride generation techniques (Ddina and Tsalev 1995).

Through hydride generation, selenium is concentrated and most matrix elements are removed

or reduced before measurement. However, hydride generation introduces other

complications. Transition metals act on the hydride generation reaction as anticatalysts and

additional sample preparation steps become necessary to reduce interferants to below tolerance levels. Such techniques must also maintain selenium in solution during solution preparation. Thus, a large volume of literature concerning selenium determination has centred on particular preparation requirements for specific sample matrices (Ddina and

Tsalev 1995).

The development of inductively coupled plasma high-resolution mass spectrometers

(ICPHRMS) has prompted a considerable improvement for geochemical determination of most elements (Feldmann et al. 1994; Giessmann and Greb 1994). However, the use of argon as plasma and carrier gas presents issues for selenium because argon isotopes (40Ar, 39Ar,

38Ar) form polyatomic interferences on the two most abundant isotopes of selenium (78Se,

80Se), effectively removing 75% of the possible signal. These interferences are non- resolvable at present, even with ICPHRMS, but most of the interferences on the less abundant isotopes (76Se, 77Se, 82Se) can be resolved at high-mass resolution.

Determination of selenium contents in geochemical samples, particularly sulphides, continues to require improvement in analytical performance. Consequently, any development of new analytical techniques is beneficial. The present research addresses this by two separate endeavours: the development of a routine method for sample preparation of sulphides for selenium determination by hydride generation inductively coupled plasma mass spectrometry (HG-ICPMS) and the development of a process for the production of selenium calibration standards for laser ablation inductively coupled plasma mass spectrometry (LA-

ICPMS).

1.02 Selenium and Ore Deposits

Historically, most industrial selenium demand has been met by secondary production at copper refineries so that there has been little economic incentive towards exploration for selenium or research into its occurrence. In the former Soviet Union, the strategic importance of selenium outweighed economic consideration, so that a great deal of investigation of selenium in ore deposits was undertaken (Sindeeva 1964). In the earliest geochemical research o selenium, it was initially postulated that selenium contents in sulphides had a direct positive relationship with temperature, selenium content rising with temperature

(Goldschmidt and Hefter 1933; Goldschmidt and Strock 1935). However, this was later shown to be incorrect, with regional geological factors affecting selenium contents of sulphides (Edwards and Carlos 1954; Tischendorf 1959; Tischendorf 1966).

Recent concerns about the toxic effects of selenium prompted research into its near- surface and surface geochemical behaviour and increased regulatory controls have encouraged study of selenium behaviour during ore processing (Jacobs 1989; Frankenberger and Benson 1994; Baker et al. 2000a; Baker et al. 2000b). In addition, the “anti-oxidant” properties of selenium have prompted medical research into anti-cancer applications

(Rayman 2005). Selenium behaviour has also recently been investigated in Se-rich VHMS deposits (Hannington et al. 1999; Layton-Matthews et al. in press). Investigations of selenium in other deposit types have been largely mineralogical in orientation and, while it is unlikely that selenium will ever become an element of primary interest for an ore deposit, its routine measurement may provide insights into the genesis of other ore deposit types (Simon and Essene 1996; Simon et al. 1997). As part of this study, the utility of Se/S ratios in the

study of ore deposits of various types was investigated; primarily the identification of multiple fluids and the identification of their sources.

The three ore types investigated in this study are volcanic hosted massive sulphide

(VHMS), iron oxide hosted copper gold (IOCG), and high sulphidation epithermal Au-Ag deposits (Hitzman et al. 1992; Barton and Johnson 1996; Einaudi et al. 2003; Sillitoe 2003;

Franklin et al. 2005). These three deposit types were chosen based on sample availability as studies of these deposits by other researchers were underway. The deposits are the

Mantoverde district IOCG deposits, the Pierina high sulphidation epithermal Au Ag deposit, and the Trout Lake and Harmin VHMS deposits of the Flin Flon area (Rainbow et al. 2005;

Benavides et al. 2007; Polito et al. 2007). In addition, these three deposit types represent different degrees of knowledge concerning selenium behaviour and occurrence. The occurrence and behaviour of selenium in VHMS is best known as a result of the study of selenium-enriched deposits, but VHMS deposits with more typical selenium contents are less well studied (Hannington et al. 1999; Layton-Matthews et al. in press). Epithermal Au-Ag deposits, generally only the low-sulphidation type, are noted for selenide mineral occurrences, but little research has been undertaken on selenium contents in high- sulphidation epithermal deposits (Simon and Essene 1996; Simon et al. 1997). As an emerging and evolving deposit type, the nature of selenium in IOCG deposits is scarcely known and is restricted to a few instances of selenide occurrences (Henley et al. 1975; Large and Mumme 1975; Adshead et al. 1998; Williams and Pollard 2001; Cabral et al. 2002a;

Cabral et al. 2002b; Cabral et al. 2002c; Skirrow and Walshe 2002).

The earliest research on the relationship between sulphur isotopic compositions and sulphide Se/S concentration ratios did not show clear relationships for various deposit types

(Zainullen 1960; Yamamoto et al. 1968; Malakhov et al. 1974; Kovalenker et al. 1975). A

theoretical development of the relationship was made by Yamamoto (1976), for a limited pH

range (3-5). It has been suggested that the relationship between the isotopic composition and

Se/S ratio is fixed for sulphides precipitating from a single fluid. It is unaltered by small

changes in the physicochemical conditions and that the influence from other fluids can be

detected by deviations from the fixed relationship (Yamamoto et al. 1983; Yamamoto et al.

1984). With new analytical instrumentation available, the relationship between sulphide 34S

values and Se/S ratios in VHMS is worthy of reinvestigation, in addition to the investigation

of other deposit types that have not been studied.

The potential utility of selenium in ore deposit studies stems from its chemical

similarity to sulphur. Selenium matches sulphur behaviour at high temperature

(magmatic/hydrothermal), but segregates at lower temperatures due to its differing geochemical behaviour governed by pH and oxygen fugacity and by its disparate affinities

for other elements (Huston et al. 1995; Simon and Essene 1996; Xiong 2003). By measuring the Se/S ratios in sulphide minerals, insight into the origin of these various mineral deposits

may be gained. In particular, the presence of multiple fluids and their possible sources can be

assessed by Se/S concentration ratios of sulphides because of characteristic Se/S ratios of

potential fluid sources. In addition, the measurement of selenium in ore deposit types,

currently poorly represented, adds to the available database of selenium concentration data.

1.03 Scope of Investigations

This project was designed to take advantage of new analytical instrumentation to

develop new analytical methods for selenium determination in sulphides. In addition, Se/S

ratios in sulphides are applied in studies of selected ore deposit types. A sample preparation

technique of autochthonous precipitation and column separation was developed to prepare

samples for hydride generation to permit solution sample introduction. This technique was

required to reduce the content of transition metal interferants to below tolerance levels

without the use of hard-to-handle reagents for hydride generation.

The acquisition of a 213 nm laser ablation system offered new opportunities for

selenium determination. However, this required the production and verification of multiple

calibration standards suitable for laser ablation. A technique for the production of calibration

standards by a sol-gel process was developed and tested.

A number of ongoing research projects on various deposits provided well-

characterised sulphide mineral samples. These deposits are the Trout Lake and Harmin Lake

VHMS deposits, affiliated barren sulphide bodies (Manitoba), the Pierina (Peru) high-

sulphidation-epithermal deposit, and the IOCG deposits of the Mantoverde District (Chile).

Sulphide mineral samples from these deposits were measured for their Se/S ratios to assess

the presence of single or multiple mineralizing fluids and, possibly, to identify their sources

in conjunction with previously determined and published selenium concentration and sulphur

isotopic data.

1.04 The Scientific Contributions of this Study

This research project was undertaken to contribute in two fields: geochemical

analysis and the application of geochemical data to ore deposit studies. The most important contributions of this project are as follows.

1.04.1 Geochemical Analysis

1. Development of a sample preparation method for sulphides that removes transition metals

by co-precipitation and column separation to produce a sample suitable for hydride

generation introduction for ICP-MS or other instrumentation.

2. The measurement of selenium in a set of natural sulphide mineral samples suitable for

further use as calibrations standards.

3. Illustrating the utility of the sol-gel processes for producing solid calibration standards for

laser ablation inductively coupled plasma mass spectrometry.

4. Evaluation of the available concentration data for selenium and sulphur in NIST SRM 610 and NIST SRM 612.

5. Showing the differences in signal response for sulphur and selenium between glass based

and sulphide based calibration standards and the consequent necessity for sulphide

calibration standards when measuring selenium in sulphide minerals.

6. Establishing limitations of the sol-gel process for the production of multi-element

standards.

1.04.2 Ore Deposit Studies

From an ore deposit studies perspective, the main contributions of the research are:

1. The measurement of selenium contents in sulphides from ore deposits not previously

investigated for their selenium content.

2. Demonstration of the ambiguous nature of sulphide Se/S ratios in identifying sources of

ore-forming solutions.

3. Identification of the presence of a single mineralizing fluid for ore deposition at the Trout

Lake and Harmin VHMS deposits.

4. Identification of a low Se/S ratio mineralizing fluid in a high-sulphidation epithermal deposit.

5. Demonstration of the ability of sulphide Se/S ratios to show the progressive mixing of two fluids in an IOCG ore deposit.

1.05 Structure of Thesis

To fulfil the requirements of the School of Graduate Studies and Research at Queen’s

University, this thesis has been structured in manuscript form. Three manuscripts constitute the main body of this thesis. Their titles and brief descriptions are listed below.

Chapter 2

Fitzpatrick, A. J., Kyser, T. K. and Chipley, D. Selenium measurement in sulphides by

hydride generation high-resolution inductively coupled plasma mass spectrometry. in

press (2008), Geochemistry: Exploration, Environment and Analysis

Outline: A method of measuring selenium in sulphides by hydride generation high-resolution

inductively coupled plasma mass spectrometry is documented. This method presents

a novel means of separating those transition metals that interfere with hydride

generation from the selenium using sorption to metal hydroxides and

chromatagraphic column separation.

Chapter 3

Fitzpatrick, A. J., Kyser, T. K. Chipley, D, and Beauchemin, D.. Fabrication of solid

calibration standards by a sol–gel process and use in laser ablation ICPMS. Journal of

Analytical Atomic Spectrometry 2008, 23, 244 – 248

Outline: The production of solid calibration standards for accurate selenium measurement by

laser ablation ICPHRMS by a sol-gel process is detailed. The synthetic standards are

compared against sulphide mineral calibration standards and the resultant calibration

curves are used to measure sulphur in NIST glass standards. (This is an expanded

version of the published paper.)

Chapter 4

Fitzpatrick, A. J., Kyser, T. K., Chipley, D., Alan H. Clark, and Oates C. Selenium/sulphur

ratios in sulphide minerals and their significance for the genesis of volcanic-hosted

massive sulphide, high-sulphidation epithermal, and iron oxide-copper-gold deposits.

Submitted Mineralium Deposita.

Outline: Selenium/sulphur ratios are determined in sulphides from VHMS, high-sulphidation

epithermal Au-Ag, and IOCG deposits by the laser ablation ICP-MS technique

established in Chapter 3. The sulphide ratios are used in combination with other

geochemical data to calculate the Se/S ratios of the ore-forming fluids. The fluid

ratios are assessed as indicators of the sources of the fluids on the basis of established

typical Se/S ratios for magmatic fluids and seawater and an indicator of the presence

of multiple fluids.

Chapter 2. Selenium Measurement in Sulphides by Hydride

Generation High-Resolution Inductively Coupled Plasma

Mass Spectrometry

2.01 Abstract

Selenium concentrations of transition metal-sulphides, albeit low, may be an

important tool in exploration for economic ore deposits. These low concentrations necessitate

the use of hydride generation for sample introduction, a very sensitive means of pre-

concentration that results in low interference. However, transition metals interfere with the

production of selenium hydride so that their removal from solutions made from dissolution of

transition metal sulphides is necessary for hydride generation of selenium to be effective. We

have devised a two step process for analysis of selenium concentrations in small samples (~

50 mg) of sulphide minerals wherein dissolved transition metals are removed by precipitation

as metal hydroxides under alkaline conditions (pH~12) to prevent sorption of selenium, followed by further metal removal by chelating resin. Determinations made by hydride

generation inductively coupled plasma mass spectrometry on the CCU-1c certified reference

material and concentration standards showed quantitative recoveries (100±5 %) of selenium.

Using the technique, we find that sulphide minerals from the Horne volcanic hosted massive

sulphide deposit give high concentrations ranging from 250 to 750 g g-1. Average precision,

expressed as relative standard deviation of selenium concentration for a triple replicate, is 10

% and the detection limit is 4 g g-1 of selenium in a sulphide mineral. The procedure offers a

method for selenium determination of sulphides that is operationally simpler than many other

methods.

2.02 Introduction

Selenium concentrations of sulphide minerals may be used to distinguish the

economic potential of sulphide bodies thus serving as a vector to economic ore deposits (Cox

and Singer 1992; Hinchey et al. 2005). To date, only high concentrations of selenium in

sulphides have been determined with sufficient precision because of high detection limits or

problems with interferences. With the advent of inductively coupled high-resolution plasma

mass spectrometers (ICPHRMS), many isobaric interferences are resolvable but with a

significant reduction of signal response. As polyatomic argon molecule interferences with the

two most abundant selenium isotopes (78Se, 80Se) are not resolvable, even at the mass resolution of ICPHRMS, the less abundant selenium isotopes are measured. The resulting decrease in signal response raises the detection limit above a useful value for solutions resulting from the simple dissolution of sulphides. Coupling a hydride generator to the

ICPHRMS effectively concentrates the sample selenium before introduction to the

ICPHRMS so signal response is improved and detection limits are lowered (down to 4 ng g-

1). In addition to pre-concentrating the selenium, the hydride generator simplifies the matrix

so that only the gaseous hydride components reach the plasma.

Hydride generation is a common means of introduction for the measurement of

elements that form stable hydrides such as arsenic, selenium, antimony, lead, tin, germanium,

and bismuth, and there are varieties of hydride generation techniques (Ddina and Tsalev

1995; Tsalev 1999). Hydride generation is most commonly used with atomic absorption

spectroscopy (AAS), atomic fluorescence spectroscopy (AFS), and ICPMS (Ddina and

Tsalev 1995; González Lafuente et al. 1998; Tsalev 1999; Menegário and Giné 2000;

Wallschläger and Bloom 2001; García et al. 2005; Qiu et al. 2006). The choice of ICPHRMS

detection rather than AAS or AFS in the present study is based on operational flexibility and

lower instrumental detection limits for ICPHRMS. More recently, hydride generation has

been shown to have the best analytical performance in a comparison of five sample

introduction methods for the determination of selenium isotope measurement (Elwaer and

Hintelmann 2007).

Many transition metals inhibit selenium hydride production, making determination of

selenium in sulphides difficult regardless of the analytical detector (Ddina and Tsalev 1995;

Tsalev 1999). We have developed a two-step method for sample preparation that partially removes transition metals by metal hydroxide precipitation followed by further transition metal removal by an iminodiacetic acid chelating resin. Each step, if used alone, does not remove sufficient transition metals to allow for quantitative production of selenium hydride.

The removal of metals by metal hydroxide precipitation is limited by the solubility of the metal hydroxides and the use of the chelating resin requires a pH at which metal hydroxide precipitation will occur.

A typical hydride generation reaction involves the reduction of the oxidized analyte by mixing a reagent solution of sodium borohydride and sodium hydroxide with an acidified sample (Ddina and Tsalev 1995; Tsalev 1999). Borohydride is unstable in acidic to neutral solution so the presence of sodium hydroxide is necessary to maintain borohydride in solution. The commonly employed hydride generation reaction (2.1) is specific to the Se(IV) state such that Se(VI) does not participate, so pre-reduction is necessary to ensure that all

selenium is Se(IV). Hydrochloric acid reduces Se(VI) to Se(IV) quantitatively (Bye and

Lund 1988). The alkalinity present in the sodium-borohydride/sodium-hydroxide solution is

neutralized by the acidity present in the sample allowing the hydride generation reaction for

selenium as follows:

+ - 3H + 3BH4 + 4H2SeO3 4H2Se + 3H2O + 3H3BO3 (Ddina and Tsalev 1995; Tsalev 1999) (2.1)

Se(IV) is reduced to Se(-II) which forms gaseous selenium hydride (H2Se).

The presence of transition metals in solution significantly impairs the hydride generation process due to both direct and indirect effects. One direct effect is the formation of insoluble transition metal selenides that precipitate in the hydride generator, removing selenium from solution (Welz and Schubert-Jacobs 1986). Indirect effects are anti-catalytic in nature. Transition metals accelerate the decomposition of borohydride before selenium hydride formation and transition metal borides, formed as a side reaction, decompose selenium hydride (Smith 1975; Kirkbright and Taddia 1978; Agterdenbos and Bax 1986; Bye

1986a; Hershey and Keliher 1986). Some transition metals have particularly strong effects; the presence of copper impairs hydride generation due to the formation of sparsely soluble copper selenides (Welz and Schubert-Jacobs 1986). The similarly strong inhibiting effects of iron are not fully understood because iron (III) can also increase tolerance levels of nickel and copper for selenium and arsenic determinations under highly acidic conditions whereas iron (II) is itself an inhibitor of hydride generation (Welz and Melcher 1984a; Welz and

Melcher 1984b; Bye 1986b; Halicez and Russell 1986; Bye 1987). The direct and indirect effects are such that both the concentration of transition metals and the ratio of transition metals to selenium are of concern. In samples with low transition metal content (e.g., waters,

biological materials, silicates) the inhibitory effects of transition metals can be reduced by

complexation and by kinetic modification of the hydride generation reactions (Vijan and

Leung 1980; Bye et al. 1983; Bye 1985; Bye 1986b; Halicez and Russell 1986; Bye 1987).

The high contents of transition metals in many sulphides and corresponding high metal to selenium ratios require that, following dissolution of the sulphide, the metals must

be removed from solution prior to the hydride generation reaction (Smith 1975; Kirkbright

and Taddia 1978; Agterdenbos and Bax 1986; Bye 1986a; Hershey and Keliher 1986.

Removal of transition metals and pre-concentration of selenium has been achieved with

varying degrees of success by a number of techniques but are limited to samples of low

transition metal content. Co-precipitation of selenium on lanthanum hydroxide has been used

for both ICPMS and AAS analysis, but as lanthanum hydroxide also co-precipitates copper

and iron it is not effective for the analysis of samples with high transition metal/selenium ratios (Reichel and Bleakley 1974; Maher 1983; Ebdon and Wilkinson 1987; Hall and

Pelchat 1997a; Hall and Pelchat 1997b).

Ion-exchange resins, both anion and cation, for pre-concentration of selenium and removal of transition metals are effective, but only over a limited pH range (Hershey and

Keliher 1989; Itoh et al. 1989; Offley et al. 1991; Örnemark and Olin 1994). Recent

refinement of a thiol-cotton-fiber technique (TCF) for selenium capture is effective for

selenium pre-concentration but does not necessarily ensure separation from transition metals

(Shan and Hu 1985; Marin et al. 2003; Layton-Matthews et al. 2006). The TCF technique

also captures potential interferants platinum, palladium, gold, tellurium, arsenic, mercury,

antimony, bismuth, tin, silver, copper, indium, lead, cadmium, zinc, cobalt, nickel, and

thallium, so that selenium must be liberated from the TCF without liberating these transition

metals (Yu et al. 1983; Yu et al. 2001; Yu et al. 2002). The most recent work ascribes 100 % selenium recovery from reference materials, despite a lack of concentration measurements, on the basis of no significant isotope fractionation occurring during both pre-concentration and hydride generation (Layton-Matthews et al. 2006). However, the certified reference material containing high transition metal content (CCRMP WMS-1) does not have prior isotope data available for a basis of comparison so 100 % selenium recovery has not been established for samples of high transition metal content. There remains a need for a technique that can remove transition metals from samples of high content while retaining and pre- concentrating selenium. The technique presented here provides this capability.

2.03 Experimental Section

2.03.1 Reagents

All reagent and sample preparation was done in a Class 100 clean laboratory.

Deionized water (>18.2 M) is used in all reagent preparation. All solid reagents were of

ACS certified grade or better. Stock solution of 1N sodium hydroxide was prepared from solid pellets (Fisher Scientific, Ottawa, Canada). The analysis of the sodium hydroxide pellets showed significant concentrations of transition metals so the sodium hydroxide solution was purified by passing it through a column of Chelex® 100 iminodiacetic acid resin (100-200 mesh, Bio-Rad Ltd., Hercules, California) to remove transition metals. A sufficient quantity (generally 1 liter) of 0.5 % sodium borohydride in 1 N sodium hydroxide solution was prepared on a daily basis by adding powdered sodium borohydride (Fisher

Scientific, Ottawa, Canada) to the previously prepared 1 N sodium hydroxide stock solution.

It was found that the sodium borohydride dissolved completely and no filtration was

necessary. Dilute nitric and hydrochloric acids are prepared from reagent grade acids that

have been purified by sub-boiling Teflon™-still distillation. Calibration solutions for a multi-

point least square regression linear calibration were prepared daily by serial dilution of

nominal 1000 mg L-1 selenium standard (Spex CertiPrep, Metuchen, NJ). Copper-selenium

standards were prepared using a nominal 1000 mg l-1 copper standard (Spex CertiPrep,

Metuchen, NJ) and the selenium standard. All standards were prepared in hydrochloric acid

solutions because nitric acid is reported to have detrimental effects on hydride generation

(Cutter 1983).

2.03.2 Chelating Resin Columns

The choice of Chelex® 100 resin for use in the columns was based on the selectivity

of the resin for transition metals. Chelating iminodiacetic acid resin has a 10 times greater

selectivity for divalent transition metals than the commonly employed and less selective

sulphonic acid cation-exchange resins (Bio-Rad ; Bio-Rad). In contrast, anions, such as

selenium, pass through an iminodiacetic-acid resin column unhindered (Jones et al. 1982;

Hershey and Keliher 1989). The iminodiacetic acid resin is effective for transition metal

capture above a pH of 4, allowing a broad pH range where transition metals can be separated

from selenium (Narasaki 1988).

The columns contain 12 mL of Chelex® 100 loaded as resin-water slurry into acid

cleaned 20 mL polypropylene columns (17 mm X 120 mm) with glass frits. The quantity of

resin was optimized such that the milliequivalents of active sites on the resin are eight times greater than the total milliequivalents of the transition metals in 50 mg of chalcopyrite

(CuFeS2). Washing and regeneration of the columns follows the manufacturers

recommendations. The column scheme is shown in Table 2.1 with the initial cleaning

represented by steps 1 and 2.

2.03.3 Reference Materials

The choice of CCu1-c (CCRMP, NRCan, Ottawa, Canada) as a reference material

was based on its similarity to the sulphides measured in this study and the lack of other

suitable certified reference materials (Salley et al. 2000). The CCRMP WMS-1 reference

material shares similar selenium and transition metal concentrations to CCu1-c but has only

an informational value for selenium concentration. The CCu1-c reference material contains:

107±15 g g-1 Se, 25.62±0.05 wt. % Cu, and 29.34±0.28 wt. % Fe. These concentrations

produce the ratios: Se/Cu = 0.418±0.062*10-3 and Se/Fe = 0.365±0.054*10-3, the lowest

ratios in certified or standard reference materials.

2.03.4 Sample Preparation

Portions of discretely identifiable sulphide minerals, from hand samples previously collected from ore deposits, were separated using a dental drill and placed in clean containers. The ore deposits are: the Horne volcanic hosted massive sulphide deposit

(Rouyn-Noranda, Quebec), the Gaspe copper porphyry deposit (Murdochville, Quebec) and the Bingham Canyon copper porphyry deposits (Bingham Canyon, Utah) (Lanier et al. 1978;

Allcock 1982; Barrett et al. 1991; Gibson et al. 2000). Selenium concentrations of bulk

sulphide mineral samples from the Horne Deposit have been measured previously by other

methods and provide a basis of comparison to assess this preparation and measurement

method (Hawley and Nichol 1959; Barrett et al. 1991). CCu1-c reference material was

supplied as a powder and was used directly. Samples and reference materials prepared more

Table 2.1. Column Scheme (Chelex™ 100) Step Description Solution Volume Comments 1a Initial 2N Nitric 2 X 12 mL cleaning acid 1b Rinse Water 5 X 12 mL 2a Regeneration 1N Sodium 2 X 12 mL Hydroxide 2b Rinse Water 5 X 12 mL 3a Load Sample Sample 6 to 8 mL Collect eluent for selenium 3b Wash 1N Sodium 3 X 6 mL determination Hydroxide 2N Nitric Removal of transition metals from 4a=1a Cleaning 4 X 6 mL Acid column. Collect eluent of cleaning and rinse steps for detection of transition 4b=1b Rinse Water 5 X 12 mL metals when required 5a=2a Regeneration 1N Sodium 2 X 12 mL Hydroxide 5b=2b Rinse Water 5 X 12 mL

than once from powder are referred to as sample replicates and replicate analyses of the same sample solutions are referred to as analytical replicates.

A 50 mg portion of sample or reference material was placed in a 5 mL PFA screw-top beaker (Savillex Corp.), to which 1 gram of 2N nitric acid was added to dissolve the sample.

A procedure blank and one or more sample replicates of CCu-1c reference material were included in each batch of ten samples. The batch of containers were sealed and heated at 60 to 70 °C for a period of 72 hours to dissolve the sulphides. The contents of the containers were transferred to 15 mL centrifuge tubes using de-ionized water to flush the vial and centrifuged at 10,000 rpm for 10 minutes to separate any undissolved silicates and other refractory phases that may be present in the samples. Following centrifuging, the solutions were decanted into 30 mL centrifuge tubes, the residue washed by de-ionized water, and the solution centrifuged and added to the original decant. 1N NaOH was added to the sample solutions drop wise to adjust the pH to 12±0.2 resulting in the precipitation of metal

hydroxides. The samples were left for 24 hours at room temperature to allow desorption of selenium from the hydroxides. Following desorption, samples were centrifuged for 10 minutes at 10,000 rpm to remove the metal hydroxide precipitates from solution. The solutions were decanted into 60 mL HDPE bottles and the centrifuged solids washed 3 times with water to remove all selenium from solids. This results in a range of sample volumes of 6 to 8 ml. Precipitates were dissolved by nitric acid to test for the presence of copper and iron.

The samples, calibration standards, reference materials, and blanks were loaded on the columns and the metal-free portions of the eluents were collected in polyethylene bottles

(Table 2.1, Steps 3-5). Selenium calibration standards and mixed solutions of copper and selenium were used to verify the recovery of selenium from the columns and the final rinse

(Table 2.1. Step 4b) and the first three sample batches were collected to test for the presence of copper and iron to establish the presence of the metals in the sample prior to ion exchange.

The time required for sample preparation (except pre-reduction) was 5 days.

Solutions containing selenium were pre-reduced to ensure that all selenium is in the

Se(IV) state by the addition of 1g (approximately 1 mL) of concentrated (~10N) hydrochloric acid and subsequent heating at 60 to 70 °C for 3 hours followed by an hour of cooling at room temperature prior to introduction to the hydride generation apparatus. The pre- reduction stage was performed on the day of analysis during the period of instrument start-up and tuning. The calibration standards were prepared identically.

2.03.5 Instrumentation

An Element™ (Finnigan MAT) ICPHRMS and a LI-2 Advanced Membrane Cold-Vapor and

Hydride Generation System (Figure 2-1; further referenced as LI-2; (Klaue ; Klaue and Blum

1999)) are used with typical operating parameters listed in Table 2.2. The multiple runs and

passes of a single determination can produce a relative standard deviation that provides a

measure of the instrument stability.

Flow rates of the sample, acid, reductant, and waste are manually controlled by a four channel peristaltic pump and variable pump tubing diameters. The hydride generation process produces only a gaseous sample stream to the ICPHRMS so that samples with total dissolved solid contents above the recommended limit of 0.1 % for the ICPHRMS can be introduced into the hydride generator with no adverse effects on the ICPMS. The choice of concentration parameters for hydride generation are made based on HG-AAS literature, with limitation of reagent consumption and maximum transition metal tolerance the goals (Ddina

-1 and Tsalev 1995; Tsalev 1999). The choice of a 0.5 % m v concentration of NaBH4 is on the low end of literature values. A low concentration, while restricting signal response, has benefits in its improved tolerance to metal interferences, reduced hydrogen gas production,

and reduced build up of NaNO3 and Na3BO3 in the LI-2. The acidity level is chosen for

similar reasons.

to Element acid from peristaltic additional NaOH/ pump gas from NaBH4 Element from peristaltic Teflon pump sample from filter peristaltic pump sample gas from Element

frosted glass gas-liquid drain to peristaltic pump separator

Figure 2-1. Sketch of LI-2 Hydride Generation System On a daily basis, lens and gas flow parameters of the ICPHRMS are adjusted to maximize

sensitivity and maintain resolution. Tuning at high mass resolution of ca. 9300 (m m-1 at 5

% peak height) is accomplished using hydride generation and a selenium solution (200-250 ng g-1). The use of an internal standard for selenium measurement by hydride generation is

precluded by the need for the internal standard to be similarly converted to a hydride.

Indium, in common use as an internal standard for ICPHRMS, generates hydride in a

inconsistent and non-quantitative fashion and so is unsuitable for use (Liao and Li 1993).

Other hydride generating elements, with predictable behaviour, can be present in significant

concentrations in the transition metal sulphides and so do not meet the requirements of an

internal standard.

Table 2.2. Typical Operating Conditions of HG-ICP-MS 1. ICP-MS Instrument Element™ ICPHRMS Cones Aluminium Resolution Mode High Resolution > 9300 m m-1 at 5 % peak height RF Power 1250 W Sample Gas 0.3 L min-1 Additional Gas 0.7 L min-1 Auxiliary Gas 0.80 L min-1 Cool Gas 14.00 L min-1 Guard Electrode Yes Isotopes measured 74Se, 76Se, 77Se, 78Se, 82Se Runsa 30 Passesb 2 Samples Per Peak 10 Sample Time 0.01 seconds 2. Hydride Generation

NaBH4 concentration 0.5 % NaOH concentration 1 N -1 NaOH/NaBH4 flow rate 0.33 mL min HCl concentration 5 % HCl flow rate 0.33 mL min-1 Sample flow rate 0.33 mL min-1 a The number of data bins used to calculate mean of an analysis b The number of mass scans measured for each run

There are six stable isotopes of selenium (Table 2.3); however, the two of highest

abundance (80Se, 78Se) are subject to isobaric interferences by polyatomic argon molecules that require mass resolutions greater than that achievable by the Element™ for separation. Of

the remaining isotopes, 77Se is the optimal isotope for measurement; 74Se cannot be resolved

from 74Ge and has low abundance, and the potential isobaric interferences on 76Se (36Ar40Ar)

and 82Se (82Kr) are irresolvable. Although the abundance of krypton in the argon gas is low, a

simple blank subtraction to correct the 82Se signal for 82Kr is not possible so that the

instrument cannot be run at the medium resolution setting to measure 82Se. As a poor ionizer,

the ionization efficiency of 82Kr is subject to matrix influence and so the 82Kr signal will be

inconsistent between blank and samples.

All isotope signals, except 80Se, are recorded as the additional data serve as indicators of the state of hydride generation and plasma conditions. Iron and copper in the dissolved precipitates and column washes are measured at a medium resolution setting (m m-1 at 5 %

peak height: ~4000) using a conventional Scott spray chamber and Teflon™ microflow

concentric nebulizer (Elemental Scientific Inc.).

2.04 Results and Discussion

2.04.1 The Effects of pH Adjustment, Co-precipitation, and Tolerance Levels

The addition of sodium hydroxide to both pyrite and chalcopyrite sample solutions to

raise pH and to precipitate metal hydroxides during sample preparation produced orange-

brown precipitates containing iron. Green precipitates, suggestive of copper or iron(II)

(oxy)hydroxides, were not observed, although copper was detected by conventional

ICPHRMS analysis of the orange brown precipitates from chalcopyrite samples, indicating either mixed iron-copper hydroxides or sorption of copper onto the precipitates. In some pH

Table 2.3. Selenium isotopes and potential interferences Isotope Abundance1 Interferants Abundances of Required Source of Interferants1 Resolution Interferants 74Se 0.889 % 74Ge 36.5 % 56938 Sample (minor) 76Se 9.366 36Ar40Ar 0.34 9511 Plasma Gas 77Se 7.635 40Ar37Cl 24 9182 Sample & Plasma Gas 78Se 23.772 38Ar40Ar 0.06 9970 Plasma Gas 78Kr 0.35 25192 Plasma Gas 80 40 Se 49.607 Ar2 99 9688 Plasma Gas 79Br1H 50.6 8283 Reagents 82Se 8.731 82Kr 11 25392 Plasma Gas 81Br1H 49.3 11040 Reagents 1 Rosman and Taylor (1998)

ranges co-precipitation of both transition metals and selenium can occur (Benjamin and

Leckie 1981b; Benjamin and Leckie 1981a). Indeed, co-precipitation of selenium on iron hydroxide has been used as a means of pre-concentration for selenium (Ohta and Suzuki

1975), but as this technique does not remove transition metals, it is not suitable in the present case.

The influence of pH on the sorption behaviour of selenium on iron hydroxides is opposite to that of transition metal cations. Thus, the pH ranges of co-precipitation for selenium and transition metals are not identical (Figure 2-2). Selenium sorption decreases with increasing pH from maximum sorption of Se(IV) in acidic conditions to a minimum at a pH of 10. Se(VI) is sorbed only at low pH whereas cation sorption increases with increasing pH (Davis and Leckie 1980; Leckie et al. 1980; Hayes et al. 1988). A high pH results in the removal of transition metals with selenium remaining in solution. A practical upper limit of pH is dictated by the solubility of iron hydroxide; increased solubility of iron and other hydroxides at high pH results in less effective removal of transition metals, particularly iron

(Figure 2-2). At pH 12, some transition metals remain in solution but a partial separation of

selenium from the transition metals is achieved. During the adjustment of sample solutions to

pH 12, precipitation of hydroxides begins at about pH 3 and continues as pH is increased. It

is not possible for samples to be adjusted upwards to the minimum pH of 4 needed for the

chelating resin to be effective in capturing transition metals without hydroxide precipitation

resulting in sorption and co-precipitation of selenium. The precipitation of the hydroxides in

the operating pH range of the chelating resin prevents the use of the chelating resin alone.

Copper and iron were detected in the sample solutions after hydroxide precipitation,

but before passing through the resin columns. Hydride generator extraction of selenium from

sample solutions after metal hydroxide precipitation, but prior to the use of the chelating

resin, resulted in selenium signal intensities measured by ICPHRMS up to 80% below

expected values and precipitation of a silvery-grey substance in the hydride generator, most

likely an iron precipitate. The detrimental effect of transition metals on hydride generation is persistent; the selenium signal of transition metal-free solutions passed through the hydride generator was also reduced to 20% of the expected value if they followed solutions containing transition metals. The presence of the aforementioned silvery-grey substance, possibly acting as an anti-catalyst for hydride generation, may be the direct cause of the diminished signal. Although the bulk of the transition metals (> 99%) contained in the sample solutions are removed by co-precipitation of the hydroxides, it is evident that a single step of co-precipitation is inadequate to reduce transition metals to levels tolerable for hydride generation. The maximum concentration of metals in the un-exchanged sample solutions can be taken as conservative tolerance limits for hydride generation. These concentrations are defined by the solubility of the hydroxides and other complexes, suggesting that concentrations of iron of ~ 5 g g-1 and copper of ~ 6 g g-1 interfere with the

hydride generation of selenium. The actual concentrations and corresponding tolerance levels

are likely to be lower given the co-precipitation of transition metals with the iron hydroxides.

Reduction of iron and copper concentrations in a chalcopyrite sample to the conservative

tolerance levels by simple dilution would require an approximately 70,000-fold dilution. This

dilution level would bring all but the highest concentrations of selenium below the

100 10

80 5

Cu (II) Cu(OH) 2 Se(IV) 60 0

40 -5 Sorption (%) Solubility (M)

Fe(OH) 3 20 -10

Se(VI) 0 -15 4 6 8 10 12 pH

Figure 2-2. Effect of pH on sorption of selenium and copper ionic species and solubility of copper and iron hydroxides. Percent sorption of 7.9 μg mL-1 selenium or 635 μg mL-1 Cu(II) solutions onto 0.1 g mL-1 ferrihydrite (amorphous iron hydroxide) for Se(IV): —Se(VI): —

— Cu(II): ••• and solubility of Fe(OH)3: — • — and Cu(OH)2: • • • at 25°C (Schultz et al. 1987; Hayes et al. 1988; Stumm and Morgan 1996)

instrumental detection limit so that simple dilution is not adequate for sample preparation for hydride generation.

Following desorption of selenium from the iron hydroxides at a pH of 12 and the

physical removal of iron hydroxide precipitates, the sample solutions transit the ion exchange

columns. As previously noted, precipitation of hydroxides begins at a pH of 3, well outside

of the effective range of the resin, so that co-precipitation is necessary before the use of the

chelating resin. Removal of copper and iron remaining in solution following hydroxide

precipitation was indicated by a change in colour of the resin, to orange-brown for pyrite

sample solutions and to green for chalcopyrite sample solutions, and by the detection of iron

and copper in the washes of the resin columns.

2.04.2 Calibrations, Detection Limits and Method Blank

Calibrations are linear in the range of 5 to 250 ng g-1 with a limit of detection of 4 ng

g –1. Method blanks have selenium concentrations below the limit of detection for the

ICPHRMS. Typical precisions on a single analysis of calibration standards, expressed as

relative standard deviations, are less than 10 %. Precisions from analytical replicates (3) of calibration solutions are further improved with typically relative standard deviations of 5 %,

similar to that previously reported for other HG-ICPMS methods (Heitkemper and Caruso

1990; Hall and Pelchat 1997b; Hall and Pelchat 1997a; González Lafuente et al. 1998;

Menegário and Giné 2000). Using our procedure for preparing the natural samples, which

results in a maximum 1000-fold dilution, in conjunction with the detection limit of 4 ng g-1

using the hydride generator and ICPHRMS, the detection limit for selenium in a sulphide

mineral is 4 g g-1. The thousand-fold dilution factor is the combination (all dilution factors

nominal) of a twenty-fold dilution of acid digestion, 2 three-fold dilutions from the two

washings that follow centrifuging, a three-fold dilution from the addition of sodium

hydroxide, and a two-fold digestion from the addition of acid prior to analysis. The

Table 2.4. Selenium recovery from selenium and copper standards Gravimetric ng g-1 Measured ng g-1 Recovery Standard Se/Cu *10-3 Se Cu *103 Se (3 replicates) % Cu/Se 1 81.3±0.7 0.969±0.13 83.9±1.1 80.5±12.0 99±16 Cu/Se 2 80.7±0.7 6.36±0.04 12.7±0.2 83.6±10.4 104±14 Cu/Se 3 73.3±0.6 98.9±0.5 0.741±0.001 71.5±15.0 98±21 Se standard 187±1 N/A N/A 185±20.0 99±11

individual degree of dilutions for any sample at any preparation stage is known from the

gravimetric measurements that follow each preparation stage and the variability in dilution

factor is small (< 5%) so that differences in dilution factor have little influence on analytical

performance. Some reduction of dilution factor might be possible with a decrease of the

volume of nitric acid used for digestion, but this may increase digestion time. In addition, a

better method of sample washing or he use of higher strength base would reduce dilution

from those preparation stages.

2.04.3 Analysis of standards and reference materials

Recovery of selenium from synthetic solutions prepared from selenium and copper

concentration standards, in varying proportions, followed by our separation procedure gives recoveries of 100±10 % (Table 2.4). Furthermore, copper has been reduced to a concentration below which inhibition of hydride generation occurs, otherwise low recoveries of selenium would result. Concentrations measured for sample replicates of selenium standards individually passed through the ion exchange columns show variation (~8 %) similar to analytical replicates of the calibration standards, whereas the variation of concentrations in the sample replicates of mixed copper-selenium standards are slightly higher (15 %).

Agreement between the certified value for selenium in CCU1-c and the mean of 5 concentrations determined by our separation scheme and HG-ICPHRMS analysis was within

8 % (Table 2.5). Selenium calibration curves produced over a day can show declining and more erratic signal response, possibly due to precipitates in the hydride generator and deposition of material on the sample cones of the ICPHRMS. This may also be a more simple effect of instrumental drift but the increase in signal response variation suggests the non-systematic effects of precipitation or cone deposition to be a more likely cause. The maximum-recorded loss was a 15 % loss of 77Se signal as measured from two aliquots of a

100 g g-1 selenium standard separated by a period of 10 hours. The relative standard deviation of the measurements of simple selenium solutions of known concentration and that of CCu-1c might be considered high in the context of modern instrumental analysis but are not much larger than that observed for single analyses of the single-element calibration standards and can be attributed to non-systematic and ephemeral variations in hydride generation and plasma conditions. The effects of a consistent change in the conditions of the apparatus and instrumentation can be minimized by regular recalibration but, in the absence

Table 2.5. Determination of selenium in five measurements of reference material CCU1-c Se Concentration g g-1 Difference from certified value % (three replicates) Certified Value1 107±15 - 1 109±11 1.9 2 99±23 7.4 3 94±27 12 4 90±22 16 5 87±25 18 Mean of sample replicates 96±9 10

1 (Salley et al. 2000)

of an internal standard, ephemeral variations cannot be corrected. The relative standard deviations of the measurements are consistent with previous selenium determination by HG-

ICPMS where internal standards have not been used (Heitkemper and Caruso 1990; Hall and

Pelchat 1997b; Hall and Pelchat 1997a; González Lafuente et al. 1998; Menegário and Giné

2000). One can surmise on the basis of quantitative recoveries of selenium from solution standards and from certified reference materials that the separatory technique by itself does not introduce imprecision, does not alter accuracy by loss or gain of selenium, and, by removing transition metals, a source of both imprecision and inaccuracy is removed.

2.04.4 Analysis of natural sulphides

Sample replicates of a sulphide show larger variation (8 %) in concentration than analytical replicates (2 %), probably due to the natural variation of selenium concentration in natural sulphides (Sindeeva 1964). Selenium concentrations measured in sulphides from the

Horne deposit are consistent with the values and distributions reported previously (Table

2.6). Measured selenium concentrations between 350 to 1000 g g-1 are similar to the high

values reported elsewhere (Hawley and Nichol 1959; Barrett et al. 1991). The higher

measured concentrations of selenium in pyrite as compared to chalcopyrite and the large

differences in measured concentrations between samples of pyrite are consistent with prior

data from the Horne ore deposit (Table 2.6) and reflect lower temperatures of formation of

pyrite, an interpretation supported by experimental studies and thermodynamic data (Franz

1971; Simon and Essene 1996). It is important to note that the selenium concentrations in the

Horne ore deposit are anomalously high compared to other ore deposits (Table 2.6). Other ore deposits of the same type from the Noranda district, near the Horne ore deposit, have much

Table 2.6. Concentrations of selenium in sulphides from the Horne and other ore deposits

Concentration (3 analytical replicates Sample (g g-1) except as noted) Pyrite: Present Study Gaspe 50±5 Bingham 13±3 1 measurement, error from multiple spectra Horne 16 490±4 Horne 18 384±8 Horne 18 402±32 3 sample replicates Horne 20 754±20 Horne 21 243±121

Pyrite: Ranges of Previous Studies Horne Upper Orebodies1 390 to 1000 n=6 Horne “H” Ore body2 284 to 635 mostly pyrite n=66 Below detection Noranda District VHMS1 n=16 to 320 Russian copper porphyry deposits3 28 to 90 unspecified

Chalcopyrite: Present Study Horne 14 384±58 Horne 16 418±63 Horne 18 383±58 Horne 19 297±41

Chalcopyrite: Range of Previous Studies Horne Upper Orebodies 1 360 to 535 n=7 Noranda District VHMS 1 23 to 280 n=12

1 (Hawley and Nichol 1959) X-ray spectrography 2 (Barrett et al. 1991), NAA 3 (Karamyan 1962; Chitaeva 1965; Filimonova 1972), unknown lower selenium concentrations (Table 2.6). The measured selenium concentrations of sulphides from the Gaspe and Bingham Canyon show the capacity of the method to measure lower concentrations of selenium in sulphides and are consistent with the low concentrations generally found in porphyry copper deposits (Karamyan 1962; Chitaeva 1965; Filimonova

1972).

2.05 Conclusions

Removal of transition metals that interfere with selenium determination by HG-

ICPHRMS of solutions prepared from sulphide minerals has been accomplished by raising the pH of sample solutions to 12, causing co-precipitation of iron hydroxides and other metals, followed by further separation of selenium from remaining transition metals via chelating ion-exchange resin. Both precipitation and chelating ion-exchange resin steps are required to achieve sufficient transition metal removal. This method of selenium purification in conjunction with HG-ICPHRMS detection results in analytical accuracies and precisions for selenium similar to those for previously reported methods using hydride generation for samples with low transition metal contents where no metal removal was required. The method proved useful for determining selenium concentrations of natural sulphides.

Chapter 3. Fabrication of Solid Calibration Standards by a

Sol-Gel Process and Use in Laser Ablation ICPMS

3.01 Abstract

Synthesis of solid multi-element calibration standards, suitable for laser ablation, by a

sol-gel process is described. The addition of an analyte (selenium) and an internal standard

(sulphur) to a normal sol-gel method does not impair the production of the glass-like discs

(xerogels) nor does it introduce detectable heterogeneity. The xerogel standards show only

small deviations from the gravimetrically predicted concentrations of selenium and sulphur.

Heterogeneities of selenium and sulphur concentrations in the xerogels are less than NIST

SRM 610 and 612 glass standards, most likely a result of temperature differences between

the two production methods and the temperature dependence of selenium and sulphur

volatility. Small differences in slopes of calibrations based on sulphide standards and those

based on xerogel standards reflect differential matrix effects. The calculated sulphur contents

in the NIST SRM 610 (630±150 g g-1) and 612 (133±17 g g-1), using the xerogels as

standards, are comparable to available sulphur concentration data. Multiple element

standards of selenium, sulphur, and transition metals are hampered by the formation of

inclusions resulting in visible heterogeneity. The xerogels are potentially useful as standards for the determination of a variety of elements in glasses, minerals, and other materials.

3.02 Introduction

Laser ablation coupled to an inductively coupled plasma mass spectrometer (LA-

ICPMS), is an analytical technique of great utility for in-situ sampling of a variety of

materials (Durrant and Ward 2005; Günther and Hattendorf 2005; Mokgalaka and Gardea-

Torresdey 2006). Unlike conventional methods of solution analysis where sample mass

requirements (milligrams to grams) preclude examination of small-scale spatial data, LA-

ICPMS can be used to obtain chemically useful information on a micrometer-scale spatial

resolution (Heinrich et al. 2003). However, the utility of the laser ablation technique has been limited by difficulties in quantification, especially the absence of suitable standards for

calibration and validation. Calibration has been addressed by the use of a dual inlet apparatus

to allow the use of calibration solutions or by a standard additions approach, (Durrant and

Ward 2005; Günther and Hattendorf 2005; Mokgalaka and Gardea-Torresdey 2006;

O’Connor et al. 2006). However, these methods greatly increase the complexity of the

analysis and do not address the problems with the ablation process. Therefore, developing

appropriate calibration standards that behave similarly to samples remains the theoretically

optimal approach for quantification of LA-ICPMS.

A calibration standard should have spatially homogeneous and known concentrations

of the analytes. The ideal calibration material is matrix-matched to the samples. However, if

correct measurement of reference materials with matrices similar to the sample is achieved,

interferences and matrix effects are minimal and non-matrix matched standards can be used.

Calibration standards are still necessary because the mathematical relationship between signal and concentration is needed.

Calibration standards for the analysis of sample solutions are relatively easy to make, but the production of solid calibration standards is much less routine. The most widely used solid calibration standards for LA-ICPMS are the NIST SRM glasses (SRM 610-615)

(Durrant and Ward 2005; Günther and Hattendorf 2005; Mokgalaka and Gardea-Torresdey

2006). The use of a reference material as a calibration standard is a compromise, as the proper use of reference material is to verify a technique. Although there is development of glass-based reference materials and calibration standards by conventional glass production,

these are difficult to produce because the high temperatures involved can result in

volatilization of some elements and the question of inhomogeneities (Latkoczy et al. 2005;

Oedegaard et al. 2005). A method for routine production of solid calibration standards for

LA-ICPMS would be advantageous.

The sol-gel process is defined as “the preparation of ceramic materials by preparation

of a sol, gelation of the sol, and the removal of the solvent” (Brinker 1990). The sol-gel

process is suitable for small-scale glass production and thus for making solid calibration

standards. The products of sol-gel processes have a wide variety of physical forms that are

useful in many industrial applications, including insulation, antireflective films for optical

lens, and glass fibers. In the field of chemical analysis, sol-gel techniques have multiple

applications. Some recent examples are the incorporation of biosensors into solid matrices,

production of absorbance standards, and production of sample matrices for radio frequency

glow discharge optical emission spectrometry (Aubonnet and Perry 2000; Davis et al. 2005;

Ting et al. 2006). Recently, sol-gel processes were used to produce lead and chromium

standards for a variety of laser spectrometry techniques (Viger et al. 2005; Brouard et al.

2007).

The sol-gel process for the production of a silica glass begins with hydrolysis of silica

alkyloxide and subsequent polymerization to particles (sols). The sols grow and aggregate to

form chains and network structures that encase the fluids (gel). Either an acid or a base catalyzes the process and silica linkages are increased by the addition of a simple alcohol that acts as a solvent. The net reaction using tetraethyl orthosilicate (TEOS) is

C8 H20 SiO4 + 2H2O 4C2H2OH + SiO2 (Brinker 1990) (3.1) The liquids evaporate or remain in pores. The result is a rigid, amorphous, and porous

product that is not considered a glass. Conversion to a non-porous glass requires heating at an

elevated temperature (400 to 1000°C) for a short period (~24 hours) (Brinker 1990).

The potential of a sol-gel process for making calibration standards for LA-ICPMS

was tested using selenium and sulphur. Both elements are among the most difficult to

analyze by ICPMS, despite their utility as indicators of ore forming processes in metal

deposits, sources of salts in soils and as discriminants for glass identification (Eckstrand et al.

1989; Hinchey and Hattori 2005). Determination of selenium by ICPMS is impaired by its low ionization efficiency (Pupyshev et al. 1999), and the inability to resolve 80Se+, the most

40 + abundant selenium isotope, from Ar2 . Consequently, determination of selenium is

normally made from solutions by ICP(HR)MS preceded by hydride generation to pre-

concentrate the selenium (Hall and Pelchat 1997a; Martinez et al. 1997). However, transition

metals can interfere with hydride generation making determination of selenium in sulphides

minerals difficult (Waleerz et al. 1993; Ding and Sturgeon 1997). Although sulphur

determination by ICPMS is also hampered by low ionization efficiency and spectral

+ interferences from O2 , the spatial resolution advantages provided by LA-ICPMS have

resulted in the increasing use of LA-ICPMS for sulphur determination of sulphides (De Hoog

et al. 2001; Bendall et al. 2006; Mason et al. 2006). Determination of selenium by laser ablation techniques has been limited because the selenium cannot be pre-concentrated and the suite of suitable standards is limited (Perkins et al. 1997; Fan 2002).

The adoption of an analyte for use as an internal standard is common practice for analysis of solutions by ICPMS and is critical for LA-ICPMS due to the additional sources of temporal variation in signal response (Cheatham et al. 1993). The internal standard should closely match the behaviour of the analyte of interest to minimize any matrix effects. Sulphur is chosen as an internal standard for selenium for its stochiometrically defined concentrations in sulphide minerals associated with ore deposits and it has an ionization potential of 10.36 eV, similar to selenium at 9.752 eV (Lide 2007).

The objective of the work presented herein was to develop a sol-gel process for the production of xerogel calibration standards for LA-ICPMS, focusing on selenium and sulphur analysis, but also transition metals. The xerogels were examined by scanning electron microscopy (SEM) and electron microprobe analysis (EMPA) for their fine-scale characteristics and comparisons of their selenium and sulphur contents were made with glass standards, sulphide reference materials, and natural sulphides whose sulphur and selenium concentrations have been determined by other techniques.

3.03 Experimental Section

3.03.1 Preparation of Xerogels

Xerogel preparation was conducted in a class 100 clean laboratory. Deionized (> 18.2

M) water was used for reagent preparation. Tetraethyl orthosilicate (TEOS, 99.999%,

Aldrich) and methanol (spectrophotometric grade, Aldrich) were used as received. Selenium,

sulphur, iron, copper, zinc, cobalt, lead, and nickel were sourced from 1000 g ml-1 solution standards (Spex CertiPrep™). Transition metal solutions of 20 g g-1 nominal concentrations

for each metal were prepared. Reagent grade nitric acid (Fisher Scientific) was further

purified by sub-boiling Teflon™-still distillation.

The quantities of reagents were chosen to produce a nominal

TEOS:water:acid:methanol molar ratio of 5:35:50:1 as used by others (Nogami and Moriya

1980). A total volume of 30 ml corresponds to 9.4 ml TEOS, 8.0 ml methanol, 0.2 ml

concentrated nitric acid, and a total water volume of 8.0 ml. The selenium and sulphur

concentrations were varied to produce various concentration ratios, limited by the solubility

of both selenium and sulphur.

The water and nitric acid were added to a new, acid cleaned, 60 ml HDPE bottle.

Selenium and sulphur were added, as appropriate, directly from solutions. Transition metals,

when used, were added from the stock solutions at the same time as sulphur and selenium.

TEOS and methanol were added last to minimize losses from evaporation. The bottles were

capped and shaken vigorously for 30 seconds. Self-diffusion was relied on to achieve to

solution homogeneity. The solution was poured into moulds, and then most were sealed with

laboratory film (Parafilm™). Eliminating or piercing the laboratory film was used to vary

evaporation rates. Retaining part of the solution in the mixing bottle produces a xerogel with

the slowest rate of evaporation when the bottle cap is loosely screwed on the bottle. The

filled moulds were left in the clean lab and were weighed daily. The sol-gel process was

considered complete when the resulting xerogels achieve a constant mass ( 0.5% daily

change).

A number of xerogels were heated. A xerogel fragment for each series was selected and placed in ceramic crucibles and heated for 24 hours in a baffle furnace at a temperature of 600 °C.

3.03.2 Calibration Standards

The USGS PS-1 standard was used as supplied (Wilson et al. 2002). The values of sulphur and selenium in this standard have been determined by single techniques and uncertainties are not given. A relative uncertainty of 10% was assigned to the Se/S concentration ratio on the basis of LA-ICPMS analysis (Wilson et al. 2002). A small quantity of the CCRMP CCu-1c certified reference material was pressed, without a binding agent, into a 7.5 mm disc using a handheld press. The natural sulphides (HORNE series) are polished chalcopyrite and pyrite samples from the Horne ore deposit (Barrett et al. 1991).

The selenium contents in these sulphides were obtained by a hydride generation ICPHRMS method (Chapter 2). Stochiometrically defined sulphur contents were used for the sulphides; replacement of sulphur by selenium has been addressed by the measurement of selenium concentration. Both natural pyrites and chalcopyrite have close to ideal molar stochiometry and differences in sulphur concentration are small. The replacement of iron in pyrite by metallic elements and the replacement of sulphur by selenium and tellurium, at up to the maximum recorded concentrations of the trace elements, results in a relative change of sulphur concentration from its stochiometric definition of less than 1% (Abraitis et al. 2004).

Accordingly, a conservative 5% relative uncertainty was assigned to the sulphur concentration of the pyrite grains. The replacement of sulphur in chalcopyrite and variations in the Cu/Fe ratio cause less than a 0.1% relative deviation of sulphur concentration from its

Table 3.1. Concentrations of sulphur and selenium in natural and reference sulphide materials Type S Se Se/S Ccu-1ca Cu concentrate 33.3±0.3 wt. % 107±15 g g-1 3.21±0.45 x 10-4 (pressed disc) PS-1 Synthetic sulphide 27.6 wt.% 53 g g-1 1.92±0.19 x 10-4 (pressed disc) Horne14CPY Chalcopyrite 34.9±0.7 wt. % 384±58 g g-1 9.97±1.52 x 10-4 Horne16CPY Chalcopyrite 34.9±0.7 wt. % 418±63 g g-1 11.98±1.82 x 10-4 Horne18CPY Chalcopyrite 34.9±0.7 wt. % 383±60 g g-1 10.97±1.73 x 10-4 Horne19CPY Chalcopyrite 34.9±0.7 wt. % 300±41 g g-1 8.60±1.19 x 10-4 Horne16PY Pyrite 53.5±2.7 wt. % 498±75 g g-1 9.38±1.49 x10-4 Horne20PY Pyrite 53.5±2.7 wt. % 754±113 g g-1 14.09±2.23 x 10-4 Horne21PY Pyrite 53.5±2.7 wt. % 300±45 g g-1 5.61±0.88 x 10-4 T25 Synthetic selenide 2.3±0.2 wt. % 22.8±0.2 wt. % 9.91±0.99 T26 Synthetic selenide 4.8±0.5 wt. % 17.7±0.5 wt. % 3.69±0.38 T27 Synthetic sulphide 7.5±0.8 wt. % 12.2±0.8 wt. % 1.62±0.19 T28 Synthetic sulphide 10.3±0.6 wt. % 6.4±0.6 wt. % 0.62±0.07 a Certified values

stochiometric definition (Klein and Hurlbut 1985; Raghavan 2004): a conservative 2% relative uncertainty is assigned to the sulphur concentration of the chalcopyrite.

A series of synthetic minerals (T-series) of the clausthalite (PbSe) –galena (PbS) solid solution series are also used as calibration standards (Earley 1950). The mol. % values

(subsequently converted to g g-1) of the T-series were confirmed on the basis of crystal bond length (Earley 1950). As pure synthetic materials, the stochiometry of the T-series are assumed correct with little contamination by other elements, so the absolute uncertainties of the sulphur and selenium concentrations should be equal. Accordingly, the analyte with the smaller concentration was assigned a 10% relative uncertainty and the uncertainty of the analyte with greater concentration was calculated so that the absolute errors of the two analytes are equal. The certified and other values of reference and natural sulphides are summarized in Table 3.1.

The variation in the Se/S concentration ratio of the calibration standards dictates the

precision of the analysis. With the exception of PS-1, there has been no previous assessment

of the spatial heterogeneity of the materials. The relationship of selenium to sulphur in

sulphides (direct substitution) ensures, under controlled synthesis or with a homogenization

process, a selenium concentration proportional to sulphur concentration. Diminished sulphur

concentration, because of contamination by non-sulphide material, results in proportionally

diminished selenium concentration. Although, the molar sum of selenium and sulphur

remains constant for a sulphide, differences in selenium concentration at its typically small value causes a small relative change in the sulphur concentration. At these small selenium concentrations, uncertainty of the Se/S concentration ratio is adequately described by

standard propagation from the uncertainty of sulphur and selenium concentrations. At the

greater selenium concentrations of T-series, the change in sulphur concentration with

changes in selenium concentration is significant. The uncertainties of the T-series

concentration ratios were also propagated normally although the true uncertainty may be

greater. In general, the uncertainty of the selenium concentration defines the uncertainty of

the Se/S concentration ratio. The uncertainties of the Se/S concentration ratios are included in

Table 3.1.

The NIST SRM 610 and NIST SRM 612 reference materials were used as supplied.

Most elements added to the NIST glasses have nominal concentrations of 500 g g-1 (SRM

610) and 50 g g-1 (SRM 612) and most certified values are close to these. The certification

is for the entire disc, whereas homogeneity of replicate analyses of 10 m spots has been reported for many elements (Pearce et al. 1997; Rocholl et al. 1997; Trejos and Almirall

2005; Luo et al. 2007).

Table 3.2. Available sulphur and selenium concentrations for NIST SRM glasses Element Analytical Method Sample Size Concentration g g-1 Reference NIST SRM 610 S Laser plasma ionization 91 mg Fragment 456±32 (Rocholl et al. mass spectrometry 1997) Secondary ionization mass Multiple Spots 693±194 (Jochum et al. spectrometry 2006) Se Particle induced x-ray Multiple Spots 108.0±4.5 (Benjamin et al. emissions 1988) Particle induced x-ray Multiple Spots 110±6 (Rogers et al. emissions 1987) Particle induced x-ray Multiple Spots 114±7 (Rogers et al. emissions 1987) Particle induced x-ray Multiple Spots 183±16 (Rocholl et al. emissions 1997) NIST SRM 612 S Laser ablation spark source Spot 16±2 (n=1) (Bonham and mass spectrometry Quattlebaum 1989) Secondary ionization mass Multiple Spots 350±35 (Jochum et al. spectrometry 2006) Se ICPMS 1 mg 59±1 (Zurhaar and Mullings 1990) ICPMS 10 mg 20.0±4.3 (n=81) (Duckworth et al. 2000) ICPMS 200 mg 19.0±2.2 (n=10) (Parouchais et al. 1996)

However, there are no certified values for selenium and sulphur. Published values for sulphur

and selenium contents of the NIST glasses are summarized in Table 3.2. The poor agreement

and paucity of concentrations for sulphur and selenium in the NIST glass standards indicates

that these cannot be used as sulphur and selenium calibration standards, and are treated as

unknowns for this study.

3.03.3 Instrumentation and Measurement

3.03.3.1 Bulk Chemical Composition and Sulphur Isotope Ratios of Xerogels

The effects of the sol-gel process on the analyte and the internal standard were not

known initially so that it was necessary to measure the bulk concentrations of a subset of the

produced calibration standards to ascertain retention of the elements of interest. The analyses

included electron impact mass spectrometry and neutron activation, which precluded bulk

concentration analyses of all xerogels because of the quantities of material required.

Sulphur concentration and isotope ratios were measured with a MAT-252 IRMS

(Thermo Finnigan) coupled to a NCS 2500 elemental analyzer (Thermo Electron) optimized

for sulphur isotope ratio determinations. Xerogels were hand-ground to sand size with a

pestle in an agate mortar. Weighed aliquots of samples were placed in tin cups and sealed.

Physical limitations of sample size result in a detection limit of 200 g g-1 sulphur. The

concentration analysis was calibrated by a DL-methionine standard and isotope abundances were calibrated by certified and in-house isotope reference standards (Rainbow et al. 2005).

Duplicate analyses indicate an uncertainty in concentration of 10% and 0.3 per mil in the sulphur isotopic compositions. The isotope ratios are reported relative to the Canon Diablo

34 Troilite standard ( SCDT).

Selenium in xerogels was determined by neutron activation analysis (NAA) at the

Centre for Neutron Activation at McMaster University. Samples were ground in the same

fashion as for sulphur analysis. A sample aliquot was transferred into a pre-cleaned high-

density polyethylene vial and heat-sealed. Standards and blanks were similarly prepared. For

the determination of selenium, samples were irradiated for 7 seconds in a thermal irradiation

site (nominal flux 5x10+12 n cm-2 s-1), with a delay to count of 7 seconds and a counting time

of 30 seconds. Gamma spectra to measure 76Se and 77mSe were collected with a hyper-pure

germanium detector (efficiency 20%, FWHM 1.8 keV at 1332 keV) on a PC based multi

channel analyzer. The gamma-ray photopeak at 161.9 keV was integrated to measure the

selenium. The system was calibrated with in-house selenium standards and certified

reference materials were analyzed as unknowns with each run. The detection limit was 1 g

g-1 for high level samples (>1 g g-1) and 0.5 g g-1 for low-level samples (<1 g g-1). A 10% relative error was assigned to the NAA results based on results observed elsewhere (Gladney and Knab 1981; Gladney et al. 1987).

3.03.3.2 Scanning Electron Microscopy and Electron Microprobe Analysis

Electron microscope examination of xerogels was made using the JEOL 6400 digital scanning electron microscope at Carleton University (Ottawa, Ontario). Xerogels were placed on aluminum slides and sputter coated by gold and palladium. Full details of theory and practice are available elsewhere (Goldstein et al. 1992; Potts et al. 1995).

Electron microprobe analysis was by a Camebax MBX electron microprobe also at

Carleton University. EMPA samples were polished thin sections of xerogel fragments coated by a carbon film. A 15kV beam was used with a 40 second measurement counting time and a

80 second background counting time. Calibration was based on in-house mineral standards.

Detection limits were ~100 g g-1 for both selenium and sulphur (P. Jones, pers. comm.).

Full details of the operations and theory are available elsewhere (Goldstein et al. 1992; Potts

et al. 1995).

3.03.3.3 LA-ICPMS Instrumentation and Parameters

An Element™ ICPHRMS (Finnigan MAT) and a UP213 Nd-YAG laser ablation

system (New Wave Research) were used with parameters as listed in Table 3.3. The output

Table 3.3. Laser and mass spectrometer conditions Laser: Model New Wave Research Merchantek UP-213 213 m wavelength (1064 m frequency quintupled Nd-YAG) Mode: Spot Spot Size 100 m Power Density ~4.5 mJ m-2 Rate 2 Hz ICPMS Model Finnigan Element™ Resolution Mode High Resolution (m/m at 5% 9500-10000 peak height) Isotopes Measured: 77Se, 32S, Isotopes Monitored: 82Se, 34S, 54Fe, 65Cu, 70Zn Sample Time: 32S 0.0033 seconds 77Se 0.300 seconds Others 0.0025 seconds Cones Aluminum Cooling gas 14 l min-1 Auxiliary gas 0.8 – 1.0 l min-1 Sampling gas 0.95 – 1.20 l min-1 Spray Chamber Scott double pass Run in time 30 seconds Samples per Peak 25 Runs 20 Passes 1

of the sample chamber of the laser ablation system was coupled to the ICPHRMS via a spray

chamber used without he use of a nebulizer. On a daily basis, lens and gas flow parameters

were adjusted to maximize sensitivity and resolution for lithium, lanthanum, and uranium isotopes while ablating the NIST SRM 612 glass. Tuning at high resolution to maximize resolution was achieved by adjustment of lens parameters while the 40Ar16O signal was

monitored. The process achieved resolution near 10,000 (m m-1 at 5% peak height), suitable

for separation of 77Se from most interferants. It is also sufficient for the separation of 32S

16 from O2 interference.

There are six stable isotopes of selenium; however, the two of highest abundance

(80Se, 78Se) are subject to isobaric interferences by polyatomic argon molecules that require

mass resolutions for separation that are greater than that achievable by the ICPHRMS. Taken

together these two isotopes account for 73.4% of total selenium abundance. Of the other

isotopes, 74Se has very low abundance resulting in large measurement error, and isobaric

interferences from potential sample components on 76Se and 82Se are irresolvable, so that

77Se is the optimal isotope for measurement. 82Se is recorded as well to serve as an indication

of the instrumental stability. 32S is the isotope of choice for sulphur because of its high

abundance. The sampling times for sulphur and selenium have been optimized based on

isotope abundance to minimize counting error. Additional isotopes were chosen to achieve the highest signal while avoiding irresolvable interferences.

The laser conditions were set to maximize the selenium signal while maintaining spatial resolution consistent with the needs of the research. The choice of a spot for ablation maximizes the number of suitable sulphide grains within any geological sample. Laser power and spot size were optimized to maximize repeatability by minimizing the relative standard deviation of the 77Se/32S signal ratio on five measurements of the PS-1 sulphide reference

material. Relative standard deviations were minimal at a power density of 4.5 mJ m-2 and a

100 m spot size. Better precisions were found in the measurement of sulphur isotopes from

pyrite using large spot sizes ( 80 m) (Bendall et al. 2006) and a large spot size was

required for a sufficient and consistent 77Se signal. The choice of a 2 Hz laser firing rate was

due to poorer reproducibility recorded at higher repetition rates for other materials analyzed

using this instrumental setup.

An analysis was the ablation of three to five well-separated spots on the xerogel,

sulphide, or glass. Each ablation was preceded by the measurement of a gas blank where argon gas is flowing through the sample chamber.

3.03.4 Data Treatment and Calibration

Data were processed off-line by calculating mean blank corrected signals from 20 analyses for selenium and sulphur. The resulting means were used to calculate the 77Se/32S

signal ratio. The ratios for a standard were averaged and the result was plotted against the

known Se/S concentration ratio. Only those xerogel series (numbers 3 and 10) with measured

selenium and sulphur concentrations determined by other techniques were used. The

operating software of the mass spectrometer corrected for dead time.

The suite of standards (xerogels or sulphides) was used to produce a least squares

regression fit calibration. The suites were required to be separated because the combination

of the two suites did not produce an acceptable calibration. In the construction of a composite

calibration curve, a rejection criterion removes data with a blank corrected 77Se signal of less

than 25 cps or a 77Se/32S signal ratio outside of 3 standard deviations of the overall mean

77Se/32S signal ratio. The slope of the calibration is the 77Se/32S sensitivity ratio. The

concentration ratio was calculated by multiplying the 77Se/32S signal ratio by the 77Se/32S

sensitivity ratio. To calculate the selenium concentration, the concentration ratio was

multiplied by the sulphur concentration of the sample as follows:

signal 77 Se []Se Sample = []S Sample m + b (3.2) signal 32 S where m is the slope of the calibration curve (i.e. the 77Se/32S sensitivity ratio) and b is the x-

intercept. As it proved necessary to use selenium as the known element in the measurement

of the NIST SRM glasses, the inverse equation was required to determine sulphur concentration.

signal 77 m Se + b signal 32 S []S Sample = (3.3) []Se Sample

3.04 Results and Discussion

3.04.1 Formation and Physical Aspects of the Xerogels

The xerogels are colourless (Figure 3-1) and, under the optical microscope, show no apparent heterogeneity in the matrix beyond variations in surface topography that result from the presence of pores. The xerogels are brittle and can fracture during microscopic examination. Heat treatment results in a ‘glass’ with greater transparency and increased

Figure 3-1. Intact xerogel (SG10A) evaporated under partial atmospheric isolation– sealed mould. Scale is centimeters.

100%

Fully Isolated 80%

Partially Isolated 60%

40%

% of Initial mass Open 20%

0% 0 100 200 300 400

Time from casting (hours) Figure 3-2. Drying of xerogel with varying atmospheric isolation durability as a result of increased silica linkage and collapse of pores (Yamane 1988).

Gelation of the xerogel solutions occurred within 24 hours and a consistent mass (less then 1% relative decrease in mass from previous day) was reached after 14 to 21 days (Figure

3-2) depending on the degree of atmospheric isolation. Elevated temperature has been reported to reduce the time for evaporation without negative structural effects, but volatilization of the selenium and sulphur precludes this approach (Yamane 1988). Rapid formation of xerogels was however accompanied by extensive fracturing, often resulting in small fragments (<2 mm diameter) that require mounting. Fracturing is a common occurrence in sol-gel processes and can be limited by chemical and physical control of evaporation rate (Yamane 1988; Brinker 1990). In the present case, atmospheric isolation of the xerogels is sufficient to reduce fracturing to an acceptable level.

The theoretical mass loss of a xerogel cast is calculated by subtracting the final mass

[masses of added silicon (from TEOS), sulphur, selenium, transition metals (if present) and

oxygen (twice the moles of silicon)] from the original mass of the solution. The mass loss

reflects the evaporation of fluids from the xerogel solution to form silica (SiO2), with full

retention of the added analytes. As the masses of the individual xerogel casts are different,

the mass losses are expressed as a percentage of initial total mass of each cast. The

theoretical mass losses are 91 ± 1% while actual mass losses at 86 ± 2 % are less. The

volume loss of 85 to 95%, matches the mass loss.

The mass loss during heat treatment of xerogels is similar to the difference between

actual and theoretical mass losses during xerogel formation. This suggests that there is

retention of a small amount of the reagent solutions in the pore spaces of the xerogels.

3.04.1.1 Bulk Composition of Xerogels

Comparison between the gravimetric calculation and analytical determinations of

concentrations allows the retention of the analytes to be determined. Sulphur and selenium

bulk concentrations and 34S values for the xerogels are given in Table 3.4. There is a

difference of less than 10% between the calculated and measured selenium concentrations,

which is within instrumental error.

Loss of up to 75% of sulphur (Table 3.4) cannot be accounted for by instrumental error, but can be attributed to volatilization. The volatilization temperature of sulphur is lower than that of selenium (Lide 2007) so there can be volatilization of sulphur without concurrent selenium volatilization. The variability in 34S of the xerogels (Table 3.4) does

not allow a complete attribution of all sulphur loss to volatilization.

Table 3.4. Analyte contents, Se/S concentration ratios and 34S values of xerogels (Atmos. Isol. = Atmospheric Isolation, Mod. = moderate Gravi. = Gravimetric, Anal. = Analysis) S μg g-1 Se μg g-1 Pb Fe Atmos. 34 -1 Xerogel Loss Loss Se/S SCDT μg g Isol. Gravi. Anal. Gravi. Anal. % % ‰ Gravi. SG3I Mod. 682±68 506±25 25 591±59 587±59 ~0 1.16±0.13 14.1±0.3 x 100 SG3J Mod. 613±61 591±30 3 723±72 732±73 ~0 1.24±0.14 14.1±0.3 x 100 Not present SG3L High 359±36 311±15 13 550±50 470±47 ~0 1.51±0.16 12.5±0.3 x 100 SG10A Low 842±84 209±10 75 8±1 7±1 ~0 3.34±0.36 13.6±0.3 x 10-2 SG5Aa Low 593±60 - - 75±8 85±9 ~0 - 14.3±0.3 131±13 188±19

a Not used for calibration The major effect from heat treatment of the xerogels to 600oC is loss of both selenium

and sulphur. Xerogels that gravimetrically should have contained 880 ppm selenium and 530

ppm sulphur had both elements below detection limit, indicating losses of 90% or greater of

their initial contents. Thus, heat treatment of xerogels containing volatile elements should be

avoided.

3.04.1.2 Physical Effects of Ablation

Ablation of the xerogels produces craters that have the same characteristics as those

Figure 3-3 (A). SEM image of ablation crater in xerogel. (B) Showing spalling. Surface non- orthogonal to image

Table 3.5. Typical relative standard deviations of the 77Se/32S signal ratio from multiple ablation spots and combined concentration uncertainty Signal Ratio RSD Combined S & Se concentration uncertainty % Standard/Xerogel Series % NIST SRM 610 20 Unknown NIST SRM 612 25 Unknown Ccu-1c 15 14 PS-1 15 10 HORNE16CPY 10 15 HORNE19CPY 15 14 SG10 10 25 SG3 10 11

produced by ablation of conventional glass. The craters are circular and well defined with

occasional spalling (Figure 3-3). Craters are typically surrounded by small ‘fall-back’ zones

of irregular fragments, an effect commonly observed during the ablation of glassy materials

(Lahaye et al. 1997; Motelica-Heino et al. 2001). The amount of this fall back material

appeared to be much less than 1% of the amount ablated.

Fracturing of xerogels during ablation was restricted to xerogels that previously

fractured during formation. Fracturing is not spatially linked to the ablation location; instead,

it appears to be the result of areas of stress in the xerogel. The fragments that resulted from

fracturing did not appear to be of a consistent size.

3.04.2 Detection Limits, Error, and Variation

The analytical method described above can be used to determine concentrations of

sulphur in the xerogels used for calibration, all of which had 200 g g-1. Better definition of

the practical detection limit for sulphur using LA-ICPMS is not possible since there are no

xerogels with sulphur contents below 200 g g-1. In the case of selenium, concentrations of 1

g g-1 could be detected in the xerogels, but consistent detection was only achieved at

concentrations greater than 5 g g-1 selenium.

The relative standard deviations of the 77Se/32S signal ratios of the xerogels, sulphide

standards and sulphide minerals of known concentration are similar to the combined

uncertainty of sulphur and selenium concentration (Table 3.5). The signal ratios of the NIST

glasses have higher relative standard deviations than the other materials, resulting from

possible heterogeneity of sulphur and selenium in the NIST glasses, matrix induced instrumental error unrelated to heterogeneity, or the lower selenium and sulphur concentrations of the NIST glasses.

The relative standard deviation of the 32S signal on single ablation spots on xerogels

and SRMs over the twenty spectra of a pass is between 5 and 25%, but the relative standard

deviation of the intensity of the 32S signal across multiple ablation spots can be as high as

50%. Variation in 32S signal from spot to spot can be related to ablation conditions such as

Figure 3-4. Electron backscatter images of xerogels at smaller (A) and larger (B) scales). Darker patches in upper centre of B are thinner portions of the thin section (also observed under optical microscopy). Linear features are of topographic origin

Table 3.6. Electron microprobe analysis of xerogels and NIST SRM 610; with analysis of inclusion and matrix in SG5A and comparison to bulk composition (Rel. var. = relative variation) Measure- Si ––––––––Se––––––– ––––––––S––––––– Pb Fe ments Wt. % g g-1 Rel. var. g g-1 Rel. var. g g-1 g g-1 SRM 610 5 31.78±0.18 214±121 57% 508±35 7% Not measured SG3J 8 37.60±0.40 159±56 35% 370±65 18% Not Present SG3L 12 33.11±1.02 723±114 16% 839±263 31% Not Present SG10A 3 34.52±0.10 165±75 45% 430±67 16% Not Present SG5A Inclusions 1 32.54±0.22 2400±700 29% 3600±500 14% 26900±800 790±121 Matrix 7 34.11±0.17 100±100 100% 500±100 20% 100±100 300±100 (detection limit) Bulk a N/A 33b 70±10 14% 590±10 2% 131±10c 188±10c a Other methods b Theoretical, based on SiO2 composition and 30 wt. % residual fluid c Gravimetric calculation

position of the sample within the laser chamber and focus of the laser energy. Changes of

signal with changes in position in the laser chamber were greater during this study than

reported elsewhere (Berends-Montero et al. 2006), but variations in signal intensities were

similar for both selenium and sulphur, so that the ratio did not change. The cause of the

greater variation of signal with laser chamber position is unidentified but is likely related to

differences in gas flows.

SEM and EMPA were used to examine the spatial variability of the xerogels and

elemental concentrations. SEM examination of the transition metal free xerogels shows no

evidence of chemical heterogeneity at the micrometer scale but linear features on the surface

of the xerogels (Figure 3-4) may be responsible for variations in signal intensities as laser

focus changes. Polishing the surface of the xerogels minimizes variations in intensity, as is

true for all samples. Electron microprobe analysis shows selenium concentration variation in

single xerogels (Table 3.6) to be no greater than the concentration variation found in NIST

SRM 610. This suggests equal heterogeneity for selenium in the xerogels and NIST SRM

610 at the detection limit of 100 g g-1 for the microprobe. Variation in sulphur concentration in the xerogels is greater than that found in NIST SRM 610, but the poor stability of both sulphur and the xerogels under the microprobe is likely responsible; the xerogel, prepared as a thin section fractures under the microprobe beam.

Since the apparent heterogeneity in the NIST glasses is higher for sulphur and selenium than other elements, the heterogeneities may reflect the properties of selenium and sulphur. As volatile elements, selenium and sulphur behaviours are greatly influenced by temperature. The fundamental external difference between the production processes of the

NIST glasses and the xerogels is temperature. Xerogel formation occurs at low temperature

(~25°C) whereas glass formation requires high temperature (~1500°C). This difference in temperature may lead to differences in the behaviour of selenium and sulphur during the formation of the two media.

The form of selenium and sulphur in the xerogels and the glasses are unknown.

Crystals of selenium grow in organic-based gels at low temperature and in fused silica (Blank et al. 1968; Henderson et al. 1998). In the present study, SEM examination of xerogels reveals no crystals or inclusions (except those xerogels containing transition metals). The lack of the characteristic red colour of nanometer-sized particulate selenium in the xerogels indicates the absence of particulate selenium (Paul 1975). Selenium may be incorporated into the matrix of a xerogel, and in the absence of particulate native selenium, this is the likely process leading to homogeneous distribution of selenium (Hodge et al. 2006).

It is unknown if sulphur can be incorporated into the xerogel structure.

Thermodynamic data indicate that precipitation of sulphur should not occur under the

conditions of xerogel formation. Sulphur may sorb to the silica, inasmuch as solid acid catalysts are made by loading sulphuric acid onto silica gel (Riego et al. 1996). There is no colour suggestive of particulate sulphur.

3.04.3 Signal Response

The mean sulphide and xerogel calibrations are (Figure 3-5):

Signal Se 77Se = 0.222 []+ 0.003 (R2 = 0.95) for sulphide (3.4) Signal S 32S [] and

Signal Se 77Se = 0.0197 []+ 0.01 (R2 = 0.35) for xerogel (3.5) Signal S 32S [] Slopes of the calibration lines are distinct for sulphide standards and xerogels. If there is no

101 Xerogels Sulphides 100 T- series sulphide /selenides -1 10 SG3

10-2 Xerogel S Signal Ratio

32 calibration CCU1c Sulphide calibrationSG10 Se/ 10-3 77

10-4 Other Sulphides PS-1 10-5 10-4 10-3 10-2 10-1 100 101 Se/S Concentration Ratio Figure 3-5. Calibration standard results and derived calibrations

elemental fractionation from any source during analysis, the slope of the calibration curve

should reflect the relative isotope abundance of the two analytes. An unfractionated 77Se/32S

senstivity, as calculated from natural isotope abundance, would be 7.73 x 10-2 (Rosman and

Taylor 1998). It is unlikely that the natural isotope abundances reflect the actual isotopic

compositions of either sulphides or xerogels but it can serve as a basis of comparison. It is

equally unlikely that the difference in isotope abundance between the xerogels and sulphide

is significant. The 34S value for the xerogels and the HORNE sulphides differ from each other by ~ 10 ‰, the xerogels being enriched in 34S, but this corresponds to a 1% difference

in the abundance of 32S. Although selenium isotopic abundances were not measured in the standards, the reported 82Se/76Se range is only 15 ‰, corresponding to a difference of 1.5%

in the abundance of 77Se in natural selenium (Krouse and Thode 1962; Rouxel et al. 2002).

For elements with poor ionization efficiencies, the matrix can greatly affect the signal

that is detected by ICPMS; ionization is dependent on both which other ions are present and

the temperature of the plasma (itself dependent on the sample load in the plasma)

(Hanselman et al. 1994; Pupyshev et al. 1999; Chan et al. 2001; Wang et al. 2006). Both

selenium and sulphur have poor ionization efficiencies, with sulphur being the poorer ionizer.

Factors that affect the plasma, such as the character of the matrix, can also effect the relative

ionization of all elements, although for most elements and matrices, this is not a significant

effect. Differences between the slope of the calibration lines for selenium and sulphur using

xerogels, a silica-rich matrix, and sulphide standards would suggest that matrix does affect

the relative ionization of these two elements. The fractionation may also occur during

ablation or vapourization.

3.04.4 Sulphur Content of NIST SRMs 610 and 612

Table 3.7. Sulphur contents (μg g-1) of NIST SRM glasses as determined with xerogel calibration Se S NIST SRM N g g-1 Min. Mean ±1 Max. 610 7 110 351 650±290 741 612 7 20 108 171±100 148

The LA-ICPMS method results in Se/S concentration ratios rather than concentrations. Thus, the concentration of one of the elements must be known to calculate the concentration of the other. As neither element is certified or well characterized in the

NIST SRM glass, the choice of a concentration is a source of error that is transferred to the final concentration of the unknown element. The better available data for selenium in both the NIST and xerogel glasses (Table 3.2) as compared to sulphur leads to the choice of selenium as the known element, from which the sulphur concentration can be calculated using equation (3.5). The values of selenium used for the calculation are listed in Table 3.7.

The values of the signal ratios of the two NIST SRM glasses are similar to each other which, given the identical fabrication process of the glasses, suggests that the processes altering the selenium and sulphur concentrations are proportional. The sulphur contents of the NIST

SRM 610 and 612 glasses (Table 3.7) calculated from xerogel calibration and the adopted selenium concentrations are 630±150 g g-1 and 133±17 g g-1, respectively. The value for

SRM 610 more closely matches published values; this is possibly a result of less sulphur heterogeneity. The published sulphur concentrations for SRM 612 show much greater variation (Table 3.2).

3.04.5 Multi-element Xerogel Standards and Further Prospects

The addition of transition metals to xerogels resulted in significant heterogeneity of all analytes, precluding their use as calibration standards. Electron backscatter images of the

transition metal containing xerogels reveal the presence of ~4 m sized inclusions (Figure

3-6) with elevated concentrations of lead, iron, sulphur, and selenium compared to bulk and

matrix concentrations (Table 3.6). They are also enriched in selenium relative to sulphur in

keeping with the affinity of lead towards selenium (Wright et al. 1965). The intrusion of the xerogel into the inclusions suggests that the inclusions precipitate before final gelation of the xerogel.

LA-ICPMS analysis of the transition metal containing xerogels gives elevated

77Se/32S ratios relative to the value predicted from the bulk concentration ratio of the xerogels. The ablation spots were chosen without reference to the inclusions, the inclusions not being visible with the microscope used. The elevated ratio suggests that the surface being ablated is enriched in selenium relative to bulk selenium and sulphur. This enrichment can be accounted for by the presence of the Se-enriched inclusions at the surface and is a source of

Figure 3-6. Electron backscatter image of series 5 xerogel (SG5A) with selenium, sulphur and metal rich inclusions [bright spots] (A), with close-up of inclusions (B)

heterogeneity. This limits the maximum concentrations of transition metals in a xerogel

containing selenium and sulphur.

The production method of multi-element calibration standards must consider the

possibility of the formation of precipitates. Precipitation imposes a limit on which elements

can be used together and their concentrations. The matrix concentrations of lead (100 g g-1) and iron (300 g g-1; Table 3.6) are maximum contents that will not result in precipitation of solid phases in the presence of sulphur or selenium.

3.05 Conclusions

The production of multi-element solid calibration standards by a sol-gel process is

feasible. The fabrication method is shown to be suitable for use on a small scale in a manner

similar to solution standards. The simple approach to adding analytes, while convenient,

limits the range of concentrations that can be produced. The maximum combined

concentration of sulphur and selenium in the xerogels was 0.1 %, although the theoretical

maximum is 3%. With transition metals, precipitation limits concentrations to levels of transition metals to the order of ~0.01%, depending on the metal.

In the present case of selenium, as normalized by sulphur, variability from all materials is less than that from NIST glass reference materials. Concentrations of sulphur in the NIST glasses, using the xerogels as standards, are similar to previously published values, indicating that the xerogels share similar ablation behaviour with the NIST glasses. Thus, the xerogels are suitable for calibration of glasses in general and, by extension, are suitable for silicate matrices where concentrations of analytes are suitably low. Many disparate matrices have been calibrated for LA-ICPMS using the NIST glasses (e.g. silicate minerals, carbonate

minerals, glasses, biological material; industrial material), and these could be calibrated by

xerogels (Durrant and Ward 2005; Günther and Hattendorf 2005; Mokgalaka and Gardea-

Torresdey 2006). However, use of xerogels as standards to analyze the sulphur and selenium contents of materials having very different matrices, such as sulphide minerals, does not produce accurate results.

The production of multi-element standards is hampered by heterogeneity introduced by precipitation. Careful consideration of possible interactions can be made to eliminate precipitation.

Chapter 4. Selenium/Sulphur Ratios in Sulphide Minerals

and Their Significance for Ore Deposits

4.01 Abstract

Selenium/sulphur weight ratios of sulphide minerals from volcanic hosted massive sulphide (VHMS) deposits of the Flin Flon area in Canada, the Pierina high-sulphidation epithermal Ag-Au deposit in Peru, and iron oxide copper gold (IOCG) and iron oxide deposits in the Mantoverde district, Chile, are determined using a laser ablation inductively coupled plasma mass spectrometry technique. The Se/S ratios determined for sulphide minerals from VHMS deposits range from 10-4 to 10-3, and are similar to those from previous studies, whereas Se/S ratios from sulphide minerals from IOCG and high-sulphidation epithermal deposits are much smaller, ranging from 10-5 to 10-4. Thermodynamic data, mineral assemblages and 34S values define the physicochemical conditions of deposition of the sulphides, thereby enabling Se/S ratios of the ore generating fluids to be determined.

34 High Se/S ratios and near 0 ‰ SCDT values generally reflect fluids from magmatic sources, typical of VHMS and epithermal deposits, whereas low Se/S ratios and high 34S values reflect basinal or evaporitic sources, such as recorded by Cu-sulphides from IOCG deposits in northern Chile. Ratios of Se/S in sulphide minerals in conjunction with phase relations and sulphur isotopes can be used to determine the character of ore generating fluids as well as the origin of Se and S in these fluids.

4.02 Introduction

The potential utility of sulphide mineral Se/S ratios in refining the origin of sulphide

minerals in ore deposits is anticipated from the chemical similarity between Se and S.

Considerable research concerning selenium contents of sulphides was conducted in the

1950’s and 60’s, but due to analytical limitations only large cumulate samples could be analyzed (Edwards and Carlos 1954; Hawley and Nichol 1959; Tischendorf 1966). Selenium concentrations in rocks vary widely, with typical concentrations in granite of 70 ppm in basalt of 300 ppm in shale of 600 ppm and in chondrite meteorites of 9 ppm (Fischer and

Leutwein 1972; Mason and Moore 1982; Yudovich and Ketris 1985; Strawn et al. 2002;

Perkins et al. 2004). The Se/S ratios of rocks and minerals also vary similarly, with igneous rocks, primary magmatic sulphide minerals (i.e. pentlandite), and volcanic gases having Se/S ratios near 10-3.5, consistent with the Se/S ratios of magmatic fluids, which are ~10-4

(Schneider 1975; Hattori 1993; Huston et al. 1995; Hattori et al. 2002; Lorand et al. 2003).

These ratios contrast with those in modern seawater, which have a much lower Se/S ratio of

10-7 (Measures and Burton 1980; Li 1991), and imply that the source of Se and S in ore

deposits should be distinguished using the Se/S ratio of their sulphide minerals (Yamamoto

1976; Huston et al. 1995; Xiong 2003). However, S and Se do not need to come from the same source and other data may be required to distinguish these different sources of selenium and sulphur.

Sulphide mineral Se/S ratios have been used in the study of magmatic nickel- platinum group element (Ni-PGE) deposits, where they are proxies for crustal contamination

(Eckstrand 1996; Arndt et al. 2005; Hinchey et al. 2005; Mungall et al. 2005). These ratios have also been used as a means to identify S sources for volcanic hosted massive sulphide

deposits (VHMS) (Huston et al. 1995) and to define the depositional conditions of Se-rich deposits such as the Au-Se deposits of China (Xiong 2003). In general, the Se/S ratios of sulphide minerals have seen limited use in sulphide ore deposit studies, primarily due to analytical difficulties of determining Se contents (Ddina and Tsalev 1995). However, recent developments in analytical techniques have reduced the difficulty of Se measurements making them potentially routine (Chapter 3), so that the utility of Se/S ratios to delineate sources of fluids in the generation of ore deposits can be more effectively assessed.

This study uses Se/S weight ratios determined using a laser ablation ICPMS technique (Chapter 3) in well-characterized sulphide minerals from different types of ore deposits and integrates these data with 34S values of the sulphide minerals to evaluate the utility of Se in elucidating critical processes associated with the generation of ore deposits.

The relationships between S isotopic compositions and Se/S ratios in sulphide minerals have been studied for VHMS deposits (Yamamoto 1976; Yamamoto et al. 1983; Yamamoto et al.

1984), but other deposit types have received much less attention. The deposits in this study include VHMS deposits of the Flin Flon area in Canada, the Pierina high-sulphidation epithermal Au-Ag deposit in Peru, and iron oxide copper gold deposits (IOCG) of the

Mantoverde district, Chile. These deposits, unlike most previously investigated for Se

(Edwards and Carlos 1954; Hawley and Nichol 1959; Tischendorf 1966; Xiong 2003;

Layton-Matthews et al. in press), were found in this study to have low Se contents.

4.03 Analytical Techniques

Selenium/sulphur weight ratios were determined by the laser ablation inductively coupled plasma spectrometry (LA-ICPMS) technique described in Chapter 3. The LA-

Table 4.1. Laser and mass spectrometer settings used for LA-ICPMS analysis of sulphide minerals Laser Model New Wave Research Merchantek Power Density ~4.5 mJ m-2 UP-213 Mode Spot Rate 2 Hz Spot Size 100 m ICPMS Model Finnigan Element™ Mode High Resolution 9500-10000 Cones Aluminum Spray Chamber Scott double pass Isotopes Measured 77Se, 32S Sample Time (s) 0.300, 0.0033 Monitored 82Se, 34S, 54Fe, 65Cu, 70Zn 0.0025 Gases (l min-1) Cool 14 Auxiliary 0.8-1.0 Sampling 0.95-1.2 Other Run-in time (s) 30 Samples/ Peak 25 Runs 20 Passes 1

ICPMS technique offers numerous advantages over conventional analyses, including the ability to measure small samples, high spatial resolution of chemical data, and minimal sample preparation. The apparatus is a Merchantek UP 213 laser ablation system coupled to a

Thermo Finnigan Element ICPHRMS (Table 4.1). Samples are prepared as polished thick sections to allow for identification of sulphide minerals and to supply sufficient material for measurement. An analysis is the ablation of three to five well-separated spots on the mineral grain being analyzed. A calibration is derived from the blank corrected 77Se/32S signal ratio relative to the Se/S concentration ratio of the calibration standards. The standards used are

CCRMP CCu-1c, USGS PS-1, a series of previously measured sulphide minerals, and a series of synthetic lead sulphide-selenides (Chapter 2; (Earley 1950; Salley et al. 2000;

Wilson et al. 2002). All results are reported as Se/S weight ratios.

The detection limit of the analytical method is determined by the absolute and relative

concentrations of Se and S in the sulphide minerals. The sulphide minerals analyzed have S

contents in the tens of percent and produce a blank corrected 32S signal of up to 106 counts

per second so that the limiting factor of the detection limit is the 77Se signal. A blank

corrected 77Se signal of 25 counts per second is the signal detection limit. At a typical calibration slope of 0.2 (Figure 3-5), the signal ratio detection limit corresponds to a typical

Se/S weight ratio of 5 x 10-6, which is equal to a 3 g g-1 detection limit of Se in pyrite. The

weight ratio detection limit varies with sulphide mineral, but remains the same order of

magnitude. All samples analyzed in the present study have Se/S weight ratios that are more

than an order of magnitude greater than the detection limit. An estimate of maximum

analytical precision is 15%, which is the variability of the 77Se/32S signal ratios measured

from the CCu-1c and PS-1 reference materials.

Where sulphide minerals coprecipitate at a known temperature, a Se/S partitioning

coefficient can be defined from the measured Se/S weight ratios. This is related to the Se

partitioning coefficient, differing by the difference in sulphur concentrations of the two

sulphide minerals. Thus, if the precipitation temperature of a sulphide mineral is known, the

Se/S partitioning coefficient can be integrated with the measured Se/S weight ratio of one

sulphide mineral to estimate the Se/S weight ratio of a second sulphide mineral. This

approach was used to estimate and compare the Se/S ratios of the same sulphide minerals

from various deposits even though the sulphide was not present or had been altered.

a. Snow Flin Lake Flon

WINNIPEG

WINNIPEG Major Provincial City Flin Flon Regional town Major lake VHMS deposit or prospect Tr = Trout Lake, H = HArmin

SNOW LAKE Ordovician/ Drillhole Silurian Deposit Sedimentary Town No Outcrop Pre-Cambrian Intrusive Sedimentary, Volcanic & Intrusive Volcanic, Intrusive & Sedimentary NIM 34

HAR 58

HAR 05 HAR 13 HAR 01 HAR 07 Harmin NIM 37 10 km

Figure 4-1.(a) Location map of Trout Lake and Harmin VHMS deposits, and (b) sample locations for barren Fe sulphide mineral bodies in vicinity of Harmin deposit (Hargrave River samples). Modified from Polito et al. (2007)

4.04 Geology

4.04.1 VHMS Deposits and Barren Sulphide Mineral Bodies in the Flin Flon

Area, Canada

VHMS deposits and barren sulphide mineral bodies investigated in the present study are located in the Paleoproterozic Flin Flon area of Northern Canada, one of the largest

VHMS districts in the world (Syme et al. 1999). The availability of sulphide mineral samples with established paragenetic relationships, chemical compositions and 34S values (Polito et al. 2007) prompted the choice of the Trout Lake and Harmin deposits and several barren Fe sulphide mineral bodies in the vicinity of the Harmin deposit for investigation (Figure 4-1).

In addition to testing the identification of S and Se sources from the Se/S ratios of sulphide minerals, the ratio was measured to assess its use in distinguishing between Cu-Zn deposits and barren Fe sulphide mineral bodies in much the same way as differences in Se/S ratios distinguish barren pyrrhotite bodies from magmatic Ni deposits (Eckstrand et al. 1989).

The stacked Trout Lake VHMS deposit, hosted by the Proterozoic Amisk Group

(Healy and Petruk 1988; Healy and Petruk 1990; Polito et al. 2007), is located 5 km NE of

Flin Flon (Figure 4-1a). The deposit has undergone post-deposition metamorphism to a lower greenschist grade as well as tectonism, and has a complex ore paragenesis, with nine distinct sulphide ore types (Healy and Petruk 1988; Healy and Petruk 1990; Polito et al. 2007). The bulk Se/S ratios of the nine ore types (Table 4.2) show a positive correlation between Se and

Cu, a characteristic seen throughout the ore deposit (Healy and Petruk 1988). In this study, a distinction is made between sulphide minerals from barren zones and those from ore zones.

Pyrite and pyrrhotite were sampled from ore and barren zones, whereas galena, chalcopyrite, and sphalerite were sampled from ore zones. Ore zone pyrrhotite and chalcopyrite were sampled exclusively from the chalcopyrite stringer zone. Pyrite shows petrographic features indicative of a primary origin such as fracturing and the rounding of grains with significant replacement of pyrite by chalcopyrite, sphalerite, pyrrhotite, and galena. Consequently, the pyrite does not appear to have co-precipitated with other sulphide minerals. Sphalerite formed interstitial fillings and massive grains, and replaces pyrite, and can contain inclusions of the galena-clausthalite solid solution series as a replacement texture

(Healy and Petruk 1992). Sphalerite is generally affected by “chalcopyrite-disease”, also a replacement texture, and has Hg, Cd, and Cu concentrations at levels detectable by microprobe analysis (Healy and Petruk 1988). Galena from Trout Lake is both paragenetically early and late, although only the late galena is Se bearing. The pyrrhotite and chalcopyrite of the chalcopyrite stringer zone are interpreted to be coeval (Healy and Petruk

1988). Information as to exact location of samples within the ore bodies was unavailable to

Table 4.2. Bulk Se/S, Cu/(Cu+Zn+Pb) ratios and gangue mineral composition of Trout Lake ore types (Healy and Petruk 1988). = standard deviation Ore type N Se/S Cu/ Gangue (*10-4, Mean ±1 ) Cu+Zn+Pb Minerals (wt. %) 1. Massive sphalerite 4 0.0079±0.0132 0.0502 17.8% 2. Banded pyrite-sphalerite 4 0.0077±0.0103 0.0352 13.5 3. Massive pyrite 2 0.0093 0.0716 24.6 4. Mixed/banded chalcopyrite-sphalerite 2 0.078 0.259 42.7 5. Massive chalcopyrite-pyrrhotite 3 5.61±4.25 0.963 21.1 6. Chalcopyrite stringer 4 6.97±1.83 0.787 46.6 7. Disseminated pyrite-chalcopyrite 2 2.80 0.409 63.0 8. Sheared chalcopyrite- sphalerite 4 2.02±1.13 0.269 30.0 9. Chalcopyrite, quartz vein 1 4.10 0.880 26.9

the author.

The multi-lensed Harmin deposit is 170 km east-southeast of Flin Flon and 70 km

southeast of Snow Lake (Figure 4-1b). The Pre-Cambrian geology of the area is not fully

known as it is buried by Ordovician to Silurian sedimentary rocks, but is believed to form

part of the Proterozoic Burntwood Group (Jungwirth et al. 2000). As part of the Flin Flon

area, the Proterozoic units have been affected by the regional lower greenschist to middle amphibolite grade metamorphism and tectonism (Polito et al. 2007).

Pyrrhotite in the Harmin deposit occurs as aggregates with chalcopyrite, sphalerite, and pyrite. Chalcopyrite occurs as monomineralic grains, can contain complex inclusions and intergrowths of sphalerite, pyrrhotite, and quartz, and can occur as chalcopyrite–pyrite veinlets. Pyrite occurs with chalcopyrite and sphalerite, with textures suggestive of re- crystallization. Sphalerite occurs intergrown with chalcopyrite and pyrrhotite. Microprobe analyses of sulphide minerals from Harmin show variable Se contents with elevated Se contents in sphalerite and chalcopyrite (Table 4.3). Pyrite, pyrrhotite, sphalerite and chalcopyrite have been sampled from drill core, but without ore type distinction, as the geology of the deposit has not been fully delineated (Polito et al. 2007).

Near the Harmin deposit, there are multiple barren iron-sulphide mineral bodies that share similar regional geology (Figure 4-1b). Pyrite and pyrrhotite were sampled from drill

Table 4.3. Selenium contents of Harmin sulphide minerals determined with electron microprobe (Polito, unpublished data). N = number of samples Mineral N N with < 100 N with N with > 1000 g g-1 100-1000 g g-1 g g-1 Chalcopyrite 6 3 2 1 Pyrrhotite 7 4 3 - Pyrite 3 2 1 - Sphalerite 15 9 6 -

core that intersected these bodies. The iron-sulphide mineral bodies are composed of assemblages of pyrite and pyrrhotite with variable contents of graphite associated with minor chalcopyrite and sphalerite (Polito et al. 2007). These iron-sulphide mineral bodies have a spatial relationship with the Harmin ore body and share the same geophysical characteristics.

4.04.2 High-sulphidation Epithermal Au-Ag Deposits: Pierina Au-Ag Deposit

Epithermal deposits are noted for selenide minerals as part of their primary mineral assemblage (Simon and Essene 1996; Simon et al. 1997). However, the occurrence of selenide minerals is generally restricted to low-sulphidation deposits (Sillitoe and Hedenquist

2003). Sulphidation is a parameter that combines S fugacity and temperature to account for reactions. Segregation of high-sulphidation epithermal deposits from low- and intermediate- sulphidation deposits (Hedenquist et al. 2000; Sillitoe and Hedenquist 2003; Simmons et al.

2005) is on the basis of the tennantite-enargite and chalcopyrite-bornite+pyrite sulphidation reactions (Einaudi et al. 2003). The high-sulphidation state, indicated by the presence of enargite in epithermal deposits, limits pH to low values (<5) and the common occurrence of barite in high-sulphidation epithermal deposits indicates that most high-sulphidation epithermal deposits are of intermediate to high oxygen fugacity (Sillitoe and Hedenquist

2003).

The Pierina deposit is located in Ancash Department, Peru (Figure 4-2). The Middle

Miocene deposit, which is described in detail elsewhere (Fifarek and Rye 2005; Rainbow et al. 2005; Rainbow et al. 2006a), consists of epithermal Au-Ag mineralization hosted by volcaniclastic rocks and an older dacitic flow dome complex (Figure 4-2b). Selenium-rich rocks have not been found near the deposit (A. Rainbow pers. comm. 2007). Soler (1987) has reported bulk Se contents from ores and concentrates of the Peruvian polymetallic province

below 30 g g-1, but with higher contents (> 350 g g-1) in ores and concentrates from

unidentified epithermal deposits. The availability of samples, the rarity of selenide mineral

occurrences in high-sulphidation deposits and the lack of data for Se in high-sulphidation

deposits prompted the investigation of this deposit.

A 5-stage paragenetic sequence has been delineated for Pierina by Rainbow et al.

(2005). This consists of I) hydrothermal alteration, II) polymetallic sulphide and barite

mineralization, III) low temperature oxidation, IV) precipitation of barite and acanthite, and

finally V) supergene processes. Stage I hydrothermal alteration is defined by acid-leaching

and vuggy silica alteration of the host rocks, with associated alteration mineral assemblages

of quartz-alunite ± pyrite, dickite ± kaolinite ± pyrophyllite ± pyrite, and illite- montmorillinite ± kaolinite. Also present are alunite, diaspore, and minor rutile, sphalerite

and galena.

The second stage, from which the sulphide minerals were selected, is a polymetallic

sulphide and barite mineralization stage and represents an increase in oxygen fugacity over

that of stage I. In stage II, galena occurs as coarse grains with sphalerite in veins, or alone as

fine-grained aggregates. In addition to occurring with galena, sphalerite occurs in cavities

with pyrite. Pyrite is intergrown with sphalerite and enargite as breccia cement and is

particularly enriched in Au and Ag (Rainbow et al. 2005). Other minerals identified in this

stage are enargite, bismuthinite-stibnite needles, barite, and minor albandite. The presence of

enargite defines this paragenetic stage as a high-sulphidation environment.

Stage III occurs as the result of deposit-wide oxidation of the stage I and stage II

sulphide mineral assemblages and their near-pervasive replacement by hematite and goethite

a. Columbia Ecuador

Peru Brazil Pierina Huarez

Cerro de Pasco Lima Bolivia

Pacific Ocean

Chile

Cretaceous b. sedimentary rocks Mina Santa Fe lower andesite Quartz Feldspar Porphyry Upper Andesite Pierina Lower Open Pit Andesite Volcaniclastic N Sediments "feeder structure" Dacitic Flow Domes Dacitie Hydrothemal Breccia

Lithic Tuff

lower andesite

Santo Toribio

012 kilometers Figure 4-2. (a) Regional map of South America showing location of Pierina high- sulphidation epithermal Au Ag deposit, and (b) regional geology of Pierina area. Geology from Rainbow et al. (2001).

with little preservation of the earlier sulphide minerals. This occurs due to the influx of

oxidizing fluids, with isotopic compositions consistent with meteoric waters (Rainbow et al.

2005). The Fe oxides and hydroxides of this stage are Au-enriched. The Ag and S released by

the destruction of the early stage sulphide minerals by stage III oxidation are ultimately incorporated into barite and acanthite during Stage IV. The Stage V supergene stage is defined by the local formation of Fe oxides and hydroxides primarily as fracture staining under supergene conditions.

4.04.3 IOCG Deposits of the Mantoverde District

The IOCG deposit type and the controversy surrounding its definition as a clan are comprehensively reviewed elsewhere (Sillitoe 2003; Williams et al. 2005). A fundamental uncertainty in the IOCG genetic model is the source of the Cu-bearing fluid and how this is related to the Fe-oxide event. Recent results from Benavides et al. (2007) on the Cu-Au

deposits of Mantoverde District (Figure 4-3) has identified two distinct fluid sources, a

magmatic fluid and an evolved seawater-derived basinal fluid, with the second fluid

associated with the increase in Cu grade. The involvement of both magmatic and basinal

fluids has been demonstrated at other South American IOCG deposits (Ullrich and Clark

1999; Ullrich et al. 2001; Chiaradia et al. 2006).

In general, Se has not been well investigated in this deposit type, with only sporadic

reports of selenide mineral occurrences (Large and Mumme 1975; Adshead et al. 1998;

Williams and Pollard 2001; Cabral et al. 2002c; Skirrow and Walshe 2002). However, as

Se/S ratios of magmatic fluids and seawater are distinctly different, it should be possible to

detect the influence of these two fluid sources in an IOCG deposit by the Se/S ratios of the

sulphide minerals. The IOCG deposits in the Mantoverde District, having had mixing

demonstrated by other data, provide a test for the utility of Se/S ratios in identifying multiple

fluids and their sources.

In the Mantoverde District, there are several Fe oxide and Fe oxide-Cu (-Au) deposits

of variable economic grade (Figure 4-3b). The Late Cretaceous age deposits are hosted by

Devonian-Carboniferous metasedimentary rocks and Permian-Triassic plutonic and

volcaniclastic rocks (Vila et al. 1996; Benavides et al. 2007). Sulphide mineralization occurs

in four stages. Stage I pyrite forms irregular grains that co-precipitated with stage I magnetite

and both are cut by later stage III chalcopyrite, the main mineralizing event. Stage II pyrites

are of minor occurrence, usually associated with hematite, chlorite, and sericite. In stage III, there are multiple mineral associations requiring its division for the present study into sub- stages, with sub-stage IIIa consisting of early quartz-calcite-chalcopyrite-pyrite-siderite veins while the later sub-stage IIIb is marked by an assemblage of pyrite or chalcopyrite with hematite. Sub-stage IIIa chalcopyrite replaces earlier stage pyrite. Pyrite was sampled from the first three stages and chalcopyrite was sampled from stage III (Benavides et al. 2007).

There is no occurrence of sulphide minerals in two later stages of quartz calcite veins and supergene oxidation.

a. 26°30'40"S b.

BOLIVIA Manto Ruso 70°20'05"W

MVF AFS. cemtral branch AFS. eastern branch Laura Chañral Manto Verde

Copiapo

ARGENTINA Mantoverde Main Open Pit Santiago Pacific Ocean

Mantoverde Sur

Montecristo CHILE

Franco MVF Trillizos

70°17'39"W 26°36'03" S

0 1000 metres Atlantic Ocean

VOLCANIC/SEDIMENTARY ROCKS Altered Units Neogeme/Quaternary a) Tectonic Breccia (mineralized cataclastic rock) alluvial deposits b) Green Breccia (chlorite/quartz bearing hydrothermal breccia) La Negra Formation andesite c) Felsic Body MINERALIZATION UNITS PLUTONIC ROCKS a) Sulfide-bearing stockwork b) Sulfide-bering hydrothermal breccias c) Magnetite-pyrite Fault; observed, covered d) Magnetite-apatite-pyrite e) Calcite veins Figure 4-3. (a) Location map of Mantoverde District in Chile and (b) deposits/sulphide mineral bodies within Mantoverde district. Geology simplified from Benavides et al. (2007). MVS and AFS refer to Mantoverde Fault and Atacama Fault System, respectively.

4.05 Results

4.05.1 VHMS Deposits: Flin Flon Area

The Se/S ratios and associated 34S values of sulphide minerals from the VHMS

deposits and barren sulphide mineral bodies in the Flin Flon area are listed in Table 4.4 and

are included as appendices A, B and C. At Trout Lake (Appendix A), pyrite mean Se/S ratios

of 3.83 x 10-4 correspond to typical magmatic sulphide mean ratios of 3 x 10-4, with a

difference between the means of the ore (3.83 x 10-4) and the barren zones (2.60 x 10-4).

Pyrrhotite mean Se/S ratios (5.25 x 10-4) are greater than the mean ratios in pyrite, and the

mean ratios of pyrrhotite from ore (6.34 x 10-4) are higher than from barren zones (3.81 x 10-

4). Trout Lake sphalerite has a large range of Se/S ratios (2.39 to 18.29 x 10-4, mean 7.19 x

10-4), with a difference in the means between Zn-rich ore zones (3.27 x 10-4) and other ore

zones (8.87 x 10-4). Chalcopyrite has higher mean Se/S ratios (6.73 x 10-4) than pyrite, and the one galena Se/S ratio is the highest (206.84 x 10-4). The relationship between 34S values

and Se/S ratios at Trout Lake distinguishes Fe sulphide minerals from barren and ore zones

(Figure 4-4a). Iron sulphides from barren zones show positive correlation between 34S

values and Se/S ratios, whereas sulphides from ore zones are negatively correlated. The 34S

values of all sulphide minerals at Trout Lake are typical of magmatic values (Table 4.4)

a previous geochemical modeling (see text). Temp. = temperatur VHMSHarmin deposits sulphide bodies mineral at and barren maximum, andmaximum, mean values of the Se/S ratios. Se/S ratios and 4.4. Table Harmin Polito Trout Lake Trout Hargrave Location Location River River et al. (2007) (2007) Pyrrhotite Pyrite Chalcopyrite Sphalerite Pyrrhotite Pyrite Galena Chalcopyrite Other 2. Zn-zone 1. Sphalerite Ore2. zones 1. Barren Pyrrhotite 2. 1. Barren P y

Ore rite Mineral Mineral

zones

34 +2.8 to +10.0 to +2.8 +1.8 to +5.6 +1.4 to +3.2 +1.5 +1.2 to +3.9 +0.9 to +2.0 +1.8 +2.3 to +3.5 +1.8 to +3.0 +1.9 to +2.9 +1.8 to +3.0 +2.1 to +2.5 +2.0 to +2.7 +2.0 to + 2.7 +2.1 -1.4 to +6.4 -1.4 S values of sulphide minerals, and calculated fluid and calculated fluid S values sulphide of minerals,

to to to S

+6.4 +2.9 +3.5 ‰ a

- 350 - 125 - 350 100 - 125 125 - - - - 350 200 Temp (°C)

16 12 12 4 18 21 1 3 7 3 10 3 3 6 12 7

0.73 0.73 0.80 0.22 3.31 0.18 0.94 20.68 3.77 2.39 2.57 2.39 5.07 3.34 3.34 1.05 1.28 1.05 Min Sul e, N= number of samples, min, max and mean are minimum, p Hargrave River. estimated on the basis River. Temperatures ofHargrave

hide

7.37 7.37 11.47 23.85 29.42 7.02 29.86 - 8.45 18.29 4.65 18.29 11.25 4.21 11.25 6.81 5.35 6.81 Max

Se/S

( *

3.00 3.00 5.64 5.79 12.15 2.91 5.43 - 6.73 8.87 3.27 7.19 7.71 3.81 5.76 3.83 2.60 3.38 Mean 10

-4

)

Se/ MeanSe (ppm) (ppm) 117 301 202 400 113 290 279 235 292 108 239 300 148 224 205 139 181 S ratios from the Trout Lake and Lake S ratios from the Trout

- -4.5 - -4.2 - -4.8 - - -4.4 -4.4 - - - - -4.2 -4.9 - Min Fluid Se/S (Log

- -3.4 - -3.0 - -3.3 - - -3.2 -3.8 - - - - -3.4 -3.3 - Max

- -4.0 -8.4 - -3.8 to -3.5 -4.3 to -3.9 - - - - -3.6 -4.6 - - -3.7 - -3.9

Mean Se/

to to

-3.4 -8.1 S)

210 a. Barren Ore 200 Po 15 Py

ore sulphides Cpy Zn -rich Sph Gal

5 barren sulphides

0 -1.5 -1 123456 7 b. 15 -4 10

Ore trend ? Se/S (*10 ) 5

Barren trend?

0 C.

5 Mixing trend

0 0 1 2 3 4 5 6 7 34 ‰ δ SCDT Figure 4-4. Relationship between Se/S ratios and 34S values for sulphide minerals from VHMS deposits and barren Fe sulphide mineral bodies at (a) Trout Lake, (b) Harmin, (c) Hargrave River. Lines show the trends of sulphides from ore zones and from barren zones. Sulphur isotope data from Polito et al. (2007).

The mean Se/S ratios for pyrite (5.43 x 10-4) and pyrrhotite (2.91 x 10-4) from Harmin

(Appendix B) are similar to those from Trout Lake, (Table 4.4). The Se/S ratios of

chalcopyrites from Harmin have a larger range but a similar mean value to those of Trout

Lake (Table 4.4), whereas the range and the mean ratio of sphalerite (12.15 x 10-4) from

Harmin are similar to those from Trout Lake. Coeval pyrite and chalcopyrite indicate that Se preferentially partitions into chalcopyrite, whereas coexisting pyrrhotite and chalcopyrite have similar Se/S ratios. The 34S values are negatively correlated to the Se/S ratios for

pyrite, sphalerite, and chalcopyrite from Harmin (Figure 4-4b). However, Se/S ratios are not

correlated consistently with 34S values for pyrrhotite (Figure 4-4b). The 34S values of all

sulphide minerals at Harmin are of typical magmatic value (Table 4.4).

The Se/S ratios and 34S values of sulphide minerals from the barren iron-sulphide mineral bodies from the Hargrave River (Appendix C) region are listed in Table 4.4. The

34S values of sulphide minerals from the barren bodies are greater than typical magmatic

values (Polito et al., 2007). Pyrite and pyrrhotite from the barren iron-sulphide mineral

bodies of the Hargrave River region have Se/S ratios that are indistinguishable from the

sulphide minerals from Harmin and Trout Lake (Table 4.4). However, the iron sulphides

define a mixing line between a reservoir with a high Se/S ratio and a low 34S value and

another with a low Se/S ratio and a high 34S value. The 34S values for sulphide minerals

from Hargrave River are positively correlated with Se/S ratios (Figure 4-4c).

4.05.2 High-sulphidation Epithermal Au-Ag Deposits: Pierina

Although the data (Appendix D) are limited because of the paucity of original

sulphides at Pierina, Se/S ratios for pyrite and sphalerite (Table 4.5, Figure 4-5) from stage II

(1.22 to 2.46 x 10-4) are less than the values from the VHMS deposits (3.0 to 3.5 x 10-4).

Similarly the Se/S ratios for galena (3.66 x 10-4) are low, especially given that the great

affinity of galena for Se would result in ratios much larger than those in pyrite and sphalerite

(Barin and Platzki 1995). The Se/S ratios are consistent with a meteoric source as are oxygen

and hydrogen isotopic compositions from stage II sulphates (Rainbow et al. 2006b). Despite this, the 34S values of the sulphide minerals are typical of a magmatic source (Table 4.5,

Figure 4-5).

Table 4.5. Se/S ratios and 34S values of stage II sulphide minerals and calculated fluid Se/S ratios from Pierina. N= number of samples. Temperature = 200°C

34 a Sulphide Se (ppm) Fluid Mineral S ‰ N -4 Se/S (*10 ) Log Se/S Pyrite –2.3 to 3.2 2 1.45 to 2.46 78 to 131 -6.8 to -4.6 Sphalerite 1.8 to 2.6 1 1.22 40 -6.6 to -4.6 Galena –1.3 to -0.5 1 3.66 49 -10.2

a Rainbow et al. (2005)

6 Pyrite Sphalerite 5 Galena

4 -4 3

2 Se/S (*10 )

0 -3 -2 -1 0123 34 ‰ δ SCDT

Figure 4-5. Relationship between Se/S ratios and 34S values for sulphide minerals from Pierina high-sulphidation epithermal Ag-Au deposit. Sulphur isotope data from Rainbow et al. (2005).

a b

Benavides calculation based onThermodynamic midpoint of temperature range c IIIb pyrite IIIb IIIa Chalcopyrite IIIb IIIa III II I Pyrite deposits.district N= number of samples, Min. 4.6 Table by the pyrite-chalcopyrite Se/S partitioning in Stage IIIa genetic Stage Sample/Para Calculated Se/S from chalcopyrite ratios using a pyrite-cha . Se/S ratios and c et al

. (2007). - 230-250 210-280 - 230-350 210-280 - 350 550 a,b Temp •C

+1.4 t0 +10.0 t0 +1.4 +11.2 to +1.9 –6.8 to –6.8 +11.2 +6.8 to +8.0 34 -6.6 to +5.1 -0.9 t0 +4.9 -0.6 + +2.0 S values of sulphide minerals and calculated fluid fluid S values sulphide of minerals and calculated 34 S ‰ - - - a

= minimum, Max = maximum. Temp. = Temperature 17 10 19 N 8 9 4 3 7 2 -

0.20 0.20 0.46 5.85 0.46 1.46 1.95 1.46 0.86 3.06 0.86 Min Min Sulphide Se/S (*10 lcopyrite Se/Slcopyrite partitioning coefficient of as defined 2.3 Max Max 11.46 11.46 4.98 4.98 15.8 15.8 4.67 4.67 6.63 3.19 3.25 6.63 1.89 1.89 4.35 10.37 7.54 2.96 4.42 2.34 2.13 3.15 2.68 Mean -4 ) (ppm) (ppm) Mean 101 152 362 263 158 236 125 114 168 143 Se/S ratios from Mantoverde Se -7.5 - - - -6.6 -6.5 - -6.3 -4.2 - Min FluidLog ( FluidLog -6.1 - - - -6.1 -4.0 - -5.7 -3.7 - Max Max

Se/ -6.5 - - - -6.3 -6.1 tp - -6.0 -4.2 to - 41 37 Mean S)

4.05.3 IOCG Deposits: Mantoverde District Deposits

Se/S ratios of sulphide minerals from the Mantoverde district IOCG deposits and associated 34S values (Appendix E) are listed in Table 4.6 and the relationship of the two parameters are shown in Figure 4-6. The 34S values increase with paragenetic stage, ranging from magmatic values in Stage I magnetite-pyrite to much higher values in Stage III (Table

4.6). Stage I pyrite has Se/S ratios (3.00 to 3.24 x 10-4) that are similar to the magmatic values from VHMS deposits, whereas Stage II pyrite has Se/S ratios that are lower (0.86 to

3.19 x 10-4, mean 2.13 x 10-4). The 34S values of stage I pyrite are consistent with a magmatic source while those of stage II pyrite indicate the addition of a non-magmatic component. Sub-stage IIIa and IIIb pyrite and chalcopyrite have variable 34S values and

Se/S ratios (pyrite 1.46 to 6.63 x 10-4, chalcopyrite 0.46 to 15.80 x 10-4; Table 4.6). The Se/S ratios of sub-stage IIIa chalcopyrite are 2 to 3 times higher than the pyrite Se/S ratios and the means of the chalcopyrite and pyrite Se/S ratios define a Se/S partitioning coefficient of 2.3

(Table 4.6). This coefficient was used to predict the theoretical Se/S ratio of pyrite (0.20 to

4.98 x 10-4 mean 1.89 x 10-4) in equilibrium with the late chalcopyrite of sub-stage IIIb, where pyrite does not precipitate. The relationship between 34S values and Se/S ratios in

Stage III pyrite and chalcopyrite define a mixing curve between a component with a high

Se/S ratio and a near zero 34S value, and a component with a low Se/S ratio and high 34S value fluid (Figure 4-6b). The IIIa sub-stage is clearly separated from the following IIIB sub- stage by its higher Se/S ratios in chalcopyrites.

16 a. Stage I Stage II 14 Stage IIIa Stage IIIb 12

6 Magmatic 4

2 -4 0 16 b.

Se/S (*10 ) Stage IIIa 14 Stage IIIb

Magmatic 8 Mixing Curve

4 Basinal, Seawater Derived ~+20-30‰ 2 ΣSe/ΣS ~ 1X10-8

0 -4 -2 0 2 4 6 8 10 12

34 S (‰) δ CDT Figure 4-6. Relationship between Se/S ratios and 34S values for (a) pyrite, (b) chalcopyrite from deposits in the Mantoverde area of Chile. IIIa = calcite veins, altered host and magnetite hosted, IIIb = hematite breccia. Sulphur isotope data from Benavides et al. (2007). Magmatic field in (b) is based on a pyrite-chalcopyrite partition factor for Se/S of 2.3 as defined by Stage IIIa pyrite-chalcopyrite partitioning.

4.06 Discussion

With the exception of VHMS deposits, the behaviour of Se in ore deposits is poorly characterized. This is primarily due to a lack of an economic incentive for the mining of Se although the previous requirement of large sample volumes has limited the routine measurement of selenium. Selenium is produced mainly as a by-product of electrolytic Cu refining (Jensen 1985) so that much of the research on Se in ore deposits is restricted to mineral processing and to the occurrence of selenide minerals in VHMS deposits (Dana et al.

1997; Simon et al. 1997; Cepedal et al. 2006; Ciobanu et al. 2006). Research on Se in other deposit types is represented by reports of Se concentrations in whole-rock samples, selenide mineral occurrences in ores and descriptions of complex Se-rich mineral assemblages.

Assessment of Se behaviour in an ore deposit type based on selenide mineral occurrence is not straightforward. Selenide minerals are generally paragenetically late and reflect low temperatures and high oxygen fugacities (Simon and Essene 1996; Simon et al. 1997). The presence of selenide minerals is an indicator of high Se-2/S-2 ratios in an ore-forming fluid, probably a result of high oxygen fugacity, rather than a high Se/S ratio in the fluid.

Similarly, the absence of selenide minerals is not necessarily an indicator of low Se/S ratios in an ore-forming fluid.

Published Se concentrations in sulphide minerals from ore deposits and other occurrences have been used to construct a dataset of sulphide mineral Se/S ratios (full dataset available as Electronic Supplementary Material). Where the S concentration of the sulphide mineral has not been analytically determined, mineral stochiometry was used to calculate S concentration. For pyrrhotite, the mineral formula is fixed at Fe0.9S, the midpoint of the

typical pyrrhotite compositional range. The solid solution series galena-clausthalite is divided by the midpoint composition of PbSe0.5S0.5, in accordance with mineralogical convention

(Nickel and Grice 1998), fixing the maximum concentration of Se and the Se/S ratio in

galena to 15.03 wt. % and 2.46, respectively. Galena data with Se concentrations greater than

15.03 wt. % are regarded as clausthalite and are included in the compilation as such.

The Se/S ratios (Table 4.7 and Figure 4-7a-e) calculated from the published Se

concentration data indicate that the range of the weight ratios is strongly differentiated

amongst sulphide minerals. This reflects the variable affinity of sulphide mineral structures

for Se, varying with the counter ion and the stochiometry of the sulphide mineral (Elrashidi

et al. 1987; Barin and Platzki 1995; Simon and Essene 1996; Xiong 2003).

The variety of conditions, particularly temperature, under which pyrite precipitates result in

the large range and the log normal distribution of calculated pyrite Se/S ratios (Figure 4-7a).

The large difference between the mean ratio (8.53 x 10-4) and the geometric mean (0.70 x 10-

4) is primarily the result of the range of Se concentrations found in pyrites of sedimentary

Table 4.7. The Se/S ratios of sulphide minerals from various ore deposits and other occurrences determined from published Se concentration data (See Appendix F). BDL = below detection limit, Min = minimum, Max = maximum, = Standard Deviation, Geom. = Geometric –––––––––––– Se/S (*10-4) –––––––– Geom. Log (Se/S Mean Mean Sulphide N Geom. Geom. Se Min Max Mean ± 1 Se Mean Mean ± 1) (ppm) (ppm) Pyrite 618 BDL 935.39 8.53±60.03 0.70 -4.155±0.724 456 37 Chalcopyrite 241 BDL 657.74 6.43±42.48 1.75 -3.757±0.723 225 61 Sphalerite 159 BDL 48.63 2.51±6.53 0.60 -5.222±0.837 83 20 Pyrrhotite 100 BDL 9.63 1.46±1.75 0.79 -4.102±0.544 57 31 Galena 211 BDL 1176.47 352.54±158.77 2.39 -3.622±1.304 4725 32

origin. These concentrations range from below detection limit to tens of weight percent, with lower Se concentrations being more prevalent in the dataset. The range of chalcopyrite Se/S

ratios is similarly large and shares a similar log normal distribution (Figure 4-7b) and a similar mean ratio (6.43 x 10-4) to pyrite. The higher geometric mean ratio (1.75 x 10-4) for chalcopyrite reflects the greater affinity of chalcopyrite for Se. The lesser affinity of sphalerite for Se produces the small range and geometric mean (0.60 x 10-4) of Se/S ratios

(Table 4.7). The distribution of the ratios for sphalerite is also log normal (Figure 4-7c) and suggests that a solid solution series between stillite (ZnSe) and sphalerite does not occur naturally, although it has been synthesised (Klemm 1961). The Se/S ratios derived from published Se concentration data of pyrrhotite have the smallest range and mean of the sulphide minerals under consideration (Table 4.7). The geometric mean of pyrrhotite is however slightly higher than both pyrite and sphalerite. The small range of Se/S ratios may in part be due to the limited amount of published Se data, but may more probably reflect the limited and higher temperature conditions of pyrrhotite precipitation compared to the other sulphide minerals. Pyrrhotite Se/S ratios show a log normal distribution (Figure 4-7d). The natural occurrence of the full range of the galena-clausthalite solid solution (Earley 1950;

Coleman 1959) is indicated by the large range of Se/S ratios for galena (Table 4.7) and the multi-modal distribution of Se/S ratios (Figure 4-7e).

The order of affinity of sulphide minerals for Se based on the geometric means of

Se/S ratios is galena > chalcopyrite > pyrrhotite > pyrite > sphalerite (Table 4.7). These relative affinities are also indicated by the Se/S ratios determined in the present study (Table

4.4-4.6), although the distribution of Se/S ratios in this study is more limited (Figure 4-7a-d) and, except for chalcopyrite, are generally higher than the geometric means. This is because

the published data include sulphide minerals from a variety of deposits and temperatures, both of which affect the partitioning of Se (Huston et al. 1995; Xiong 2003).

40 14 b. a. Published N = 611 Published N = 240 200 80 This Study N = 82 35 This Study N = 32 12

30 10 150 60 25 8 20 100 40 6 15 4 50 10 20 2 5

0 0 0 0 14 40 50 c. Published N = 157 6 d. Published N = 99 This Study N = 14 This Study N = 40 12 35 40 30 10 Count (This Study) 4 25 30 8 20 6 20 15 2 4

Count (Published) 10 10 2 5

0 0 0 0 -6 -5 -4 -3 -2 -1 0 1

35 e. Published N=211 IOCG 30

25 epithermal

20 VHMS 15

0 -6 -5 -4 -3 -2 -1 0 1

Log Se/S Figure 4-7. Distribution of Se/S ratios in sulphide minerals from ore deposits and other occurrences from published data (curve, Appendix F) and the present study (columns). (a) Pyrite, (b) Chalcopyrite, (c) Sphalerite, (d) Pyrrhotite, (e) Galena.

The largest set of published Se concentration data for sulphide minerals from a

specific deposit type are from VHMS deposits (Table 4.8). The Se/S ratios for pyrrhotite and

pyrite from the published data are comparable in value and distribution (Table 4.8, Figure

4-8a, b) to our Se/S ratio data from VHMS deposits in the Flin Flon area (Table 4.4). The

marked difference in Se concentrations of sphalerite from Zn and Cu rich zones of VHMS

deposits (Auclair et al. 1987; Huston et al. 1995) produces the bimodal log distribution of

Se/S ratios (Table 4.8, Figure 4-8c). Our data for sphalerite from VHMS deposits in the Flin

Flon area, mostly sampled from Cu rich zones (Table 4.4), broadly matches the higher valued

peak of the VHMS Se/S ratio distribution (Figure 4-8c). The Se/S ratios of chalcopyrite from

VHMS deposits at Flin Flon are similar to published values (Table 4.8).

Table 4.8. The Se/S ratios of sulphide minerals from VHMS deposits determined from published data (See Appendix F). Abbreviations as for Table 4.7. –––––––––– Se/S (*10-4) ––––––––– Log (Se/S) Mean Geom. Sulphide N Geom. Geom. Se Mean Min Max Mean ± 1 Mean Mean ± 1 (ppm) (ppm) Pyrite 95 BDL 43.03 2.77±4.77 1.36 -3.866±0.587 148 73 Pyrrhotite 19 0.13 9.63 3.18±2.70 2.09 -3.680±0.477 124 81 Sphalerite 39 BDL 48.63 4.78±10.86 0.91 -4.041±1.163 157 30 Chalcopyrite 61 0.02 47.97 6.90±8.22 3.53 -3.452±0.604 241 123 Galena 14 BDL 932.71 85.36±245.36 9.26 -3.033±1.508 1141 123

a. Published N = 94 40 This Study N = 52

0 Published N = 18 b. This Study N = 40

5 Count (Published, This Study a,b)

0 Published N = 37 c. This Study N = 13 5

10 4

5 2 Count (This Study c) 1

0 0 -6 -5 -4 -3 -2 -1 Log Se/S Figure 4-8. Distribution of Se/S ratios in sulphide minerals from VHMS deposits from the literature (curve) (Appendix F) and present study (columns) for (a) Pyrite, (b) Pyrrhotite, (c) Sphalerite

The incorporation of Se into a sulphide mineral can be modelled using

thermodynamics (Huston et al. 1995; Layton-Matthews et al. in press). The incorporation of

Se into a sulphide mineral is described by:

MeSn + nH2Seaq <=> MeSen + nH2Saq 4.1 where Me is a metal ion. This reaction can also be expressed with HSe- and HS- or with Se-2

and S-2 (D'yachkova and Khodakovskiy 1968; Yamamoto 1976; Xiong 2003). The

equilibrium constant for reaction 4.1 is defined as:

log K = log a a nlog a a 4.2 1 ()MeSen MeSen ( H2Se H2S ) For simple sulphide and selenide minerals with ideal solid solution, the mole fractions (X) of

the mineral phases approximate their activity, hence:

log K n = log X X log H Se /HS 4.3 ()1 ()MeSen MeSn ()[]2 []2 Simplifying and accounting for the difference in atomic mass of Se and S,

K 1 n 32.06 78.96 Se S H Se H S 4.4 1 = ()• ()mineral ()[]2 []2

where Se/Smineral is the measured weight ratio in the sulphide mineral. The differences in the relative affinity of sulphide minerals for selenium result in differences in equilibrium constants that describe the Se incorporation into sulphide minerals (K1, Table 4.9). Thus, the

H2Se/H2S ratio of a fluid in equilibrium with a sulphide mineral can be calculated using a

temperature dependent equilibrium constant (Table 4.9).

The sulphide mineral Se/S ratio is controlled by the Se/S ratio of the ore-forming

fluid, which is subject to modification by a number of mechanisms. Because the equilibrium

constants indicate different partitioning of Se between the fluid and each sulphide mineral

(Table 4.9), a closed system results in the progressive increase or decrease of the total

Se/total S (Se/S) ratio of an ore-forming fluid, depending on which sulphide minerals precipitate and at which temperature. Thus, for a magmatic fluid with a typically low Se

content, fractional crystallization of sulphide minerals can result in varying sulphide mineral

Se/S ratios without changes in pH, temperature, pressure, or the input of other fluids. The

effect of fractional crystallization is greater on sulphide mineral Se/S ratios than 34S values

due to the lower abundance of Se and the larger partition constants of Se relative to 34S

fractionation. The equilibrium constant describing Se incorporation into pyrite at 300°C

(100.13, Table 4.9) is much larger than the equilibrium constant (100.0005, (Ohmoto and

34 Goldhaber 1997) describing the fractionation of S from H2S to pyrite. In systems where

more Se compatible sulphide minerals such as acanthite or galena are present, Se contents in

less Se compatible sulphide minerals such as pyrites will be low (Huston et al. 1995; Xiong

2003). In contrast, Se contents will be high in pyrites precipitating from fluids where acanthite or galena has not precipitated.

Table 4.9. Equilibrium constants for Se incorporation reactions at various temperatures –––––––––––––––––––– Log Ka –––––––––––––––––––– Reaction 100°C 125°C 200°C 240°C 300°C 350°C

FeSe2 +2HS2 <=> FeS2 +2HSe2 -2.45 -2.14 -1.21 -0.76 -0.13 0.37

ZnSe+H2S <=> ZnS+H2Se -0.47 -0.42 -0.33 -0.31 -0.31 -0.33

PbSe+H2S <=> PbS+H2Se -6.83 -6.38 -5.36 -4.96 -4.74 -4.16

a. Calculated from equations of Huston et al. (1995b)

Speciation also controls the relations between fluid and sulphide mineral Se/S ratios

(Huston et al. 1995; Layton-Matthews et al. in press). The H2Se/H2S ratio, which is used to calculate the equilibrium constants for Se incorporation into sulphide minerals, differs from the Se/S ratio in a manner that can be predicted by differences in S and Se speciation

(Figure 4-9). A zone of no deviation of the H2Se/H2S ratio from the Se/S ratio is defined

-2 +6 by the S /S reaction and the H2Se dissociation constant (Figure 4-9a-c; hatched area). A

zone of no deviation of the HSe-/HS- ratio from the Se/S ratio can also be defined (Figure

4-9a-c; crosshatched area). The control of pH on the deviation is dictated by the differences

in the dissociation constants of H2Se and H2S. The H2Se/H2S ratio is smaller than the Se/S

ratio where pH is greater than the H2Se dissociation constant. In general, the deviation of a

reduced species ratio from the Se/S ratio is controlled more by oxygen fugacity than pH

(D'yachkova and Khodakovskiy 1968; Huston et al. 1995; Xiong 2003).

To estimate the Se/S ratio of a fluid in equilibrium with a sulphide mineral, the physicochemical conditions of deposition must be known. Temperature can be used to determine the H2Se/H2S ratio of a fluid, but this may not indicate the Se/S ratio of a fluid.

The other physiochemical conditions of ore deposition (pH, ƒO2) can be estimated from

mineral assemblages and other geochemical data, particularly those that indicate oxygen

fugacity buffers such as the co-occurrence of hematite and pyrite. When oxygen fugacity is

known, the deviation of the H2Se/H2S ratio from Se/S ratio can be fixed over large pH ranges (Figure 4-9). With the deviation known, the Se/S ratio of a fluid in equilibrium

-20 a. – –2 300°C HSO 4 SO 4 HSeO – SeO –2 Σ –2 H2SeO3 3 3 S=10 m ΣSe=10-6 m

-25 HSe– Se–2 2 Hm 1 0 – Py HSO – -1 H Se HSe 4 -2 2 H S 2 -3 -30 –2 -4 SO4 Hm Mt – H2 S HS

Py Mt

-35 Po -25 b. H SeO – –2 200°C 2 3 HSeO3 SeO 3 ΣS=10–2 m Σ -6 -30 Se=10 m H Se 2 – SO –2 HSO4 4 2 -35 Hm Py 2 0 1 log ƒO

-1 -40 -2 Hm -3 Mt -4 H2 S HS – Py Mt HSe– H2Se -45 Po -40 c. HSeO – –2 3 SeO3 H2Se

-45 HSO – SO –2 – 100°C 4 4 HSe Σ –2 1 S=10 m -6 0 Hm ΣSe=10 m -1 -2 Py –2 -50 -3 Se

-4 Hm –2 Mt SO4 -55

H S HS – Mt 2 Py HSe– H2Se -60 2 4 6810 12 14 pH Figure 4-9. Speciation of S and Se, Fe mineral predominance, and variation of Se-2/S-2. Total S concentration = 10-2 m, total Se concentration = 10-6 m. (a) T= 300°C (b) T=200°C, (c) T=100°C. Dashed dot lines are contours of log Se-2/S-2. Dotted lines define speciation fields of S. Hm = hematite, Mt = magnetite, Py= pyrite, Po =pyrrhotite. Selenium thermodynamic data is taken from D’yachova and Khodalovskiy (1968). Hatched area represents conditions where there is no deviation of H2Se/H2S from Se/S and crosshatched area represents conditions where there is no deviation of HSe-/HS- from Se/S

with a sulphide mineral can be estimated by calculating the H2Se/H2S ratio of the fluid using the equilibrium constant and then using the deviation of H2Se/H2S ratio from the Se/S ratio. An additional cause of change in the relationship between sulphide mineral Se/S and fluid Se/S ratios is the addition of other fluids. These additions may be detectable by other evidence such as S, H, and O isotopic compositions or other recorded changes in physiochemical conditions. The primary effect of addition of other fluids is direct changes in the fluid Se/S ratio due to decreases or increases in Se concentration relative to S concentration as the fluids mix to produce a dilution factor but may also influence fluid chemistry, in particular oxygen fugacity. The influence of a highly oxygenated yet selenium poor fluid such as a seawater may intially produce sulphides with higher Se/S ratios as the dilution effect is intially countered by the effect of higher oxygentation.

The thermodynamic approach is limited by incomplete thermodynamic data for Se and its minerals, extrapolation of thermodynamic data to higher temperatures, and the non- ideality of Se substitution in many sulphide minerals. In the present study, the lack of thermodynamic data for eskebornite (FeCuSe2) and achavalite (FeSe) precludes the calculation of the Se/S ratio of fluids in equilibrium with chalcopyrite and pyrrhotite. In addition, the replacement of S by Se in pyrite is non-ideal and the full range of possible depositional temperatures is not encompassed by the available thermodynamic data (Franz

1983; Huston et al. 1995; Yakovleva et al. 2003). The effect of native Se precipitation on the relationship of the H2Se/H2S and Se/S ratios can be ignored for the deposits under investigation because there is no evidence of native Se in any of the deposits (Yamamoto

1976).

4.06.1 VHMS Deposits

VHMS deposits and their modern seafloor sulphide deposit analogues have received considerable attention regarding Se contents and behaviour (Yamamoto et al. 1983;

Yamamoto et al. 1984; Fouquet et al. 1988; Huston et al. 1995; Hannington et al. 1999;

Rouxel et al. 2004; Layton-Matthews et al. in press). This focus on VHMS deposits is a result of their relatively high Se contents, which is a major source for refined Se metal production (Jensen 1985). Selenide minerals are rare in VHMS deposits because the low oxygen fugacity and high temperature that typify most VHMS deposits are conducive to incorporation of Se into sulphide minerals (Simon et al. 1997). However, late clausthalite and

Se-enriched galena have been recorded in some VHMS deposits, co-precipitating with chalcopyrite (Healy and Petruk 1992; Huston et al. 1995; Layton-Matthews et al. in press).

Other selenide mineral occurrences have been interpreted to result from metamorphic re- equilibration (Hannington et al. 1999; Gaspar 2002). Selenide minerals in VHMS deposits influenced by the supergene environment occur as a result of the high oxygen fugacity and low temperature of this environment (Yakovleva et al. 2003).

The Se/S ratios of sulphide minerals have been used to assess the relative contributions of possible S sources to the formation of VHMS deposits, but the assignment of magmatic fluid sources to explain high Se/S ratios in sulphide minerals has been recently questioned due to the multiplicity of possible Se sources in VHMS systems (Huston et al.

1995; Gaspar 2002; Layton-Matthews et al. in press). Suggested sources of Se in VHMS deposits include degassing of magmatic volatiles, leaching of volcanic, volcaniclastic, and intrusive rocks during hydrothermal fluid circulation, leaching of sedimentary rocks during hydrothermal circulation and seawater (Bowers et al. 1985; Koski et al. 1988; Large 1992;

Sedwick et al. 1992; McMurty et al. 1993; Zierenberg et al. 1993; Doe 1994). The multiplicity of sources also offers the possibility of separate sources of selenium and sulphur.

4.06.1.1 Trout Lake and Harmin VHMS deposits

At Trout Lake, both the high Se/S ratios and 34S values near 0‰ suggest that there has been minimal influence from seawater, although leaching of volcanic rocks could produce the same results. The deposit has been metamorphosed so its mineral assemblage is not reflective of original depositional conditions. However, Se/S ratios in massive pyrite are reportedly unaltered by metamorphism (Yamamoto et al. 1983; Yamamoto et al. 1984;

Huston et al. 1995) but the lack of alteration is likely to be dependent on the grade of metamorphism.

The original deposition temperatures of the various minerals of the Trout Lake deposit must be estimated. For the purposes of this study, the system was greatly simplified by adopting single temperatures for each mineral association.

High precision and accuracy for temperature is not warranted since the thermodynamic data is imprecise. The temperatures at which sulphide minerals of VHMS deposits are precipitated have a wide range (25-450°C) (Bowers et al. 1985; Janecky and Shanks 1988; Franklin et al.

2005) depending on the relative proportions of the fluids mixing and the chemical compositions of the fluids. Temperatures for initial precipitation of pyrite, calculated from thermodynamic modelling, can vary from 300 to 350°C (Bowers et al. 1985; Janecky and

Shanks 1988). The temperature of the initial precipitation of other sulphide minerals is similarly variable, with temperatures of 125 to 250°C calculated for sphalerite (Bowers et al.

1985; Janecky and Shanks 1988). A temperature of 300°C has been used to model pyrite

Se/S ratios in VHMS deposits (Huston et al. 1995), but the minimal influence of seawater

suggested by the 34S values of the pyrites from Trout Lake has prompted the adoption of a

350°C temperature for the calculation of the Se/S fluid ratio in equilibrium with ore zone

pyrites. Higher temperatures for pyrite precipitation have been calculated where there is less influence of seawater (Bowers et al. 1985; Janecky and Shanks 1988).

Mineral assemblages can reflect other physiochemical conditions. The pH range of

3.5 to 4.5 is constrained by the presence of muscovite and pyrite and the oxygen fugacity is

below the hematite-pyrite buffer. Under these conditions, the H2Se/H2S ratio should

approximate the Se/S ratio of the fluid (Figure 4-9a, hatched area). The calculated Se/S

ratio of a fluid in equilibrium with ore zone pyrite is 10-3.6 (Table 4.4), similar to the

magmatic Se/S fluid ratio of ~10-4 (Huston et al. 1995; Xiong 2003). The temperature of

deposition for the barren zone pyrites is presumed to be less than that of the ore zone as they are a greater distance from the centre of the deposit (Healy and Petruk 1988; Franklin et al.

2005; Polito et al. 2007). A temperature of 200°C is used for the present calculation of the

Se/S. At the same pH and oxygen fugacity conditions defined for the ore zone pyrite, the

H2Se/H2S approximates the Se/S ratio (Figure 4-9b). The calculated Se/S ratio of a

fluid in equilibrium with the lower temperature pyrite is 10-4.6 (Table 4.4), considerably less

than the Se/S ratio of fluid in equilibrium with ore zone pyrite.

Paragenetic relationships indicate that sphalerite replaces pyrite, so it is likely that sphalerite precipitates at a lower temperature (~125°C) than pyrite (Bowers et al. 1985;

Healy and Petruk 1988). The lower temperature of sphalerite precipitation increases the deviation of H2Se/H2S from Se/S as the speciation of Se and S changes with the H2Se/H2S

ratio becoming marginally smaller then the Se/S ratio. Under similar oxygen fugacity and

100

pH conditions, the deviation is dependent on the exact pH, and expressed as a ratio, varies

from 10-0.05 to 10-0.3 (Figure 4-9c). Selenium/sulphur ratios of the fluid in equilibrium with

sphalerite (10-3.9 to 10-3.6) are similar to those of the Se/S ratios of the fluid in equilibrium

with the ore zone pyrite (Table 4.4). The similarity of the ratios suggests that, during

replacement of pyrite by sphalerite, Se/S ratios are preserved. The distinctly different ranges

of Se/S ratios for the Zn-rich ore zone relative to other ore zones (Table 4.4) reflects the

common negative correlation of Se with Zn and the spatial control of Zn and Cu distributions

in VHMS deposits (Auclair et al. 1987; Huston et al. 1995; Franklin et al. 2005; Layton-

Matthews et al. in press). No evidence of Se-rich inclusions, previously noted at Trout Lake in sphalerite (Healy and Petruk 1992), was detected during LA-ICPMS analyses, so the high contents cannot be ascribed to the presence of such inclusions.

The high Se/S ratio of the particular galena sample from Trout Lake is attributed to an

evolved fluid that was also responsible for the occurrence of the late Se-rich galena-

clausthalite and chalcopyrite inclusions in sphalerite (Healy and Petruk 1992). The galena

likely precipitated at a temperature lower than that of pyrite due to the higher solubility of galena. Consequently a 100°C temperature is used to the calculate the Se/S ratio of a fluid in equilibrium with the galena (Bowers et al. 1985). The deviation of H2S/H2Se from Se/S

under this temperature is the same as at 125°C (Figure 4-9c). The low Se/S ratio

calculated for the fluid in equilibrium with galena (10-8.4, Table 4.4) is consistent with the

fractionation of Se from the ore forming fluid by the precipitation of clausthalite and galena

with greater Se contents preceding the precipitation of this particular galena sample (Healy

and Petruk 1988). The strong fractionation of Se from the fluid into clausthalite-galena

during precipitation (Table 4.9) markedly decreases the Se content of the fluid, leading to the

101

low Se/S ratio of the fluid in equilibrium with the galena sample analyzed. Clausthalite is less

soluble than galena and consequently can precipitate at a higher temperature than galena

(Barin and Platzki 1995; Layton-Matthews et al. in press).

The Se/S ratios of chalcopyrite and ore-zone pyrrhotite from Trout Lake (Table 4.4)

are similar to other VHMS deposits (Table 4.8) and, when they co-precipitate, show

partitioning of Se into the two sulphide minerals to produce near equal Se/S ratios. A similar

equal partitioning between chalcopyrite and pyrrhotite is also recorded in Japanese VHMS

deposits (Yamamoto et al. 1983; Yamamoto et al. 1984) although these deposits are not

deformed nor metamorphosed to the same degree as Trout Lake.

The relationship between 34S values and Se/S ratios of all sulphide minerals from the

ore zone at Trout Lake differs from that of Fe sulphide minerals from the barren zone (Figure

4-4a). The 34S values and Se/S ratios of sulphide minerals from the ore zone are inversely correlated, whereas they are positively correlated for the barren zone Fe sulphide minerals.

At a fixed temperature of 350°C, S is preferentially partitioned into pyrite relative to Se from

the fluid, so that an increase in the Se/S ratio of the fluid, and concurrently an increase in

the Se/S ratio in later pyrites, is expected from pyrite precipitation in a closed system (Table

4.9). Similarly, 34S is preferentially partitioned into pyrite relative to the fluid, albeit only

slightly, so the 34S values of later pyrites should decrease with progressive sulphide mineral precipitation in a closed system. This is consistent with the negative correlation of 34S

values and Se/S ratios observed for ore zone pyrites. A temperature of 300°C would result in

fractionation of Se to pyrite and a positive correlation between 34S values and Se/S ratios if thermodynamic data is correct.

102

The influence of temperature on the incorporation of Se into chalcopyrite and

pyrrhotite is not well established. Chalcopyrite and pyrrhotite in the stringer zone of the

deposit probably precipitated at a high temperature (> 400°C) so it is possible that Se

fractionates into the fluid rather than the sulphide minerals in a similar manner to pyrite

(Franklin et al. 2005). The small range, less than an order of magnitude of Se/S ratios for ore

zone pyrite, pyrrhotite, and chalcopyrite, and the range of 34S values for each sulphide

mineral is less than 2.2 ‰ (Table 4.4, Figure 4-4a), consistent with the effect of closed system fractionation. Selenium fractionates from fluid into sphalerite at temperatures up to

350°C (Table 4.9), so that the effect of closed system fractionation of sphalerite should produce a positive correlation between 34S values and Se/S ratios, the opposite to what is observed (Figure 4-4a). Thus, the replacement of pyrite by sphalerite, where zinc replaces iron on a one to one basis, with little change in volume due to similar unit cell dimensions of sphalerite and pyrite (Klein and Hurlbut 1985), appears to maintain the relationship of Se/S ratios and the 34S values established by the earlier and higher temperature pyrite, suggesting little change of sulphur or selenium concentration during the replacement process.

At the lower temperature (~200°C) ascribed to the barren zone and at any temperature below 312°C, Se preferentially partitions into pyrite relative to S (Table 4.9). Consequently,

the effect of progressive pyrite precipitation in a closed system is reversed from that of the

ore zones, with the Se/S ratio of the ore-forming fluid decreasing as pyrite precipitation

progresses. As fractionation of 34S continues in the same manner as in the ore zones, the

correlation between 34S values and Se/S ratios is positive (Figure 4-4a). Positive correlation

between 34S values and Se/S ratios for barren zone pyrrhotite would result from the same process. Alternatively, the positive correlation between the barren zones Fe sulphide minerals

103

may indicate multiple fluids, one with a relatively low 34S value and Se/S ratio and the

other having a high 34S value and Se/S ratio. The latter is consistent with the larger range

of 34S values from the Fe sulphide minerals from the barren zones compared to those of the

ore zones (Table 4.4). As cooler temperatures promote incorporation of selenium into pyrite,

differences in Se/S ratios between the two fluids need not be great if the second fluid has a low temperature. The mixed fluid would have a temperature lower than that of the first fluid and the Se/S ratios of sulphides precipitating from the mixed fluid will be larger than what would occur at a higher temperature.

Data from Harmin are similar to those from Trout Lake (Table 4.4, Figure 4-4b). The

depositional conditions at Harmin may be different then those of Trout Lake given an as yet

undefined difference in metamorphic grade. However, in the absence of definitive evidence,

identical depositional conditions to those at Trout Lake are assumed, the calculated Se/S

ratio of a fluid in equilibrium with pyrite from Harmin (10-4.0) is consistent with a magmatic

fluid. Applying the same deposition conditions established at Trout Lake for sphalerite

precipitation, the Se/S ratio of a fluid in equilibrium with sphalerite from Harmin is 10-3.9

to 10-3.4, similar to the Trout Lake ratios. The 34S values and Se/S ratios of the Harmin

sulphide minerals (Table 4.4) define two separate groups, one having a positive correlation

and one having a negative correlation (Figure 4-4b), the positive correlation being defined by

pyrrhotites. Although ore zones and barren zones were not comprehensively distinguished for

this deposit at the time of this study, the general similarity between Trout Lake and Harmin

suggest that the two correlations are reflective of barren and ore zones. Other similarities

between Trout Lake and Harmin data suggest that the group of pyrrhotites defining the

104

positive correlation between their 34S and Se/S ratios are from barren zones (Figure 4-4b).

These pyrrhotites also have higher 34S values, consistent with less of a magmatic influence.

The range of Se/S ratios and 34S values of pyrite and chalcopyrite are consistent with the

effect of fractionation in a closed system at 350°C.

Some additional paragenetic information can be inferred from the 34S and Se/S values of Harmin. The 34S values and Se/S ratios in pyrrhotite and pyrite from the same

samples at Harmin show inconsistent partitioning, so that it is unlikely that pyrrhotite and

pyrite co-precipitate. The near-equal Se/S ratios in pyrrhotite and chalcopyrite, as observed at

Trout Lake and in Japanese VHMS deposits (Yamamoto et al. 1983; Yamamoto et al. 1984),

indicate that chalcopyrite and pyrrhotite are coeval, relationships that are consistent with

what is generally observed at VHMS deposits (Franklin et al. 2005).

The magmatic 34S values in sulphide minerals from Trout Lake and Harmin have

been ascribed to leaching of volcanic rocks, also a source of the Cu and Zn, by a primarily

magmatic fluid (Polito et al. 2007). The Se/S ratios of the sulphide minerals are similar to

sulphide minerals of magmatic origin, but could also result from leaching of volcanic rocks.

Selenium contents in sulphide minerals similar to those measured at Trout Lake and Harmin

have been measured at the KZK VHMS deposit (Yukon, Canada), where Se was primarily

derived from the leaching of volcanic rocks and magmatic degassing (Layton-Matthews et al.

in press). The relationship between 34S values and Se/S ratios for all ore zone sulphide

minerals at Trout Lake is consistent with a single ore-forming fluid (Yamamoto 1976). If

selenium and sulphur were to be sourced from different sources a more complex fluid history

would be required and likely would be indicated by geochemical data.

105

4.06.1.2 Hargrave River Barren Sulphide Mineral Bodies

Selenium/sulphur ratios of many of the pyrites and pyrrhotites from the Hargrave

River barren sulphide mineral bodies are similar to those of Harmin and Trout Lake, but

some have much higher Se/S ratios (Table 4.4; Figure 4-4c). The 34S values of the iron

sulphide minerals from Hargrave River are much higher than those from Harmin and Trout

Lake, and are not consistent with a magmatic origin nor with leaching from volcanic rocks.

Furthermore, the positive correlation between 34S values and Se/S ratios (Figure 4-4c) is

similar to the trend recorded by iron sulphide minerals in barren portions of the Trout Lake

deposit, but in marked contrast to the inverse correlation defined by sulphide minerals from

the ore zone at Trout Lake and Harmin. Consequently, the sulphide mineral-forming fluid at

Hargrave River is distinct from the ore-forming fluid at Harmin and Trout Lake, despite the

overlap in their Se/S ratios.

Selenium leached from black shale by hydrothermal fluids results in considerable Se

enrichment in sulphide minerals at the Wolverine VHMS deposit (Layton-Matthews et al. in

press). Local occurrences of black shale in the Hargrave River region could account for the

higher and variable Se/S ratios in sulphides from the barren Hargrave River bodies. The high

and variable 34S values from the barren sulphide mineral bodies are most easily accommodated by the addition of a seawater component, but the high Se/S ratios require

leaching of sources of high Se concentration, such as black shales. Thus, the high and

variable Se/S ratios and 34S values from the barren sulphide mineral bodies result primarily

from mixing between magmatic fluids, seawater and leaching of sedimentary rocks. If

sulphur and selenium do not come from the same source then alternative relationships are

possible.

106

Sulphide minerals with low Se/S ratios and low 34S values are consistent with those

that may have precipitated from a fluid that was dominantly magmatic. Low Se/S ratios in

sulphide minerals from the GP4F deposit (Yukon, Canada) have been attributed to Se

sourced from magmatic degassing (Layton-Matthews et al. in press). For many VHMS

deposits, however, Se/S ratios in combination with 34S values are potentially sensitive indicators of the addition of components from black shales.

4.06.2 High-sulphidation Epithermal Au-Ag Deposits

The low pH and high oxygen fugacity conditions that favour formation of high- sulphidation epithermal deposits are also conducive to precipitation of selenide minerals.

Elements such as Ag, Sb, Pb, and Bi that are typically at high concentration in the 100-200°C fluids responsible for epithermal deposits readily form selenide minerals because they have lower solubilities than the equivalent sulphide minerals (Barin and Platzki 1995). However, selenide minerals in these deposits are rare (Sillitoe 1999), and when they occur, most are late in the paragenesis, as part of Se-Pb-Bi-Sb-Ag-Te mineral assemblages (Hedenquist et al.

1998; Kovalenker et al. 2003; Popov et al. 2003; Plotinskaya et al. 2006; Squire et al. 2007).

Isotopic compositions of H and O of minerals from stages I and II at Pierina, primarily alunite and sulphide minerals, are consistent with a significant meteoric fluid component, whereas S isotopic compositions reflect primarily a magmatic origin for this element (Rainbow et al. 2005; Rainbow et al. 2006b). Sulphide minerals from stage II at

Pierina, which are rare because the deposit has been greatly modified by supergene processes

(Rainbow et al., 2006), have Se/S ratios lower than ratios commonly identified as of

107

magmatic origin in VHMS deposits (Figure 4-8, Table 4.8). The Se/S ratio of galena at 3.36

x 10-4 is notably low, given that this mineral has a strong affinity for Se.

The Se/S ratios of the ore-forming fluid for stage II can be estimated since the

depositional conditions are well constrained (Rainbow et al. 2005). A temperature of 200°C

for stage II is assumed, the pH was low (<5) as restricted by the presence of enargite, and the

oxygen fugacity was high as barite formed at an intermediate stage (Einaudi et al. 2003;

Rainbow et al. 2005) (Einaudi et al. 2003; Rainbow et al. 2005). The H2Se/H2S ratio of the

ore-forming fluid ranges from being equal to a hundred times the Se/S ratio (Figure 4-9b).

Given these parameters, fluids in equilibrium with pyrite and sphalerite are similar in their

Se/S ratios (pyrite 10-5.8 to 10-4.6, sphalerite 10-5.6 to 10-4.6; Table 4.5), consistent with the

co-precipitation of the pyrite and sphalerite. The Se/S ratios are much smaller than the

typical magmatic value of 10-4, suggesting that the ore-forming fluid initially had a low ratio

as would be expected for meteoric waters. The low Se/S ratios of the fluid in equilibrium

with pyrite and sphalerite are not the product of prior fractional crystallization in a closed

system because the magmatic 34S values of the pyrites are inconsistent with the extensive

fractional crystallization necessary to decrease the Se/S ratio of the ore-forming fluid from

a value more typical of magmatic origin (Ohmoto and Goldhaber 1997; Rainbow et al.

2005).

As the pyrite and sphalerite precipitate, the Se/S ratio of the fluid will decrease as

Se fractionates into these sulphide minerals. The dilution by the low Se/S ratio of the

meteoric would also contribute to the decline. This decrease with time would account for the

very low Se/S ratio of the fluid in equilibrium with the galena (10-10.2), which occurs late

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in the paragenetic stage with barite. The precipitation of galena and bismuthinite-stibnite

throughout stage II suggests that the Se/S ratio of the ore-forming fluid declines rapidly

during stage II as Se strongly partitions into these minerals. The precipitation of galena and

bismuthinite-stibnite throughout stage II suggests that the Se/S ratio of the ore-forming fluid declined abruptly during stage II as Se strongly partitions into these minerals.

Lack of published data on Se contents in sulphide minerals from high-sulphidation epithermal Au-Ag deposits precludes a full conclusion regarding the typical Se/S ratio of a high-sulphidation epithermal fluid. Selenium/sulphur ratios of sulphide minerals from high- sulphidation epithermal deposits of the Pangagyurishte District in Bulgaria are consistent with magmatic values (Se/S= 2 to 4 x 10-4), as is a Se/S ratio of 3 x 10-4 for a pyrite concentrate from the Kairagach deposit in Uzbekistan (Tischendorf 1966; Kovalenker et al.

2003; Popov et al. 2003; Moritz et al. 2005). However, it is unclear if these ratios are typical for high-sulphidation epithermal deposits since they either are from or are spatially close to selenide mineral-bearing deposits.

As is the case for VHMS deposits, sulphide mineral Se/S ratios are somewhat ambiguous for fluid source identification of high-sulphidation epithermal deposits. In the present case of the Pierina high-sulphidation epithermal deposit, low sulphide mineral Se/S ratios, sulphate S, H and O isotopic compositions (Rainbow et al. 2005; Rainbow et al.

2006b) and the absence of selenide minerals indicate a non-magmatic fluid source, but S isotopic compositions of sulphides are consistent with a magmatic fluid-source.

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4.06.3 IOCG Deposits

The Se/S ratios of sulphide minerals from the Mantoverde district are quite variable

(Table 4.6, Figure 4-6). The physiochemical conditions during deposition of iron-oxide

bodies and IOCG deposits in the Mantoverde district are not constant and changes are

recorded by mineral assemblages, 34S values, and fluid inclusion temperatures (Benavides et

al. 2007). On the basis of field relations, mineral paragenesis, stable isotopes and

geochemistry, Benavides et al. (2007) proposed that the early, high-temperature magnetite-

pyrite stage are derived from magmatic-related fluids whereas the later stages involve

increasingly greater contributions from a marine source, possibly an evolved seawater-

derived basinal fluid.

Pyrite from high-temperature stage I has Se/S ratios consistent with pyrite

precipitating from a magmatic fluid under reducing conditions (Table 4.6). The magnetite-

pyrite assemblage fixes pH but the oxygen fugacity is less well defined, ranging across the S-

2/S+6 equilibrium boundary (Figure 4-9a). The thermodynamic data needed to calculate

Se/S fluid ratios and selenium speciation at 550°C are unavailable, but, at temperature of

300°C, the range of oxygen fugacity defines the H2Se/H2S ratio at 1 to 32 times that of the

Se/S ratio (Figure 4-9a). The Se/S ratios of the stage I fluid (Table 4.6), calculated from the thermodynamic parameters at 350°C (Table 4.9), and 34S values (Benavides et al. 2007) are typical of magmatic sources.

The Se/S ratios of stage II pyrites are lower than normal magmatic ratios, suggesting that a second fluid with a low Se/S ratio, such as seawater or a seawater-derived basinal fluid, has diluted the Se content of the fluid precipitating the pyrite. The depositional

110

conditions of stage II are well defined with a temperature of 350°C and a hematite-pyrite-

sericite-chlorite mineral assemblage fixing the oxygen fugacity and pH (3.5 to 5.5). The

H2Se/H2S ratio is fixed at 100 times the Se/S ratio (above hatched area, Figure 4-9a) by

the depositional conditions. The calculated Se/S ratio of the fluid in equilibrium with pyrite is 10-5.9 (Table 4.6); approximately 100 times lower than a typical magmatic fluid (10-

4). The low Se/S ratio and the high 34S values of the sulphide minerals are both consistent

with modified seawater as the source of the extraneous fluid. The Se/S ratios of stage II

pyrites would imply a maximum of 10% magmatic component based on Se/S ratios of magmatic fluids and seawater of 10-4 and 10-7, respectively. However, calculated 34S values

(+9.1 to +14.1 ‰) for the stage II fluid would define a magmatic component of 50% using

magmatic and seawater 34S values of 0 and 30 ‰, respectively (Benavides et al. 2007).

Disparity in mixing ratios may be partly explained by precipitation of stage I sulphide

minerals that would have lowered the Se/S ratio of the evolved magmatic fluid.

The temperature of sub-stage IIIa is 210 to 280 °C, the oxygen fugacity is buffered by

the hematite-pyrite assemblage and the presence of calcite and siderite defines a pH range of

6 to 8 (Benavides et al. 2007). Under these conditions, the H2Se/H2S ratio is at most 100

times greater than the Se/S ratio of the ore-forming fluid (above and between hatched and

cross-hatched areas, Figure 4-9b). This results in a minimum Se/S ratio of the fluid in

equilibrium with pyrite of 10-6.1 (Table 4.6). In sub-stage IIIb, the temperature is 240-250°C and the absence of calcite and siderite indicates a pH below 6 (Benavides et al. 2007). The hematite-pyrite oxygen fugacity buffer fixes the deviation of H2Se/H2S from Se/S ratio at

111

100 times (above hatched area, Figure 4-9b) and the mean Se/S ratio of the fluid at 10-6.3

(Table 4.6), more than two orders of magnitude lower than the magmatic Se/S ratio.

The oxygen fugacity of the late chalcopyrite phase of sub-stage IIIb is not well

defined by the chalcopyrite-hematite assemblage; consequently the H2Se/H2S ratio may be

more than 100 times the Se/S ratio of the fluid (above hatched area, Figure 4-9b), so that

the calculated Se/S ratios of the fluid are be a minimum. The mean ratio, calculated from

the theoretical pyrite Se/S ratio, is 10-6.5 and the calculated minimum Se/S ratio of the late sub-stage IIIb fluid in equilibrium with chalcopyrite is 10-7.5 (Table 4.6). This ratio is close to

the Se/S ratio of seawater (10-7), consistent with the ore-forming fluid at the end of stage

III being seawater-derived basinal fluids as proposed by Benavides et al. (2007).

The mixing curve defined by the relationship between 34S values and Se/S ratios of

stage III pyrite and chalcopyrite (Figure 4-6) can be attributed to mixing of magmatic (high

Se/S ratio, low 34S value) and seawater-derived basinal fluids (low Se/S ratio, high

34S value). The chalcopyrite samples of sub-stage IIIa with the lowest 34S values record higher pH conditions of the early phase of the sub-stage (Figure 4-6b) when the influence of seawater-derived basinal fluids is at a minimum. The continued mixing of fluids results in a further decrease of pH, marking the change in paragenesis from sub-stage IIIa to sub-stage

IIIb as calcite and siderite cease to precipitate. The pyrite of sub-stage IIIb occurs before the chalcopyrite of sub-stage IIIb, so that the pyrite shows an intermediate stage of mixing while the chalcopyrite records the final stage of mixing. The calculated mean fluid Se/S ratios

(Table 4.6) of the successive sub-stages (IIIa pyrite 10-6.1, IIIb pyrite 10-6.3, IIIb chalcopyrite

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10-6.5) illustrate progressive mixing, with the Se concentration becoming diluted by the low

Se content in the seawater-derived basinal fluid (Benavides et al. 2007).

Continued decrease in the Se/S ratios of sulphide minerals at Mantoverde is

consistent with the progressive mixing of a magmatic fluid with an evolved, seawater-

derived basinal fluid (Benavides et al. 2007). The fluid Se/S ratio as recorded by the sulphide

Se/S ratios is progressively diluted from a magmatic-like value to a value more consistent

with modern seawater. Mixing of similar fluids has also been proposed for other South

American IOCG deposits (Ullrich and Clark 1999; Ullrich et al. 2001; Chiaradia et al. 2006).

Sulphide mineral Se/S ratios provide an additional tracer of fluid sources in the formation of

an IOCG deposit. However, fluctuating depositional conditions that characterize these

deposits vary the deviation of the H2Se/H2S ratio from the Se/S ratio in the ore-forming fluid, so that mineral assemblages must be used to define the deviation.

4.06.4 Utility of Sulphide Mineral Se/S ratios in Deposit Studies

The Se/S ratios of ore-forming fluids from various ore deposits estimated in the present study demonstrate that this ratio can be affected by pH, temperature, and oxygen fugacity. They are also affected by the dilution of the fluid Se/S ratio by the mixing of fluids.

It also possible for selenium and sulphur to arise from different and multiple sources.

However, sulphide mineral Se/S ratios can still be useful in the study of ore deposits because variations in Se/S ratios reflect processes associated with the formation of the ore deposit.

The utility of Se/S ratios is extended when combined with 34S values, because typical

magmatic fluids have high Se/S ratios and low 34S values, whereas seawater or basinal

113

fluids have low Se/S ratios and high 34S values. The relationship between 34S values and

Se/S ratios in sulphide minerals records these conditions.

The 34S values and Se/S ratios in fluids and sulphide minerals at Trout Lake and

Harmin VHMS deposits are consistent with a fluid source modified by leaching of volcanic rocks, but the association of magmatic Se/S ratios with non-magmatic 34S values in the sulphide minerals from the barren Hargrave River sulphide mineral bodies indicate that Se/S ratios alone cannot identify a S or Se source without additional data. Similarly, sulphide mineral Se/S ratios alone cannot distinguish a barren zone in an economic VHMS deposit from a barren sulphide body. The utility of Se/S ratios in VHMS deposits is the identification of the influence of single or multiple fluids. In the present study, single fluids are identified at both Harmin and Trout Lake as the relationship between 34S value and Se/S ratio is maintained as later sulphide minerals replace pyrite in the ore zones. However, the post- deposition metamorphism of the deposits may also have played a role. Multiple fluids can be distinguished for barren sulphide ore bodies of Hargrave River by virtue of the positive correlation between 34S values and Se/S ratios, a feature that is also evident in Fe sulphide minerals from the barren zones of Trout Lake.

At Pierina, low Se/S ratios in sulphide minerals and calculated fluid Se/S ratios are consistent with the influence of meteoric fluids indicated by H and O isotopic data. The incorporation of selenium to sulphide minerals produced by high oxygen fugacity is countered by the dilution of fluid selenium concentration by the presumed low selenium content of the meteoric fluid. At Mantoverde, high Se/S ratios and low 34S values characterize the early magmatic fluid and low Se/S ratios and high 34S values reflect a

114

seawater-derived basinal fluid. The magmatic Se/S fluid ratio is progressively diluted by the

lower Se/S fluid ratio of the second fluid with the initial increase in Se/S ratios in sulphides;

from increased oxygen fugacity, diminishing in time; from decreasing fluid Se/S ratio. The

data of the present investigation supports the conclusion of Benavides et al. (2007) that two

fluids mixed during the formation of the ore deposit.

4.07 Conclusions

The Se/S weight ratios of sulphide minerals from various ore deposit types were

measured by LA-ICPMS to determine the utility of Se in elucidating critical processes of ore

genesis, particularly the sources of fluids responsible for the ore deposits. In VHMS deposits

and barren sulphide mineral bodies, the sulphide mineral Se/S ratio is ambiguous in defining the fluid source. The previous suggestion (Huston et al. 1995) that Se does not fractionate

from S during fluid transport so that there are invariant Se/S ratios of fluid sources does not appear to be universally applicable. It is possible for Se and S to arise from different sources. Whereas the Se/S ratios and 34S values in sulphide minerals from the VHMS deposits in this study are consistent with magmatic sources, barren sulphide mineral bodies in the same area have higher 34S values and elevated Se/S ratios, consistent with leaching of

shale as a source for selenium. In contrast, sulphide minerals from the Pierina high-

sulphidation epithermal deposit have lower Se/S ratios than expected from magmatic fluid

sources, in agreement with the D and 18O values of alunite which predicate conditions

from meteoric waters.

The Se/S ratio in sulphide minerals is most informative when used in conjunction with 34S values. Mixing between magmatic and seawater-derived basinal fluids in the IOCG

115

deposits of the Mantoverde district is supported by the relationship between Se/S ratios and

34S values in paragenetically constrained sulphide minerals. Magmatic fluids are associated with barren and early magnetite-pyrite mineralization and have low 34S values and high

Se/S ratios whereas the seawater-derived basinal fluids are associated with hematite- chalcopyrite mineralization and have high 34S values and low Se/S ratios.

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Chapter 5. Conclusions and Recommendations

The aim of this research project was to take advantage of improvements in analytical

instrumentation to produce accurate and precise measurements of selenium contents in sulphide minerals and to assess the utility of sulphide mineral Se/S weight ratios in ore

deposit studies. First, two analytical methods were developed, one for the preparation of

samples as solutions and one for solid calibration standard production. These techniques

were then used to measure sulphide mineral Se/S weight ratios in selected ore deposits and

the resulting data applied, in conjunction with sulphur isotopic compositions, to the understanding of ore deposits of multiple types, in particular the identification of mineralizing fluids and their sources. Sulphide Se/S weight ratios were thus assessed to be useful for ore deposit studies.

The solution sample preparation method provides a simple method of preparation of sulphide samples for hydride generation (HG) introduction for instrumental analysis. This method allowed for the measurement of selenium in sulphide samples that are later used as calibration standards for the assessment of solid calibration standards developed by the second analytical technique.

The development of solid calibration standards by a sol-gel process was the second analytical technique. This method allowed for the production of calibration standards that may be suitable for the calibration of the measurement of glasses and silicate materials but are not suitable for the measurement of selenium and sulphur in sulphides. However, in the assessment of the sol-gel calibration standards, the suitability of available sulphide materials for use as calibration standards was verified.

117

Measurement of selenium contents of sulphides by laser-ablation ICPMS was also

developed to assess the utility of Se/S ratios in characterizing mineralizing fluids and their

sources for VHMS, high-sulphidation epithermal, and IOCG ore deposits.

5.01 Scientific Results

5.01.1 Analytical

Removal of transition metals that interfere with selenium measurement by HG-

ICPHRMS of solutions prepared from sulphide minerals has been accomplished by raising the pH of sample solutions to 12, thereby causing precipitation of iron hydroxides and co- precipitation of other metals, leaving Se in solution. This is followed by further separation of selenium from any remaining transition metals via chelating ion-exchange resin. Neither the precipitation nor chelating ion-exchange resin steps achieves the necessary removal of transition metals so that both are required. This method of selenium purification in conjunction with HG-ICPHRMS detection results in analytical accuracies and precisions for selenium similar to those of previously reported methods using hydride generation for samples with low transition metal contents. The method proved useful for determining selenium concentrations of natural sulphides. These sulphide minerals were used as calibration standards for the laser ablation ICPMS technique used to measure Se/S ratios and as part of the sulphide calibration suite in the evaluation of the sol-gel solid standards.

The second analytical technique developed showed that the production of multi- element solid calibration standards by a sol-gel process is feasible. The fabrication method is shown to be suitable for use on a small scale in a manner similar to solution standards. The simple approach to adding analytes, while convenient, limits the range of concentrations that

118

can be produced. The maximum combined concentration of sulphur and selenium in the

produced standards (xerogels) was 0.1 %, although the theoretical maximum is 3%. With

transition metals, precipitation limits the total concentration of transition metals to the order

of ~0.01%, depending on the metal.

In the case of selenium contents measured by LA-ICPMS and normalized to sulphur

contents, variability from all sol gels and other solid standards is less than that reported for

NIST glass reference materials. Concentrations of sulphur in the NIST glasses using the

xerogels as standards are similar to previously published values, indicating that the xerogels

share similar ablation behaviour with the NIST glasses. Thus, the xerogels are suitable for

calibration of glasses in general and, by extension, are suitable for silicate matrices where concentrations of analytes are suitably low. However, use of xerogels as standards to analyze the sulphur and selenium contents of materials having very different matrices, such as sulphide minerals, does not produce accurate results.

While the determination of the Se/S ratios in sulphides did not utilize the xerogel standards, the development of xerogel standards may have applications beyond this particular study and the testing of the sulphide calibration suite during the development of the xerogels allowed the sulphide calibration standards to be used.

5.01.2 Ore Deposit Studies

Measuring the Se/S ratio of sulphides from ore deposits was done to test their utility to determine the sources of fluids responsible for ore deposits. In the VHMS deposits and barren sulphide bodies from the Flin Flon district in Canada, sulphide Se/S ratios are ambiguous in defining the fluid source. Whereas elevated Se/S ratios in sulphides from the

VHMS deposits investigated are consistent with magmatic 34S values, barren sulphide

119

bodies with 34S values that reflect some influence from seawater also have elevated Se/S

ratios typical of magmatic sources.

The full utility of a Se/S concentration ratio is hampered by the lack of experimental

data detailing the incorporation of selenium into sulphides. Thermodynamic data for certain key selenides are not yet available. The utility of the Se/S concentration ratios will increase as further measurements are made and the mechanisms of partitioning of selenium from sulphur in natural systems are identified and quantified.

The predictions of Yamamoto (1976) regarding the relationship of sulphide 34S

values and Se/S ratios for single fluids in VHMS deposits are confirmed and can be extended

to other deposit types.

5.02 Recommendations

This research has made relevant contributions in both analytical techniques and ore deposit studies. There are two parts to these recommendations, those dealing with the developed analytical methods, and those dealing with the geochemical utility of Se/S concentration ratios.

5.02.2 Analytical

Refinements in both analytical techniques developed are possible to improve sample handling, sample throughput and reagent use. Reduction of volumes of reagents used in the precipitation/column technique could lead to lesser dilution and a decrease in the detection limit of the method. This could involve the optimization of reaction vessels, temperature, and time.

120

The utility of the sol-gel technique for other elements should be tested and

refinements of the technique can be made in terms of reduction of production time and reagent usage. The application of heat treatment, a process that was shown to be inappropriate for selenium and sulphur, should be attempted for xerogels produced with other non-volatile elements.

Improvements in resolution in multi-collector ICPMS instrumentation are likely in the near future and may allow for the routine measurement of selenium isotope ratios. In this context, existing analytical methods will have to be evaluated to ascertain the degree of selenium isotope fractionation.

5.02.3 Geochemical

As is the case for most geochemical research, a larger database will enhance our assessment of the utility of Se/S concentration ratios. This research project only touched on the large number of ore deposit types and studies of other deposits will define better the typical ranges of selenium in particular ore types. In addition, the number of selenium measurements is limited compared to other elements of geochemical interest.

The thermodynamic database for selenium needs to be expanded particularly with respect to the selenides in order to model the incorporation of selenium into geologically important sulphides, such as chalcopyrite and pyrrhotite. Experimental studies into the selenium incorporation into sulphide are also to be desired. The source of selenium in sulphides can also perhaps be better identified by the measurement of selenium isotopes within the sulphides. This may also provide information on the existence of separate sulphur and selenium sources.

121

Particular recommendations can also be made for the individual deposits. As the

Harmin deposit continues to be explored, the definition of paragenesis will be improved and

the Se/S values could be re-evaluated as this proceeds. It is unlikely that the barren sulphide

ore bodies of Hargrave River will deem further research but a better definition of their

depositional conditions will identify better the sources of selenium for each of the sulphide

bodies. At Pierina, Se/S ratios from sulphides of Stage II (enargite. stibnite-bismuthinite) and

the measurement of the Se/S ratio from stage IV sulphides would expand the understanding

of behaviour of selenium in this deposit.

As selenium isotope ratios become more routine with multi-collector ICPMS or other

instrumentation (Layton-Matthews et al. 2006), it may become, in a manner analogous to sulphur isotope ratios, possible to identify better the fluid and selenium sources on the basis of comparison.

122

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159

Appendix A. Trout Lake Data

Sulphur isotope data from Polito et al (2007). Py = pyrite, sph =sphalerite, qtz =quartz

Pyrrhotite Sphalerite Pyrite Chalcopyrite Galena Sample Description Se/S Se/S Se/S Se/S Se/S N 34S N 34S N 34S N 34S N 34S CDT (*10-4) CDT (*10-4) CDT (*10-4) CDT (*10-4) CDT (*10-4) Cu-Zn Ore Zones J79007 Chloritized rhyolite, stringer zone 1 2.3 8.45 J79014 Chloritized rhyolite, stringer zone 1 3.0 3.06 J79020 Chloritized rhyolite, stringer zone 1 2.5 5.07 J79023 Chloritized rhyolite, stringer zone 1 2.5 11.25 1 3.0 7.97 J79040 Chloritized rhyolite, stringer zone 1 3.3 3.77 J79044 Chloritized rhyolite, stringer zone, qtz veins 1 2.1 6.82 J79011 Solid sulphides, C-1 horizon, sph rich 1 1.9 4.65 1 2.3 6.05 J79012 Solid sulphides, C-1 horizon, sph rich, banded 1 2.3 2.60 1 2.8 3.87 J79025 Solid sulphides, C-2 horizon, sph rich, banded 1 2.9 2.57 J79017 Solid sulphides, chiefly py, C-1 horizon 1 3.2 3.78 J79045 Solid sulphides, C-1 horizon, banded 1 3.5 3.06 J79027 Solid sulphides, chiefly py, C-1 horizon, banded 3 2.1 14.32 3 2.5 3.29 J79030 Solid sulphides, chiefly py, C-2 horizon, banded 3 2.4 16.47 5 3.0 6.81 J79032 Solid sulphides, chiefly py, C-1 horizon, banded 2 18.29 4 2.1 4.48 3 1.9 206.84 J79033 Solid sulphides, chiefly py, C-1 horizon, banded 1 2.4 3.60 1 3.1 1.05 J79035 Solid sulphides, chiefly py, C-1 horizon, banded 3 2.4 4.21 4 2.9 2.80 J79037 Solid sulphides, chiefly py, C-1 horizon, banded 1 2.9 4.06 J79046 Solid sulphides, C-1 horizon 1 2.9 2.39 1 3.3 3.66 J79043 Solid sulphides, C-2 horizon, banded 1 3.0 2.84 Barren J79016 Mineralized argillite, cubic py. 1 -1.4 5.35 J79015 Mineralized argillite, cubic py. 1 2.0 3.34

160

J79019 Mineralized argillite, weakly graphitic 1 3.0 1.28 J79031 Argillite, weakly mineralized 1 2.7 3.87 J79034 Mineralized argillite, amorphous pyrite 1 2.7 1.93 J79038 Mineralized graphitic argillite along contact 1 3.4 1.41 J79039 Mineralized argillite, slightly graphitic 1 3.7 4.33 J79047 Amorphous py, solid sulphides, low values 1 2.7 4.21 J79048 Mineralized argillite 1 2.9 2.26 J79049 Graphitic argillite, slightly mineralized 1 6.4 1.68

161

Appendix B. Harmin Data

Sulphur isotope data from Polito et al (2007)

Pyrrhotite Sphalerite Pyrite Chalcopyrite Drill hole Depth Se/S Se/S Se/S Se/S 34 -4 34 -4 34 -4 34 -4 N SCDT (*10 ) N SCDT (*10 ) N SCDT (*10 ) N SCDT (*10 ) NIM 41 163.6 1 1.8 0.18 1 1.14 NIM 41 164.9 1 1.28 5.73 NIM 41 169.0 1 1.8 2.49 1 2.18 1 4.51 NIM 41 175.0 1 6.88 NIM 42 147.3 1 3.78 NIM 42 147.8 1 3.44 NIM 42 158.1 1 5.22 1 1.2 4.10 NIM 43 175.0 1 1.70 2.94 NIM 43 183.0 1 1.7 3.07 1 3.2 2.22 NIM 43 183.2 2 29.42 1 1.69 12.07 NIM 43 194.9 1 5.56 1 1.49 3.71 2 1.79 3.72 1 1.8 5.48 NIM 43 284.3 NIM 46 174.4 1 1.61 1 2.93 NIM 48 276.3 1 29.86 NIM 48 281.7 1 2.08 1 3.31 1 1.4 2.38 NIM 48 284.3 1 0.93 2.32 NIM 48 290.6 1 3.9 2.88 1 4.50 NIM 48 295.9 1 1.9 1.09 2 1.4 8.31 NIM 48m-05 1 1.86 1 1.87 NIM 56 139.0 2 4.39 1 11.11 2 2.0 23.85 NIM 56 139.6 2 1.5 1.20 1 1.57 NIM 56 139.7 1 1.25 1 5.33 2 5.79 NIM 56 142.9 1 1.8 2.22 NIM 58 367.1 1 1.63 1 13.83 NIM 58 391.2 1 3.84 1 3.98 NIM 60 138.9 3 1.2 7.02 NIM 60 140.0 1 5.74 1 12.18 NIM 60 141.9 1 2.2 0.89 1 2.0 0.94 1 0.22 NIM 62 431.1 1 2.8 1.43 1 1.40 1 1.79

162

Appendix C. Hargrave River Data

Sulphur isotope data from Polito et al (2007)

Pyrrhotite Pyrite Drill hole Depth Se/S Se/S 34 -4 34 -4 N SCDT (*10 ) N SCDT (*10 ) HAR 01 164.6 2 3.3 2.51 HAR 02 142.2 1 3.3 3.42 HAR 02 148.3 1 2.6 3.07 HAR 05 157.1 4 4.3 4.24 HAR 05 166.4 2 4.3 11.47 HAR 07 156.3 1 10 3.69 HAR 07 215.0 1 3.4 3.14 HAR 13 127.0 2 4.5 1.63 HAR 13 162.5 2 3.5 6.64 HAR 58 104.5 1 3.7 0.73 1 4.0 0.62 HAR 58 124.1 4 5.39 11.16 HAR 58 128.2 1 0.87 1 5.0 0.80 HAR 58 151.9 2 4.9 5.05 3 3.8 4.26 HAR 58 185.7 1 2.19 2 5.8 7.62 HAR 58 288.1 1 4.4 4.14 HAR 58 297.0 1 5.0 0.97 1 4.7 1.28 HAR 58 300.7 3 0.93 4 2.2 1.92 NIM 34 111.0 1 5.6 6.29 NIM 34 111.1 1 5.6 11.28 NIM 34 133.1 4 4.2 7.37 NIM 34 133.9 1 3.1 2.59 NIM 34 173.6 1 3.7 2.42 NIM 37 141.3 2 4.1 3.97

163

Appendix D. Pierina, Santa Fe, and Santo Toribio Data

Pierina sulphur isotope data From Rainbow et al. (2005)

Pyrite Chalcopyrite Sphalerite Galena Sample Description Se/S Se/S Se/S Se/S 34 -4 34 -4 34 -4 34 -4 N SCDT (*10 ) N SCDT (*10 ) N SCDT (*10 ) N SCDT (*10 ) Santo Toribio 779 Vein 3 3.8 2.71 2 3.5 1.17 1 5.0 2.92 2 1.7 5.77 783 Disseminated 1 3.2 3.39 785 Disseminated 1 3.2 3.63 1 830 Disseminated 3 3.7 1.62 838 Vein 2 3.3 1.91 839 Vein 2 3.2 1.91 840 Disseminated 1 0.63 1 5.8 1.89 1 3.9 3.31 2 3.47 Santa Fe Sf1 3 0.9 2.57 2 1.1 9.53 Sf2 3 2.5 3.60 2 3.2 2.83 1 1.3 5.29 Sf3 3 3.2 4.00 1 2.5 2.43 Sf4 2 3.0 2.13 2 3.4 3.50 Sf5 1 2.9 3.65 Sf6 2 2.4 3.36 1 2.9 3.51 Pierina A11A 3 1.8 1.45 165A 1 -2.3 2.46 A11C 1 1.8 1.22 1 -1.5 3.66

164

Appendix E. Mantoverde District Data

Sulphur isotope values from Benavides et al. (2007), iron = ironstone, chl=chlorite, qtz =quartz, spec =specular Pyrite Chalcopyrite Sample Stage Location Host Rock Se/S *10- Se/S 4 34 -4 34 N SCDT N *10 SCDT 2389 Iron (I) Ferrifera Magnetite 2 3.06 0.9 2359 I Magnetite 1 3.25 -0.6 1356 II East Laura Chlorite 1 1.95 4.9 2357 II SE Main pit Chlorite 1 2.24 1.0 2394 II Trillizos Sericite 1 2.71 1.1 2395 II SE Pit South Chlorite 1 2.74 -0.9 2426 II N Pit South Chlorite 2 1.42 -0.5 2459 II AFS East Main Pit Chlorite 2 1.51 0.1 155682 II S-SSW Franco Chl-qtz/magnetite 1 3.19 0.9 155687 II S-SSW Franco Chl-qtz/magnetite 1 0.86 0.5 155686 II S-SSW Franco Chl-qtz/magnetite 1 2.04 -0.4 155685 II S-SSW Franco Chl-qtz/magnetite 1 2.58 1.4 MVAJF09 IIIa Calcite 1 4.67 1.1 MVAJF06 IIIa Calcite 1 7.16 -0.5 1361 IIIa East Laura Calcite 1 5.85 0.1 1362 IIIa East Laura Calcite 1 12.52 -0.2 1363 IIIa East Laura Calcite 1 9.26 0.9 NW M. V. Pit 2427 IIIa South Altered host 2 15.80 -1 1400 IIIa SE Manto Ruso Calcite 1 1.95 2.8 2398 IIIa NW Ferrifera Chlorite-sericite 1 6.63 0.0 2470 IIIa SE M.V. Main Pit Calcite 1 9.65 -1.8 1363-2 IIIa East Laura Calcite 1 6.09 -2.6 1400B IIIa Se Manto Ruso Calcite 1 11.98 -0.4 1373 IIIb Manto Ruso Spec hematite 1 2.63 4.6 1 11.46 1398 IIIb SE Manto Ruso Spec hematite 1 3.17 2.5 2469 IIIb Manto Ruso Spec hematite 1 4.89 3.9 2496 IIIb NW Ferrifera Spec hematite 1 1.46 5.0 1399B IIIb SE Manto Ruso Spec hematite 1 5.94 5 NNE MV Main 2475A IIIb Pit Spec hematite 1 2.84 5.3 NNE MV Main 2475C IIIb Pit Spec hematite 1 0.46 8.7 JB0431A IIIb Spec hematite 2 2.92 3.3 155008 IIIb Manto Ruso Spec hematite 1 1.14 10 154856 IIIb Manto Ruso Spec hematite 1 4.91 7.2 154866 IIIb Manto Ruso Spec hematite 1 3.09 1.9

165

Appendix F. Se/S Ratios in Sulphide Minerals Calculated

From Published Se Concentration Data

Pyrite

Deposit/Locality (Pyrite) Deposit/Geology Type Se/S Reference (*10-4) Abagas Skarn Fe 0.49 (Vakhru shev and Dorosh 1966) Abakan Skarn Fe 0.24 (Vakhru shev and Dorosh 1966) Adams Uranium Company mine Sandstone U 0.06 (Coleman and Delevaux 1957) Adams Uranium Company mine Sandstone U 0.11 (Coleman and Delevaux 1957) AEC No. 8 mine Sandstone U 0.56 (Coleman and Delevaux 1957) AEC No. 8 mine Sandstone U 1.12 (Coleman and Delevaux 1957) AEC No. 8 mine Sandstone U 93.54 (Coleman and Delevaux 1957) AEC No. 8 mine Sandstone U 447.12 (Coleman and Delevaux 1957) AEC No. 8 mine Sandstone U 752.05 (Coleman and Delevaux 1957) AEC No. 8 mine Sandstone U 336.74 (Coleman and Delevaux 1957) AEC No. 8 mine Sandstone U 0.56 (Coleman and Delevaux 1957) AEC No. 8 mine Sandstone U 1.12 (Coleman and Delevaux 1957) AEC No. 8 mine Sandstone U 93.54 (Coleman and Delevaux 1957) Agarak Porphyry Cu 1.12 (Sindeeva 1964) Agdarinsk Unspecified Pb-Zn 0.51 (Martiro syan and Babayeva 1974) Agincourt VHMS 0.11 (Huston et al. 1995) Ajmer Unspecified 0.09 (Tischendorf 1966) Akhtalsk Unspecified polymetallic 1.02 (Martirosyan and Babayeva 1974) Aldermac VHMS 1.05 (Hawley and Nichol 1959) Almalyk Porphyry Cu Mo 1.26 (Tischendorf 1966) Almalyk Porphyry Cu Mo 1.31 (Tischendorf 1966) Almalyk Porphyry Cu Mo 0.33 (Tischendorf 1966) Almalyk Porphyry Cu Mo 0.52 (Tischendorf 1966) Altay ore district Regional Mean 1.52 (Berrow and Ure 1989) Altin-Topkansk Unspecified Pb Zn 0.37 (Tischendorf 1966) Ampalyk Skarn Fe 1.31 (Vakhrush ev and Dorosh 1966) Anazas Skarn Fe 0.37 (Vakhrush ev and Dorosh 1966) Annaberg Metasediment Hosted Ag Pb Zn 0.21 (Tischendorf 1966) Austria Unspecified 1.78 (Rockenbauer 1960) Austria Unspecified 0.37 (Rockenbauer 1960) Balcombe Bay Tertiary (Sedimentary) 0.02 (Edwards and Carlos 1954) Ball Ground Homestake Au 1.50 (Williams and Byers 1934) Basin No. 1 mine Sandstone U 35.54 (Coleman and Delevaux 1957) Batavia Downs Bore Cretaceous (Sedimentary) 0.10 (Edwards and Carlos 1954) Beaconsfield Low sulphidation epithermal Au Ag 0.09 (Edwards and Carlos 1954) Beloretsk Skarn Fe 0.39 (Vakhrush ev and Do rosh 1966) Belousov VHMS 1.93 (Malakhov et al. 1974) Belousov VHMS 1.95 (Malakhov et al. 1974) Berggiesshübel Skarn Fe 1.74 (Tischendorf 1966) Berggiesshübel Skarn Fe 0.52 (Tischendorf 1966) Bessie G. Mine Low sulphidation epithermal Au-Ag 0.37 (Coleman and Delevaux 1957) Big Bell Mine Homestake Au 0.84 (Edwards and Carlos 1954) Big Hill Mine SEDEX Pb-Zn 1.02 (Edwards and Carlos 1954) Big Horn No. 18 claim Sandstone U 0.56 (Coleman and Delevaux 1957)

166

Deposit/Locality (Pyrite) Deposit/Geology Type Se/S Reference (*10-4) Biwender Gangzug Metasediment Ag Pb Zn 0.89 (Tischendorf 1966) Biwender Gangzug Metasediment Ag Pb Zn 1.05 (Tischendorf 1966) BKW Berzdorf Sedimentary 0.27 (Tischendorf 1966) Black King Mine Sandstone U 3.18 (Coleman and Delev aux 1957) Blackstone No.6 mine Sandstone U 15.15 (Coleman and Delev aux 1957) Blanding Water Tunnel Unspecified deposit 1.87 (Coleman and Delevaux 1957) Blowout mine Sandstone U 561.23 (Coleman and Delevaux 1957) Blue Lizard mine Sediment hosted Cu 0.04 (Coleman and Delev aux 1957) Bocksberg bei Probstzella Sedimentary 0.87 (Tischendorf 1966) Boliden Mine VHMS 3.18 (Bergenfelt 1953) Borieva Skarn Pb Zn 0.75 (Tischendorf 1966) Borieva Skarn Pb Zn 2.06 (Tischendorf 1966) Bottle Creek Hot Spring Hg 0.47 (Davidson 1960) Branch River Sedimentary 0.24 (Edwards and Carlos 1954) Brand-Erbisdorf Metasedimentary Hosted Ag Pb Zn 0.18 (Tischendorf 1966) Brand-Erbisdorf Metasedimentary Hosted Ag Pb Zn 0.19 (Tischendorf 1966) Brand-Erbisdorf Metasedimentary Hosted Ag Pb Zn 0.14 (Tischendorf 1966) Breitenbrunn Skarn 2.67 (Tischendorf 1966) Breitenbrunn Skarn 0.11 (Tischendorf 1966) Bremen Sedimentary 0.09 (Williams and Byers 1934) Brigham Regional Mean 0.28 (Williams and Byers 1934) Bukuka-Belukha Vein W 3.27 (Sindeeva 1964) Burro canyon Sandstone U 935.39 (Coleman and Delevaux 1957) Busfield lease mine Sandstone U 0.07 (Coleman and Delevaux 1957) Calbona Porphyry Cu 187.08 Cape Paterson Jurassic (Sedimenatry) 0.26 (Edwards and Carlos 1954) Captain’s Flat Ordovician (Sedimentary) 0.09 (Edwards and Carlos 1954) Caribou Low sulphidation epithermal Au-Ag 0.13 (Hawley and Nichol 1959) Carrizo Mountains Unspecified 0.01 (Coleman and Delevaux 1957) Cathroy Larder Homestake Au 0.13 (Hawley and Nichol 1959) Caucasus Unspecified 2.74 (Gusev 1978) Channel Claim Sandstone U 1.87 (Coleman and Delevaux 1957) Chon-Koi Hot Spring Hg 0.18 (Chung 1962) Colorado Unspecified 1.95 (Desborough et al. 1976) Copper Rand/Portage Vein Cu 0.95 (Hawley and Nichol 1959) Corona Silica Carbonate Hg 0.47 (Davidson 1960) Coschütz bei Dresden Sedimentary 0.20 (Tischendorf 1966) Cottonwood No.3 mine Sandstone U 12.16 (Coleman and Delevaux 1957) Cow Flat Unspecified hydrothermal 1.97 (Edwards and Carlos 1954) Cow Flat Uspecified hydrothermal 1.52 (Edwards and Carlos 1954) Cow Flat Unspecified Hydrothermal 1.74 (Edwards and Carlos 1954) Cowarra Low sulphidation epithermal Au Ag 0.97 (Edwards and Carlos 1954) Crackpot mine Sandstone U 4.86 (Coleman and Delevaux 1957) Craney Draw Sandstone U 1.03 (Coleman and Delev aux 1957) Crouse Regional Sedimentary Mean 0.71 (Williams and Byers 1934) Czechoslovakia hydrothermal Unspecified hydrothermal 0.78 (Tischendorf 1966) Czechoslovakia sedimentary Unspecified Sedimentary 0.22 (Tischendorf 1966) Dallas Low sulphidation epithermal Au Ag 4.68 (Williams and Byers 1934) Dastakert Porphyry Cu 0.67 (Sindeeva 1964) Dead Cow area Sandstone U 0.56 (Coleman and Delevaux 1957) Disappointment Valley Sandstone U 2.58 (Coleman and Delev aux 1957) Disney uranium mine Sandstone U 1.50 (Coleman and Delevaux 1957) Donna B. claims Sandstone U 0.06 (Coleman and Delev aux 1957) Draketown Low sulphidation epithermal Au-Ag 0.56 (Williams and Byers 1934) Dry Fork Sandstone U 0.06 (Coleman and Delevaux 1957) Dry River South VHMS 0.36 (Huston et al. 1995) Duchess Unknown 1.46 (Edwards and Carlos 1954) Ducktown VHMS 0.02 (Williams and Byers 1934) Dumfries Low sulphidation epithermal Au-Ag 2.34 (Williams and Byers 1934) Dundas Metasediment hosted Ag Pb Zn 0.19 (Edwards and Carlos 1954)

167

Deposit/Locality (Pyrite) Deposit/Geology Type Se/S Reference (*10-4) Dundas Metasediment hosted Ag Pb Zn 0.19 (Edwards and Carlos 1954) Dundas Metasediment hosted Ag Pb Zn 0.41 (Edwards and Carlos 1954) Dzhilau Skarn Cu 1.87 (Tischendorf 1966) Eagle’s Nest Jurassic (Sedimentary) 0.12 (Edwards and Carlos 1954) Eastern View Tertiary (Sedimentary) 0.08 (Edwards and Carlos 1954) Eimen Sedimentary 0.21 (Tischendorf 1966) ELA Au showing Clastic Sed. Assoc. Shear Hosted Au- 0.43 (Hawley and Nichol 1959) Cu Elbingerode SEDEX Pb Zn 0.10 (Tischendorf 1966) Elbingerode SEDEX Pb Zn 0.06 (Tischendorf 1966) Elbingerode SEDEX Pb Zn 0.07 (Tischendorf 1966) Elbingerode SEDEX Pb Zn 0.13 (Tischendorf 1966) Elbingerode SEDEX Pb Zn 0.06 (Tischendorf 1966) Elbingerode SEDEX Pb Zn 0.10 (Tischendorf 1966) Eldorado Quartz Pebble Conglomerate U 0.52 (Hawley and Nichol 1959) Eldorado Quartz Pebble Conglomerate U 0.77 (Hawley and Nichol 1959) Eldorado Quartz Pebble Conglomerate U 0.79 (Hawley and Nichol 1959) Eldorado Quartz Pebble Conglomerate U 0.79 (Hawley and Nichol 1959) Eldorado Quartz Pebble Conglomerate U 1.48 (Hawley and Nichol 1959) Eldorado Quartz Pebble Conglomerate U 0.13 (Hawley and Nichol 1959) Eldorado Quartz Pebble Conglomerate U 0.16 (Hawley and Nichol 1959) Ellen No. 2 mine, North Wash Sandstone U 42.09 (Coleman and Delevaux 1957) Elshica VHMS 2.62 (Tischendorf 1966) Elshica VHMS 1.78 (Tischendorf 1966) Eschweiler Ver. Coal Deposit 0.15 (Goldschmidt 1958) F. O. Manol mine Sandstone U 2.62 (Coleman and Delevaux 1957) Fall Creek Mine Sandstone U 76.70 (Coleman and Delev aux 1957) Fetterman Creek Sandstone U 0.19 (Coleman and Delev aux 1957) Fichtenhübel Skarn Fe 0.90 (Tischendorf 1966) Fischer’s Gully Low sulphidation epithermal Au Ag 3.84 (Williams and Byers 1934) Flin Flon VHMS 2.49 (Jonasson and Sangster 1983) Flin Flon VHMS 4.12 (Hawley and Nichol 1959) Flin Flon VHMS 0.13 (Hawley and Nichol 1959) Flopover mine Sandstone U 0.09 (Coleman and Delev aux 1957) Flux Quarry VHMS 0.10 (Edwards and Carlos 1954) Foley Uranium Company mine Sandstone U 0.04 (Coleman and Delev aux 1957) Found claim Sandtone Y 4.68 (Coleman and Delev aux 1957) Fox Lake VHMS 3.70 (Jonasson and Sangster 1983) Freiberg Metasediment Hosted Ag Pb Zn 0.49 (Tischendorf 1966) Gai VHMS 1.31 (Yushko-Zakharova et al. 1978) Gallen VHMS 0.04 (Jonasson and Sangster 1983) Geco VHMS 1.12 (Hawley and Nichol 1959) Geco VHMS 1.12 (Hawley and Nichol 1959) Geco VHMS 1.31 (Hawley and Nichol 1959) Geco VHMS 1.81 (Hawley and Nichol 1959) Geco VHMS 1.81 (Hawley and Nichol 1959) Geco VHMS 1.87 (Hawley and Nichol 1959) Geco VHMS 2.24 (Hawley and Nichol 1959) Geco VHMS 2.38 (Hawley and Nichol 1959) Geco VHMS 2.49 (Hawley and Nichol 1959) Geco VHMS 2.90 (Hawley and Nichol 1959) Geco VHMS 2.99 (Hawley and Nichol 1959) Geco VHMS 3.05 (Hawley and Nichol 1959) Geco VHMS 3.55 (Hawley and Nichol 1959) Geco VHMS 5.80 (Hawley and Nichol 1959) Geco VHMS 0.26 (Cabri et al. 1985) Geyer Sn Greissen 0.08 (Tischendorf 1966) Geyer Sn Greissen 0.37 (Tischendorf 1966) Gismo mine Sandstone U 0.05 (Coleman and Delev aux 1957) Glasebach Metasediment Hosted Ag Pb Zn 0.78 (Tischendorf 1966)

168

Deposit/Locality (Pyrite) Deposit/Geology Type Se/S Reference (*10-4) Glasebach Metasediment Hosted Ag Pb Zn 0.31 (Tischendorf 1966) Glasebach Metasediment Hosted Ag Pb Zn 1.17 (Tischendorf 1966) Golden Plateau Epithermal 0.37 (Edwards and Carlos 1954) Granada Homestake Au 0.13 (Hawley and Nichol 1959) Grant claim Sandstone U 12.347 (Coleman and Delev aux 1957) Great Musselroe Bay Unspecified Sn Deposit 0.56 (Edwards and Carlos 1954) Grimmen Sedimentary 0.21 (Tischendorf 1966) Grossmuckrow Sedimentary 0.30 (Tischendorf 1966) Grunow Sedimentary 0.35 (Tischendorf 1966) Guadalupe mine Silica Carbonate Hg 0.47 (Davidson 1960) Guadalupe mine Silica Carbonate Hg 0.47 (Davidson 1960) Guadalupe mine Silica Carbonate Hg 0.47 (Davidson 1960) Guadalupe mine Silica Carbonate Hg 0.47 (Davidson 1960) Guadalupe mine Silica Carbonate Hg 0.47 (Davidson 1960) Guanajuato Comstock epithermal veins 0.09 (Lindgren 1933) Gumeracha Talc Deposits Talc 0.14 (Edwards and Carlos 1954) Hackett River Camp Lake VHMS? 0.69 (Jonasson and Sangster 1983) Halde bei Gauern nahe Greiz Sedimentary 2.74 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag 0.46 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag 0.35 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag 0.39 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag 0.29 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag 0.35 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag 0.31 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag 0.15 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag 0.25 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag 0.28 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag 0.26 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag 0.40 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag 0.25 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag 0.37 (Tischendorf 1966) Happy Jack mine Sandstone U 0.06 (Coleman and Delev aux 1957) Happy Surprise claim Sandstone U 0.06 (Coleman and Delevaux 1957) Heath Steele VHMS 0.37 (Hawley and Nichol 1959) Helen May Claim Sandstone U 3.55 (Coleman and Delev aux 1957) Henneberg Unspecified 0.41 (Tischendorf 1966) Hercules Mine VHMS 0.95 (Edwards and Carlos 1954) Hercules mine VHMS 0.36 (Edwards and Carlos 1954) Hercules Mine VHMS 0.21 (Edwards and Carlos 1954) Hidden Splendor mine Sandstone U 0.34 (Coleman and Delev aux 1957) Hideout mine Sandstone U 0.28 (Coleman and Delev aux 1957) High Cliff, N. Branch Irwin River Permian (Sedimentary) 0.07 (Edwards and Carlos 1954) Hohenleuben Sedimentary 1.21 (Tischendorf 1966) Homestake mine Sandstone U 3.18 (Coleman and Delev aux 1957) Horne VHMS 0.19 (Jonasson and Sangster 1983) Horne VHMS 0.71 (Hawley and Nichol 1959) Horne VHMS 0.84 (Hawley and Nichol 1959) Horne VHMS 1.18 (Hawley and Nichol 1959) Horne VHMS 1.40 (Hawley and Nichol 1959) Horne VHMS 2.21 (Hawley and Nichol 1959) Horne VHMS 2.24 (Hawley and Nichol 1959) Horne VHMS 2.47 (Hawley and Nichol 1959) Horne VHMS 2.53 (Hawley and Nichol 1959) Horne VHMS 2.58 (Hawley and Nichol 1959) Horne VHMS 2.62 (Hawley and Nichol 1959) Horne VHMS 2.66 (Hawley and Nichol 1959) Horne VHMS 2.68 (Hawley and Nichol 1959) Horne VHMS 2.99 (Hawley and Nichol 1959) Horne VHMS 3.12 (Hawley and Nichol 1959) Horne VHMS 3.27 (Hawley and Nichol 1959)

169

Deposit/Locality (Pyrite) Deposit/Geology Type Se/S Reference (*10-4) Horne VHMS 3.31 (Hawley and Nichol 1959) Horne VHMS 3.93 (Hawley and Nichol 1959) Horne VHMS 4.71 (Hawley and Nichol 1959) Horne VHMS 4.90 (Hawley and Nichol 1959) Horne VHMS 5.14 (Hawley and Nichol 1959) Horne VHMS 5.61 (Hawley and Nichol 1959) Horne VHMS 6.17 (Hawley and Nichol 1959) Horne VHMS 8.32 (Hawley and Nichol 1959) Horne VHMS 11.04 (Hawley and Nichol 1959) Horne VHMS 2.96 (Hawley and Nichol 1959) Howey-Hasaga Homestake Au 0.13 (Hawley and Nichol 1959) Hunt No. 2 claim Sandstone U 1.68 (Coleman and Delev aux 1957) Iceland Unspecified 3.74 (Ganzhenko 1979) III Internatsional Unspecified Cu Deposit 1.09 (Yushko-Zakharova et al. 1978) Inya Skarn Fe 0.47 (Vakhrush ev and Dorosh 1966) Irbin Skarn Fe 0.49 (Vakhrush ev and Dorosh 1966) Iron Duke Mine Vein Sn 0.63 (Edwards and Carlos 1954) Iron King Homestake Au 0.94 (Edwards and Carlos 1954) Isle Of Elba Sedimentary 0.01 (Williams and Byers 1934) J. J. Mine Sandstone U 37.42 (Coleman and Delevaux 1957) J. J. Mine Sandstone U 102.89 (Coleman and Delev aux 1957) Japan Unspecified 0.09 (Berrow and Ure 1989) Japan Unspecified 0.24 (Berrow and Ure 1989) Japan Unspecified 0.07 (Tischendorf 1966) Jeanette mine Sandstone U 5.61 (Coleman and Delev aux 1957) Johanngeorgenstadt Unspecified 0.26 (Tischendorf 1966) Kadzharan Porphyry Cu 1.20 (Faramazy an and Zary an 1973) Kadzharan Porphyry Cu 1.50 (Faramazy an and Zary an 1973) Kadzharan Porphyry Cu 1.55 (Faramazy an and Zary an 1973) Kadzharan Porphyry Cu 1.89 (Faramazy an and Zary an 1973) Kadzharan Porphyry Cu 2.62 (Faramazy an and Zary an 1973) Kadzharan Porphyry Cu 0.69 (Sindeeva 1964) Kafan Porphyry Cu 1.35 (Zaryan 1962) Kafan Porphyry Cu 0.29 (Zaryan 1962) Kafan Porphyry Cu 1.20 (Zaryan 1962) Kafan Porphyry Cu 1.50 (Zaryan 1962) Kafan Porphyry Cu 1.38 (Zaryan 1962) Kalgoorlie Super Pit Homestake Au 0.83 (Edwards and Carlos 1954) Kaliostrovskoye Skarn Fe 0.15 (Vakhrushev and Dorosh 1966) Karamazar Low sulphide epitherma l Au-Ag ? 1.66 (Badalov et al. 1969) Khabzas Skarn Fe 0.45 (Vakhrushev and Dorosh 1966) Khayleol’skoye Skarn Fe 0.58 (Vakhrushev and Dorosh 1966) Kidd Creek VHMS 9.35 (Thorpe et al. 1976) Kidd Creek VHMS 0.19 (Cabri et al. 1985) Kidd Creek VHMS 0.84 (Cabri et al. 1985) Kidd Creek VHMS 5.28 (Cabri et al. 1985) King Island Scheelite Mine Skarn W 1.44 (Edwards and Carlos 1954) King No. 4 mine Sandstone U 46.77 (Coleman and Delev aux 1957) Kingslake, West Quarry Lower Devonian (Sedimentary) 0.09 (Edwards and Carlos 1954) Kirovskoye Low sulphidation epithermal Au-Ag 0.36 (Tischendorf 1966) Komsomol’skoye Skarn Fe 0.02 (Vakhrushev and Dorosh 1966) Kondoma gp Skarn Fe 0.30 (Vakhrushev and Dorosh 1966) Kovurmadarinsk Unspecified Pb-Zn Deposit 0.29 (Martirosy an and Babayeva 1974) Kul-Yurt-Tau VHMS 43.03 (Palei 1957) La Sal Mountains Sandstone U 1.12 (Coleman and Delevaux 1957) La Sal Mountains Sandstone U 1.50 (Coleman and Delev aux 1957) La Sal No. 2 mine Sandstone U 0.07 (Coleman and Delevaux 1957) Lake George Mines VHMS 0.97 (Edwards and Carlos 1954) Lake George Mines VHMS 9.94 (Edwards and Carlos 1954) Lauthenthal Unspecified hydrothermal 0.54 (Tischendorf 1966)

170

Deposit/Locality (Pyrite) Deposit/Geology Type Se/S Reference (*10-4) Lebedinsk bei Gubkein Sedimentary 0.10 (Tischendorf 1966) Lebedskoye Skarn Fe 0.60 (Vakhrushev and Dorosh 1966) Lefroy Low sulphidation epithermal Au Ag 0.30 (Edwards and Carlos 1954) Lehesten Sedimentary 0.69 (Tischendorf 1966) Leksdal VHMS 0.09 (Carstens 1941) Leutenberg Skarn 0.36 (Tischendorf 1966) Linda Sedimentary 0.14 (Edwards and Carlos 1954) Little Eva mine Sandstone U 0.56 (Coleman and Delevaux 1957) Livingston Unspecified Vein Au 0.15 (Williams and Byers 1934) Löbejün Porphyry 0.29 (Tischendorf 1966) Lökken Unspecified 0.13 (Carstens 1941) Lökken Unspecified 0.47 (Carstens 1941) Long Park No. 1 mine Sandstone U 0.19 (Coleman and Delevaux 1957) Long Park No. 1 mine Sandstone U 7.30 (Coleman and Delevaux 1957) Lorinna Unspecified Vein Sn 0.43 (Edwards and Carlos 1954) Lucky Mc Mine Sandstone U 14.95 (Coleman and Delevaux 1957) Lucky Strike Mine Sandstone U 0.37 (Coleman and Delevaux 1957) Lynn Lake Synorogenic-synvolcanic Ni Cu 2.39 (Jonasson and Sangster 1983) MacLeod-Cockshutt-Hardrock Homestake Au 0.13 (Hawley and Nichol 1959) Madison Sedimentary 0.01 (Williams and Byers 1934) Magnitogorsk Skarn Fe 1.16 (Tischendorf 1966) Makan Sediment Hosted Cu 1.21 (Malakhov 1983) Makan Sediment Hosted Cu 0.88 (Malakhov 1983) Makan Sediment Hosted Cu 1.46 (Malakhov 1983) Makan Sediment Hosted Cu 0.84 (Malakhov 1983) Makan Sediment Hosted Cu 1.24 (Malakhov 1983) Makansk Sediment hosted Cu? 0.26 (Malakhov et al. 1974) Makansk Sediment hosted Cu? 0.69 (Malakhov et al. 1974) Makansk Sediment hosted Cu? 0.73 (Malakhov et al. 1974) Makansk Sediment hosted Cu? 0.75 (Malakhov et al. 1974) Makansk Sediment hosted Cu? 0.92 (Malakhov et al. 1974) Makansk Sediment hosted Cu? 0.94 (Malakhov et al. 1974) Makansk Sediment hosted Cu? 1.05 (Malakhov et al. 1974) Makansk Sediment hosted Cu? 1.09 (Malakhov et al. 1974) Makansk Sediment hosted Cu? 1.12 (Malakhov et al. 1974) Makansk Sediment hosted Cu? 1.33 (Malakhov et al. 1974) Makansk Sediment hosted Cu? 1.52 (Malakhov et al. 1974) Makansk Sediment hosted Cu? 1.53 (Malakhov et al. 1974) Makansk Sediment hosted Cu? 1.72 (Malakhov et al. 1974) Makansk Sediment hosted Cu? 1.80 (Malakhov et al. 1974) Makansk Sediment hosted Cu? 1.98 (Malakhov et al. 1974) Marietta Skarn Fe 2.75 (Williams and Byers 1934) Marmora Skarn Fe 0.13 (Hawley and Nichol 1959) Mauk VHMS 0.90 (Yushko-Zakharova et al. 1978) Maybe mine Sandstone U 0.06 (Coleman and Delev aux 1957) McCarthy-Coleman claim Sandstone U 0.03 (Coleman and Delevaux 1957) McElmo Creek Sandstone U 0.07 (Coleman and Delev aux 1957) McIntyre Homestake Au 0.41 (Hawley and Nichol 1959) McIntyre Homestake Au 0.41 (Hawley and Nichol 1959) McIntyre Homestake Au 0.62 (Hawley and Nichol 1959) McIntyre Homestake Au 1.12 (Hawley and Nichol 1959) McIntyre-Hollinger Homestake Au 0.62 (Hawley and Nichol 1959) Meggen SEDEX Pb Zn 0.02 (Goldschmidt 1958) Meiseberg Metasediment hosted Ag Pb Zn 0.17 (Tischendorf 1966) Mekhmanisk Unspecified polymetallic deposit 0.21 (Martirosy an and Babayeva 1974) Mi Vida mine Sandstone U 0.07 (Coleman and Delev aux 1957) Middle Urals pyritic Unspecified 5.43 (Ivanov and Yushko-Zakharova 1977) Midson Rd Quarry Triassic (Sedimentary) 0.05 (Edwards and Carlos 1954) Mineral Unspecified vein deposit 0.75 (Williams and Byers 1934) Mineral Joe mine Sandstone U 13.84 (Coleman and Delev aux 1957)

171

Deposit/Locality (Pyrite) Deposit/Geology Type Se/S Reference (*10-4) Mineral Joe mine Sandstone U 18.71 (Coleman and Delev aux 1957) Mineral Joe mine Sandstone U 72.96 (Coleman and Delev aux 1957) Mineral Joe no.2 mine Sandstone U 0.75 (Coleman and Delev aux 1957) Miscell-Renabi Low sulphidation epithermal Au-Ag 0.13 (Hawley and Nichol 1959) Miskhana Porphyry Cu 1.50 (Sindeeva 1964) Monument No. 2 mine Sandstone U 0.07 (Coleman and Delevaux 1957) Moravia & Silesia Unspecified 2.71 (Kvaek 1974) Mount Bischoff Replacement Sn 0.37 (Edwards and Carlos 1954) Mount Chalmers VHMS 0.15 (Huston et al. 1995) Mount Charlotte Homestake Au 0.06 (Edwards and Carlos 1954) Mount Charlotte Homestake Au 0.06 (Edwards and Carlos 1954) Mount Ellison Mine Unspecified hydrothermal 0.70 (Edwards and Carlos 1954) Mount Isa SEDEX Pb-Zn 0.93 (Edwards and Carlos 1954) Mount Isa SEDEX Pb-Zn 0.86 (Edwards and Carlos 1954) Mount Lyell VHMS 0.98 (Edwards and Carlos 1954) Mount Lyell VHMS 4.90 (Edwards and Carlos 1954) Mount Lyell VHMS 2.34 (Edwards and Carlos 1954) Mount Lyell VHMS 1.29 (Edwards and Carlos 1954) Mount Lyell VHMS 1.72 (Edwards and Carlos 1954) Mount Lyell VHMS 0.73 (Edwards and Carlos 1954) Mount Lyell VHMS 0.19 (Edwards and Carlos 1954) Mount Lyell VHMS 2.04 (Edwards and Carlos 1954) Mount Morgan VHMS 0.98 (Edwards and Carlos 1954) Mount Oxide Mine Sediment hosted Cu 1.09 (Edwards and Carlos 1954) Mul’ga Skarn Fe 0.17 (Vakhrushev and Dorosh 1966) Muran plateau Unspecified 0.59 (Berrow and Ure 1989) Muran Plateau Unspecified 0.59 (Ivanov 1967) Nairne Sedimentary Pyrite Deposit 0.31 (Edwards and Carlos 1954) Nairne Sedimentary Pyrite Deposit 0.49 (Edwards and Carlos 1954) Nairne Sedimentary Pyrite Deposit 0.76 (Edwards and Carlos 1954) Nairne Sedimentary Pyrite Deposit 0.83 (Edwards and Carlos 1954) Natal’yevka Skarn Cu 0.30 (Vakhrushev and Dorosh 1966) Neudorf Metasedimentary Hosted Ag Pb Zn 0.25 (Tischendorf 1966) Neudorf Metasedimentary Hosted Ag Pb Zn 0.29 (Tischendorf 1966) Neugeboren Kindlein Metasedimentary Hosted Ag Pb Zn 0.16 (Tischendorf 1966) Neves-Corvo VHMS 12.62 (Gaspar 2002) New Loch Fyne Mine Low sulphidation epithermal Au-Ag 0.90 (Edwards and Carlos 1954) New North Mount Farrell Mine Unspecified Sn Deposit 0.36 (Edwards and Carlos 1954) Niederschlema Vein U 0.15 (Tischendorf 1966) Nikolayevsk Porphyry Cu 2.47 (Malakhov et al. 1974) Nikolayevsk Porphyry Cu 4.34 (Malakhov et al. 1974) Nikolayevsk Porphyry Cu 1.87 (Kulikova 1971) No. 4 mine 1.12 (Coleman and Delevaux 1957) Norilsk Norilsk Cu Ni PGE 0.47 (Zainullen 1960) Norilsk 0.02 (Tischendorf 1966) Normetal VHMS 2.90 (Hawley and Nichol 1959) Normetal VHMS 0.13 (Hawley and Nichol 1959) North Branch Irwin River Permian (Sedimentary) 0.14 (Edwards and Carlos 1954) North Mesa No. 9 mine, Temple Mtn Sandstone U 2.24 (Coleman and Delev aux 1957) North Mesa No. 9 mine, Temple Mtn Sandstone U 5.61 (Coleman and Delevaux 1957) North star mine Sandstone U 2.62 (Coleman and Delevaux 1957) North Wiseman’s Creek Mine Unspecified Hydrothermal 2.55 (Edwards and Carlos 1954) Northern Caucasus copper-pyritic Unspecified 2.90 (Ivanov and Yushko-Zakharova 1977) Northern Caucasus pyritic Unspecified 5.43 (Ivanov and Yushko-Zakharova 1977) Notch No. 1 mine Sandstone U 0.06 (Coleman and Delevaux 1957) Novoye Sediment Hosted Cu 0.37 (Malakhov et al. 1974) Novoye Sediment Hosted Cu 0.73 (Malakhov et al. 1974) Nuratinsk group Skarn W 1.78 (Ismailov 1964) Odinochnoye Skarn Fe 0.73 (Vakhrushev and Dorosh 1966)

172

Deposit/Locality (Pyrite) Deposit/Geology Type Se/S Reference (*10-4) Okie mine Sandstone U 0.37 (Coleman and Delevaux 1957) Okie mine Sandstone U 0.56 (Coleman and Delevaux 1957) Orlovsk (1, 2, 3) Skarn W 3.31 (Malakhov et al. 1974) Orlovskiy Skarn W 3.01 (Malakhov et al. 1974) Pechenga Komatitc Ni Cu 0.15 (Tischendorf 1966) Pechtelsgrün Skarn W 0.56 (Tischendorf 1966) Pechtelsgrün Skarn W 0.52 (Tischendorf 1966) Pechtelsgrün Skarn W 0.47 (Tischendorf 1966) Pechtelsgrün Skarn W 0.74 (Tischendorf 1966) Pechtelsgrün Skarn W 0.68 (Tischendorf 1966) Pechtelsgrün Skarn W 0.58 (Tischendorf 1966) Pechtelsgrün Skarn W 0.99 (Tischendorf 1966) Pechtelsgrün Skarn W 0.77 (Tischendorf 1966) Pechtelsgrün Skarn W 0.99 (Tischendorf 1966) Pechtelsgrün Skarn W 1.46 (Tischendorf 1966) Pechtelsgrün Skarn W 0.86 (Tischendorf 1966) Pechtelsgrün Skarn W 1.08 (Tischendorf 1966) Pechtelsgrün Skarn W 0.49 (Tischendorf 1966) Pechtelsgrün Skarn W 0.34 (Tischendorf 1966) Pechtelsgrün Skarn W 0.91 (Tischendorf 1966) Pechtelsgrün Skarn W 1.71 (Tischendorf 1966) Pechtelsgrün Skarn W 0.54 (Tischendorf 1966) Pechtelsgrün Skarn W 0.39 (Tischendorf 1966) Pechtelsgrün Skarn W 0.39 (Tischendorf 1966) Pechtelsgrün Skarn W 0.36 (Tischendorf 1966) Pechtelsgrün Skarn W 0.55 (Tischendorf 1966) Pechtelsgrün Skarn W 0.51 (Tischendorf 1966) Pechtelsgrün Skarn W 1.78 (Tischendorf 1966) Pechtelsgrün Skarn W 0.69 (Tischendorf 1966) Pechtelsgrün Skarn W 0.54 (Tischendorf 1966) Pechtelsgrün Skarn W 0.62 (Tischendorf 1966) Pechtelsgrün Skarn W 0.67 (Tischendorf 1966) Pechtelsgrün Skarn W 1.41 (Tischendorf 1966) Pechtelsgrün Skarn W 0.67 (Tischendorf 1966) Pechtelsgrün Skarn W 0.83 (Tischendorf 1966) Pechtelsgrün Skarn W 0.53 (Tischendorf 1966) Pechtelsgrün Skarn W 0.44 (Tischendorf 1966) Pechtelsgrün Skarn W 0.51 (Tischendorf 1966) Pechtelsgrün Skarn W 0.18 (Tischendorf 1966) Pechtelsgrün Skarn W 0.86 (Tischendorf 1966) Pechtelsgrün Skarn W 0.43 (Tischendorf 1966) Pechtelsgrün Skarn W 0.77 (Tischendorf 1966) Pechtelsgrün Skarn W 0.54 (Tischendorf 1966) Pete Lyssy claim Sandstone U 4.49 (Coleman and Delev aux 1957) Pitchfork mine Sandstone U 3.55 (Coleman and Delev aux 1957) Plötz bei Halle Porphyry 0.34 (Tischendorf 1966) Point Pember Eocene (Sedimentary) 0.13 (Edwards and Carlos 1954) Poison Canyon mine Sandstone U 187.08 (Coleman and Delev aux 1957) Poowong Jurassic (Sedimentary) 0.06 (Edwards and Carlos 1954) Pörmitz SEDEX Pb Zn 2.85 (Tischendorf 1966) Powell Rouyn Low sulphidation epithermal Au-Ag 0.64 (Hawley and Nichol 1959) Pretzschendorf Metasedimentary hosted Ag Pb Zn 0.86 (Tischendorf 1966) Priorskoye VHMS 2.69 (Milovskiy et al. 1971) Pyriton Low sulphidation epithermal Au Ag 1.40 (Williams and Byers 1934) Que River Metasedimentary hosted Ag Pb Zn 1.16 (Edwards and Carlos 1954) Queensland Unspecified (Sedimentary) 0.06 (Edwards and Carlos 1954) Quemont VHMS 2.24 (Hawley and Nichol 1959) Rand No. 2 Algoma type iron formation 0.14 (Hawley and Nichol 1959) Ravensworth Permian (Sedimentary) 0.09 (Edwards and Carlos 1954) Ravensworth Permian (Sedimentary) 0.12 (Edwards and Carlos 1954)

173

Deposit/Locality (Pyrite) Deposit/Geology Type Se/S Reference (*10-4) Regan Lake Low sulphidation epithermal Au-Ag 0.09 (Jonasson and Sangster 1983) Renison Bell Replacement Sn 0.76 (Edwards and Carlos 1954) Renison Bell Replacement Sn 0.36 (Edwards and Carlos 1954) Ridder-sokol VHMS 2.71 (Malakhov et al. 1974) Ridder-sokol VHMS 6.44 (Malakhov et al. 1974) Ridge No. 1 mine Sandstone U 0.15 (Coleman and Delev aux 1957) Rifle mine Sandstone U 26.19 (Coleman and Delev aux 1957) Rocky Cape Group Sedimentary 0.96 (Edwards and Carlos 1954) Ronneburg Sandstone U? 2.72 (Tischendorf 1966) Ronneburg Sandstone U? 1.65 (Tischendorf 1966) Ronneburg Sandstone U? 0.45 (Tischendorf 1966) Rosebery VHMS 0.84 (Edwards and Carlos 1954) Rosebery VHMS 0.64 (Edwards and Carlos 1954) Rosebery VHMS 0.03 (Edwards and Carlos 1954) Rosebery VHMS 0.28 (Huston et al. 1995) Rügen Sedimentary 0.14 (Tischendorf 1966) Rügen Sedimentary 0.66 (Tischendorf 1966) Rum Jungle Unconformity associated U 1.05 (Edwards and Carlos 1954) Russia Unspecified 0.52 (Malakhov et al. 1974) Russia Unspecified 1.63 (Malakhov et al. 1974) Russia Unspecified 2.43 (Malakhov et al. 1974) Russia Unspecified 1.14 (Ivanov and Yushko-Zakharova 1977) Russia copper-pyritic Unspecified 1.31 (Ivanov and Yushko-Zakharova 1977) Russia Cu-Mo Porphyry Cu-Mo 1.12 (Ivanov and Yushko-Zakharova 1977) Russia lead zinc polymetallic Unspecified Pb Zn 1.68 (Ivanov and Yushko-Zakharova 1977) Russia lead-zinc-barite Unspecified Pb Zn 0.19 (Ivanov and Yushko-Zakharova 1977) ploymetallic Russia Pb Zn Skarn Skarn 0.30 (Ivanov and Yushko-Zakharova 1977) Salida Low sulphidation epithermal Au-Ag 9.35 (Kieft and Oen 1973) Salida Low sulphidation epithermal Au-Ag 9.35 (Kieft and Oen 1973) Salida Low sulphidation epithermal Au-Ag 9.35 (Kieft and Oen 1973) Samson Skarn Fe 0.26 (Vakhru shev and Dorosh 1966) Sandy Claim Sandstone U 0.03 (Coleman and Delev aux 1957) Saratoga Unspecified Pb, Zn deposit 0.19 (Williams and Byers 1934) Sarcophagus Butte Sandstone U 0.37 (Coleman and Delev aux 1957) Savage River Mine Skarn Fe 0.71 (Edwards and Carlos 1954) Schmiedefeld Unspecified Hydrothermal 0.78 (Tischendorf 1966) Schmiedefeld Unspecified Hydrothermal 0.44 (Tischendorf 1966) Schneeberg Metasedimentary Hosted Ag Pb Zn 0.11 (Tischendorf 1966) Schönbrunn Unspecified Hydrothermal 0.12 (Tischendorf 1966) Schuyler Unspecified Vein Au 1.12 (Williams and Byers 1934) Schweissing Sedimentary 3.08 (Tischendorf 1966) Section 08 T07S R22E Sandstone U 0.37 (Coleman and Delevaux 1957) Section 23 T08S R03E Sandstone U 0.13 (Coleman and Delevaux 1957) Section 23 T09S R04E Sandstone U 0.15 (Coleman and Delevaux 1957) Section 35 T07S R02E Sandstone U 0.19 (Coleman and Delevaux 1957) Seeberg bei Gotha Unspecified 0.15 (Tischendorf 1966) Shamlug Porphyry Cu 1.40 (Martirosyan and Babayeva 1974) Shannon oil company claims Sandstone U 0.08 (Coleman and Delevaux 1957) Shepherd and Murphy Mine Vein Sn 0.32 (Edwards and Carlos 1954) Shinarump No. 3 mine Sandstone U 0.03 (Coleman and Delevaux 1957) Sibay VHMS 0.64 (Yushko-Zakharova et al. 1978) Sibay VHMS 0.40 (Yushko-Zakharova et al. 1978) Sibay VHMS 1.55 (Yushko-Zakharova et al. 1978) Sibay VHMS 0.64 (Yushko-Zakharova et al. 1978) Sicily Unspecified 4.68 (Coleman 1956) Sinyukha Skarn Cu 0.49 (Vakhru shev and Dorosh 1966) Siptenfelde Metasedimentary Hosted Ag Pb Zn 0.77 (Tischendorf 1966) Siptenfelde Metasedimentary Hosted Ag Pb Zn 0.18 (Tischendorf 1966) Siptenfelde Metasedimentary Hosted Ag Pb Zn 0.21 (Tischendorf 1966)

174

Deposit/Locality (Pyrite) Deposit/Geology Type Se/S Reference (*10-4) Siptenfelde Metasedimentary Hosted Ag Pb Zn 0.71 (Tischendorf 1966) Siptenfelde Metasedimentary Hosted Ag Pb Zn 1.15 (Tischendorf 1966) Siptenfelde Metasedimentary Hosted Ag Pb Zn 1.20 (Tischendorf 1966) Siptenfelde Metasedimentary Hosted Ag Pb Zn 0.25 (Tischendorf 1966) Skellefte VHMS 2.85 (Bergenfelt 1953) Sloane and Scotchman’s Mine Low sulphidation epithermal Au-Ag 0.95 (Edwards and Carlos 1954) Smolnik Unspecified Cu district 0.77 (Baban and Iiavsk 1966) Sno Ball No. 1 mine Sandstone U 0.94 (Coleman and Delevaux 1957) Solotusinsk Unspecified Polymetallic 0.80 (Tischendorf 1966) Solotusinsk Unspecified Polymetallic 0.64 (Tischendorf 1966) Solotusinsk Unspecified Polymetallic 2.28 (Tischendorf 1966) Solotusinsk Unspecified Polymetallic 0.39 (Tischendorf 1966) Sondersbausen VHMS 0.37 (Tischendorf 1966) Sondersbausen VHMS 0.32 (Tischendorf 1966) Sondersbausen VHMS 0.39 (Tischendorf 1966) Southern Urals Copper Sulfide Unspecified 2.43 (Chitaeva 1965) Southern Urals Copper Sulfide Unspecified 3.55 (Chitaeva 1965) Southern Urals Copper Sulfide Unspecified 1.12 (Chitaeva 1965) Southern Urals Copper Sulfide Unspecified 1.63 (Tischendorf 1966) Southern Urals Copper Sulfide Unspecified 1.52 (Tischendorf 1966) Southern Urals Copper Sulfide Unspecified 0.28 (Tischendorf 1966) Southern Urals Copper Sulfide Unspecified 0.37 (Tischendorf 1966) Soviet Union Co-As Arsenide Co As veins 0.60 (Tischendorf 1966) St. Louis Mine Unspecified 1.12 (Coleman and Delevaux 1957) Stangengrün Unspecified Hydrothermal 0.23 (Tischendorf 1966) Stangengrün Unspecified Hydrothermal 0.56 (Tischendorf 1966) Stangengrün Unspecified Hydrothermal 0.40 (Tischendorf 1966) Stirling Valley Mine Metasedimentary Hosted Ag Pb Zn 1.52 (Edwards and Carlos 1954) Stitt River Sedimentary 0.29 (Edwards and Carlos 1954) Stolberg Metasedimentary Hosted Ag Pb Zn 0.08 (Tischendorf 1966) Storey‘s Creek Unspecified Sn 0.51 (Edwards and Carlos 1954) Sudbury Astrobleme associated Ni Cu 0.94 (Hawley and Nichol 1959) Sudbury Astrobleme associated Ni Cu 2.43 (Hawley and Nichol 1959) Suffield VHMS 0.13 (Hawley and Nichol 1959) Sugarleaf Mining Property Sandstone U 1.12 (Coleman and Delevaux 1957) Tailholt mine Sandstone U 2.81 (Coleman and Delevaux 1957) Tailholt mine Sandstone U 3.37 (Coleman and Delevaux 1957) Talsperre Wendefurth Sedimentary 1.21 (Tischendorf 1966) Talsperre Wendefurth Sedimentary 0.59 (Tischendorf 1966) Tambour Major Mine Low sulphidation epithermal Au-Ag 0.14 (Edwards and Carlos 1954) Tasmania Unspecified (Sedimentary) 0.02 (Edwards and Carlos 1954) Tayat Skarn Fe 0.51 (Vakhru shev and Dorosh 1966) Terra Arsenide Ag-Co veins 0.04 (Jonasson and Sangster 1983) Teya Skarn Fe 0.09 (Vakhru shev and Dorosh 1966) Thornleigh Quarry Triassic (Sedimentary) 0.02 (Edwards and Carlos 1954) Tilkerode Unspecified Epithermal 0.41 (Tischendorf 1966) Tilkerode Unspecified Epithermal 0.42 (Tischendorf 1966) Tishin VHMS 2.64 (Malakhov et al. 1974) Tishin VHMS 2.26 (Malakhov et al. 1974) Tisova Stratiform Cu 1.17 (Tischendorf 1966) Torquay Tertiary (Sedimentary) 0.02 (Edwards and Carlos 1954) Torquay Tertiary (Sedimentary) 0.09 (Edwards and Carlos 1954) Trail Fraction claim Sandstone U 0.75 (Coleman and Delevaux 1957) Trial Harbour Skarn Sn 0.41 (Edwards and Carlos 1954) Tsentral’noye Low sulphidation epithermal Au-Ag 0.06 (Vakhru shev and Dorosh 1966) Tullah Metasedimentary Hosted Ag Pb Zn 0.32 (Edwards and Carlos 1954) Tuva Sedimentary 246.70 (Burianova 1961) University of Western Aust.Coll. Unspecified 0.75 (Michael and White 1976) unknown mine, Dolores Canyon Sandstone U 0.13 (Coleman and Delevaux 1957) unknown mine, Dolores Canyon Sandstone U 0.17 (Coleman and Delevaux 1957)

175

Deposit/Locality (Pyrite) Deposit/Geology Type Se/S Reference (*10-4) Ute Mountains Sandstone U 0.75 (Coleman and Delevaux 1957) Van No. 1 claim Sandstone U 31.80 (Coleman and Delevaux 1957) Villa Rica Low Sulfidation Epithermal Au Ag 0.84 (Williams and Byers 1934) Virgin No. 3 mine Sandstone U 1.68 (Coleman and Delevaux 1957) Vitro Mine Sandstone U 16.35 (Coleman and Delevaux 1957) Wabana Ironstone 0.13 (Goldschmidt 1958) Warragamba Dam Sedimentary or Supergene 0.02 (Edwards and Carlos 1954) Waterloo VHMS 0.82 (Huston et al. 1995) Wellmitz Sedimentary 0.35 (Tischendorf 1966) Wellmitz Sedimentary 0.33 (Tischendorf 1966) Wellmitz Sedimentary 0.28 (Tischendorf 1966) Westland Unspecified 0.01 (Wells 1966) Wheal Ellen Mine SEDEX Pb-Zn 0.26 (Edwards and Carlos 1954) Williamsford Road Vein Stockwork Sn W 0.11 (Edwards and Carlos 1954) Willow Creek Sandstone U 0.75 (Coleman and Delevaux 1957) Wiseman’s Creek Mine Unspecified hydrothermal 2.60 (Edwards and Carlos 1954) Wissenbach SEDEX Pb Zn 0.09 (Goldschmidt 1958) Witwatersrand Quartz Pebble Conglomerate Au 2.06 (Davidson 1966) Woodrow Pipe mine Sandstone U 0.08 (Coleman and Delevaux 1957) Woody Island Unspecified 1.16 (Edwards and Carlos 1954) Wurzbach Sedimentary 14.04 (Tischendorf 1966) Yubileynoye VHMS 0.88 (Malakhov et al. 1974) Yubileynoye VHMS 0.94 (Malakhov et al. 1974) Yubileynoye VHMS 1.50 (Malakhov et al. 1974) Yuzhno-Makansk Sediment hosted Cu 0.34 (Malakhov et al. 1974) Yuzhno-Makansk Sediment hosted Cu 1.50 (Malakhov et al. 1974) Yuzhno-Makansk Sediment hosted Cu 1.61 (Malakhov et al. 1974) Yuzhno-Makansk Sediment hosted Cu 2.84 (Malakhov et al. 1974) Yuzhnoye, Dzerzhinskoye VHMS 0.60 (Yushko-Zakharova et al. 1978) Zeehan Metasedimentary Hosted Ag Pb Zn 0.39 (Edwards and Carlos 1954) Zirabulak group Skarn W 0.13 (Ismailov 1964) Zyryanovsk Sediment hosted Cu 0.26 (Malakhov et al. 1974) Zyryanovsk Sediment hosted Cu 0.60 (Malakhov et al. 1974) Zyuzel’skoye VHMS 2.47 (Yushko-Zakharova et al. 1978)

Chalcopyrite

Deposit/Locality (Chalcopyrite) Deposit/Geology Type Se/S Reference (*10-4) Abagas Skarn Fe 0 (Vakhrushev and Dorosh 1966) Aberfoyle Mine Vein Sn 1.08 (Edwards and Carlos 1954) Agarak Porphyry Cu 1.14 (Sindeeva 1964) Akhtalsk Unspecified Polymetallic 0.23 (Martiro syan and Babayeva 1974) Aldermac VHMS 3.86 (Hawley and Nichol 1959) Almalyk Porphyry Cu Mo 1.43 (Tischendorf 1966) Almalyk Porphyry Cu Mo 2.72 (Tischendorf 1966) Almalyk Porphyry Cu Mo 0.86 (Tischendorf 1966) Almalyk Porphyry Cu Mo 0.29 (Tischendorf 1966) Almalyk Porphyry Cu Mo 0.14 (Tischendorf 1966) Altin-Topkansk Unspecified Pb Zn 0.26 (Tischendorf 1966) Austria Unspecified 4.15 (Rockenbauer 1960) Balcooma VHMS 3.15 (Huston et al. 1995) Bashilbelsk Unspecified Polymetallic 0.34 (Martirosyan and Babayeva 1974) Beloretsk Skarn Fe 8.30 (Vakhrushev and Dorosh 1966) Belousov VHMS 2.60 (Malakhov et al. 1974) Belousov VHMS 4.01 (Malakhov et al. 1974) Berggiesshübel Skarn Fe 2.68 (Tischendorf 1966)

176

Deposit/Locality (Chalcopyrite) Deposit/Geology Type Se/S Reference (*10-4) Berggiesshübel Skarn Fe 3.20 (Tischendorf 1966) Berggiesshübel Skarn Fe 1.83 (Tischendorf 1966) Berggiesshübel Skarn Fe 0.73 (Tischendorf 1966) Berggiesshübel Skarn Fe 2.80 (Tischendorf 1966) Blue Lizard mine Sediment Hosted Cu 0.05 (Coleman and Delevaux 1957) Boliden Mine VHMS 30.05 (Bergenfelt 1953) Brand-Erbisdorf Metasedimentary Hosted Ag Pb Zn Vein 0.12 (Tischendorf 1966) Brand-Erbisdorf Metasedimentary Hosted Ag Pb Zn Vein 0.06 (Tischendorf 1966) Breitenbrunn Skarn 3.27 (Tischendorf 1966) Broken Hill SEDEX Pb Zn 1.07 (Edwards and Carlos 1954) Bukuka-Belukha Skarn W 0.34 (Tischendorf 1966) Caucaus Co-Mo Porphyry Cu-Mo 0 (Ivanov and Yushko-Zakharova 1977) Clausthal Metasedimentary Hosted Ag Pb Zn Vein 0.03 (Tischendorf 1966) Coast Copper Porphyry Cu 3.58 (Jonasson and Sangster 1983) Colorado Unspecified 7.87 (Desborough et al. 1976) Copper Rand/Portage Vein Cu 1.66 (Hawley and Nichol 1959) Copper Rand/Portage Vein Cu 1.83 (Jonasson and Sangster 1983) Dastakert Porphyry Cu 0.86 (Sindeeva 1964) Dry River South VHMS 0.29 (Huston et al. 1995) Duchess Unspecified 3.50 (Edwards and Carlos 1954) Duchess Unspecified 3.31 (Edwards and Carlos 1954) Ducktown VHMS 0.29 (Williams and Byers 1934) Dzhilau Skarn Cu 4.01 (Tischendorf 1966) Engidzhinsk Unspecified Polymetallic 0.24 (Martiro syan and Babayeva 1974) Eustis VHMS 4.01 (Jonasson and Sangster 1983) Fichtenhubel Skarn Fe 0.66 (Tischendorf 1966) Five Mile Rise Mine Skarn Sn 1.28 (Edwards and Carlos 1954) Flin Flon VHMS 6.87 (Jonasson and Sangster 1983) Flin Flon VHMS 7.18 (Hawley and Nichol 1959) Fox Lake VHMS 9.19 (Jonasson and Sangster 1983) Gai VHMS 1.20 (Yushko-Zakharova et al. 1978) Geco VHMS 0.03 (Jonasson and Sangster 1983) Geco VHMS 4.86 (Hawley and Nichol 1959) Geco VHMS 4.86 (Hawley and Nichol 1959) Geco VHMS 7.44 (Hawley and Nichol 1959) Geco VHMS 11.02 (Hawley and Nichol 1959) Geco VHMS 0.20 (Cabri et al. 1985) Glasebach Metasedimentary Hosted Ag Pb Zn Vein 0.54 (Tischendorf 1966) Granisle Porphyry Cu 7.13 (Jonasson and Sangster 1983) Great Cobar Mine Unspecified Cu 0.47 (Edwards and Carlos 1954) Happy Jack mine Sandstone U 0.04 (Coleman and Delevaux 1957) Hercules Mine VHMS 0.11 (Edwards and Carlos 1954) High Lake VHMS 4.55 (Jonasson and Sangster 1983) Hollinger Homestake Au 0.66 (Hawley and Nichol 1959) Horne VHMS 7.44 (Jonasson and Sangster 1983) Horne VHMS 12.31 (Hawley and Nichol 1959) Icon-Sullivan Vein Cu 1.37 (Jonasson and Sangster 1983) III Internatsional Unspecified Cu 0.09 (Yushko-Zakharova et al. 1978) III Internatsional Unspecified Cu 2.09 (Yushko-Zakharova et al. 1978) India Unspecified 5.09 (Tischendorf 1966) Japan Unspecified 0.53 (Berrow and Ure 1989) Joutel VHMS 11.79 (Jonasson and Sangster 1983) Kadzharan Porphyry Cu 1.49 (Tischendorf 1966) Kadzharan Porphyry Cu 2.52 (Faramazyan and Zaryan 1973) Kadzharan Porphyry Cu 2.69 (Faramazyan and Zaryan 1973) Kadzharan Porphyry Cu 4.55 (Faramazyan and Zaryan 1973) Kadzharan Porphyry Cu 4.86 (Faramazyan and Zaryan 1973) Kadzharan Porphyry Cu 6.44 (Faramazyan and Zaryan 1973) Kadzharan Porphyry Cu 6.58 (Faramazyan and Zaryan 1973) Kadzharan Porphyry Cu 6.90 (Faramazyan and Zaryan 1973)

177

Deposit/Locality (Chalcopyrite) Deposit/Geology Type Se/S Reference (*10-4) Kafan Porphyry Cu 1.55 (Zaryan 1962) Kafan Porphyry Cu 3.81 (Zaryan 1962) Kafan Porphyry Cu 3.00 (Zaryan 1962) Kafan Porphyry Cu 2.23 (Zaryan 1962) Kafan Porphyry Cu 1.09 (Zaryan 1962) Kamsdorf-Könitz Unspecified 0.54 (Tischendorf 1966) Karamazar Low Sulphidation Epithermal Au Ag 1.72 (Badalov et al. 1969) Kidd Creek VHMS 47.97 (Thorpe et al. 1976) Kidd Creek VHMS 3.22 (Cabri et al. 1985) Kidd Creek VHMS 5.69 (Cabri et al. 1985) Kidd Creek VHMS 19.17 (Cabri et al. 1985) Kirovskoye Low Sulphidation Epithermal Au Ag 0.16 (Sindeeva 1964) Kola Peninsula Regional Mean 1.14 (Zainullen 1960) Könitz Unspecified 5.82 (Tischendorf 1966) Kusa Bushveld Fe Ti V 1.43 (Ivanov and Yushko-Zakharova 1977) La Sal Mountains Sandstone U 4.58 (Coleman and Delevaux 1957) Lac Dufault VHMS 9.70 (Jonasson and Sangster 1983) Lake George Mines VHMS 0.95 (Edwards and Carlos 1954) Lauterberg Unspecified Hydrothermal 4.19 (Tischendorf 1966) Lebedskoye Skarn 2.95 (Vakhrushev and Dorosh 1966) Levikha XIV VHMS 2.32 (Yushko-Zakharova et al. 1978) Lökken Unspecified Hydrothermal 5.67 (Carstens 1941) Lynn Lake Synorogenetic Synvolcanic Ni Cu 2.92 (Jonasson and Sangster 1983) Makansk Sediment Hosted Cu 0.11 (Malakhov et al. 1974) Makansk Sediment Hosted Cu 1.00 (Malakhov et al. 1974) Makansk Sediment Hosted Cu 1.00 (Malakhov et al. 1974) Makansk Sediment Hosted Cu 1.32 (Malakhov et al. 1974) Makansk Sediment Hosted Cu 1.49 (Malakhov et al. 1974) Makansk Sediment Hosted Cu 1.57 (Malakhov et al. 1974) Manitou-Barvue VHMS 10.87 (Jonasson and Sangster 1983) Mansfeld Sediment Hosted Cu 3.55 (Tischendorf 1966) Mattagami Lake Mines VHMS 15.37 (Jonasson and Sangster 1983) Mattagami Lake Mines VHMS 13.22 (Cabri et al. 1985) Mauk VHMS 6.67 (Yushko-Zakharova et al. 1978) Mekhmanisk Unspecified Polymetallic 0.22 (Martirosyan and Babayeva 1974) Mel’ga Skarn Fe 0.92 (Vakhrushev and Dorosh 1966) Middle Asia Cu-Mo Porphyry Cu-Mo 2.89 (Ivanov and Yushko-Zakharova 1977) Monchegorsk Unspecified 1.20 (Tischendorf 1966) Moonta Mines Vein Cu 1.12 (Edwards and Carlos 1954) Mount Chalmers VHMS 4.31 (Huston et al. 1995) Mount Cleveland Mine Replacement Sn 1.14 (Edwards and Carlos 1954) Mount Elliott Mine Skarn Cu 0.72 (Edwards and Carlos 1954) Mount Isa SEDEX Pb Zn 1.36 (Edwards and Carlos 1954) Mount Isa SEDEX Pb Zn 1.42 (Edwards and Carlos 1954) Mount Lyell VHMS 1.24 (Edwards and Carlos 1954) Mount Lyell VHMS 1.43 (Edwards and Carlos 1954) Mount Lyell VHMS 3.26 (Edwards and Carlos 1954) Mount Morgan VHMS 1.07 (Edwards and Carlos 1954) Mount Perry Vein Cu 1.07 (Edwards and Carlos 1954) Natal’yevka Skarn Cu 2.72 (Vakhru shev and Dorosh 1966) Neudorf Metasedimentary Hosted Ag Pb Zn Vein 1.86 (Tischendorf 1966) Neves-Corvo VHMS 13.05 (Gaspar 2002) Neves-Corvo VHMS 9.24 (Gaspar 2002) Niederludwigsdorf Unspecified Hydrothermal 0.44 (Tischendorf 1966) Nikolayevsk Porphyry Cu 5.72 (Malakhov et al. 1974) Nikolayevsk Porphyry Cu 6.27 (Malakhov et al. 1974) Nikolayevsk Porphyry Cu 6.32 (Malakhov et al. 1974) Nikolayevsk Porphyry Cu 3.15 (Kulikova 1971) Nikolayevsk Porphyry Cu 5.18 (Malakhov et al. 1974)

178

Deposit/Locality (Chalcopyrite) Deposit/Geology Type Se/S Reference (*10-4) Nolilsk Norilsk Cu Ni PGE 3.23 (Zainullen 1960) Norilsk Norilsk Cu Ni PGE 3.58 (Tischendorf 1966) Norilsk Norilsk Cu Ni PGE 2.17 (Tischendorf 1966) Normetal VHMS 3.26 (Hawley and Nichol 1959) Normetal VHMS 6.64 (Jonasson and Sangster 1983) Northland Unspecifed 7.33 (Wells 1966) Novoye Sediment Hosted Cu 0.31 (Malakhov et al. 1974) Nuratinsk group Skarn W 0 (Ismailov 1964) Oberschlema Arsenide U Ag Vein 0.51 (Tischendorf 1966) Odinochnoye Skarn Fe 1.32 (Vakhru shev and Dorosh 1966) Opemiska Vein Cu 1.97 (Jonasson and Sangster 1983) Orchan VHMS 9.87 (Jonasson and Sangster 1983) Orlovsk (1, 2, 3) Skarn W 7.13 (Malakhov et al. 1974) Orlovskiy Skarn W 1.49 (Malakhov et al. 1974) Panagyjuristhe District High Sulphidation Epithermal au Ag 2.52 (Tischendorf 1966) Panagyjuristhe District VHMS 3.81 (Tischendorf 1966) Panagyjuristhe District High Sulphidation Epithermal Au Ag 2.35 (Tischendorf 1966) Panagyjuristhe District VHMS 8.21 (Tischendorf 1966) Pechenga Komatitic Ni Cu 1.03 (Ivanov and Yushko-Zakharova 1977) Pechenga Komatitic Ni Cu 0.66 (Tischendorf 1966) Peko IOCG 1.18 (Edwards and Carlos 1954) Pöhla Skarn Sn 1.05 (Tischendorf 1966) Poirier VHMS 12.48 (Jonasson and Sangster 1983) Pörmitz SEDEX Pb Zn 22.66 (Tischendorf 1966) Priorskoye VHMS 10.67 (Milovskiy et al. 1971) Quemont VHMS 4.21 (Hawley and Nichol 1959) Rammelsberg SEDEX Pb Zn 20.09 (Tischendorf 1966) Rammelsberg SEDEX Pb Zn 3.53 (Tischendorf 1966) Rammelsberg SEDEX Pb Zn 1.94 (Tischendorf 1966) Ridder-Sokol VHMS 4.84 (Malakhov et al. 1974) Ridder-Sokol VHMS 8.33 (Malakhov et al. 1974) Rosebery VHMS 0.49 (Edwards and Carlos 1954) Rosebery VHMS 0.14 (Huston et al. 1995) Rottleberode Unspecified Vein 2.50 (Tischendorf 1966) Rottleberode Unspecified Vein 2.71 (Tischendorf 1966) Rozna Arsenide Ag Co Vein 28.62 (Kvaek 1977) Russia Unspecified 2.46 (Ivanov and Yushko-Zakharova 1977) Russia chalcopyrite-sphalerite Unspecified 3.46 (Ivanov and Yushko-Zakharova 1977) Russia copper-pyritic Unspecified 2.60 (Ivanov and Yushko-Zakharova 1977) Russia copper-pyritic Unspecified 2.00 (Ivanov and Yushko-Zakharova 1977) Russia Cu Ni sulphide Unspecified 1.72 (Ivanov and Yushko-Zakharova 1977) Russia Cu-Mo Porphyry Cu Mo 4.38 (Ivanov and Yushko-Zakharova 1977) Russia lead zinc polymetallic Unspecified Pb-Zn 4.29 (Ivanov and Yushko-Zakharova 1977) Russia lead-zinc-barite ploymetallic Unspecified Pb-Zn 0.23 (Ivanov and Yushko-Zakharova 1977) Russia Skarn Skarn 1.72 (Berrow and Ure 1989) Salida Low Sulphidation Epithermal Au ag 14.31 (Kieft and Oen 1973) Schmalkalden Unspecified Hydrothermal 2.96 (Tischendorf 1966) Schmalkalden Unspecified Hydrothermal 2.61 (Tischendorf 1966) Schmalkalden Unspecified Hydrothermal 1.44 (Tischendorf 1966) Schmiedefeld Unspecified Hydrothermal 0.30 (Tischendorf 1966) Schönbrunn Unspecified Hydrothermal 0.24 (Tischendorf 1966) Shamlug Porphyry Cu 0.33 (Martiro syan and Babayeva 1974) Sibay VHMS 1.46 (Yushko-Zakharova et al. 1978) Sibay VHMS 4.01 (Yushko-Zakharova et al. 1978) Sibay VHMS 2.06 (Yushko-Zakharova et al. 1978) Sibay VHMS 3.97 (Yushko-Zakharova et al. 1978) Sibay VHMS 0.51 (Yushko-Zakharova et al. 1978) Sibay VHMS 1.14 (Yushko-Zakharova et al. 1978) Sibay VHMS 1.60 (Yushko-Zakharova et al. 1978) Sinyukha Skarn Cu 0.66 (Vakhru shev and Dorosh 1966)

179

Deposit/Locality (Chalcopyrite) Deposit/Geology Type Se/S Reference (*10-4) Siptenfelde Metasedimentary Hosted Ag Pb Zn 0.73 (Tischendorf 1966) Skellefte VHMS 30.19 (Bergenfelt 1953) Smolnik Cu District 1.43 (Berrow and Ure 1989) Snow Lake VHMS 5.67 (Jonasson and Sangster 1983) Sohland Unspecified Magmatic-Hydrothermal 2.03 (Tischendorf 1966) Sohland Unspecified Magmatic-Hydrothermal 1.98 (Tischendorf 1966) Solotusinsk Unspecified 3.26 (Tischendorf 1966) Solotusinsk Unspecified 4.86 (Tischendorf 1966) Solotusinsk Unspecified 1.86 (Tischendorf 1966) Solotusinsk Unspecified 4.29 (Tischendorf 1966) Solotusinsk Unspecified 1.26 (Tischendorf 1966) Southern Urals Copper Sulfide Unspecified 2.58 (Tischendorf 1966) Strassberg Metasedimentary Hosted Ag Pb Zn 0.27 (Tischendorf 1966) Sudbury Astrobleme Associated Ni Cu 0.97 (Hawley and Nichol 1959) Sudbury Astrobleme Associated Ni Cu 2.78 (Hawley and Nichol 1959) Sudbury Astrobleme Associated Ni Cu 2.86 (Hawley and Nichol 1959) Sudbury Astrobleme Associated Ni Cu 2.00 (Tischendorf 1966) Sudbury Astrobleme Associated Ni Cu 2.58 (Cabri et al. 1984) Sudbury Astrobleme Associated Ni Cu 4.38 (Cabri et al. 1984) Talnakh Magmatic Ni Cu PGE 2.58 (Ivanov and Yushko-Zakharova 1977) Tannenglasbachsthal Unspecified Hydrothermal 0.79 (Tischendorf 1966) Terra Arsenide Ag Co Veins 0.77 (Jonasson and Sangster 1983) Thomson River Copper Mine Norilsk Cu Ni PGE 1.08 (Edwards and Carlos 1954) Tishin VHMS 6.44 (Malakhov et al. 1974) Tisova Stratiform Cu 0.83 (Tischendorf 1966) Trekelano Unspecified Vein Cu 1.52 (Edwards and Carlos 1954) Tuva Sedimentary 657.74 (Burianova 1961) U. West. Australia Collection Unspecified 0.80 (Michael and White 1976) Waite-Amulet VHMS 11.30 (Hawley and Nichol 1959) Waterloo VHMS 0.17 (Huston et al. 1995) Western(Lynx) SEDEX Pb Zn 0.23 (Jonasson and Sangster 1983) Wiedersberg Unspecified Hydrothermal 0.49 (Tischendorf 1966) Yubileynoye VHMS 1.32 (Malakhov et al. 1974) Yuzhno-Makansk Sediment Hosted Cu 1.00 (Malakhov et al. 1974) Yuzhno-Makansk Sediment Hosted Cu 2.38 (Malakhov et al. 1974) Yuzhnoye, Dzerzhinskoye VHMS 0.37 (Yushko-Zakharova et al. 1978) Yuzhnoye, Dzerzhinskoye VHMS 2.32 (Yushko-Zakharova et al. 1978) Zobes Skarn 1.07 (Tischendorf 1966) Zobes Skarn 0.30 (Tischendorf 1966) Zschorlau Vein W 0.40 (Tischendorf 1966) Zyryanovsk Sediment Hosted Cu 1.20 (Malakhov et al. 1974) Zyuzel’skoye VHMS 0.77 (Yushko-Zakharova et al. 1978) Zyuzel’skoye VHMS 4.58 (Yushko-Zakharova et al. 1978)

Sphalerite

Deposit/Locatity (Sphalerite) Deposit/Geology Type Se/S Reference (*10-4) Aberfoyle Mine Vein Sn 0.21 (Edwards and Carlos 1954) Agdarinsk Unspecified Pb Zn 0.28 (Martirosyan and Babayeva 1974) Agordo Unspecified Polymetallic 0.03 (Rockenbauer 1960) Akhtalsk Unspecified Polymetallic 0.20 (Martirosyan and Babayeva 1974) Almalyk Porphyry Cu 0.15 (Tischendorf 1966) Altay ore District Unspecified Pb Zn 2.67 (Tischendorf 1966) Altenberg Sn Greissen 0.12 (Tischendorf 1966) Altin-Topkansk Unspecified Pb Zn 0.24 (Tischendorf 1966)

180

Deposit/Locatity (Sphalerite) Deposit/Geology Type Se/S Reference (*10-4) Bad Grund Metasedimentary Hosted Ag Pb Zn 1.88 (Goldschmidt and Strock 1935) Bad Grund Metasedimentary Hosted Ag Pb Zn 0.06 (Tischendorf 1966) Bashilbelsk Unspecified Polymetallic 0.16 (Martiro syan and Babayeva 1974) Berggiesshübel Skarn Fe 2.20 (Tischendorf 1966) Berggiesshübel Skarn Fe 2.20 (Tischendorf 1966) Bleischarley Mississippi Valley Pv Zn 0.09 (Goldschmidt and Strock 1935) Bleischarley Mississippi Valley Pv Zn 1.55 (Tischendorf 1966) Bloomsbury Unspecified 0.99 (Edwards and Carlos 1954) Bottle Creek Epithermal Hg 27.35 (Coleman and Delevaux 1957) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 1.30 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.28 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.11 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.52 (Tischendorf 1966) Breitenbrunn Skarn 5.30 (Tischendorf 1966) Breitenbrunn Skarn 3.56 (Tischendorf 1966) Breitenbrunn Skarn 1.29 (Tischendorf 1966) Breitenbrunn Skarn 5.12 (Tischendorf 1966) Breitenbrunn Skarn 2.63 (Tischendorf 1966) Breitenbrunn Skarn 2.93 (Tischendorf 1966) Broken Hill SEDEX Pb Zn 0.14 (Edwards and Carlos 1954) Broken Hill SEDEX Pb Zn 0.17 (Edwards and Carlos 1954) Broken Hill SEDEX Pb Zn 0.28 (Edwards and Carlos 1954) Broken Hill SEDEX Pb Zn 0.13 (Edwards and Carlos 1954) Bukuka-Belukha Vein W 0.52 (Sindeeva 1964) Burgstäder Zug Metasedimentary Hosted Ag Pb Zn 0.18 (Tischendorf 1966) Clausthal Metasedimentary Hosted Ag Pb Zn 0.06 (Tischendorf 1966) Clausthal Metasedimentary Hosted Ag Pb Zn 0.19 (Tischendorf 1966) Colorado Unspecified 2.80 (Desborough 1977) Coniagas VHMS 0.06 (Jonasson and Sangster 1983) Dastakert Porphyry Cu 0.76 (Sindeeva 1964) Engidzhinsk Unspecified Polymetallic 0.20 (Martirosyan and Babayeva 1974) Errington VHMS 0.40 (Jonasson and Sangster 1983) Europe Unspecified 0.06 (Tischendorf 1966) Flin Flon VHMS 4.62 (Jonasson and Sangster 1983) Fox Lake VHMS 9.82 (Jonasson and Sangster 1983) Freiberg Metasedimentary Hosted Ag Pb Zn 0.25 (Tischendorf 1966) Freiberg Metasedimentary Hosted Ag Pb Zn 0.42 (Tischendorf 1966) Freiberg Metasedimentary Hosted Ag Pb Zn 0.45 (Tischendorf 1966) Gai VHMS 0.85 (Yushko-Zakharova et al. 1978) Geco VHMS 0.61 (Cabri et al. 1985) Georgenthal Metasedimentary Hosted Ag Pb Zn 0.03 (Tischendorf 1966) Gyumushing Unspecified Pb Zn 0.01 (Martirosyan and Babayeva 1974) Hacket River Camp Lake VHMS? 0.61 (Jonasson and Sangster 1983) Halsbrücke Metasediment hosted vein Ag 0.43 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag Pb Zn 0.60 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag Pb Zn 0.25 (Tischendorf 1966) Hercules Mine VHMS 0.18 (Edwards and Carlos 1954) Hermsdorf Mississippi Valley Pb Zn 0.54 (Tischendorf 1966) High Lake VHMS 4.38 (Jonasson and Sangster 1983) III Internatsional Unspecified Cu 0.21 (Yushko-Zakharova et al. 1978) Japan Unspecified 0.06 (Tischendorf 1966) Joutel VHMS 12.52 (Jonasson and Sangster 1983) Kadzharan Porphyry Cu 1.43 (Ismailov 1964) Kafan Porphyry Cu 2.10 (Zaryan 1962) Kidd Creek VHMS 6.23 (Jonasson and Sangster 1983) Kovurmadarinsk Unspecified Pb Zn 0.12 (Martirosyan and Babayeva 1974) Kumyshakan Regional Mean 0.12 (Kulikova 1966) Lac Dufault VHMS 3.28 (Jonasson and Sangster 1983) Lake George Mines VHMS 0.93 (Edwards and Carlos 1954) Lauthenthal Metasedimentary Hosted Vein Ag Pb Zn 0.34 (Tischendorf 1966)

181

Deposit/Locatity (Sphalerite) Deposit/Geology Type Se/S Reference (*10-4) Lengefeld Unspecified 0.03 (Tischendorf 1966) Lengefeld Unspecified 0.50 (Tischendorf 1966) Lengefeld Unspecified 0.41 (Tischendorf 1966) Levikha XIV VHMS 0 (Yushko-Zakharova et al. 1978) Manitou-Barvue VHMS 0.67 (Jonasson and Sangster 1983) Mattabi VHMS 0.52 (Jonasson and Sangster 1983) Mattagami Lake Mines VHMS 6.11 (Jonasson and Sangster 1983) Mattagami Lake Mines VHMS 2.86 (Cabri et al. 1985) Mauk VHMS 4.80 (Yushko-Zakharova et al. 1978) Meggen SEDEX Pb Zn 0.34 (Tischendorf 1966) Mekhmanisk Unspecified Polymetallic 0.23 (Martirosyan and Babayeva 1974) Moravia & Silesia Unspecified 1.67 (Kvaek 1974) Mount Bischoff Replacement Sn 0.48 (Edwards and Carlos 1954) Mount Cleveland Mine Replacement Sn 0.55 (Edwards and Carlos 1954) Mount Isa SEDEX Pb Zn 0.03 (Edwards and Carlos 1954) Mount Lyell VHMS 0.17 (Edwards and Carlos 1954) Mount Lyell VHMS 0.27 (Edwards and Carlos 1954) Mount Lyell VHMS 0.94 (Edwards and Carlos 1954) Nanisivik Mississippi Valley Pb Zn 0.30 (Jonasson and Sangster 1983) Nanisivik Mississippi Valley Pb Zn 1.61 (Cabri et al. 1985) Nepal Unspecified 0.06 (Tischendorf 1966) Neves-Corvo VHMS 48.63 (Gaspar 2002) Neves-Corvo VHMS 48.63 (Gaspar 2002) New Calumet SEDEX Pb Zn 0.76 (Jonasson and Sangster 1983) New North Mount Farell Mine Unspecified Sn 0.24 (Edwards and Carlos 1954) New North Mount Farell Mine Unspecified Sn 1.82 (Edwards and Carlos 1954) Niederschlema Vein U 0.25 (Tischendorf 1966) Normetal VHMS 1.46 (Jonasson and Sangster 1983) Orchan VHMS 3.53 (Jonasson and Sangster 1983) Pfaffenberg Metasedimentary Hosted Ag Pb Zn 0.39 (Tischendorf 1966) Pfaffenberg Metasedimentary Hosted Ag Pb Zn 0.31 (Tischendorf 1966) Pfaffenberg Metasedimentary Hosted Ag Pb Zn 0.34 (Tischendorf 1966) Pöhla Skarn Sn 0.81 (Tischendorf 1966) Pöhla Skarn Sn 0.99 (Tischendorf 1966) Priorskoye VHMS 1.79 (Milovskiy et al. 1971) Protheroe Unspecified Pb Zn 0.15 (Edwards and Carlos 1954) Rammelsberg SEDEX Pb Zn 0.59 (Tischendorf 1966) Renison Bell Replacement Sn 0.36 (Edwards and Carlos 1954) Rosebery VHMS 0.44 (Edwards and Carlos 1954) Rosebery VHMS 0.36 (Edwards and Carlos 1954) Salida Low Sulphidation epithermal Au Ag 15.20 (Kieft and Oen 1973) Salida Low Sulphidation epithermal Au Ag 15.20 (Kieft and Oen 1973) Salida Low Sulphidation epithermal Au Ag 15.20 (Kieft and Oen 1973) Sarykan Skarn 0.06 (Kulikova 1966) Schau Unspecified Hydrothermal 0.03 (Tischendorf 1966) Schwarzenberg Skarn Pb Zn 1.57 (Tischendorf 1966) Schwarzenberg Skarn Pb Zn 1.35 (Tischendorf 1966) Shamlug Porphyry Cu 0.23 (Martirosyan and Babayeva 1974) Sibay VHMS 0.12 (Yushko-Zakharova et al. 1978) Sibay VHMS 0.15 (Yushko-Zakharova et al. 1978) Sibay VHMS 0.27 (Yushko-Zakharova et al. 1978) Sibay VHMS 0.37 (Yushko-Zakharova et al. 1978) Siptenfelde Metasedimentary Hosted Vein Ag Pb Zn 0.38 (Tischendorf 1966) Siptenfelde Metasedimentary Hosted Vein Ag Pb Zn 0.57 (Tischendorf 1966) Siptenfelde Metasedimentary Hosted Vein Ag Pb Zn 0.28 (Tischendorf 1966) Siptenfelde Metasedimentary Hosted Vein Ag Pb Zn 0.38 (Tischendorf 1966) Siptenfelde Metasedimentary Hosted Vein Ag Pb Zn 0.70 (Tischendorf 1966) Skellefte VHMS 13.75 (Bergenfelt 1953) Smolnik Cu district 17.29 (Baban and Iiavsk 1966) Solotusinsk Unspecifed 1.70 (Tischendorf 1966)

182

Deposit/Locatity (Sphalerite) Deposit/Geology Type Se/S Reference (*10-4) Solotusinsk Unspecifed 0.79 (Tischendorf 1966) Soviet Union Co-As deposits Arsenide Co Ag Veins 1.09 (Tischendorf 1966) Sparnberg Skarn 0.92 (Tischendorf 1966) Sparnberg Skarn 1.33 (Tischendorf 1966) St Wolfgamg am Hinterhennenberg Skarn 2.27 (Tischendorf 1966) Tannenglasbachsthal Unspecified Hydrothermal 0.57 (Tischendorf 1966) Tannenglasbachsthal Unspecified Hydrothermal 0.43 (Tischendorf 1966) Tannenglasbachsthal Unspecified Hydrothermal 1.77 (Tischendorf 1966) Tetreault VHMS 1.34 (Jonasson and Sangster 1983) U. West. Australia Collection Unspecified 0.02 (Michael and White 1976) USGS Collection Unspecified 0.18 (Michael and White 1976) Vulcano Unspecified 12.16 (Noddack 1936) Waratah District Skarn Pb Zn 0.42 (Edwards and Carlos 1954) Waratah District Skarn Pb Zn 0.30 (Edwards and Carlos 1954) Webb’s Consols Metasedimentary Hosted Ag Pb Zn 0.09 (Edwards and Carlos 1954) Weitisberga Skarn 1.00 (Tischendorf 1966) West Macdonald VHMS 0.02 (Jonasson and Sangster 1983) Westland Unspecified 0.24 (Wells 1966) Wiesloch Metasedimentary Hosted Ag Pb Zn 1.26 (Tischendorf 1966) Yuzhnoye, Dzerzhinskoye VHMS 0.49 (Yushko-Zakharova et al. 1978) Zeehan Metasedimentary Hosted Ag Pb Zn 0.64 (Edwards and Carlos 1954) Zinnwald/Cinovec Vein Sn 2.04 (Tischendorf 1966) Zinnwald/Cinovec Vein Sn 1.75 (Tischendorf 1966) Zirabulak group Skarn W 1.37 (Ismailov 1964)

Galena

Deposit/Locality (Galena) Deposit/Geology type Se/S Reference (*10-4) Agdarinsk Unspecified Pb Zn 0.08 (Martirosyan and Babayeva 1974) Akhtalsk Unspecified Polymetallic 0.11 (Martirosyan and Babayeva 1974) Almalyk Porphyry Cu 1.12 (Tischendorf 1966) Almalyk Porphyry Cu 16.98 (Tischendorf 1966) Almalyk Porphyry Cu 0.37 (Tischendorf 1966) Altay ore district Unspecified 29.32 (Tischendorf 1966) Altayskiy Kray Regional Mean 5969.35 (Aksenov et al. 1968) Altin-Topkansk Unspecified Pb Zn 14.40 (Tischendorf 1966) Altin-Topkansk Unspecified Pb Zn 35.18 (Tischendorf 1966) Antonsthal Metasediment hosted vein Ag Pb Zn 0.45 (Tischendorf 1966) Austria Unspecified 149.23 (Rockenbauer 1960) Azerbaidzhan Regional Mean 3.32 (Berrow and Ure 1989) Bad Grund Metasedimentary Ag Pb Zn 0.06 (Goldschmidt and Strock 1935) Bad Grund Metasedimentary Ag Pb Zn 0.06 (Tischendorf 1966) Bashilbelsk Unspecified Polymetallic 0.06 (Martirosyan and Babayeva 1974) Bear Creek Mine Sandstone U 11764.71 (Coleman and Delevaux 1957) Berikul’skiy Skarn Fe 3.51 (Vakhrushev and Dorosh 1966) Biwender Gangzug Metasediment hosted vein Ag Pb Zn 9.00 (Tischendorf 1966) Bleischarley Mississippi Valley Pb Zn 0.13 (Goldschmidt and Strock 1935) Boliden Mine VHMS 932.71 (Bergenfelt 1953) Borieva Skarn Pb Zn 1.79 (Tischendorf 1966) Borieva Skarn Pb Zn 0.37 (Tischendorf 1966) Borieva Skarn Pb Zn 5.67 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.15 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.51 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.15 (Tischendorf 1966)

183

Deposit/Locality (Galena) Deposit/Geology type Se/S Reference (*10-4) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.05 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.44 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.21 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.28 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.29 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.53 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.04 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.06 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.30 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.04 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.04 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.04 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.04 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.06 (Tischendorf 1966) Brand-Erbisdorf Metasediment hosted vein Ag Pb Zn 0.05 (Tischendorf 1966) Broken Hill SEDEX Pb Zn 0.05 (Edwards and Carlos 1954) Broken Hill SEDEX Pb Zn 0.15 (Edwards and Carlos 1954) Bukuka-Belukha Vein W 8.66 (Sindeeva 1964) Bytom Mississippi Valley Pb Zn 0.24 (Tischendorf 1966) ChalAta Unspecified Pb Zn 3.51 (Tischendorf 1966) Chibina Unspecified Pegmatite 70.89 (Tischendorf 1966) Clausthal Metasediment hosted vein Ag Pb Zn 0.04 (Tischendorf 1966) Clausthal Metasediment hosted vein Ag Pb Zn 0.07 (Tischendorf 1966) Clausthal Metasediment hosted vein Ag Pb Zn 0.14 (Tischendorf 1966) Colorado Unspecified 3.66 (Desborough et al. 1976) Coniagas VHMS 0.82 (Jonasson and Sangster 1975) Darwin SEDEX Pb Zn 9.309 (Czamanske and Hall 1975) Darwin SEDEX Pb Zn 116.186 (Czamanske and Hall 1975) Darwin SEDEX Pb Zn 6362.58 (Czamanske and Hall 1975) Dastakert Porphyry Cu 4.25 (Sindeeva 1964) Dzhilau Skarn Cu 10819.44 (Tischendorf 1966) Engidzhinsk Unspecified Polymetallic 0.07 (Martirosyan and Babayeva 1974) Freiberg Metasediment hosted vein Ag Pb Zn 1.41 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 2.19 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 1.01 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 1.10 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 10.96 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 8.90 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 13.96 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 3.90 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 6.91 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 6.07 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 1.75 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 3.71 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 2.06 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 6.22 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 2.59 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 6.96 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 5.45 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 2.30 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 2.34 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 1.89 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 0.26 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 0.62 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 1.24 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 1.28 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 2.04 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 1.11 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 0.95 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 23.94 (Tischendorf 1966)

184

Deposit/Locality (Galena) Deposit/Geology type Se/S Reference (*10-4) Freiberg Metasediment hosted vein Ag Pb Zn 7.83 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 4.81 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 4.44 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 3.94 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 6.38 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 3.63 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 6.42 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 11.11 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 3.16 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 3.50 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 2.54 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 2.21 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 1.85 (Tischendorf 1966) Freiberg Metasediment hosted vein Ag Pb Zn 0.22 (Tischendorf 1966) Freital-Döhlen Unspecified hydrothermal 0.17 (Tischendorf 1966) Gai VHMS 2.24 (Yushko-Zakharova et al. 1978) Garfield mine Sandstone U 6461.82 (Coleman and Delevaux 1957) Garfield mine Sandstone U 6043.96 (Coleman and Delevaux 1957) Garfield mine Sandstone U 5290.33 (Coleman and Delevaux 1957) Geco VHMS 54.47 (Jonasson and Sangster 1983) Gyumushing Unspecified Pb Zn 0.11 (Martirosyan and Babayeva 1974) Halsbrücke Metasediment hosted vein Ag Pb Zn 0.10 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag Pb Zn 0.22 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag Pb Zn 13.08 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag Pb Zn 0.22 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag Pb Zn 0.22 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag Pb Zn 0.45 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag Pb Zn 0.90 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag Pb Zn 0.23 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag Pb Zn 0.79 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag Pb Zn 0.22 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag Pb Zn 0.22 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag Pb Zn 0.53 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag Pb Zn 0.03 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag Pb Zn 0.07 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag Pb Zn 0.07 (Tischendorf 1966) Halsbrücke Metasediment hosted vein Ag Pb Zn 88.24 (Tischendorf 1966) Henneberg Mississippi Valley Pb Zn 3.36 (Tischendorf 1966) Hermsdorf Mississippi Valley Pb Zn 1.86 (Tischendorf 1966) Hermsdorf Mississippi Valley Pb Zn 2.62 (Tischendorf 1966) Hermsdorf Mississippi Valley Pb Zn 0.08 (Tischendorf 1966) Hermsdorf Mississippi Valley Pb Zn 2.65 (Tischendorf 1966) Jervois Range Unspecified Polymetallic 0.10 (Edwards and Carlos 1954) Kadzharan Porphyry Cu 3.28 (Faramazyan and Zaryan 1973) Kadzharan Porphyry Cu 2.171 (Faramazyan and Zaryan 1973) Karamazar Low sulphidation epithermal Au Ag 2.01 (Tischendorf 1966) Kidd Creek VHMS 34.32 (Cabri et al. 1985) Kongsberg Unspecified Ag 1223.24 (Tischendorf 1966) Kovurmadarinsk Unspecified Pb Zn 0.07 (Martirosyan and Babayeva 1974) Kumyshakan Regional Mean 3.06 (Kulikova 1966) Lake George Mines VHMS 0.10 (Edwards and Carlos 1954) Lengefeld Unspecified 16.78 (Tischendorf 1966) Manitou-Barvue VHMS 5.07 (Jonasson and Sangster 1983) Mansfeld Sediment Hosted Cu 0.07 (Tischendorf 1966) Mechernich Metasediment hosted vein Ag Pb Zn 0.08 (Tischendorf 1966) Meiseberg Metasediment hosted vein Ag Pb Zn 1.19 (Tischendorf 1966) Mekhmanisk Unspecified Polymetallic 0.06 (Martirosyan and Babayeva 1974) Mishikol Unspecified Pb Zn 8.95 (Tischendorf 1966) Moravia & Silesia Unspecified 130.58 (Berrow and Ure 1989) Mount Farell Metasediment hosted vein Ag Pb Zn 0.15 (Edwards and Carlos 1954)

185

Deposit/Locality (Galena) Deposit/Geology type Se/S Reference (*10-4) Mount Isa SEDEX Pb Zn 0.05 (Edwards and Carlos 1954) Mount Lyell VHMS 0.71 (Edwards and Carlos 1954) Murgul Sediment Hosted Cu 729.45 (Willgallis et al. 1990) Nelson Unspecified 0.69 (Wells 1966) Neudorf Metasediment hosted vein Ag Pb Zn 0.36 (Tischendorf 1966) Neudorf Metasediment hosted vein Ag Pb Zn 0.14 (Tischendorf 1966) Neudorf Metasediment hosted vein Ag Pb Zn 1.61 (Tischendorf 1966) Neves-Corvo VHMS 8.208 (Gaspar 2002) Neves-Corvo VHMS 0 (Gaspar 2002) Olkuc Mississippi Valley Pb Zn 0.37 (Tischendorf 1966) Perevalnoe Unspecified Polymetallic 37.23 (Tischendorf 1966) Pfaffenberg Metasediment hosted vein Ag Pb Zn 5.32 (Tischendorf 1966) Pfaffenberg Metasediment hosted vein Ag Pb Zn 11.33 (Tischendorf 1966) Pfaffenberg Metasediment hosted vein Ag Pb Zn 3.54 (Tischendorf 1966) Pfaffenberg Metasediment hosted vein Ag Pb Zn 0.93 (Tischendorf 1966) Pfaffenberg Metasediment hosted vein Ag Pb Zn 0.61 (Tischendorf 1966) Protheroe Unspecified Pb Zn 0.10 (Edwards and Carlos 1954) Rammelsberg SEDEX Pb Zn 0.24 (Tischendorf 1966) Ridder-sokol VHMS 26.71 (Ivanov and Yushko-Zakharova 1977) Rifle mine Sandstone U 8804.79 (Coleman and Delevaux 1957) Rosebery VHMS 0.66 (Edwards and Carlos 1954) Russia Unspecified 4.10 (Ivanov and Yushko-Zakharova 1977) Russia MVT Mississippi Valley Type 0.22 (Ivanov and Yushko-Zakharova 1977) Russia Pb-Zn Unspecified Pb-Zn 2.61 (Ivanov and Yushko-Zakharova 1977) Russia Pb Zn Skarn Skarn 9.25 (Ivanov and Yushko-Zakharova 1977) Russia pyritic gal-sph-cpy Unspecified polymetallic 41.04 (Ivanov and Yushko-Zakharova 1977) Russia SEDEX SEDEX 2.09 (Ivanov and Yushko-Zakharova 1977) Sadon Metasedimentary Hosted Ag Pb Zn 19.40 (Berrow and Ure 1989) Salida Low Sulphidation Epithermal Au Ag 37.31 (Kieft and Oen 1973) Salida Low Sulphidation Epithermal Au Ag 111.93 (Kieft and Oen 1973) Salida Low Sulphidation Epithermal Au Ag 37.31 (Kieft and Oen 1973) Salida Low Sulphidation Epithermal Au Ag 261.16 (Kieft and Oen 1973) Sarykan Skarn Pb Zn 3.36 (Kulikova 1966) Schleifensteinal Metasediment hosted vein Ag Pb Zn 0.16 (Tischendorf 1966) Schneeberg Metasediment hosted vein Ag Pb Zn 0.15 (Tischendorf 1966) Schwarzenberg Skarn Pb Zn 0.71 (Tischendorf 1966) Shamlug Porphyry Cu 0.10 (Martirosyan and Babayeva 1974) Siptenfelde Metasediment hosted vein Ag Pb Zn 0.30 (Tischendorf 1966) Siptenfelde Metasediment hosted vein Ag Pb Zn 0.68 (Tischendorf 1966) Siptenfelde Metasediment hosted vein Ag Pb Zn 0.59 (Tischendorf 1966) Siptenfelde Metasediment hosted vein Ag Pb Zn 140.15 (Tischendorf 1966) Smolnik Unspecified Copper District 59.69 (Baban and Iiavsk 1966) Solotusinsk Unspecified Polymetallic 26.86 (Tischendorf 1966) Solotusinsk Unspecified Polymetallic 82.08 (Tischendorf 1966) Solotusinsk Unspecified Polymetallic 41.04 (Tischendorf 1966) Solotusinsk Unspecified Polymetallic 264.89 (Tischendorf 1966) Spain Unspecified 0.22 (Tischendorf 1966) Tannenglasbachsthal Unspecified Hydrothermal 1.20 (Tischendorf 1966) Tannenglasbachsthal Unspecified Hydrothermal 3.27 (Tischendorf 1966) Tannenglasbachsthal Unspecified Hydrothermal 1.29 (Tischendorf 1966) Tannenglasbachsthal Unspecified Hydrothermal 3.58 (Tischendorf 1966) Tashbulak Unspeciifed Pb Zn 21.37 (Tischendorf 1966) Tashtagol Skarn Fe 0.30 (Vakhrushev and Dorosh 1966) Tom SEDEX Pb Zn 0.15 (Jonasson and Sangster 1983) Tsentral’noye Low Sulphidation epithermal Au Ag 2.01 (Vakhrushev and Dorosh 1966) U. Western Australia Collection Unspecified 0.08 (Michael and White 1976) U. Western Australia Collection Unspecified 6.42 (Michael and White 1976) xUSGS Collection Unspecified 32.31 (Michael and White 1976) Yerranderie Low Sulphidation Epithermal Au Ag 0.05 (Edwards and Carlos 1954) Yuzhnoye, Dzerzhinskoye VHMS 0.04 (Yushko-Zakharova et al. 1978)

186

Deposit/Locality (Galena) Deposit/Geology type Se/S Reference (*10-4) Zolotushinsk VHMS 55.14 (Ivanov and Yushko-Zakharova 1977) Zyryanovsk Sediment Hosted Cu 4.03 (Ivanov and Yushko-Zakharova 1977)

Pyrrhotite

Se/S Deposit/Locality (Pyrrhotite) Deposit/Geology Type Reference (*10-4) Aldermac VHMS 1.90 (Hawley and Nichol 1959) Alexo Komatitic Ni Cu 0.44 (Hawley and Nichol 1959) Altay Ore District Unspecified 0.59 (Tischendorf 1966) Austria Unspecified 0.13 (Rockenbauer 1960) Beloretsk Skarn Fe 0.18 (Vakhrushev and Dorosh 1966) Bodenmais Metasediment hosted vein Ag-Pb-Zn 0.13 (Rockenbauer 1960) Boliden Mine VHMS 1.16 (Bergenfelt 1953) Brand-Erbisdorf Metasediment hosted vein Ag-Pb-Zn 1.21 (Tischendorf 1966) Breitenbrunn Skarn 2.34 (Tischendorf 1966) Breitenbrunn Skarn 2.68 (Tischendorf 1966) Breitenbrunn Skarn 2.47 (Tischendorf 1966) Broken Hill SEDEX Pb-Zn 0.03 (Edwards and Carlos 1954) Broken Hill SEDEX Pb-Zn 0.87 (Edwards and Carlos 1954) Broken Hill SEDEX Pb-Zn 1.03 (Edwards and Carlos 1954) Bukuka-Belukha Vein W 0.33 (Sindeeva 1964) Copper Rand/Portage Vein Cu 0.56 (Hawley and Nichol 1959) Copper Rand/Portage Vein Cu 1.03 (Hawley and Nichol 1959) Copper Rand/Portage Vein Cu 1.69 (Hawley and Nichol 1959) Copper Rand/Portage Vein Cu 0.18 (Hawley and Nichol 1959) Cowarra Low sulphidation epithermal Au-Ag 0.83 (Edwards and Carlos 1954) Discovery-Yellowknife Unspecified Au 0.67 (Hawley and Nichol 1959) Ducktown VHMS 0.13 (Williams and Byers 1934) Dzhilau Skarn Cu 6.93 (Sindeeva 1964) Eldorado Quartz Pebble Conglomerate U 0.18 (Hawley and Nichol 1959) Fecunis Lake Astrobleme Associated Ni Cu 1.36 (Hawley and Nichol 1959) Fichtenhübel Skarn Fe 0.85 (Tischendorf 1966) Flin Flon VHMS 9.63 (Hawley and Nichol 1959) Geco VHMS 3.85 (Hawley and Nichol 1959) Geco VHMS 4.11 (Hawley and Nichol 1959) Geco VHMS 4.62 (Hawley and Nichol 1959) Great Cobar Unspecified Cu Deposit 0.13 (Edwards and Carlos 1954) Heath Steele VHMS 0.54 (Hawley and Nichol 1959) Hollinger Homestake Au 0.77 (Hawley and Nichol 1959) Horne VHMS 2.49 (Hawley and Nichol 1959) Horne VHMS 2.57 (Hawley and Nichol 1959) Horne VHMS 9.63 (Hawley and Nichol 1959) Horne VHMS 3.06 (Hawley and Nichol 1959) Inya Skarn Fe 0.72 (Vakhrushev and Dorosh 1966) Irbin Skarn Fe 0.49 (Vakhrushev and Dorosh 1966) Japan Unspecified 0.03 (Tischendorf 1966) Kiev Regional Mean 0.33 (Tokarev and Yashchenko 1968) Kola Peninsula Regional Mean 0.72 (Zainullen 1960) Kola Peninsula Regional Average 0.90 (Berrow and Ure 1989) Kola Peninsula Regional Mean 0.90 (Berrow and Ure 1989) Kusa Bushveld Fe Ti V 0.77 (Ivanov and Yushko-Zakharova 1977) Kutna Hora Metasediment hosted vein Ag-Pb-Zn 0.04 (Tischendorf 1966) Mauk VHMS 3.34 (Yushko-Zakharova et al. 1978) Monchegorsk Unspecified 0.72 (Tischendorf 1966) Moravia & Silesia Unspecified 1.18 (Berrow and Ure 1989)

187

Se/S Deposit/Locality (Pyrrhotite) Deposit/Geology Type Reference (*10-4) Mount Bischoff Replacement Sn 0.46 (Edwards and Carlos 1954) Mount Cleveland Mine Replacement Sn 0.64 (Edwards and Carlos 1954) Mount Isa SEDEX Pb-Zn 0.03 (Edwards and Carlos 1954) Mount Isa SEDEX Pb -Zn 0.04 (Edwards and Carlos 1954) Mount Isa SEDEX Pb-Zn 0.91 (Edwards and Carlos 1954) Mount Lindsay Mine Replacement Sn 1.18 (Edwards and Carlos 1954) Norilsk Norilsk Cu Ni PGE 1.31 (Zainullen 1960) Norilsk Norilsk Cu Ni PGE 2.26 (Tischendorf 1966) Norilsk Norilsk Cu Ni PGE 1.87 (Tischendorf 1966) Norilsk Norilsk Cu Ni PGE 1.31 (Tischendorf 1966) Norilsk Norilsk Cu Ni PGE 0.31 (Tischendorf 1966) Normetal VHMS 3.18 (Hawley and Nichol 1959) Nuratinsk group Skarn W 1.71 (Ismailov 1964) Odinochnoye Skarn Fe 0.08 (Vakhrushev and Dorosh 1966) Pechenga Komatitic Ni Cu 0.77 (Ivanov and Yushko-Zakharova 1977) Pechenga Komatitic Ni Cu 0.95 (Tischendorf 1966) Priorskoye VHMS 6.57 (Milovskiy et al. 1971) Quemont VHMS 5.21 (Hawley and Nichol 1959) Rand No. 2 Algoma Type Fe Formation 0.18 (Hawley and Nichol 1959) Renison Bell Replacement Sn 0.88 (Edwards and Carlos 1954) Renison Bell Replacement Sn 0.33 (Edwards and Carlos 1954) Rosebery VHMS 0.36 (Edwards and Carlos 1954) Russia Cu Ni sulphide Deposits Unspecified Cu Ni deposit 1.28 (Ivanov and Yushko-Zakharova 1977) Shalym Skarn Fe 0.39 (Vakhrushev and Dorosh 1966) Sheregeshev Skarn Fe 1.03 (Vakhrushev and Dorosh 1966) Sibay VHMS 2.13 (Yushko-Zakharova et al. 1978) Sinyukha Skarn Cu 0.21 (Vakhrushev and Dorosh 1966) Siptenfelde Metasediment hosted vein Ag-Pb-Zn 0.46 (Tischendorf 1966) Skellefte VHMS 0.77 (Bergenfelt 1953) South German Mine Low sulphidation epithermal Au-Ag 0.70 (Edwards and Carlos 1954) Soviet Union Co-As deposits Unspecified Co-As Deposits 0.39 (Tischendorf 1966) Sparnberg Skarn 1.32 (Tischendorf 1966) Sparnberg Skarn 1.64 (Tischendorf 1966) Sparnberg Skarn 0.44 (Tischendorf 1966) Sudbury Astrobleme Associated Ni Cu 1.39 (Hawley and Nichol 1959) Sudbury Astrobleme Associated Ni Cu 1.62 (Hawley and Nichol 1959) Sudbury Astrobleme Associated Ni Cu 1.85 (Hawley and Nichol 1959) Sudbury Astrobleme Associated Ni Cu 0.95 (Tischendorf 1966) Sudbury Astrobleme Associated Ni Cu 2.57 (Rockenbauer 1960) Sudbury Astrobleme Associated Ni Cu 1.87 (Cabri et al. 1984) Sudbury Astrobleme Associated Ni Cu 2.82 (Cabri et al. 1984) Talnakh Magmatic Ni Cu PGE 1.80 (Ivanov and Yushko-Zakharova 1977) Tisova Stratiform Cu Deposit 0.99 (Tischendorf 1966) Tisova Stratiform Cu Deposit 0.98 (Tischendorf 1966) Tisova Stratiform Cu Deposit 0.93 (Tischendorf 1966) Tisova Stratiform Cu Deposit 1.49 (Tischendorf 1966) Trepca Unspecified Hydrothermal 0.26 (Tischendorf 1966) Tsentral’noye Low Sulphidation epithermal Au Ag 0.08 (Vakhrushev and Dorosh 1966) U. Western Australia Collection Unspecified 1.57 (Michael and White 1976) Zirabulak group Skarn W 0.56 (Ismailov 1964)

188