Low Temperature Aqueous Solubility of Fluorite at Temperatures of 5, 25, and 50 Oc and Ionic Strengths up to 0.72M

LOW TEMPERATURE AQUEOUS SOLUBILITY OF FLUORITE AT TEMPERATURES OF 5, 25, AND 50 OC AND IONIC STRENGTHS UP TO 0.72M

Richard L. Henry A thesis submitted to the Faculty and Board of Trustees of the Colorado School of Mines

in partial fulfillment of the requirement for the degree of Doctor of Philosophy

(Geochemistry)

Golden, Colorado

Date ______

Signed: ______

Richard L. Henry

Signed: ______

Dr. Wendy J. Harrison Thesis Advisor

Golden, Colorado

Date ______

Signed: ______

Dr. M. Stephen Enders Professor and Head Department of Geology and Geological Engineering

ii ABSTRACT

Historical fluorite solubility research found that fluorite solubilities varied over three orders-of-magnitude and appear to be inconsistent with several recently determined fluorite solubilities. This research involved a comprehensive series of solubility experiments run over a period of three years using nine natural fluorites and one synthetic fluorite to determine their solubility in low temperature (5, 25, and 50oC) aqueous solutions and ionic strengths ranging from near zero to 0.72M. Equilibrium was approached from both undersaturated and supersaturated initial conditions. The fluorites were chemically and physically characterized using laboratory analyses, thin section petrography, UV fluorescence, and x-ray diffraction. The fluorite samples were generally found to have similar chemical and physical properties. The chemical composition was approximately stoichiometric, with a mean calcium concentration of 51.6 ± 0.6 wt % and mean fluorine concentration of 50.2 ± 0.7 wt %. Fluorite unit cell edge lengths, volumes, and densities averaged 5.4630 ± 0.0007 Å, 163.04 ± 0.06 Å3, and 3.181 ± 0.009 g/cm3, respectively. No pattern in the solubility measurements were correlated with the trace elements in the fluorites.

The fluorite solubility results showed that fluorite dissolved congruently and increased in solubility with both temperature and ionic strength. The fluorite solubilities determined were relatively consistent, with median log Ksp values that ranged from -10.81 ± 0.02 at 5oC, -10.63 ± 0.02 at 25oC, and -10.49 ± 0.03 at 50oC. An internally consistent set of fluorite thermodynamic data were determined from the log Ksp results which yielded a .of -1,177.7 ± 0.2 kJ/mol, ଴ of -1,226.9 ± 1.1 kJ/mol, and of 76.0 ± 3.7 J/mol*K. However,οܩ௙ the third law entropy ଴ ଴ o valueοܪ௙ determined for this study wasܵ ௙about 9% higher than the reported value S of 68.9 ± 0.3 J/mol*K. This discrepancy in entropy values likely results from the range in log Ksp values determined for the fluorites during this study. This study’s results resolve the uncertainty in past work and provides an optimal solubility dataset for fluorite going forward.

iii ACKNOWLEDGEMENTS

I would like to thank my advisor, Dr. Wendy Harrison, for her dedication, knowledge, guidance, and continued support of this long-running project. I would also like to thank Dr. Richard Wendlendt, Dr. Craig Simmons, and Dr. Richard Wanty (U.S. Geological Survey) for serving on my dissertation committee and for their knowledge, insight, and guidance. Thanks also to Dr. Maynard Slaughter who unexpectedly passed away before this research was completed.

Thanks is also extended to my employer, URS/AECOM, for providing educational benefits to support my degree program.

Much gratitude is due to my family and friends for all their love, support, and friendship through the years which helped make completing this project possible. In particular, many thanks to my mom, Winona Eastin, for always encouraging me to be curious, ask questions, and to continue learning throughout life.

And last, but most importantly, special thanks to my wife, Barbara Vance, for her love, encouragement, and patience throughout the years while I pursued this “hobby” and completed this dissertation. It certainly could not have been finished without her unwavering support.

iv TABLE OF CONTENTS

ABSTRACT ...... iii

ACKNOWLEDGEMENTS ...... iv

LIST OF TABLES ...... vii

LIST OF FIGURES ...... ix

CHAPTER 1 INTRODUCTION ...... 1

1.1 Purpose and Objectives ...... 1

1.2 Previous Work ...... 2

1.3 Historical Fluorite Solubility Summary ...... 12

1.4 Equilibrium Fluorite Solubility...... 12

CHAPTER 2 MATERIALS AND METHODS 18

2.1 Materials ...... 18

2.2 Methods ...... 18

2.2.1 Solubility Procedure ...... 18

2.2.2 Undersaturated Fluorite Solutions ...... 23

2.2.4 Fluoride Analyses ...... 24

2.2.5 Calcium Analyses ...... 25

2.2.6 Petrographic Thin Sections ...... 25

2.2.5 Ultraviolet Fluorescence ...... 26

2.2.6 Powder X-Ray Diffraction ...... 26

2.2.7 Fluorite Composition...... 26

CHAPTER 3 RESULTS AND DISCUSSION 28

3.1 Results ...... 28

3.1.1 Fluorite Petrography ...... 28 v 3.1.2 XRD Results ...... 28

3.1.3 Fluorite Density ...... 33

3.1.4 UV Fluorescence and Phosphorescence ...... 35

3.1.5 Fluorite Composition...... 35

3.1.6 Fluorite Trace Element Composition ...... 35

3.2 Fluorite Solubility Results ...... 40

3.3 Discussion...... 57

3.3.1 Temperature Dependence of Fluorite Solubility ...... 57

3.3.2 Ionic Strength Dependence of Fluorite Solubility ...... 58

3.3.3 Fluorite Thermodynamic Parameters ...... 60

3.3.4 Fluorite Activity Coefficients ...... 63

CHAPTER 4 GEOCHEMICAL APPLICATIONS 66

4.1 Fluorite Log Ksp in Geochemical Model Databases ...... 66

4.2 Fluorite Activity Diagrams ...... 66

4.3 Fluorite Saturation in Indian Groundwaters ...... 70

4.4 Fluorite Saturation in Colorado Surface Waters ...... 72

4.5 Fluorite Saturation in Groundwater at West Chicago Site ...... 74

CHAPTER 5 CONCLUSIONS ...... 77

REFERENCES ...... 79

APPENDIX A X-RAY DIFFRACTION RESULTS ...... 91

APPENDIX B LABORATORY ANALYTICAL RESULTS ...... 122

APPENDIX C PHREEQC INPUT FILES ...... 147

APPENDIX D LOG KSP CALCULATIONS ...... 172

vi LIST OF TABLES

Table 1-1 Solubility of fluorite in water at low temperature (< 50oC), ionic strength < 0.01M, and atmospheric pressure...... 3

Table 1-2 Solubility of fluorite in salt solutions at low temperature (50oC or Less), ionic strength > 0.1M, and atmospheric pressure...... 6

Table 2-1 Source and description of fluorites used in this study...... 19

Table 2-2 pH and ionic strengths of potassium chloride solutions used in this study...... 22

Table 3-1 Calculated fluorite unit cell length, volume, and density...... 34

Table 3-2 Summary of fluorescence, phosphorescence, and X-radiation effects...... 36

Table 3-3 Fluorite calcium and fluoride compositions (weight percent) ...... 37

Table 3-4 Fluorite trace element concentrations (mg/g)...... 38

Table 3-5 Summary of log Ksp results at infinite dilution at temperatures of 5, 25, and 50oC and 1 atm pressure...... 55

Table 3-6 Fluorite thermodynamic parameters determined in this study at 25oC...... 63

Table 3-7 Derived and estimated fluorite total ion activity coefficients at 25oC...... 64

Table 4-1 Comparison of log Ksp values in geochemical models with log Ksp values determined in this study...... 67

Table A- 1 BCP CrystalSleuth unit cell refinement output...... 112

Table A-2 BCW CrystalSleuth unit cell refinement output...... 113

Table A-3 CH CrystalSleuth unit cell refinement output...... 114

Table A-4 IY CrystalSleuth unit cell refinement output...... 115

Table A-5 MP CrystalSleuth unit cell refinement output...... 116

Table A-6 MX CrystalSleuth unit cell refinement output...... 117

vii Table A-7 NGB CrystalSleuth unit cell refinement output...... 118

Table A-8 NGY CrystalSleuth unit cell refinement output...... 119

Table A-9 SPD CrystalSleuth unit cell refinement output...... 120

Table A-10 SY CrystalSleuth unit cell refinement output...... 121

Table B-1 Laboratory analytical results for this study ...... 123

Table C-1 PHREEQC input file for historical literature solubility data...... 148

Table C-2 PHREEQC input file for this study’s solubility data...... 158

Table D-1 Summary of this study's log Ksp* minimum, maximum, median, and mean values...... 173

viii LIST OF FIGURES

Figure 1-1 Historical log Ksp data for fluorite solubility in water at temperatures of 0 to 50oC and ionic strengths less than 0.01M...... 13

Figure 1-2 Box and whiskers plots of historical fluorite log Ksp data in water at temperatures of 0 to 50oC and ionic strengths less than 0.01M...... 14

o Figure 1-3 Determination of synthetic fluorite log Ksp at 25 C and I =0 (infinite dilution) using data of Garand and Mucci (2004)...... 17

Figure 2-1 Photographs of fluorite samples used in this study’s experiments (a) Browns Canyon Porcelain, (b) Browns Canyon White, (c) China Green, and (d) Illinois Yellow...... 20

Figure 2-2 Photographs of fluorite samples used in this study’s experiments (a) Mexican Purple (MP, (b) Mexican Lilac (MX), (c) Northgate Blue (NGB), (d) Northgate Yellow (NGY)...... 21

Figure 2-3 Photographs of fluorite samples used in this study’s experiments (a) St. Peter’s Dome (SPD), (b) Synthetic (SY)...... 22

Figure 2-4 Example fluoride ISE calibration curve for 0.3 M KCl solution at 25oC...... 24

Figure 3-1 Photomicrographs of fluorite sample thin sections in plain light (a) Browns Canyon Porcelain (BCP), (b) Browns Canyon White (BCW), (c) China Green (CH), and (d) Illinois Yellow (IY). Field of view is 2.3 mm...... 29

Figure 3-2 Photomicrographs of fluorite sample thin sections in plain light (a) Mexican Purple (MP), (b) Mexican Lilac (MX), (c) Northgate Blue (NGB), (d) Northgate Yellow (NGY). Field of view is 2.3 mm...... 30

Figure 3-3 Photomicrograph of fluorite sample thin section in plain light (a) St. Peter’s Dome (SPD). Field of view is 2.3 mm...... 31

Figure 3-4 Indexed fluorite X-ray diffraction patterns with alumina standard (shown as black trace at bottom)...... 32

Figure 3-5 (a) Fluorite unit cell (b) plan view (Askeland and Wright 2015)...... 33

Figure 3-6 Fluoride-calcium concentration results for this study at temperatures of 5oC, 25oC, and 50oC and ionic strengths from near zero to 0.72M...... 41

Figure 3-7 Browns Canyon Porcelain (BCP) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (green triangle), and 50oC (red square)...... 42

ix Figure 3-8 Browns Canyon White (BCW) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (green triangle), and 50oC (red square)...... 43

Figure 3-9 Chinese Green (CH) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (green triangle), and 50oC (red square)...... 44

Figure 3-10 Illinois Yellow (IY) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (solid green triangle for undersaturated; open green triangle for supersaturated), and 50oC (red square)...... 45

Figure 3-11 Mexican Purple (MP) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (green triangle) and 50oC (red square)...... 46

Figure 3-12 Mexican Lilac (MX) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (solid green triangle for undersaturated; open green triangle for supersaturated), and 50oC (red square)...... 47

Figure 3-13 Northgate Blue (NGB) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (green triangle), and 50oC (red square)...... 48

Figure 3-14 Northgate Yellow (NGY) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (green triangle), and 50oC (red square)...... 49

Figure 3-15 St. Peter’s Dome (SPD) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (green triangle), and 50oC (red square)...... 50

Figure 3-16 Synthetic (SY) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (solid green triangle for undersaturated; open green triangle for supersaturated), and 50oC (red square)...... 51

Figure 3-17 Fluorite solubility log Ksp* (solid blue circles) versus ionic strength results at 5oC for all of the fluorite samples used in this study...... 52

Figure 3-18 Fluorite solubility log Ksp* (solid blue circles) versus ionic strength results at 25oC for all of the fluorite samples used in this study...... 53

Figure 3-19 Fluorite solubility log Ksp* (solid blue circles) versus ionic strength results at 50oC for all of the fluorite samples used in this study...... 54

Figure 3-20 Comparison of historical and this study’s log Ksp values...... 56

Figure 3-21 Log Ksp values at infinite dilution for samples used in this study versus temperature...... 58

Figure 3-22 Comparison of this study’s fluoride concentrations versus ionic strength at 25oC and 1 atm pressure (green triangle) with PHREEQC predicted fluoride concentrations and ionic strength (black diamond)...... 59

x Figure 3-23 Graph of log Ksp versus 1/T (K) for fluorites used in this study...... 61

Figure 3-24 Comparison of this study’s measured fluorite total ion activity coefficients at 25oC with calculated fluorite total ion activity coefficients using Debye-Huckel, PHREEQC (Truesdell Jones), and Davies activity models...... 65

Figure 4-1 F-Ca-T(oC) activity diagram at 1 atm pressure and log [F-] = 10-2, 10-3, and 10-4. .... 68

Figure 4-2 F-Ca-pH activity diagram at 25oC, 1 atm pressure, and log [F-] = 10-2, 10-3, and 10-4...... 69

Figure 4-3 Fluorite saturation in Indian groundwaters (data from Handa 1975)...... 71

Figure 4-4 Fluorite saturation in Colorado surface waters (data from Church et al. 2012)...... 73

Figure 4-5 Fluorite saturation in West Chicago groundwaters...... 76

Figure A-1 Full-scale XRD pattern for Browns Canyon Porcelain (BCP) fluorite...... 92

Figure A-2 Expanded scale XRD pattern for Browns Canyon Porcelain (BCP) fluorite...... 93

Figure A-3 Full-scale XRD pattern for Browns Canyon White (BCW) fluorite...... 94

Figure A-4 Expanded scale XRD pattern for Browns Canyon White (BCW) fluorite...... 95

Figure A-5 Full-scale XRD pattern for China Green (CH) fluorite...... 96

Figure A-6 Expanded scale XRD pattern for China Green (CH) fluorite...... 97

Figure A-7 Full-scale XRD pattern for Illinois Yellow (IY) fluorite...... 98

Figure A-8 Expanded scale XRD pattern for Illinois Yellow (IY) fluorite...... 99

Figure A-9 Full-scale XRD pattern for Mexican Purple (MP) fluorite...... 100

Figure A-10 Expanded scale XRD pattern for Mexican Purple (MP) fluorite...... 101

Figure A-11 Full-scale XRD pattern for Mexican Lilac (MX) fluorite...... 102

Figure A-12 Expanded scale XRD pattern for Mexican Lilac (MX) fluorite...... 103

Figure A-13 Full-scale XRD pattern for Northgate Blue (NGB) fluorite...... 104

xi Figure A-14 Expanded scale XRD pattern for Northgate Blue (NGB) fluorite...... 105

Figure A-15 Full-scale XRD pattern for Northgate Yellow (NGY) fluorite...... 106

Figure A-16 Expanded scale XRD pattern for Northgate Yellow (NGY) fluorite...... 107

Figure A-17 Full-scale XRD pattern for St. Peter’s Dome (SPD) fluorite...... 108

Figure A-18 Expanded scale XRD pattern for St. Peter’s Dome (SPD) fluorite...... 109

Figure A-19 Full-scale XRD pattern for Synthetic (SY) fluorite...... 110

Figure A-20 Expanded scale XRD pattern for Synthetic (SY) fluorite...... 111

Figure D- 1 Nonlinear curve fitting results for Browns Canyon Porcelain (BCP) fluorite at 5oC...... 178

Figure D-2 Nonlinear curve fitting results for Browns Canyon Porcelain (BCP) fluorite at 25oC...... 179

Figure D-3 Nonlinear curve fitting results for Browns Canyon Porcelain (BCP) fluorite at 50oC...... 180

Figure D-4 Nonlinear curve fitting results for Browns Canyon White (BCW) fluorite at 5oC...... 181

Figure D-5 Nonlinear curve fitting results for Browns Canyon White (BCW) fluorite at 25oC...... 182

Figure D-6 Nonlinear curve fitting results for Browns Canyon White (BCW) fluorite at 50oC...... 183

Figure D-7 Nonlinear curve fitting results for China Green (CH) fluorite at 5oC...... 184

Figure D-8 Nonlinear curve fitting results for China Green (CH) fluorite at 25oC...... 185

Figure D-9 Nonlinear curve fitting results for China Green (CH) fluorite at 50oC...... 186

Figure D-10 Nonlinear curve fitting results for Illinois Yellow (IY) fluorite at 5oC...... 187

Figure D-11 Nonlinear curve fitting results for Illinois Yellow (IY) fluorite at 25oC...... 188

xii Figure D-12 Nonlinear curve fitting results for Illinois Yellow (IY) fluorite at 50oC...... 189

Figure D-13 Nonlinear curve fitting results for Mexican Purple (MP) fluorite at 5oC...... 190

Figure D-14 Nonlinear curve fitting results for Mexican Purple (MP) fluorite at 25oC...... 191

Figure D-15 Nonlinear curve fitting results for Mexican Purple (MP) fluorite at 50oC...... 192

Figure D-16 Nonlinear curve fitting results for Mexican Lilac (MX) fluorite at 5oC...... 193

Figure D-17 Nonlinear curve fitting results for Mexican Lilac (MX) fluorite at 25oC...... 194

Figure D-18 Nonlinear curve fitting results for Mexican Lilac (MX) fluorite at 50oC...... 195

Figure D-19 Nonlinear curve fitting results for Northgate Blue (NGB) fluorite at 5oC...... 196

Figure D-20 Nonlinear curve fitting results for Northgate Blue (NGB) fluorite at 25oC...... 197

Figure D-21 Nonlinear curve fitting results for Northgate Blue (NGB) fluorite at 50oC...... 198

Figure D-22 Nonlinear curve fitting results for Northgate Yellow (NGY) fluorite at 5oC...... 199

Figure D-23 Nonlinear curve fitting results for Northgate Yellow (NGY) fluorite at 25oC...... 200

Figure D-24 Nonlinear curve fitting results for Northgate Yellow (NGY) fluorite at 50oC...... 201

Figure D-25 Nonlinear curve fitting results for St. Peter’s Dome (SPD) fluorite at 5oC...... 202

Figure D-26 Nonlinear curve fitting results for St. Peter’s Dome (SPD) fluorite at 25oC...... 203

Figure D-27 Nonlinear curve fitting results for St. Peter’s Dome (SPD) fluorite at 50oC...... 204

Figure D-28 Nonlinear curve fitting results for Synthetic (SY) fluorite at 5oC...... 205

Figure D-29 Nonlinear curve fitting results for Synthetic (SY) fluorite at 25oC...... 206

Figure D-30 Nonlinear curve fitting results for Synthetic (SY) fluorite at 50oC...... 207

xiii CHAPTER 1

INTRODUCTION

1.1 Purpose and Objectives

The occurrence and distribution of fluorite, a sparingly soluble ionic solid, in low temperature aqueous environments is largely controlled by its solubility which is the most important factor affecting its geochemical cycling within soil, surface water, groundwater, and seawater. The aqueous solubility of fluorite has been previously measured in numerous studies

(Table 1-1) and the determined equilibrium solubility product constants (Ksp) vary by up to three orders-of-magnitude (Table 1-1). The equilibrium solubility of fluorite in these experiments was usually measured by dissolution from an undersaturated state at atmospheric pressure. However, Garand and Mucci (2004) only performed single sample experiments. Only one of the studies (Garand and Mucci (2004) listed in Table 1-1 evaluated the equilibrium solubility of fluorite from both an undersaturated state and via crystallization from a supersaturated state.

Furthermore, natural fluorites, laboratory-precipitated calcium fluoride (CaF2), or calcium fluoride reagent used in these past studies were generally not physically or chemically characterized to determine if factors, such as grain size, crystallinity, and/or major, minor, and trace element composition, influenced the solubility results.

Nordstrom and Jenne (1977) stated that fluorite solubility can be affected by temperature, pressure, ionic strength, particle size, polymorphism, complexing capacity of the solution, and kinetic barriers. Fluorite’s solubility is also likely affected by its chemical composition and crystal lattice defects. The effects of polymorphism can be neglected in low temperature aqueous solutions because the crystalline alpha phase of fluorite is stable up to 1,151 degrees Centigrade (oC; Naylor, 1945).

The variability in fluorite’s aqueous solubility shown by previous studies (Tables 1-1 and 1-2) greatly influences the geochemical interpretation of low temperature, fluoride-bearing aqueous solutions. A literature review suggests that geochemical equilibrium modeling of some waters often predicts that they are supersaturated with respect to fluoride-bearing minerals, particularly fluorite. The predicted supersaturation may result from uncertainty in the fluorite Ksp 1 values used in these models and/or kinetically-limited precipitation (Nordstrom and Jenne, 1977;

Nordstrom and Ball, 1989). Fluorite Ksp values currently used in geochemical equilibrium models are not derived from a comprehensive study of fluorite solubility measurements, but are typically derived from a single Ksp measurement (e.g., PHREEQC) or extrapolated from historical thermodynamic data (e.g., EQ3/6).

This study provides the first comprehensive study of the low temperature aqueous solubility of fluorite at temperatures of 5, 25, and 50 oC and ionic strengths ranging from near zero to 0.72 moles per liter (M) at atmospheric pressure. The solubility experiments were performed using nine natural fluorites from various localities and a calcium fluoride reagent. Solubility equilibrium was approached from both undersaturated and supersaturated initial conditions. The fluorites and calcium fluoride reagent used in the experiments were also physically and chemically characterized.

1.2 Previous Work

Various researchers have measured the solubility of natural fluorite, precipitated calcium fluoride, or calcium fluoride reagent in water (Wilson 1847, 1849, 1850; Kohlrausch 1904, 1908; Auméras 1927; Carter1928; Mougnaud 1931; Jensen 1937; Kazakov and Sokolova (1950); Strübel 1965; Lingane 1967; McCann 1968; Ikrami et al. 1971; Roberson and Schoen 1973; Gardner and Nancollas 1976; Brown and Roberson 1977; Nordstrom and Jenne 1977; Gutiérrez and Navarro 1981; Street and Elwali 1983; Elrashidi 1985; Elrashidi and Lindsay 1986; Yang and Smith 1995; Garand and Mucci 2004; and Zhang et al 2017) and in aqueous salt solutions and artificial seawater (Anikin and Shushkanov 1963; Strübel 1965; Strübel and Schaefer 1975; and Garand and Mucci 2004) at temperatures ranging from near 0oC to 350oC. These authors found that fluorite is sparingly soluble in water and more soluble with increasing temperature and in salt solutions with increasing ionic strength. Most of these experiments determined fluorite solubility by dissolution from an undersaturated state. The results from many of these experiments are summarized in Tables 1-1 and 1-2.

Some of the earliest studies of fluorite solubility in low temperature (less than 50oC) aqueous solutions were performed by Wilson (1847; 1849; and 1850). He conducted experiments using natural fluorite which was boiled at 100oC in distilled water; the solution was subsequently 2 Table 1-1 Solubility of fluorite in water at low temperature (< 50oC), ionic strength < 0.01M, and atmospheric pressure.

Temperature Equilibrium Log K Comments Reference (oC) sp Approach1 Natural Tadzhik fluorite; distilled 0 -10.10 U Kazakov and Sokolova (1950) water; colorimetric Natural Weardale, England fluorite; 0.05 -10.80 U Kohlrausch (1908) distilled water; conductivity Natural Tadzhik fluorite; distilled 10 -9.89 U Kazakov and Sokolova (1950) water; colorimetric Calcium fluoride reagent; distilled 10 -10.46 U Ikrami et al (1971) water; colorimetric Natural pale green fluorite; distilled 15.5 -9.53 S Wilson (1850) water; gravimetric Natural Weardale, England fluorite; 16.1 -10.64 U Kohlrausch (1908) distilled water; conductivity Natural Weardale, England fluorite; 17.3 -10.62 U Kohlrausch (1908) distilled water; conductivity Precipitated calcium fluoride; distilled 17.5 -10.52 U Kohlrausch (1908) water; conductivity Precipitated calcium fluoride; distilled 18 -10.51 S Jensen (1937) water Precipitated calcium fluoride; distilled 18 -10.52 U Kohlrausch (1908) water; conductivity Precipitated calcium fluoride; distilled 18 -10.54 U Kohlrausch (1904) water; distilled water; conductivity Precipitated calcium fluoride; distilled 18 -10.54 U Mougnaud (1931) water Natural Weardale, England fluorite; 18 -10.61 U Kohlrausch (1908) distilled water; conductivity Natural fluorite; distilled water; 18 -10.62 U Kohlrausch (1904) distilled water; conductivity Precipitated calcium fluoride; distilled 18 -10.68 U Jensen (1937) water Natural fluorite; distilled water; 18 -10.71 U Kohlrausch and Rose (1893) conductivity Natural Tadzhik fluorite; distilled 20 -9.71 U Kazakov and Sokolova (1950) water; colorimetric Natural and synthetic fluorite; 20 -10.37 S Yang and Smith (1995) deionized water Calcium fluoride reagent; distilled 20 -10.39 U Ikrami et al (1971) water; colorimetric Natural and synthetic fluorite; 20 -10.56 U Yang and Smith (1995) deionized water Natural Berbés, Asturias, Spain 22.5 -10.43 U fluorite; deionized water; ISE; Gutiérrez and Navarro (1981) colorimetric Natural Madrid, Spain fluorite; 22.5 -10.46 U Gutiérrez and Navarro (1981) deionized water; ISE; colorimetric Calcium fluoride reagent; deionized 22.5 -10.58 U Gutiérrez and Navarro (1981) water; ISE; colorimetric

1 U indicates that equilibrium was approached from an undersaturated state; S indicates that equilibrium was approached from a supersaturated state. 3 Table 1-1 continued.

Temperature Equilibrium Log K Comments Reference (oC) sp Approach2 Natural Clara Mine fluorite; 0.30 to 23 -11.30 U Strübel (1965) 0.66 mm particle size Precipitated calcium fluoride; titration; 24 -8.28 S Lingane (1967) likely nonequilibrium result Precipitated calcium fluoride; distilled 25 -9.39 U Carter (1928) water; pH 6.4; gravimetric Precipitated fluorite from natural 25 -9.61 S Robertson and Schoen (1973) geothermal waters; XRD; titration Precipitated fluorite from natural 25 -9.76 S Robertson and Schoen (1973) geothermal waters; XRD; titration 25 -9.77 ----- Calculated from oxidation potentials Latimer (1952) Precipitated fluorite from natural 25 -9.89 S Robertson and Schoen (1973) geothermal waters; XRD; titration Natural Walden, Colorado fluorite; Elrashidi (1985); Elrashidi and 25 -10.21 S deionized water Lindsay (1986a) Precipitated calcium fluoride; distilled 25 -10.39 U Auméras (1927) water; gravimetric Natural Walden, Colorado fluorite; Elrashidi (1985); Elrashidi and 25 -10.40 U deionized water Lindsay (1986a) 25 -10.41 ----- Calculated from thermodynamic data Lindsay (1979)

25 -10.41 ----- Calculated from thermodynamic data Smith and Martell (1976)

Natural Illinois fluorite; NaClO4 25 -10.42 U solutions; I = 0 to 0.1 M; XRD; 60 to Brown and Robertson (1977) 140 mesh particle size 25 -10.50 U Precipitated calcium fluoride; XRD Street and Elwall (1983) Calcium fluoride reagent; I = 10-4 to 0.7 25 -10.51 US Garand and Mucci (2004) M; 20 ȝm size Natural Ontario fluorite; NaClO4 25 -10.58 U solutions; I = 0 to 0.1 M; XRD; 60 to Brown and Robertson (1977) 140 mesh particle size Regression analysis of numerous 25 -10.96 ----- Nordstrom and Jenne (1977) experiments Natural Clara Mine fluorite; 0.30 to 25 -11.25 U Strübel (1965) 0.66 mm particle size Precipitated calcium fluoride; 26.1 -10.45 U Kohlrausch (1908) conductivity Natural Clara Mine fluorite; 0.30 to 26.5 -11.24 U Strübel (1965) 0.66 mm particle size Natural Weardale, England fluorite; 26.6 -10.54 U Kohlrausch (1908) distilled water; conductivity Calcium fluoride reagent; distilled 20 -10.39 U Ikrami et al (1971) water; colorimetric

2 U indicates that equilibrium was approached from an undersaturated state; S indicates that equilibrium was approached from a supersaturated state. 4 Table 1-1 continued.

Temperature Equilibrium Log K Comments Reference (oC) sp Approach3 Precipitated calcium fluoride; mean of 34 -10.45 U 8 experiments; log Ksp range –10.42 to McCann (1968) -10.48; pH 3 to 7 Natural Clara Mine fluorite; 0.30 to 39 -10.97 U Strübel (1965) 0.66 mm particle size Natural Weardale, England fluorite; 40 -10.49 U Kohlrausch (1908) distilled water; conductivity Natural Clara Mine fluorite; 0.30 to 50 -10.74 U Strübel (1965) 0.66 mm particle size

filtered, cooled, and maintained at 15.5oC for several days prior to filtering and measuring the fluorite mass remaining in solution by evaporation. Wilson (1850) found an average fluorite solubility of 35.6 milligrams (mg) CaF2/liter (L), which is equivalent to a solubility product -9.53 constant (Ksp) of 10 or a log Ksp (log10 Ksp) of -9.53 calculated using PHREEQC and

assuming stoichiometric solubility. Ksp is the product of the equilibrium activities of the ions in a saturated solution of fluorite. It is likely that the reported fluorite solubility is overestimated because of the short time, several days, allowed for equilibration of the supersaturated solution at 15.5oC. Wilson (1847) concluded that “The solubility here indicated must be considered great for a salt hitherto reputed quite insoluble.

Kohlrausch (1904; 1908) measured the solubility of laboratory precipitated calcium fluoride and natural fluorite via dissolution in water at 18oC. The calcium fluoride concentrations were determined by electrical conductivity. Kohlrausch (1904) reported natural and precipitated calcium fluoride solubilities of 15.0 and 16.3 mg CaF2/L, respectively. Kohlrausch (1908) subsequently measured the solubility of a natural fluorite from Weardale, England in water at temperatures ranging from near 0 oC to 40oC and atmospheric pressure. The reported fluorite o o solubilities ranged from 13.1 mg CaF2/L at 0 C, 14.8 mg CaF2/L at 16.1 C, 15.0 mg CaF2/L at o o o 18 C, 16.0 mg CaF2/L at 26.6 C, and 16.7 mg CaF2/L at 40 C. Log Ksp values estimated using PHREEQC and assuming stoichiometric solubility ranged from -10.80 at 0oC to -10.49 at 40oC (Table 1-1).

3 U indicates that equilibrium was approached from an undersaturated state; S indicates that equilibrium was approached from a supersaturated state. 5 Table 1-2 Solubility of fluorite in salt solutions at low temperature (50oC or Less), ionic strength > 0.1M, and atmospheric pressure.

Ionic Strength Temperature Equilibrium Log K Comments Reference (M) (oC) sp Approach4 0.1 20 -10.89 U Natural Clara Mine fluorite; 0.1 30 -10.62 U 0.30 to 0.66 mm particle Strübel (1965) 0.1 40 -10.47 U size; NaCl solutions for I = 0.1 to 2 moles NaCl/kg H2O 0.1 50 -10.37 U 0.5 20 -11.01 U Natural Clara Mine fluorite; 0.5 30 -10.78 U 0.30 to 0.66 mm particle Strübel (1965) 0.5 40 -10.61 U size; NaCl solutions for I = 0.1 to 2 moles NaCl/kg H2O 0.5 50 -10.52 U 1.0 20 -11.13 U Natural Clara Mine fluorite; 1.0 30 -10.90 U 0.30 to 0.66 mm particle Strübel (1965) 1.0 40 -10.75 U size; NaCl solutions for I = 0.1 to 2 moles NaCl/kg H2O 1.0 50 -10.64 U

2.0 20 -11.18 U Natural Clara Mine fluorite; 2.0 30 -10.97 U 0.30 to 0.66 mm particle Strübel (1965) 2.0 40 -10.80 U size; NaCl solutions for I = 0.1 to 2 moles NaCl/kg H2O 2.0 50 -10.68 U Natural Madrid, Spain fluorite; CaCl solutions for I Gutiérrez and Various 21 -10.48 U 2 = 3 x 10-5 to 6 x 10-4M; Navarro (1981) 21.1oC; ISE; colorimetric Natural Berbés, Asturias, Spain fluorite; CaCl 2 Gutiérrez and Various 22 -10.44 U solutions for I = 3 x 10-5 to 1 Navarro (1981) x 10-3M; 21.8oC; ISE; colorimetric Calcium fluoride reagent; CaCl solutions for I = 3 x Gutiérrez and Various 23 -10.60 U 2 10-5 to 1 x 10-3M; 23.0oC; Navarro (1981) ISE; colorimetric Natural fluorite from Zhang et al 0.1 30 -10.41 S Maoniuping REE deposit, (2017) China; 0.1M NaCl Natural fluorite from Zhang et al 0.1 50 -10.30 S Maoniuping REE deposit, (2017) China; 0.1M NaCl

4 U indicates that equilibrium was approached from an undersaturated state; S indicates that equilibrium was approached from a supersaturated state. 6 Auméras (1927) while studying the solubility of laboratory precipitated calcium fluoride in hydrochloric acid determined its solubility in distilled water at 25oC. The two calcium fluorides used in the solubility experiments were prepared using hydrofluoric acid and calcium chloride or lime (CaO). The reported solubility of both calcium fluorides was 18 mg CaF2/L, which is equivalent to a log Ksp of -10.39 calculated using PHREEQC and assuming stoichiometric solubility.

Carter (1928) determined the solubility of laboratory precipitated calcium fluoride in distilled water at 25oC at a pH of 6.4. He reported a calcium fluoride solubility of 0.004 grams

(g) per 100 cubic centimeters (cc) of solution, or 40 mg CaF2/L, which is equivalent to a log Ksp of -9.39 calculated using PHREEQC and assuming stoichiometric solubility.

Mougnaud (1931) measured the solubility of laboratory precipitated calcium fluoride in water at 18oC. The average calcium fluoride solubility of four determinations was 18.3 mg

CaF2/L. Nordstrom and Jenne (1977) estimated a log Ksp of -10.55 using Mougnaud’s calcium fluoride solubility result.

Jensen (1937) measured the solubility of laboratory precipitated calcium fluoride via dissolution from an undersaturated state and crystallization from an oversaturated state at a temperature of 18oC. The calcium fluoride concentrations were measured using electrical conductivity. The calcium fluoride particle size was approximately 1 to 2 microns. The calcium fluoride solubility by dissolution was 14.3 mg CaF2/L and by crystallization was 16.4 mg CaF2/L which are equivalent to log Ksp of -10.68 and -10.51, respectively. The log Ksp values were calculated using PHREEQC assuming stoichiometric solubility.

Kazakov and Sokolova (1950) determined the solubility of natural fluorite by dissolution in distilled water at temperatures ranging from 0 to 100oC. The fluorite used in the experiments was from the Tadzhik region in the former Soviet Socialist Republic (modern-day Republic of Tajikistan.). It was crushed and sieved through a 60 mesh (0.25 millimeter) sieve. The fluorine content of the solutions was determined colorimetrically. The fluorite solubility results ranged o o o from 22.6 mg CaF2/L at 0 C, 26.7 mg CaF2/L at 10 C, 30.8 mg CaF2/L at 20 C, and 61.6 CaF2/ L o at 100 C. Log Ksp values calculated using PHREEQC and assuming stoichiometric solubility ranged from -10.10 at 0oC to -8.90 at 100oC. 7 Strübel (1965) determined the solubility of natural fluorite from the Clara Mine in Germany via dissolution in distilled water at temperatures ranging from 23oC to 350oC and pressures ranging from atmospheric to 165.4 bars. For the temperature range of interest in this o o study, 23 C to 50 C, the fluorite solubilities ranged from 8.76 ± 0.14 to 13.70 ± 0.10 mg CaF2 per kilogram of water (kg H2O). Nordstrom and Jenne (1977) estimated log Ksp values that ranged from -11.28 at 23oC to -10.70 at 50oC using Strübel’s fluorite solubility data. Log Ksp values estimated using PHREEQC and assuming stoichiometric solubility ranged from -11.30 at 23oC to -10.74 at 50oC (Table 1-1).

Strübel (1965) also determined the solubility of natural fluorite from the Clara Mine in Germany via dissolution in sodium chloride (NaCl) solutions at ionic strengths that ranged from o 0.1 to 2.0 moles NaCl/kg H2O and temperatures that ranged from 20 to 90 C. Log Ksp values estimated using PHREEQC for the temperature range of interest in this study (20 to 50oC) and assuming stoichiometric solubility are summarized in Table 1-2.

Lingane (1967) determined the solubility of calcium fluoride by titration of reagent-grade calcium chloride and sodium fluoride solutions at 24 ± 1oC. The decreasing fluoride concentrations as calcium fluoride precipitated during titration were measured with an ion selective electrode until an equivalence point was reached. Lingane reported a calcium fluoride -9 Ksp of 5.3 x 10 moles per liter (M), or a log Ksp of -8.28. He stated that the potentiometric measurements of the calcium fluoride equilibrium constant were difficult and suggested that true equilibrium may not have been reached because a distinct inflection at the equivalence point was not observed. Nordstrom and Jenne (1977) suggested that particle size effects or metastable equilibrium may have been a problem in Lingane’s determination.

McCann (1968) measured the solubility of calcium fluoride reagent as part of a study of the relationship of the solubility of fluorapatite and calcium fluoride during topical dental fluoride treatments. The solubility determinations were conducted in imidazole-hydrochloric acid, potassium acetate, and potassium formate buffered solutions at 34oC, atmospheric pressure, and pH values that ranged from 2.99 to 7.00. The log Ksp values determined ranged from -10.42 -11 to -10.48 and averaged -10.45, or a mean Ksp of 3.58 ± 0.18 x 10 .

8 Ikrami et al. (1971) while studying the solubility of alkaline earth fluorides in hydrofluoric acid solutions determined the aqueous solubility of precipitated calcium fluoride at o 10, 20, and 30 C. The solubilities in water ranged from 17 to 18 mg/L CaF2. Nordstrom and o o Jenne (1977) reported log Ksp values of 10.40 at 10 C and 10.31 at 20 and 30 C. Log Ksp values calculated using PHREEQC and assuming stoichiometric solubility ranged from -10.46 at1 0oC to -10.39 at 20 and 30oC.

Roberson and Schoen (1973) determined the solubility of fluorite in natural geothermal waters from the Snake River Basin in Idaho at 25oC and atmospheric pressure. They determine the fluorite solubility by supersaturating the geothermal waters with sodium fluoride and stored the samples for 30 days to allow the fluorite to precipitate. Fluoride and calcium activities were measured at 10 and 30 days with ion-selective electrodes. Roberson and Schoen (1973) reported the log activity products, log [Ca2+][F-]2(log Ksp), for the three waters as -9.76, -9.61, and -9.89.

Gardner and Nancollas (1976) measured the solubility of calcium fluoride reagent as part of a study of the kinetics of crystal growth and dissolution of calcium and magnesium fluorides. They determined the solubility of calcium fluoride at 15oC, 25oC, and 50oC and found solubility -11 products of 2.70, 2.85, and 3.05 ± 0.1 x 10 , or log Ksp values of -10.57, -10.55, and -10.52, respectively.

Macaskill and Bates (1977) measured the solubility of calcium fluoride in calcium chloride solutions ranging in molality from 0 to 0.13. They reported a fluorite solubility of 3.1 x 10-11 at an ionic strength of 1.0M, or a log Ksp of -10.51.

Brown and Roberson (1977) measured the solubility of natural fluorites from Rosiclare, Illinois and Madoc, Ontario at 25 ± 0.5oC in various ionic strength (0 to 0.1 molar) sodium perchlorate solutions for 3 years. Fluorites were characterized by X-ray fluorescence and found to contain traces of iron in both specimens and yttrium in the Ontario specimen. The mean and standard deviation log Ksp results were -10.58 ± 0.01 for the Ontario fluorite and -10.42 ± 0.04 for the Illinois fluorite.

Nordstrom and Jenne (1977) provided a critical review of the thermodynamic properties of fluorite and compiled and evaluated fluorite solubilities for 0oC to 50oC to determine whether 9 fluoride concentrations in hot springs and surface waters from selected geothermal areas in the western U.S. were controlled by fluorite solubility. They reviewed aqueous fluoride complexes, free energies, enthalpies, and entropies of fluorite, and the heat capacities of fluorite. Nordstrom and Jenne (1977) calculated revised estimates of these values using a regression model and o derived a log Ksp for fluorite dissolution of -10.96 at 25 C.

Gutiérrez and Navarro (1981) determined the solubility of calcium fluoride reagent and two natural fluorites, from Berbés, Asturias and Madrid, Spain, in deionized water at 22.5 ± 0.5oC while studying the constancy of calcium fluoride’s solubility product. The BET/Kr specific surface areas of the powders used in the experiments were 0.44 and 0.65 square meters per gram (m2/g) for the natural fluorites, and 3.12 m2/g for the calcium fluoride reagent. They -11 reported an average Ksp of 2.61 x 10 (log Ksp of -10.58) for calcium fluoride reagent and -11 -11 average Ksp values of 3.75 x 10 (log Ksp of -10.43) and 3.46 x 10 (log Ksp of -10.46) for the two natural fluorites.

Gutiérrez and Navarro (1981) also determined the influence of calcium chloride on the -11 Ksp of calcium fluoride reagent and natural fluorite. They reported an average Ksp of 2.5 x 10 ± o 4% (log Ksp of -10.60 ± 0.02) for calcium fluoride reagent at 23 C and average Ksp values of 3.6 -11 -11 x 10 ± 6.5% (log Ksp of -10.44 ± 0.03) and 3.3 x 10 ± 7.4% (log Ksp of -10.48 ± 0.03) for the o two natural fluorites at 21.8 and 21.1 C, respectively. The Ksp values were determined at various ionic strengths ranging from 3 x 10-5 to 1 x 10-3M.

Street and Elwali (1983) investigated the solubility of precipitated calcium fluoride in limed acid sandy soils for pH between 4.0 and 7.8. They also determined the solubility of o precipitated calcium fluoride in deionized water at 25 C. They reported a log Ksp of -10.50 for the precipitated calcium fluoride.

Elrashidi (1985) and Elrashidi and Lindsay (1986a) measured the solubility of natural fluorite from Walden, Colorado in deionized water at 25oC at atmosphere pressure and pH 6.79 from both undersaturated and supersaturated states. Four replicate samples were tested for 5 months. The mean log Ksp was -10.40 ± 0.03 for the undersaturated state and the supersaturated state mean log Ksp was -10.21 ± 0.04. Elrashidi (1985) noted that the log Ksp of -10.40 was in

10 good agreement with the log Ksp of -10.41 calculated from thermodynamic data by Sadiq and Lindsay (1979).

Nordstrom et al. (1990) published an updated summary of equilibrium constants and reaction enthalpies for aqueous ion association reactions and mineral solubilities. They reported o a log Ksp value of -10.6 for fluorite at 25 C based on the previous work of Nordstrom and Jenne (1977), Macaskill and Bates (1977), and Brown and Roberson (1977). They also reported a revised fluorite value as 4.69 kilocalories per mole (kcal/mol) or 19.6 kilojoules per mole ଴ (kJ/mol). ௥ οܪ

Yang and Smith (1995) studied the aqueous solubility of natural fluorite and laboratory o precipitated calcium fluoride at 20 ± 0.3 C and found log Ksp values to be -10.56 and -10.37 when equilibrium was reached from undersaturation and supersaturation, respectively.

The mean log Ksp was reported as -10.47.

Garand and Mucci (2004) determined the stoichiometric solubility of reagent grade calcium fluoride powder in deionized water, various ionic strength NaCl solutions (0.1 to 0.73 M), Na-Ca-Cl and Na-Mg-Ca-Cl solutions, and artificial seawater at 25oC and 1 atmosphere total pressure to determine the effect of ionic strength and the coprecipitation of seawater constituents on the solubility of fluorite. The solubility experiments were conducted for up to 64 weeks using single samples from an undersaturated state and, in some cases, a supersaturated state. The -11 results of their experiments yielded an average Ksp of 3.08 ± 0.08 x 10 or log Ksp of -10.51 ±

0.01 which is equivalent to the log Ksp value of -10.51 derived from thermodynamic data by Robie et al (1978).

Street and Elwali (1983) studied the solubility of laboratory precipitated fluorite in acid sandy soils at pH 4.0 to 7.8. Data indicated that fluorite was the solid phase controlling fluoride

activity in the pH range of 5.5 to 7.0. The log Kap for the laboratory precipitated fluorite was calculated to be -10.50.

Zhang et al (2017) determined the solubility of fluorite in Na-K-Cl solutions at temperatures up to 260oC and ionic strengths up to 4 M. For temperatures relevant to this study, they determined log Ksp values of -10.41 and -10.30 at temperatures of 30oC and 50oC, 11 respectively, and an ionic strength of 0.1M NaCl. The 50oC result was determined from undersaturation, while the 30oC result was determined from supersaturation.

1.3 Historical Fluorite Solubility Summary

Figure 1-1 summarizes the historical log Ksp values for fluorite solubility in water for temperatures ranging from 0 to 50oC. The mean and 95 percent upper and lower confidence intervals are also shown. The fluorite log Ksp values range approximately 3 orders of magnitude, from -8.28 to -11.3. For the full data set, the mean historical fluorite log Ksp is - 10.39 and the lower and upper 95 percent confidence intervals are -10.25 and -10.54, respectively. If these data were internally consistent, one would expect to see decreasing pKsp values as temperature increases, however, no evident temperature trend is observed. The largest amount of solubility data occurs between 22oC and 27oC. Review of Figure 1-1 shows about 50 percent of the fluorite log Ksp values occur in this temperature range and range from -8.28 to - 11.30. The mean fluorite log Ksp for these data is -10.32 and the lower and upper 95 percent confidence intervals are -10.08 and -10.59, respectively.

Figure 1-2 is a box and whiskers plot of the historical fluorite log Ksp data shown in Figure 1-1. The box represents the interquartile range for the 25th and 75th percentiles (quartile 1 and 3, respectively), whereas the whiskers show the interquartile range ± 1.57 of the interquartile range. The notch represents the median and 95 percent confidence intervals around the median. Filled circle symbols outside the whiskers represent potential outliers in the data. Figure 1-2 also shows that the historical log Ksp values range widely and do not appear to exhibit any pattern with increasing temperature.

1.4 Equilibrium Fluorite Solubility

The solubility of fluorite is defined as the mass of fluorite that dissolves at equilibrium in an aqueous solution of constant temperature (T), pressure (P), and ionic strength (I). The equilibrium solubility of fluorite is defined by the following reaction:

2 CaF2 (s) l Ca aq)( 2F aq)(

12 Figure 1-1 Historical log Ksp data for fluorite solubility in water at temperatures of 0 to 50oC and ionic strengths less than 0.01M.

13 p s K g o L

Temperature (C)

Figure 1-2 Box and whiskers plots of historical fluorite log Ksp data in water at temperatures of 0 to 50oC and ionic strengths less than 0.01M.

14 The thermodynamic equilibrium constant (K) for this reaction is expressed in terms of the activities of the products and reactants as shown below

2 (a 2 )(a ) K Ca F a CaF2

2+ - where ai is the equilibrium activity of the ions (Ca and F ) and the solid (CaF2). If the solid is pure, its activity is, by definition, unity, and the above equation reduces to the thermodynamic solubility product constant (Ksp) where

2 K sp (aCa 2 )(a F )

The Ksp value for a sparingly soluble salt, like fluorite, is determined experimentally, by measuring fluorite solubility in solution at a known T, P, and I. The determined values are often referred to as apparent Ksp or K*, values since they are not equal to the thermodynamic solubility product constant at infinite dilution. The K* values measured at different temperatures and ionic strengths can be used to determine the Ksp value at infinite dilution at a specific temperature using a modified method of Nordstrom and Munoz (1994) and Garand and Mucci (2004) as discussed below.

Consider the fluorite dissolution reaction

2 CaF2 (s) l Ca aq)( 2F aq)( .

The Ksp is expressed as

2 2 2 2 2 2 K sp [aCa ][aF ] (mCa 2 )(J Ca 2 )(mF () J F ) (mCa 2 )(mF () J Ca 2 )(J F )

2+ - 2+ - where mi is the Ca or F concentration and Ȗi is the Ca or F activity coefficient in a solution of known ionic strength. If one substitutes K* for the stoichiometric concentration product 2 , then ([mCa 2 ][mF )]

15 2 K (K*)(J 2 )(J ) K *J . sp Ca F CaF2

2 where, ȖCaF2 is the product of the fluorite total ion activity coefficient (i.e., (ȖCa2+)(ȖF-) .

Subsequently taking the logarithms,

logK logK *logJ sp CaF2

solving for K*,

logK* logK logJ sp CaF2 and substituting the Debye-Hückel limiting law ( logJ Az 2 I ) for logJ , yields i i CaF2

2 log K* log K sp Az i I . where, A is a temperature dependent constant for the solvent, which for water ranges from 0.492 o to 0.534 between 0 and 50 C (Langmuir 1997), and zi, is the charge number of ion species i.

From the above equation, if fluorite solubility is measured over a range of I, then a log K* versus ¥I plot should yield a straight line at ionic strengths less than 0.1M and allow extrapolation to the reference state of infinite dilution (Nordstrom and Munoz, 1994). The intercept for I = 0 will be proportional to the thermodynamic solubility-product constant (log

Ksp) as shown in Figure 1-3.

Log Ksp at infinite dilution can also be determined by plotting ionic strength (I) versus Log Ksp* values and fitting a best fit line to the data using non-linear curve fitting software such as CurveExpert Professional Version 2.6 (Hyams Development 2017). CurveExpert is capable of fitting a line to the data and determining the 95 percent confidence interval around the data which represents the experimental error. This method was used to estimate log Ksp at infinite dilution in this study.

16 o Figure 1-3 Determination of synthetic fluorite log Ksp at 25 C and I =0 (infinite dilution) using data of Garand and Mucci (2004).

17 CHAPTER 2

MATERIALS AND METHODS

2.1 Materials

Natural fluorites and calcium fluoride reagent were used in the solubility experiments (Table 2-1). Most of the fluorites used in the solubility experiments were well-crystallized fluorites of hydrothermal origin. A summary of the fluorites used in the experiments is provided in Table 2-1. Photographs of each specimen used are provided in Figures 2-1 through 2-3.

2.2 Methods

2.2.1 Solubility Procedure

The solubility of the fluorites was determined in aqueous solutions at temperatures of 5, 25, and 50 oC, ionic strengths ranging from near zero to 0.72 moles per liter (M), and 1 atmosphere pressure. Equilibrium was approached from both undersaturated and supersaturated initial conditions. The aqueous solutions used in the solubility experiments were prepared using American Society of Testing and Materials (ASTM) Type I water (resistivity of 18 megaohms·centimeter [M·cm]) and Fisher Scientific certified analytical-grade potassium chloride (Lot 876570) as a support electrolyte. Various ionic strength solutions (approximately 0.1, 0.2, 0.3, 0.5, and 0.72 M) were prepared by dissolving potassium chloride in Type I water as summarized in Table 2.2.

Fluorite solubilities were determined by placing 0.1 grams of fluorite in a Nalgene 30 milliliter (mL) high density polyethylene (HDPE) bottle. The bottles were either filled with Type I water to create an approximately zero ionic strength solution or with the various ionic strength potassium chloride solutions. Potassium chloride was used because neither potassium nor chloride is known to form any significant fluoride or calcium complexes at the experiments’ activities. The effects of fluoride complexing with other cations or anions was minimized by the use of Type I water to avoid introduction of ions (e.g., Al and Fe) that might complex with fluoride.

18 Table 2-1 Source and description of fluorites used in this study.

Sample Name Description Location/Source Tan fluorite; porcelaneous, cryptocrystalline, BCP conchoidal fracture, deposited in veins and open Puzzle Mine Brown’s Canyon spaces in likely Miocene-age epithermal hot spring Brown’s Canyon, Colorado Porcelain (119-161oC) system (Van Alstine 1969; Roedder, 1974; Wallace 2010; Simmons 2010). White to pale green and white, equigranular, medium BCW crystalline “sugar spar”, deposited in veins and open Delay and Lloyd Mine Brown’s Canyon spaces in likely Miocene-age epithermal hot spring Brown’s Canyon, Colorado White (119-161oC) system (Van Alstine 1969; Roedder, 1974; Wallace 2010; Simmons 2010). Green fluorite; up to 2 inch weakly zoned, euhedral CH Xianghualing Mine cubes; hydrothermally deposited in open veins and China Green Hunan, China cavities.

Yellow fluorite; up to 1.5 inch, euhedral cubes; weakly zoned, hydrothermal (125-150oC), Mississippi Valley- IY Minerva Mine type veins and stratabound bedding replacement Illinois Yellow Cave-In-Rock, Illinois deposits in Mississippian-age carbonate rocks (Denny et al. 2008; Spry et al. 1990).

Dark purple fluorite; up to 1.5 inch euhedral cubes; MP hydrothermal (130 to 170oC), Mississippi Valley type Múzquiz Area Mexican Purple manto deposits formed in veins and cavities in Coahuila, Mexico Cretaceous-age carbonate rocks (Kesler 1977).

White to lilac fluorite; weakly zoned, euhedral MX columnar cubes; Mississippi Valley type manto Tule Mine, Melchor Múzquiz, Mexican Lilac deposits formed in veins and cavities in Cretaceous- Coahuila, Mexico age carbonate rocks (Kesler 1977).

Blue-gray fluorite; hydrothermal (100 to 150oC), NGB columnar, botryoidal encrustations in late Tertiary (?) Camp Creek Mine Northgate Blue open fractures and faults in a quartz monzonite Northgate, Colorado intrusive (Steven 1960).

Yellow fluorite; hydrothermal (100 to 150oC) NGY columnar, botryoidal encrustations in late Tertiary (?) Camp Creek Mine Northgate Yellow open fractures and faults in a quartz monzonite Northgate, Colorado intrusive (Steven 1960).

Purple, blue, and white fluorite; massive, coarsely SPD Duffield Mine crystalline; hydrothermal vein and fracture filling in St. Peter’s Dome St. Peter’s Dome, Colorado Precambrian-age Pikes Peak Granite (Steven 1949).

SY White, microcrystalline calcium fluoride analytical Mallinckrodt Inc. Synthetic grade reagent powder. St. Louis, Missouri

19 (a) Browns Canyon Porcelain (BCP) (b) Browns Canyon White (BCW)

Figure 2-1 Photographs of fluorite samples used in this study’s experiments (a) Browns Canyon Porcelain, (b) Browns Canyon White, (c) China Green, and (d) Illinois Yellow.

20 (a) Mexican Purple (MP) (b) Mexican Lilac (MX)

Figure 2-2 Photographs of fluorite samples used in this study’s experiments (a) Mexican Purple (MP, (b) Mexican Lilac (MX), (c) Northgate Blue (NGB), (d) Northgate Yellow (NGY).

21 (a) St Peter’s Dome (SPD) (b) Synthetic (SY)

Figure 2-3 Photographs of fluorite samples used in this study’s experiments (a) St. Peter’s Dome (SPD), (b) Synthetic (SY).

Table 2-2 pH and ionic strengths of potassium chloride solutions used in this study.

Potassium Solution Ionic Specific Solution Chloride Volume5 Strength Conductance pH (g) (mL) (M) ȝS/cm) 7.46 1,000 0.1 6.79 16,210

14.91 1,000 0.2 6.56 30,800

22.37 1,000 0.3 6.54 45,300

37.28 1,000 0.5 6.14 74,100

53.68 1,000 0.72 6.16 108,500

5 Potassium chloride solutions prepared with analytical grade reagent using deionized water and a Class A 1,000 mL volumetric flask at 23oC. 22 2.2.2 Undersaturated Fluorite Solutions

Three replicate solutions were made for each temperature and ionic strength for the undersaturated fluorite solubility experiments. The replicate fluorite solutions were placed in constant temperature Precision Model 50 reciprocal shaking water baths at 25 ± 0.1 o C and 50 ± 0.1 o C and in static water baths in a refrigerator at 5 ± 0.5 o C. The solutions were retained in the water baths for approximately three years prior to analysis. Periodic analyses of the fluoride activity were made using a fluoride ISE (Section 2.2.2) to determine whether the solutions had reached equilibrium.

Once equilibrium was confirmed, aliquots of each sample were removed from the bottle and immediately filtered through a JSI Scientific Inc. 0.2 micron polypropylene syringe filter into a clean sample container for analysis. The fluoride samples were immediately analyzed using a calibrated fluoride ISE. Sample aliquots for calcium analyses were acidified with Fisher Scientific trace metal grade concentrated nitric acid (16M) to pH less than 2, and stored for subsequent calcium analysis by ICP-OES.

2.2.3 Supersaturated Fluorite Solutions

A single solution was made for selected fluorite samples (IY, MX, and SY) at 25oC temperature and ionic strengths near zero to 0.72 M to determine Ksp from a supersaturated initial condition. The supersaturated solutions were made by placing 0.1 grams of powdered fluorite in a Nalgene 30 mL HDPE bottle filled with either Type I water or various ionic strength potassium chloride solutions near 100oC. The fluorite solutions were then held at temperatures of 5, 25, and 50oC for approximately 1 year until the supersaturated solutions reached equilibrium. Periodic analyses of the fluoride activity were made to determine whether when the supersaturated solutions reached equilibrium.

Once equilibrium was reached, aliquots of each sample were removed from the bottle and immediately filtered through a JSI Scientific Inc. 0.2 micron polypropylene syringe filter into a clean sample container, acidified with Fisher Scientific trace metal grade concentrated nitric acid (16M) to pH less than 2, and stored in 15 mL BD Falcon centrifuge tubes for calcium analysis.

23 Solution aliquots were also filtered through a 0.2 micron filter and immediately analyzed for fluoride using a fluoride ISE as discussed in Section 2.2.4.

2.2.4 Fluoride Analyses

Fluoride analyses were performed using a Weiss Research Really-Flow™ Model RF03001 solid-state combination single junction fluoride ISE and a Orion Model 290A pH/ion/conductivity meter. The fluoride ISE was calibrated prior to each series of analyses using known concentration (1, 3, 5, 10, 20, and 30 mg/L) fluoride standard solutions for each ionic strength used in the experiments. An example fluoride ISE calibration curve for a 0.3M KCl solution at 25oC is shown as Figure 2- 4. The calibration curve exhibits a linear response between 1 and 30 mg/L fluoride with slope of -57.15 mV per decade of fluoride concentration which is within the acceptable range of -54 to -60 mV per decade of fluoride concentration at 25oC (Harris 2007).

Figure 2-4 Example fluoride ISE calibration curve for 0.3 M KCl solution at 25oC.

24 The standard solutions were made by dilution of a 1,000 milligram per liter (mg/L) fluoride standard solution made with 2.21 grams of analytical grade sodium fluoride. A 1,000 mg/L fluoride standard solution was made for each ionic strength solution used in the experiments so that the standards had the same ionic strength matrix as the samples. A series of diluted fluoride standard solutions were made using either Type I water or various ionic strength potassium chloride solutions. Dilution of the 1,000 mg/L fluoride standard solutions were made gravimetrically using 100 mL Class A volumetric flasks to create the various concentration standard solutions used for calibration of the ISE.

Fluoride activities were measured directly on 10 mL of sample aliquots immediately after extraction from the Nalgene sample bottles. The sample aliquots were not buffered with TISAB (total ionic strength adjustment buffer) prior to analysis as the matrix-matched ionic strength solutions were found to buffer the pH and ionic strengths so that potential fluoride complexes (e.g., HF) were eliminated. Use of the matrix-matched ionic strength standards allowed fluoride concentrations to be measured directly since the fluoride activity in the samples and standard solutions were the same.

2.2.5 Calcium Analyses

Calcium analyses were performed using a Perkin Elmer Optiva 5300 ICP-OES housed in the Department of Chemistry and Geochemistry, Colorado School of Mines. Sample aliquots were filtered through a JSI Scientific Inc. 0.2 micron polypropylene syringe filter, diluted 1:20 with Type I water, and acidified to a pH of approximately 2 using Fisher Scientific trace metal grade nitric acid (16M) prior to analysis. The acidified samples were stored at room temperature until analyzed.

2.2.6 Petrographic Thin Sections

Polished thin sections were made to examine the fluorites used in the experiments. The thin sections were prepared in the Department of Geology and Geological Engineering, Colorado School of Mines. The thin sections were visually examined using a Leica DM750P petrographic microscope under both plane and polarized light to determine whether any potential mineral impurities or fluid inclusions were present in the fluorites. The thin sections were also examined 25 under reflected light to determine if any opaque oxide or sulfide mineral or organic matter impurities were present.

2.2.5 Ultraviolet Fluorescence

Some fluorites exhibit fluorescence under ultraviolet light, a property that takes its name from fluorite. Fluorescence, and accompanying phosphorescence, may provide some insight into whether the fluorites contain hydrocarbon inclusions, significant trace element content, or may have lattice defects due to ion vacancies or substitution. The fluorite specimens used in this study were examined under a Raytech Model 10-020 hand-held, long- and short-wave (365 and 254 nanometer wavelengths, respectively) ultraviolet light to determine if any of the specimens used in this study exhibited fluorescence or phosphorescence. The specimens were exposed to each light source for one minute and the fluorescent color and phosphorescence noted.

2.2.6 Powder X-Ray Diffraction

The identification and unit cell dimensions of the fluorites used in the experiments were determined using a Scintag XDS-2000 theta-theta X-ray diffractometer with a copper (Cu-K alpha) radiation source. The samples were analyzed using an internal aluminum oxide (synthetic corundum) standard so that correction of the X-ray diffraction (XRD) powder patterns could be made as necessary. A minus 325-mesh aliquot of each fluorite sample was mixed with the aluminum oxide standard at a ratio of 80:20 sample (1.6 grams) to standard (0.4 grams). The sample was placed in a packed powder mount using standard practice to achieve random orientation.

Each sample was analyzed from 20 to 136 degrees 2-theta (2Ĭ) using a continuous scan mode with a 0.5 degree per minute scan rate. The powder x-ray powder diffraction data were collected and interpreted using Scintag DMSNT Version 1.37 and CrystalSleuth (Laetsch and Downs, 2006) software.

2.2.7 Fluorite Composition

The major, minor, and trace element composition of the fluorites used in the solubility experiments was determined by dissolving 100 milligram aliquots of each of the powdered 26 natural fluorites and calcium fluoride reagent in 10 milliliters of 0.5M Fisher Scientific Optima HCl solution for 2 hours at 70oC in a shaking water bath. After cooling, the sample solutions were filtered through a 0.2 micron polypropylene syringe filter into a 50 ml Class A volumetric flask and made up to volume with 0.5M Fisher Scientific Optima HCl. Before analysis, the samples were diluted to 1:10 with Type I water. The analyses were performed on a Perkin- Elmer Optiva 5300 DV ICP-OES.

27 CHAPTER 3

RESULTS AND DISCUSSION

3.1 Results

3.1.1 Fluorite Petrography

Figures 3-1, 3-2, and 3-3 are photomicrographs of the fluorite specimens in plain light taken through a 4X objective using a Leica DM750P petrographic microscope. The field of view in each photomicrograph is 2.3 mm. Microscopic examination indicated the fluorites had very few mineral impurities, however, trace amounts of quartz, barite, and pyrite were observed. No evidence of fluid inclusions or organic matter were observed. The lack of fluid inclusions are likely due to the thin sections being ground to thin. The fluorite textures ranged from microcrystalline (Figure 3-1a and 3-1b) to coarse crystalline crystal aggregates (Figure 3-3a), fine-grained botryoidal (Figures 3-2c and 3-2d), to well crystallized euhedral crystals that exhibited perfect octahedral {111}cleavage patterns (Figures 3-1c, 3-2a and 3-2b). Cleavage traces intersect at 70o and 110o angles, or as three intersecting lines at 60o and 120o angles (Figure 3-1c, Figure-3-2a and Figure 3-2b). However, none of these textures influenced the fluorites used in the experiments as the samples were subsequently crushed and sieved through a 325 mesh screen to obtain a uniform particle size for the solubility experiments.

3.1.2 XRD Results

A summary of the XRD patterns obtained for the fluorites used in this study are shown in the diffractograms in Figure 3-4. Individual full-scale and expanded scale diffractograms are provided in Appendix A to demonstrate fluorite sample purity. The diffractograms were run from 20o to 136o 2-theta. Aluminum oxide peaks are also shown on the XRD patterns. Aluminum oxide was mixed with the fluorites to provide an internal standard to correct for variations in sample preparation No pattern corrections were necessary as the aluminum oxide peaks on the pattern coincided with the peaks for ICDD corundum 10-173.

The peak positions on the diffractograms were measured using the peak fitting algorithm of the CrystalSleuth software (Laetsch and Downs, 2006). The d-spacings and relative 28 (a) Browns Canyon Porcelain Fluorite (b) Browns Canyon White Fluorite

(a) St Peter’s Dome Fluorite

Figure 3-3 Photomicrograph of fluorite sample thin section in plain light (a) St. Peter’s Dome (SPD). Field of view is 2.3 mm. intensities of the fluorite samples used in this study were subsequently compared to the d- spacings and relative intensities of known fluorites in the International Center Diffraction Data (ICDD) files to confirm their identity as fluorite. Diffraction data for ICDD fluorite 4-864 were used for comparison. The three strongest fluorite reflections in Figure 3-4 are located at d- spacings of 3.154, 1.931, and 1.647 Å. These reflections are consistent with the ICDD fluorite pattern (3.153, 1.931, and 1.647 Å) and correspond to hkl indices of 111, 220, and 311, respectively. Trace quartz was noted in thin sections and on the diffraction patterns for BCP, BCW, NGB, and SPD as indicated by its two most intense reflections at d-spacings of 3.343 Å and 4.263 Å.

The XRD patterns were indexed using a face-centered cubic lattice (Figure 3-5) and the unit cell refined using CrystalSleuth software (Laetsch and Downs, 2006). The d-spacings and hkl indices of the indexed peaks are shown on Figure 3-4. Full-scale and expanded scale individual indexed patterns and refined unit cell calculations are provided in Appendix A. The expanded scale patterns can be used to assess sample purity. 31 Figure 3-4 Indexed fluorite X-ray diffraction patterns with alumina standard (shown as black trace at bottom). 32 Figure 3-5 (a) Fluorite unit cell (b) plan view (Askeland and Wright 2015).

The unit cell volumes and densities were calculated using the refined unit cell edge length (a) values. The unit cell volume was calculated as a3. The unit cell density (d) was calculated as:

= ܯ כ ܼ ଷ ݀ ௔ for face-centered cubic), M is the molar ܰ 4) כwhere Z is the number of formula units per unit ܽcell

mass of CaF2 (78.075grams per mole), a is the unit cell edge length (in centimeters), and Na is Avogadro’s Number (6.0221409 x 1023 atoms per mole). A summary of the unit cell length, volume, and density results are provided in Table 3-1. The mean unit cell length compares favorably with the results of Allen (1950, 1952) who measured the unit cell lengths of 18 different fluorite samples. The error shown for the unit cell length is calculated by the CrystalSleuth software and represents potential sample preparation error. The potential sample error includes sample length, sample thickness, sample position, sample homogeneity which can affect diffraction intensity and peak position. (Moore and Reynolds 1997).

3.1.3 Fluorite Density

The fluorite densities were also measured using a modified Jolly balance approach (Nawaratne 2011) that involved measuring the mass of a solid fluorite specimen in air using a

33 scale and the mass of the fluorite suspended in a tared beaker of water. The density was calculated as the mass of the fluorite in air divided by the mass of the fluorite in water (numerically equal to the volume of the specimen, assuming the density of water is equal to 1.0 g/cm3 at 25oC).

Table 3-1 Calculated fluorite unit cell length, volume, and density.

Unit Cell Unit Cell Unit Cell Measured Sample Edge Length Volume Density Density (Å) (Å3) (g/cm3) (g/cm3) BCP 5.4631 ± 0.0012 163.05 3.181 3.157 BCW 5.4634 ± 0.0001 163.08 3.180 3.140 CH 5.4634 ± 0.0001 163.08 3.180 3.182 IY 5.4633 ± 0.0001 163.06 3.180 3.183 MP 5.4636 ± 0.0001 163.09 3.180 3.177 MX 5.4632 ± 0.0001 163.06 3.180 3.191 NGB 5.4623 ± 0.0001 162.98 3.182 3.177 NGY 5.4639 ± 0.0001 163.12 3.179 3.175 SPD 5.4634 ± 0.0001 163.08 3.180 3.183 SY 5.4604 ± 0.0001 162.81 3.185 ----- Mean 5.4630 ± 0.0007 163.04 ± 0.06 3.181 ± 0.009 3.174 ± 0.012 This Study Mean 5.4631 ± 0.0002 163.05 ± 0.01 3.181 ± 0.001 ----- Allen (1952)

The measured fluorite densities are summarized in Table 3-1 and provide a comparison to the densities calculated using the unit cell parameters. The density results presented in Table 3-1 show that the measured and calculated densities are similar given the uncertainties associated with the measurement methods, except for samples BCP and BCW which have a lower measured density because of fine grained cryptocrystalline quartz in the samples. The measured and calculated fluorite densities for the pure fluorite samples are consistent with those reported in the literature 3.18 g/cm3 (Deer et al. 1992, Neese 2000, and Klein and Hurlbut 1993) and suggest

34 that lattice defects like dislocations and ion vacancies (e.g., Schottky defects) wwhich decrease mineral density or interstitial substitutions which increase its density are not significant.

3.1.4 UV Fluorescence and Phosphorescence

Table 3-2 summarizes the UV fluorescence, phosphorescence, and X-ray results. Many of the fluorite specimens exhibited long-wave fluorescence, but only two (CH and NGB) exhibited short-wave fluorescence. Under long-wave, the fluorescent fluorites were violet, except for MP and NGB which exhibited yellow fluorescence. Violet fluorescence is often associated with Eu2+ substitution for Ca2+. Yellow fluorescence is often associated with hydrocarbon inclusions. CH and NGB were the only fluorites to exhibit short-wave fluorescence. Fluorescence occurs when the absorbed UV energy decays from an excited singlet electronic state to a singlet ground electronic state.

Five of the fluorite specimens (BCW, CH, MX, NGB, and NGY) exhibited a short-lived phosphorescence that decayed rapidly within a few seconds when the UV light was removed. Phosphorescence occurs when the absorbed UV energy decays from an excited triplet electronic state to a singlet ground electronic state (Harris 2007) and are often associated with F-centers. Three specimens (IY, MP, and SPD) also exhibited a short-lived violet color following exposure to X-rays during XRD that decayed to white (the original color of the powder) over a few hours, but these samples did not exhibit phosphorescence.

3.1.5 Fluorite Composition

The stoichiometric composition of fluorite is 51.3 weight percent calcium and 48.7 weight percent fluorine. The major ion composition of fluorites used in this study are summarized in Table 3.3.- The major ion fluorite compositions shown in Table 3-3 are within 3 percent or less of the stoichiometric composition which provides and indicates that pure fluorite samples were used in this study.

3.1.6 Fluorite Trace Element Composition

The trace element composition of fluorites used in this study are summarized in Table 3-4. The most common trace elements detected in the fluorite samples were B (0.4 to 2.9 mg/g), 35 Ba (3.3 to 59 mg/g),Co (< 0.02 to 0.19 mg/g), Fe (< 0.02 to 8.78 mg/g), K (0.6 to 6.9), Mg (0.7 to 84 mg/g), Mn (0.2 to 1.6 mg/g), Na (3 to 45 mg/g), Ni (0.07 to 5.4 mg/g), S (9 to 33 mg/g), Si (2 to 142 mg/g), and Sr (0.2 to 10 mg/g). The occurrence of Si is likely due to quartz impurities in the samples as the highest Si concentrations were noted in the samples where quartz was identified in thin section or by XRD. The occurrence of these trace constituents in fluorite has also been reported by Allen (1950, 1952), Eppinger (1988), Eppinger and Closs (1990), and Mahdy et al. (2014). No pattern in the solubility results discussed in Section 3.2 were correlated with the trace elements in the fluorites used in this study.

Table 3-2 Summary of fluorescence, phosphorescence, and X-radiation effects.

Long-Wave Short-Wave X-Ray Sample Fluorescence Fluorescence Phosphorescence Effect (Color) (Color)

BCP No No No No

Yes BCW No Yes No (Violet) Yes Yes CH Yes No (Violet) (Violet) Yes Yes IY No No (Violet) (Violet) Yes Yes MP No No (Yellow) (Violet)

MX No No Yes No

Yes Yes NGB Yes No (Yellow) (White) Yes NGY No Yes No (Violet)

SPD No No No No Yes SY No No No (Violet)

36 Table 3-3 Fluorite calcium and fluoride compositions (weight percent)

Ca F Total Fluorite (wt %) (wt %) (wt %)

BCP 51.4 51.2 102.6

BCW 49.8 50.9 100.7

CH 52.1 50.2 102.3

IY 51.9 49.3 101.2

MP 52.0 50.1 102.1

MX 50.7 48.5 99.2

NGB 51.7 49.1 100.8

NGY 52.3 50.6 102.9

SPD 50.9 51.5 102.4

SY 50.6 50.7 101.3

Mean 51.3 ± 0.6 50.2 ± 0.7 101.6 ± 0.8

Median 51.6 50.4 101.7

37 Table 3-4 Fluorite trace element concentrations (mg/g).

Analyte BCP BCW CH IY MP MX NGB NGY SPD SY

Al < 0.3 < 0.3 < 0.3 < 0.3 < 0.3 < 0.3 < 0.3 < 0.3 < 0.3 < 0.3

As < 0.2 < 0.2 < 0.2 < 0.2 < 0.2 < 0.2 < 0.2 < 0.2 < 0.2 < 0.2

B 1.92 0.61 2.00 0.46 1.51 0.40 2.87 2.43 0.48 1.41

Ba 59 4.3 3.3 4.6 4.8 15 3.8 4.4 4.8 4.0

Be < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 0.19 0.03 < 0.01 < 0.01

Cd <0.02 <0.02 <0.02 0.08 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02

Co <0.02 0.06 0.05 0.07 0.19 0.19 0.04 <0.02 0.71 0.07

Cr <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 0.03

Cu <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02

Fe <0.02 <0.02 0.58 <0.02 8.78 0.14 0.06 <0.02 <0.02 0.52

K 2.33 2.45 0.67 1.97 2.75 2.69 0.64 2.49 6.85 4.70

Li 0.07 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 0.08 <0.05

Mg 11 1.8 1.3 1.3 2.1 0.7 1.3 1.2 18 84

Mn 1.04 1.61 0.27 0.75 0.54 0.16 0.15 0.31 1.53 0.31

Mo <0.07 <0.07 <0.07 <0.07 <0.07 <0.07 <0.07 <0.07 <0.07 <0.07

38 Table 3-4 continued.

Analyte BCP BCW CH IY MP MX NGB NGY SPD SY

Na 3 6 12 32 17 9 35 18 45 5

Ni 0.07 0.10 0.87 0.09 5.4 0.34 0.15 0.22 0.12 0.72

P <0.5 0.80 0.87 <0.5 0.55 0.94 <0.5 0.75 0.62 <0.5

Pb <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

S 18 10 11 10 10 11 33 9 11 15

Sb <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

Se <0.4 <0.4 <0.4 <0.4 0.7 <0.4 <0.4 0.8 <0.4 <0.4

Si 142 54 19 6 9 17 120 38 139 2.0

Sn < 0.03 < 0.03 < 0.03 < 0.03 < 0.03 < 0.03 < 0.03 < 0.03 < 0.03 < 0.03

Sr 3.9 0.7 0.6 2.2 2.3 3.4 9.0 3.1 0.8 10

Ti < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01

Tl < 0.16 < 0.16 < 0.16 < 0.16 < 0.16 < 0.16 < 0.16 < 0.16 < 0.16 < 0.16

V < 0.16 < 0.16 < 0.16 < 0.16 < 0.16 < 0.16 < 0.16 < 0.16 < 0.16 < 0.16

Zn < 0.06 < 0.06 < 0.06 15.8 < 0.06 < 0.06 < 0.06 < 0.06 < 0.06 2.68

39 3.2 Fluorite Solubility Results

The fluorite solubility results are summarized in this section. The laboratory analytical results are provided in Appendix B. Figure 3-6 is a plot of fluoride versus calcium concentrations (in moles/L) at equilibrium for all of the fluorite samples analyzed during this study. Results for 5oC, 25oC, and 50oC and ionic strengths from near zero up to 0.72M are shown. The linear data cluster depicted on this figure demonstrates that the fluorite dissolved congruently in a 1:2 mole ratio of Ca:F and that solubility equilibrium was established for all of the samples.

The results of the individual fluorite solubility measurements are shown on Figures 3-7 through 3-16 as fluoride concentrations versus ionic strength for temperatures of 5oC, 25oC, and 50oC. The symbol shapes and colors on these figures represent the experiment temperature (i.e., 5oC is blue diamond, 25oC is green triangle, and 50oC is red square). Solubility equilibrium was approached from an undersaturated state (filled symbols) in triplicate for all of the fluorites and confirmed from a supersaturated state (open symbols) for a limited set of single samples (IY, MX, and SY) at 25oC and ionic strengths up to 0.72M.

Log Ksp* values were calculated using PHREEQC Version 3 and the equilibrium calcium and fluoride concentrations determined in this study at temperatures of 5, 25, and 50oC, and atmospheric pressure. The equilibrium calcium and fluoride concentrations used in the Ksp* calculations are provided in Appendix B. The PHREEQC input files are provided in Table C-2 in Appendix C. Figures 3-17 through 3-19 summarize the results of all of the log Ksp* values determined in this study for each temperature tested (5, 25, 50oC).

Log Ksp values at infinite dilution were calculated by fitting a line (solid red line) to the log Ksp* values shown in Figures 3-17 through 3-19 using CurveExpert Professional (Hyams Development 2017). A 95 percent lower and upper confidence interval is also shown (pink shading) around the best fit line depicted in Figures 3-17 through 3-19. The lower and upper

40 Figure 3-6 Fluoride-calcium concentration results for this study at temperatures of 5oC, 25oC, and 50oC and ionic strengths from near zero to 0.72M.

41 Figure 3-7 Browns Canyon Porcelain (BCP) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (green triangle), and 50oC (red square).

42 Figure 3-8 Browns Canyon White (BCW) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (green triangle), and 50oC (red square).

43 Figure 3-9 Chinese Green (CH) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (green triangle), and 50oC (red square).

44 Figure 3-10 Illinois Yellow (IY) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (solid green triangle for undersaturated; open green triangle for supersaturated), and 50oC (red square).

45 Figure 3-11 Mexican Purple (MP) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (green triangle) and 50oC (red square).

46 Figure 3-12 Mexican Lilac (MX) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (solid green triangle for undersaturated; open green triangle for supersaturated), and 50oC (red square).

47 Figure 3-13 Northgate Blue (NGB) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (green triangle), and 50oC (red square).

48 Figure 3-14 Northgate Yellow (NGY) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (green triangle), and 50oC (red square).

49 Figure 3-15 St. Peter’s Dome (SPD) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (green triangle), and 50oC (red square).

50 Figure 3-16 Synthetic (SY) fluorite solubility results at temperatures of 5oC (blue diamond), 25oC (solid green triangle for undersaturated; open green triangle for supersaturated), and 50oC (red square).

51 Figure 3-17 Fluorite solubility log Ksp* (solid blue circles) versus ionic strength results at 5oC for all of the fluorite samples used in this study. Red line represents best-fit line to data depicted. Pink shading represents the 95% confidence interval for the best-fit line.

52 Figure 3-18 Fluorite solubility log Ksp* (solid blue circles) versus ionic strength results at 25oC for all of the fluorite samples used in this study. Red line represents best-fit line to data depicted. Pink shading represents the 95% confidence interval for the best-fit line.

53 Figure 3-19 Fluorite solubility log Ksp* (solid blue circles) versus ionic strength results at 50oC for all of the fluorite samples used in this study. Red line represents best-fit line to data depicted. Pink shading represents the 95% confidence interval for the best-fit line.

54 Table 3-5 Summary of log Ksp results at infinite dilution at temperatures of 5, 25, and 50oC and 1 atm pressure.

Sample Log Ksp at 5oC Log Ksp at 25oC Log Ksp at 50oC

BCP -10.73 ± 0.03 -10.64 ± 0.18 -10.45 ± 0.04

BCW -10.75 ± 0.02 -10.53 ± 0.01 -10.46 ± 0.02

CH -10.81 ± 0.01 -10.63 ± 0.01 -10.53 ± 0.10

IY -10.86 ± 0.03 -10.66 ± 0.01 -10.49 ± 0.01

MP -10.83 ± 0.02 -10.63 ± 0.02 -10.59 ± 0.13

MX -10.91 ± 0.06 -10.68 ± 0.03 -10.53 ± 0.03

NGB -10.82 ± 0.02 -10.63 ± 0.01 -10.50 ± 0.03

NGY -10.80 ± 0.02 -10.59 ± 0.03 -10.54 ± 0.04

SPD -10.77 ± 0.01 -10.54 ± 0.02 -10.49 ± 0.01

SY -10.97 ± 0.48 -10.70 ± 0.09 -10.47 ± 0.02

Median -10.81 ± 0.02 -10.63 ± 0.02 -10.49 ± 0.03

Minimum -10.97 -10.70 -10.59

Maximum -10.73 -10.53 -10.45

Range 0.24 0.17 0.14

55 Figure 3-20 Comparison of historical and this study’s log Ksp values.

56 confidence intervals provide an estimate of the experimental error for the median log Ksp values determined in this study. The resulting log Ksp value at infinite dilution estimated using these graphs represents a median value for all of the fluorites used in this study (5, 25, and 50oC). The results of log Ksp at infinite dilution calculations for each individual fluorite specimen used in this study are provided in Appendix D.

A summary of the individual and median log Ksp results at infinite dilution is provided in Table 3-5. Table 3-5 also provides the median, minimum, maximum, and range of log Ksp values derived from the solubility experiments conducted during this study. Review of Table 3-5 indicates that the median log Ksp values at temperatures of 5oC, 25oC, and 50oC are -10.81 ± 0.02, . -10.63 ± 0.02, and -10.49 ± 0.03, respectively. The range in log Ksp values is largest for the 5oC results (0.24) and similar for the 25oC and 50oC results (0.17 and 0.14, respectively). The slightly larger log Ksp range for 5oC likely results from less stringent temperature control during the solubility experiments.

3.3 Discussion

The solubility results indicate that fluorite congruently dissolves and shows an increasing solubility with temperature and ionic strength. Congruent dissolution is indicated by the expected and observed 1:2 Ca:F molar ratios in solution. Ionic strength appears to exert a greater influence on solubility than temperature. Figure 3-20 compares the historical and this study’s log Ksp values. The log Ksp data from this study (red triangles) exhibits an increasing solubility trend (i.e., decreasing log Ksp) with increasing temperature. The log Ksp data derived from this study provides an internally consistent dataset for fluorite solubility in low temperature aqueous solutions compared to historical data. This study’s results resolve the uncertainty in past work and provides an optimal solubility dataset for fluorite going forward.

3.3.1 Temperature Dependence of Fluorite Solubility

The solubility experiments demonstrate that fluorite solubility increases with temperature (Figure 3-21). The data shown on Figure 3-21 are median log Ksp values at infinite dilution listed on Table 3-5. The temperature effect observed is consistent with Le Chatelier’s principle

57 (1888) which states “when a stress is applied to a system in dynamic equilibrium, the equilibrium adjusts to minimize the effect of the stress.” Thus, an increase in temperature results in a shift in the system’s equilibrium by dissolving more fluorite to minimize the effect of the temperature

increase, thus increasing its log Ksp.

Figure 3-21 Log Ksp values at infinite dilution for samples used in this study versus temperature. Solid black circles represent the log Ksp value for the fluorites used in this study. The solid red line is the best-fit line to the data. The pink shading is the 95% confidence interval around the best-fit line.

3.3.2 Ionic Strength Dependence of Fluorite Solubility

The solubility experiments demonstrate that fluorite solubility also increases with increasing ionic strength (Figure 3-22). Figure 3-22 depicts the measured fluoride concentrations versus solution ionic strength at 25oC and 1 atmosphere pressure. The graph also shows the predicted fluoride concentration at various ionic strength using PHREEQC Version 3.12. PHREEQC uses the Truesdell and Jones (1974) model to calculate the effect of ionic strength on the activity coefficients of calcium and fluoride at ionic strengths up to 1 M. Figure 3-22 shows that the fluoride concentrations measured in this study increase logarithmically with increasing ionic strength. The fluoride concentrations (green triangles) determined in this study

58 Figure 3-22 Comparison of this study’s fluoride concentrations versus ionic strength at 25oC and 1 atm pressure (green triangle) with PHREEQC predicted fluoride concentrations and ionic strength (black diamond).

59 at ionic strengths of near zero, 0.1, 0.2, 0.3, 0.5, and 0.72M are consistent with the fluoride concentrations predicted using PHREEQC (black diamonds). This increase in fluorite solubility with increasing ionic strength results from the lower ion activities at higher ionic strengths. The lower ion activities are caused by the electrostatic interactions between charged ions and the formation of hydration shells around the ions which shields them from one another resulting in increased solubility.

3.3.3 Fluorite Thermodynamic Parameters

Fluorite thermodynamic parameters ( , ) were calculated from the ଴ ଴ ଴ equilibrium constants, Ksp, determined in thisοܩ study௙ ǡοܪ using௙ ܽ݊݀ theοܵ relationships outlined in the below equations:

= ଴ οܩ௥ െܴ݈ܶ݊ܭ௦௣ where R = 8.31446 J/mol*K and temperature is in degrees Kelvin (oK) and

଴ ଴ ଴ οܩ௥ ൌοܪ௥ െܶοܵ this can be combined to obtain

଴ ଴ ௦௣ ௥ െܴ݈ܶ݊ܭ ൌοܪ െܶοܵ o and rearranged to show the linear relationship between ln Ksp and 1/T ( K)

1 + . ଴ ଴ οܪ௥ οܵ ݈݊ܭ௦௣ ൌെቆ ቇ൬ ൰ ܴ ܶ ܴ A plot of ln Ksp versus 1/T yields a straight line with a slope of / and a y- ଴ intercept of / . The and values for the fluorite dissolutionെοܪ reaction௥ ܴ can be ଴ ଴ ଴ calculated basedοܵ onܴ the linearοܪ௥ equationοܵ obtained from fitting the ln Ksp versus 1/T data on Figure 3-23. Figure 3-23 is a graph showing the ln Ksp values determined in this study at infinite dilution (Table 3-5), i.e., zero ionic strength, versus 1/T values. A linear trend line (solid red line) fit to the data is shown on the figure along with its corresponding equation. The pink

60 shading represents the 95% confidence interval around the best-fit line. The resulting slope – / (-1,517.3 ± 130.6 K) and intercept / (-19.37 ± 0.44) were used to calculate ଴ 0 ଴ ଴ (12.44οܪ௥ ܴ kJ/mol) and ǻS (-161.9 J/mol*K) forοܵ the fluoriteܴ dissolution reaction. οܪ௥

Figure 3-23 Graph of log Ksp versus 1/T (K) for fluorites used in this study.

The standard free energy of reaction ( ) for the fluorite dissolution reaction evaluated ଴ in this study is defined as: ௥ οܩ

[ ] + 2 [ ] [ ]. ଴ ଴ ଶା ଴ ି ଴ οܩ௥ ൌοܩ௙ ܥܽ οܩ௙ ܨ െοܩ௙ ܥܽܨଶ Rearranging and solving for [ ] yields ଴ οܩ௙ ܥܽܨଶ [ ] [ ] + 2 [ ] . ଴ ଴ ଶା ଴ ି οܩ௙ ܥܽܨଶ ൌοܩ௙ ܥܽ οܩ௙ ܨ െοܩ௥ Substituting the values for [ ], -553.6 kJ/mol, and [ ], -281.5 ± 0.7 kJ/mol,

o ଴ ଶା ଴ ି for 25 C from the lookup tables in οܩRobie௙ ܥܽ and Hemmingway (1995)οܩ and௙ ܨthe value o ଴ determined in this study at 25 C, 61.07 ± 0.18 kJ/mol, yields a standard free energy௥ of formation οܩ for fluorite [ ] of -1,177.7 ± 0.2 kJ/mol which compares favorably with the -1,175.3 ଴ οܩ௙ ܥܽܨଶ 61 kJ/mol value reported in Robie and Hemmingway (1995) which was obtained from the CODATA thermodynamic tables (Garvin et al. 1987). Garvin et al. (1987) developed their reported thermodynamic data for fluorite from a compilation and evaluation of historical solubility results.

Similarly, the standard formation enthalpy ( ) for fluorite can be calculated using the

2+ - ଴ formation enthalpies for Ca and F from Robie andοܪ Hemmingway௙ (1995) and the reaction enthalpy ( ) determined for this study as shown below: ଴ οܪ௥ [ ] [ ] + 2 [ ] ଴ ଴ ଶା ଴ ି οܪ௙ ܥܽܨଶ ൌοܪ௙ ܥܽ οܪ௙ ܨ െοܪ௥ Substituting values for [ ], -543.0 ± 1.0 kJ/mol, and [ ], -335.4 ± 0.7

o ଴ ଶା ଴ ି kJ/mol, for 25 C from the lookupοܪ ௙tablesܥܽ in Robie and Hemmingway (1995)οܪ௙ ܨ and the value o ଴ determined in this study at 25 C, 13.05 ± 0.26 kJ/mol, yields a standard formation enthalpy௥ for οܪ fluorite ( [ ]) of -1,226.4 ± 1.1 kJ/mol which compares favorably with the -1,228.0 ± 2 ଴ kJ/mol valueοܪ௙ reportedܥܽܨଶ in Robie and Hemmingway (1995).

The standard formation entropy ( ) for fluorite can also be calculated using the 2+ - ଴ formation entropies for Ca and F from Robieοܵ and Hemmingway (1995) and the reaction entropy ( ) determined for this study as shown below: ଴ οܵ [ ] [ ] + 2 [ ] ଴ ଴ ଶା ଴ ି οܵ ܥܽܨଶ ൌοܵ ܥܽ οܵ ܨ െοܵ௥ Substituting values for [ ], -56.2 ± 1.0 J/mol*K, and [ ], -13.8 ± 0.8

o ଴ ଶା ଴ ି J/mol*K, for 25 C from the lookupοܵ tablesܥܽ in Robie and Hemmingwayοܵ (1995)ܨ and the value o ଴ determined in this study at 25 C, -159.8 ± 1.4 J/mol, yields a standard third law entropyοܵ for fluorite [ ] of 76.0 ± 3.7 J/mol*K which is about 9% higher than the entropy value (68.9 ଴ ± 0.3 J/mol)ܵ ܥܽܨ reportedଶ in Robie and Hemmingway (1995). The discrepancy between the entropy values likely relates to the range in the log Ksp values determined in this study as shown on Figure 3-22.

The results of this study provide a set of internally consistent set of thermodynamic parameters for fluorite as shown in Table 3-6 that are comparable with those presented in Robie 62 and Hemmingway (1995). This study’s results resolve the uncertainty in past work and provides an optimal solubility dataset for fluorite going forward.

Table 3-6 Fluorite Thermodynamic Parameters Determined in This Study at 25oC.

Parameter This Study Robie and Hemmingway (1995)

-1,177.7 ± 0.2 kJ/mol -1175.3 ± 2 kJ/mol ଴ ௙ οܩ -1,226.9 ± 1.1 kJ/mol -1,228.0 ± 2 kJ/mol ଴ ௙ οܪ 76.0 ± 3.7 J/mol*K 68.9± 0.3 J/mol*K ଴ ܵ 3.3.4 Fluorite Activity Coefficients

2 The product of the fluorite total ion activity coefficient [i.e., (ȖCa2+)(ȖF-) ] for the ionic strengths used in this study were derived from the mean Ksp* values and the extrapolated mean Ksp (Table 3-4) values at infinite dilution at 25oC using the below relationship

2 ȖCaF2 = (ȖCa+2)(ȖF-) = Ksp*/Ksp.

The derived fluorite total ion activity coefficients for each ionic strength used in this study are shown in Table 3-7. The fluorite total ion activity coefficients were also calculated using the extended Debye-Hückel and Davies equations and PHREEQC for comparison. The results show that the fluorite total ion activity coefficients decrease with increasing ionic strength (Figure 3-24) as electrostatic ion interactions increase. However, the results indicate that the derived fluorite total ion activity coefficients using the Ksp*/Ksp values determined in this study are similar, but higher than the fluorite total ion activity coefficients estimated using the extended Debye-Hückel equation, the Truesdale-Jones (“B-dot”) activity model included in PHREEQC, and the Davies equation. This difference in fluorite total ion activity coefficient values highlights the uncertainty in measured versus estimated activity coefficients and the effectiveness of the activity models in predicting activity coefficients.

63 Table 3-7 Derived and estimated fluorite total ion activity coefficients at 25oC.

This Study Debye-Hückel PHREEQC Davies I(M) ȖCaF2 ȖCaF2 ȖCaF2 ȖCaF2

0.0005 0.937 0.860 0.847 0.862

0.1 0.286 0.233 0.225 0.215

0.2 0.194 0.164 0.159 0.159

0.3 0.157 0.133 0.130 0.143

0.5 0.133 0.101 0.102 0.146

0.72 0.119 0.083 0.089 0.177

64 Figure 3-24 Comparison of this study’s measured fluorite total ion activity coefficients at 25oC with calculated fluorite total ion activity coefficients using Debye-Huckel, PHREEQC (Truesdell Jones), and Davies activity models.

65 CHAPTER 4

GEOCHEMICAL APPLICATION

In this chapter, the results of the fluorite solubility products determined from the experimental results in this study were used to evaluate their geochemical significance. Several example applications were selected from the literature for comparison. Comparisons were made by running equilibrium geochemical models and comparing the results using both the fluorite log Ksp in the model’s database and an average fluorite log Ksp value derived from the range of natural fluorite log Ksp values derived in this study.

4.1 Fluorite Log Ksp in Geochemical Model Databases

Fluorite Ksp values currently used in geochemical equilibrium models are not derived from a comprehensive study of fluorite solubility measurements, but are typically derived from a single Ksp measurement (e.g., PHREEQC) or extrapolated from thermodynamic data (e.g., EQ3/6). Table 4-1 provides a summary of the log Ksp values used in these models and the median log Ksp value determined in this study at 25oC. With the exception of EQ3/6, the log Ksp values for fluorite used in the other geochemical models are consistent with the median log Ksp determine in this study. Most of the models used the WATEQF fluorite log Ksp value which is derived from a single solubility-derived log Ksp value (Brown and Roberson 1977; Nordstrom et al. 1990). The log Ksp value used in EQ3/6 was calculated using SUPCRT92 (Johnson et al. 1992) using thermodynamic data from Helgeson et al. (1978) and Stull and Prophet (1971). The log Ksp value used in Geochemist’s Workbench is sourced from Nordstrom and Jenne (1977).

4.2 Fluorite Activity Diagrams

Fluorite activity diagrams were constructed using Geochemist’s Workbench Version 11 (Bethke and Yeakel 2018) for the F--Ca2+-temperature system using the median log Ksp values derived from this study for 5oC, 25oC, and 50oC and for the F--Ca2+-pH system using the median log Ksp value at 25oC to compare the effect of temperature and pH on the fluorite stability field.

66 Activity diagrams for log [F-] of 10-4, 10-3, and 10-2 were developed as Figures 4-1 and 4-2. The boundaries of the fluorite stability fields at the various F- activities is shown as solid red lines.

Figure 4-1 shows that the fluorite stability field decreases in size (i.e., the fluorite is more soluble) with decreasing fluoride activity [F-] and increasing temperature. Figure 4-2 also shows that the fluorite stability field decreases in size with decreasing fluoride activity. Figure 4-2 also shows that calcium activity [Ca2+] increases as fluoride activity decreases, which is consistent with the inverse fluorite equilibrium line shown on Figures 4-3, 4-4, and 4-5. Fluoride (F-) is the predominant aqueous species above pH 3.2; whereas HF is the predominant aqueous species below pH 3.2. Below pH 3.2, fluorite stability is inversely related to pH and calcium activity as shown by the sloping fluorite equilibrium line between pH 3.2 and 0.

Table 4-1 Comparison of log Ksp values in geochemical models with log Ksp values determined in this study.

Log Ksp Source

PHREEQC Version 3 -10.6 (Parkhurst and Appelo 2013) Geochemist’s Workbench Version 11 -10.96 (Bethke and Yeakel 2018) WATEQF -10.6 (Plummer et al 1976) MINTEQ -10.5 (Allison et al. 1991) MINEQL+ -10.5 (Environmental Research Software 2015)

-10.04 EQ3/6 Version 8 (Wolery and Jarek 2003)

This Study -10.63 (Median)

67 Figure 4-1 F-Ca-T(oC) activity diagram at 1 atm pressure and log [F-] = 10-2, 10-3, and 10-4.

68 Figure 4-2 F-Ca-pH activity diagram at 25oC, 1 atm pressure, and log [F-] = 10-2, 10-3, and 10-4.

69 4.3 Fluorite Saturation in Indian Groundwaters

Handa (1975) and Appelo and Postma (2005) demonstrated the stability of fluorite and the relative saturation of groundwaters with respect to fluorite using its solubility product. As discussed in Chapter 1 of this study, the dissolution of fluorite is shown by the following dissociation reaction:

2+ - CaF2 = Ca + 2F

For which the solubility product based on the median log Ksp determined in this study is defined as:

2+ - 2 -10.63 o KFluorite = [Ca ][F ] = 10 at 25 C

Where [Ca2+] and [F-] represent the activities of these constituents at 25oC. The above reaction can be rewritten as:

2+ - o log KFluorite = log[Ca ] + 2log[F ] = -10.63 at 25 C

o The log KFluorite value (-10.63) used in the above equations is the median log Ksp at 25 C and 1 atm pressure determined for this study (Table 3-5). Using this relationship a graph (Figure 4-2) was constructed that shows the equilibrium relationship between fluorite solubility and groundwater Ca and F concentrations. The fluorite solubility line plots as a straight line on the log-log plot as shown in Figure 4-3. Lines representing the upper and lower 95 per cent confidence intervals (dashed black lines) around the average log Ksp value for this study are also shown, along with a fluorite solubility line (red line) representing the log Ksp (-10.96) derived by Nordstrom and Jenne (1977).

Calcium and fluoride concentrations for groundwaters from several regions of India (Handa 1975) are shown as an example. Groundwaters that plot below the fluorite equilibrium line are undersaturated with respect to fluorite, while groundwaters that plot above the line are supersaturated with respect to fluorite. Figure 4-3 suggests that an upper limit on fluoride and calcium concentrations is controlled by fluorite.

70 Figure 4-3 Fluorite saturation in Indian groundwaters (data from Handa 1975). Fluorite equilibrium lines at 25oC from this study (black line) and Nordstrom and Jenne (1977; red line). Upper and lower confidence limits for this study shown as black dashed lines. 71 The inverse fluorite solubility relationship depicted in Figure 4-3 indicates that groundwater in equilibrium with fluorite would have a low fluoride concentration when the calcium concentration is high, and conversely a high fluoride concentration when calcium concentration is low. Appelo and Postma (2005) note that this relationship could be used to treat high fluoride concentration waters by introducing a source of soluble calcium such as gypsum

(CaSO4·2H2O), lime (CaO or Ca(OH)2), or calcium chloride (CaCl2) to induce fluorite precipitation.

4.4 Fluorite Saturation in Colorado Surface Waters

The U.S. Geological Survey (Church et al. 2012) conducted a detailed environmental assessment of the effects of historical mining on U.S. Forest Service lands in central Colorado known as the Central Colorado Assessment Project (CCAP). The Colorado Mineral Belt (Tweto and Sims 1963; Wilson and Sims 2003), a Proterozoic basement structure that controlled Cretaceous-Tertiary magmatism associated with mineralization, cuts diagonally across the 53,815 square kilometer CCAP study area.

The study involved the collection of stream sediments, macroinvertebrate, and filtered and unfiltered water quality samples from streams during low flow from 2004 to 2007. Church et al. (2012) stated that the primary goal of the CCAP environmental assessment was to compare the relationship between surface water and sediment geochemistry, and metal concentrations in aquatic fauna in mined, prospected, and unmined catchments.

Calcium and fluoride concentrations measured in the CCAP surface waters ranged from 1.33 mg/L to 261 mg/L and < 0.08 mg/L to 39 mg/L, respectively. The surface water sample temperatures ranged from 0.2oC to 24.1oC, and averaged 10.6oC. The surface water calcium and fluoride concentrations are shown on Figure 4-3 along with the fluorite equilibrium lines for 5oC (red line) and 25oC (black line) using the median log Ksp values determined in this study (Table 3-5). Surface waters that plot below the fluorite equilibrium line are undersaturated with respect to fluorite, while surface waters that plot above the line are supersaturated with respect to fluorite.

72 Figure 4-4 Fluorite saturation in Colorado surface waters (data from Church et al. 2012). Fluorite equilibrium lines at 5oC (red line) and 25oC (black line) derived using median log Ksp values from this study. 73 The results shown on Figure 4-3 indicate that almost all of the surface water samples, about 98 percent, collected in the CCAP are undersaturated with respect to fluorite. Only 2.3 percent of the surface water samples (8 out of 350) collected are near saturation, saturated, or supersaturated with respect to fluorite and suggests that fluorite generally has no control on surface water fluoride concentrations in Colorado surface waters.

4.5 Fluorite Saturation in Groundwater at West Chicago Site

This impetus for this research was based on supersaturated fluoride concentrations in groundwater at an environmental cleanup site known as West Chicago in Illinois. The fluoride in groundwater at the site was largely derived from spent HF solutions used to process rare earth and thorium sands that was discharged to a disposal pond and subsequently leaked to the underlying groundwater. Groundwater at this site occurs in glacial outwash aquifers designated the E and C Stratums and a Silurian dolomite bedrock aquifer termed the K Stratum.

Groundwater calcium and fluoride concentrations from these strata are shown on Figure 4-4 along with the fluorite equilibrium lines for 5oC (red line) and 25oC (black line) using the median log Ksp values determined in this study. The results shown on Figure 4-4 indicate that about 41 percent of the samples are supersaturated with respect to fluorite. Fluorite saturation in these samples ranges from near saturation, saturation index (SI) of +0.03 to a SI of +2.04. Most of the groundwaters from the E Stratum (solid blue circle)and about half of the groundwaters from the C Stratum (solid green square) are supersaturated with respect to fluorite. The K- Stratum (solid black triangles) are undersaturated with respect to fluorite.

Geochemical modeling using PHREEQC indicates that the West Chicago groundwaters are also supersaturated with respect to fluorapatite. Fluorapatite was allowed to precipitate in PHREEQC following the initial speciation calculation and the resulting Ca and F concentrations remaining in solution were posted on Figure 4-4 as open symbols for comparison to the initial Ca and F concentrations in groundwater. Allowing fluorapatite to precipitate generally reduced the fluorite saturation in these groundwaters, but not enough to reach fluorite equilibrium. Most of the E Stratum and some of the C Stratum groundwater remain supersaturated with respect to fluorite. The supersaturated fluorite conditions might result from kinetically-inhibited fluorite

74 precipitation, competition for Ca2+ by other inorganic or organic (e.g., oxalate) aqueous species, or a fluorine-bearing mineral not currently included in the PHREEQC database. Review of the PHREEQC output reveals that F- and Ca2+ are the predominant aqueous species present in West Chicago groundwater which suggests that competition for Ca2+ by inorganic aqueous species may not be responsible for fluorite supersaturation.

75 Figure 4-5 Fluorite saturation in West Chicago groundwaters. Fluorite equilibrium lines at 5oC (red line) and 25oC (black line) derived using median log Ksp values from this study. The solid symbols represent the Ca and F concentrations in the West Chicago groundwaters. The open symbols represent the predicted Ca and F concentrations in West Chicago groundwaters allowing fluorapatite precipitation in PHREEQC. 76 CHAPTER 5

CONCLUSIONS

A review of historical fluorite solubility research found that fluorite solubilities varied over three orders-of-magnitude and appear to be inconsistent with several recently determined fluorite solubilities. Past experiments were not comprehensive. They lacked physical and chemical characterization of the fluorites, were typically short duration experiments, were conducted over limited temperatures and ionic strengths, and did not determine solubilities from both undersaturated and supersaturated states.

This research involved a series of solubility experiments run over a period of three years using nine natural fluorites and one synthetic fluorite to determine their solubility in low temperature (5, 25, and 50oC) aqueous solutions and ionic strengths ranging from near zero to 0.72M. Equilibrium was approached from both undersaturated and supersaturated initial conditions. The fluorites were chemically and physically characterized using laboratory analyses, thin section petrography, UV fluorescence, and x-ray diffraction. The fluorite samples used were generally found to have similar chemical and physical properties. The chemical composition was approximately stoichiometric, with a mean calcium concentration of 51.3 ± 0.6 wt % and mean fluorine concentration of 50.2 ± 0.7 wt %. Fluorite unit cell edge lengths, volumes, and densities averaged 5.4630 ± 0.0007 Å, 163.04 ± 0.06 Å3, and 3.181 ± 0.009 g/cm3, respectively. No pattern in the solubility measurements were correlated with the trace elements in the fluorites used in this study.

The fluorite solubility results showed that fluorite dissolved congruently and increased in solubility with both temperature and ionic strength. Ionic strength appeared to have a stronger influence on solubility than temperature. The fluorite solubilities were relatively consistent, with median log Ksp values at infinite dilution that ranged from -10.81 ± 0.02 at 5oC, -10.63 ± 0.02 at 25oC, and -10.49 ± 0.03 at 50oC. An internally consistent set of fluorite thermodynamic data were determined from the log Ksp results for all the fluorites and calcium fluoride reagent tested in this study which yielded a .of -1,177.7 ± 0.2 kJ/mol, of -1,226.9 ± 1.1 kJ/mol, and ଴ ଴ of 76.0 ± 3.7 J/mol*K. Theseοܩ௙ results are in reasonable agreementοܪ௙ with those presented in ଴ ௙ ܵ 77 Robie and Hemmingway (1995) who reported a of -1,175.3 ± 2 kJ/mol, a of -1,228.0 ± ଴ ଴ 2 kJ/mol. However, the third law entropy value οܩdetermined௙ for this study was οܪabout௙ 9% higher than the reported value Soof 68.9 ± 0.3 J/mol*K. This discrepancy in entropy values likely results from the range in log Ksp values determined for the fluorites and calcium fluoride reagent during this study.

A comparison of the log Ksp values used in various geochemical models showed that log Ksp values used ranged from -10.04 to -10.96. Most of the models used similar log Ksp values (-10.5 to -10.6) which is consistent with the log Ksp (-10.63 ± 0.02) determined in this study. Several example applications were selected from the literature and personal experience to evaluate the geochemical significance of the fluorite solubility results determined in this study. The example applications included development of Ca-F-T and Ca-F-pH activity diagrams to show the effect of temperature and pH on the fluorite stability, fluorite saturation in Indian groundwaters, fluorite saturation in Colorado surface waters, and fluorite solubility in groundwater at a former thorium processing facility in Illinois.

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90 APPENDIX A

X-RAY DIFFRACTION RESULTS

91 Figure A-1 Full-scale XRD pattern for Browns Canyon Porcelain (BCP) fluorite.

92 Figure A-2 Expanded scale XRD pattern for Browns Canyon Porcelain (BCP) fluorite. 93 Figure A-3 Full-scale XRD pattern for Browns Canyon White (BCW) fluorite. 94 Figure A-4 Expanded scale XRD pattern for Browns Canyon White (BCW) fluorite. 95 Figure A-5 Full-scale XRD pattern for China Green (CH) fluorite. 96 Figure A-6 Expanded scale XRD pattern for China Green (CH) fluorite. 97 Figure A-7 Full-scale XRD pattern for Illinois Yellow (IY) fluorite. 98 Figure A-8 Expanded scale XRD pattern for Illinois Yellow (IY) fluorite. 99 Figure A-9 Full-scale XRD pattern for Mexican Purple (MP) fluorite. 100 Figure A-10 Expanded scale XRD pattern for Mexican Purple (MP) fluorite. 101 Figure A-11 Full-scale XRD pattern for Mexican Lilac (MX) fluorite. 102 Figure A-12 Expanded scale XRD pattern for Mexican Lilac (MX) fluorite. 103 Figure A-13 Full-scale XRD pattern for Northgate Blue (NGB) fluorite. 104 Figure A-14 Expanded scale XRD pattern for Northgate Blue (NGB) fluorite. 105 Figure A-15 Full-scale XRD pattern for Northgate Yellow (NGY) fluorite. 106 Figure A-16 Expanded scale XRD pattern for Northgate Yellow (NGY) fluorite. 107 Figure A-17 Full-scale XRD pattern for St. Peter’s Dome (SPD) fluorite. 108 Figure A-18 Expanded scale XRD pattern for St. Peter’s Dome (SPD) fluorite. 109 Figure A-19 Full-scale XRD pattern for Synthetic (SY) fluorite. 110 Figure A-20 Expanded scale XRD pattern for Synthetic (SY) fluorite. 111 Table A- 1 BCP CrystalSleuth unit cell refinement output.

BCP Cubic 1.541838 1.540562 1.544390 28.2897 1 1 1 2 47.0216 2 2 0 2 55.7655 3 1 1 2 68.6573 4 0 0 2 75.8407 3 3 1 2 87.6527 4 2 2 2 94.2253 5 1 1 2 105.8217 4 4 0 2 113.0741 5 3 1 2 126.2073 6 2 0 2 135.2333 5 3 3 2

***************************************************************************** **Program REFINE Version 3.0** Kurt Bartelmehs and Bob Downs, 1998 *****************************************************************************

BCP

Symmetry constraint is: CUBIC

Wavelength #1 = 1.541838 Wavelength #2 = 1.540562 Wavelength #3 = 1.544390

Refinement after correcting for machine error

MACHINE ERROR: -0.047

OBSERVED CALCULATED DIFFERENCE 2theta d h k l Wave# 2theta d 2theta d 28.2897 3.157189 1 1 1 2 28.3167 3.154232 0.0270 0.002957 47.0216 1.932727 2 2 0 2 47.0516 1.931565 0.0300 0.001162 55.7655 1.648360 3 1 1 2 55.8065 1.647244 0.0410 0.001116 68.6573 1.366714 4 0 0 2 68.7083 1.365823 0.0510 0.000892 75.8407 1.254035 3 3 1 2 75.8884 1.253365 0.0477 0.000670 87.6527 1.112834 4 2 2 2 87.4208 1.115189 -0.2319 -0.002355 94.2253 1.051701 5 1 1 2 94.2594 1.051411 0.0341 0.000291 105.8217 0.965929 4 4 0 2 105.8447 0.965782 0.0230 0.000147 113.0741 0.923580 5 3 1 2 113.0957 0.923465 0.0216 0.000115 126.2073 0.863891 6 2 0 2 126.2254 0.863822 0.0181 0.000069 135.2333 0.833186 5 3 3 2 135.2473 0.833144 0.0140 0.000042

rmse = 0.00115999258

A =5.463(1) B =5.463(1) C =5.463(1) Alpha =90 Beta =90 Gamma =90

Volume = 163.1(1)

112 Table A-2 BCW CrystalSleuth unit cell refinement output.

BCW Cubic 1.541838 1.540562 1.544390 28.3802 1 1 1 2 47.1041 2 2 0 2 55.8514 3 1 1 2 58.5702 2 2 2 2 68.7464 4 0 0 2 75.9181 3 3 1 2 87.4540 4 2 2 2 94.2951 5 1 1 2 105.8802 4 4 0 2 113.1312 5 3 1 2 115.6339 6 0 0 2 126.2642 6 2 0 2 135.2956 5 3 3 2 ***************************************************************************** **Program REFINE Version 3.0** Kurt Bartelmehs and Bob Downs, 1998 ***************************************************************************** BCW

Symmetry constraint is: CUBIC

Wavelength #1 = 1.541838 Wavelength #2 = 1.540562 Wavelength #3 = 1.544390

Refinement after correcting for machine error

MACHINE ERROR: -0.090

OBSERVED CALCULATED DIFFERENCE 2theta d h k l Wave# 2theta d 2theta d 28.3802 3.151973 1 1 1 2 28.3588 3.154315 -0.0214 -0.002341 47.1041 1.931187 2 2 0 2 47.0930 1.931615 -0.0111 -0.000428 55.8514 1.647187 3 1 1 2 55.8477 1.647287 -0.0037 -0.000100 58.5702 1.576918 2 2 2 2 58.5605 1.577157 -0.0097 -0.000239 68.7464 1.365905 4 0 0 2 68.7491 1.365858 0.0027 0.000047 75.9181 1.253548 3 3 1 2 75.9288 1.253398 0.0107 0.000151 87.4540 1.115288 4 2 2 2 87.4608 1.115219 0.0068 0.000069 94.2951 1.051471 5 1 1 2 94.2989 1.051438 0.0038 0.000033 105.8802 0.965829 4 4 0 2 105.8835 0.965808 0.0033 0.000021 113.1312 0.923504 5 3 1 2 113.1340 0.923489 0.0028 0.000015 115.6339 0.910569 6 0 0 2 115.6333 0.910572 -0.0006 -0.000003 126.2642 0.863837 6 2 0 2 126.2623 0.863845 -0.0019 -0.000007 135.2956 0.833128 5 3 3 2 135.2828 0.833166 -0.0128 -0.000038

rmse = 0.00009695781

A =5.46343(8) B =5.46343(8) C =5.46343(8) Alpha =90 Beta =90 Gamma =90

Volume = 163.079(7)

113 Table A-3 CH CrystalSleuth unit cell refinement output.

CH Cubic 1.541838 1.540562 1.544390 28.3802 1 1 1 2 47.1041 2 2 0 2 55.8514 3 1 1 2 58.5702 2 2 2 2 68.7464 4 0 0 2 75.9181 3 3 1 2 87.4540 4 2 2 2 94.2951 5 1 1 2 105.8802 4 4 0 2 113.1312 5 3 1 2 115.6336 6 0 0 2 126.2642 6 2 0 2 135.2956 5 3 3 2

************************************************************************** **Program REFINE Version 3.0** Kurt Bartelmehs and Bob Downs, 1998 CH

Symmetry constraint is: CUBIC

Wavelength #1 = 1.541838 Wavelength #2 = 1.540562 Wavelength #3 = 1.544390

Refinement after correcting for machine error

MACHINE ERROR: -0.090

OBSERVED CALCULATED DIFFERENCE 2theta d h k l Wave# 2theta d 2theta d 28.3802 3.151976 1 1 1 2 28.3588 3.154316 -0.0214 -0.002340 47.1041 1.931188 2 2 0 2 47.0931 1.931616 -0.0110 -0.000428 55.8514 1.647188 3 1 1 2 55.8477 1.647288 -0.0037 -0.000100 58.5702 1.576919 2 2 2 2 58.5605 1.577158 -0.0097 -0.000239 68.7464 1.365906 4 0 0 2 68.7491 1.365859 0.0027 0.000047 75.9181 1.253549 3 3 1 2 75.9288 1.253398 0.0107 0.000151 87.4540 1.115288 4 2 2 2 87.4607 1.115219 0.0067 0.000069 94.2951 1.051471 5 1 1 2 94.2989 1.051439 0.0038 0.000032 105.8802 0.965829 4 4 0 2 105.8835 0.965808 0.0033 0.000021 113.1312 0.923504 5 3 1 2 113.1340 0.923489 0.0028 0.000015 115.6336 0.910571 6 0 0 2 115.6333 0.910573 -0.0003 -0.000002 126.2642 0.863838 6 2 0 2 126.2623 0.863845 -0.0019 -0.000007 135.2956 0.833128 5 3 3 2 135.2828 0.833166 -0.0128 -0.000038

rmse = 0.00009693733

A =5.46344(8) B =5.46344(8) C =5.46344(8) Alpha =90 Beta =90 Gamma =90

Volume = 163.079(7)

114 Table A-4 IY CrystalSleuth unit cell refinement output.

IY Cubic 1.541838 1.540562 1.544390 28.3123 1 1 1 2 47.0371 2 2 0 2 55.7882 3 1 1 2 58.5041 2 2 2 2 68.6761 4 0 0 2 75.8554 3 3 1 2 87.3883 4 2 2 2 94.2386 5 1 1 2 105.8267 4 4 0 2 113.0779 5 3 1 2 115.5638 6 0 0 2 126.2054 6 2 0 2 135.2317 5 3 3 2 ***************************************************************************** **Program REFINE Version 3.0** Kurt Bartelmehs and Bob Downs, 1998 ***************************************************************************** IY

Symmetry constraint is: CUBIC

Wavelength #1 = 1.541838 Wavelength #2 = 1.540562 Wavelength #3 = 1.544390

Refinement after correcting for machine error

MACHINE ERROR: -0.023

OBSERVED CALCULATED DIFFERENCE 2theta d h k l Wave# 2theta d 2theta d 28.3123 3.152116 1 1 1 2 28.2931 3.154211 -0.0192 -0.002095 47.0371 1.931203 2 2 0 2 47.0281 1.931552 -0.0090 -0.000349 55.7882 1.647095 3 1 1 2 55.7831 1.647233 -0.0051 -0.000138 58.5041 1.576906 2 2 2 2 58.4960 1.577105 -0.0081 -0.000199 68.6761 1.365970 4 0 0 2 68.6851 1.365813 0.0090 0.000157 75.8554 1.253494 3 3 1 2 75.8652 1.253356 0.0098 0.000137 87.3883 1.115278 4 2 2 2 87.3978 1.115182 0.0095 0.000097 94.2386 1.051385 5 1 1 2 94.2364 1.051404 -0.0022 -0.000019 105.8267 0.965745 4 4 0 2 105.8219 0.965776 -0.0048 -0.000031 113.0779 0.923433 5 3 1 2 113.0731 0.923458 -0.0048 -0.000025 115.5638 0.910587 6 0 0 2 115.5727 0.910542 0.0089 0.000045 126.2054 0.863808 6 2 0 2 126.2032 0.863816 -0.0022 -0.000008 135.2317 0.833119 5 3 3 2 135.2254 0.833138 -0.0063 -0.000019

rmse = 0.00010170562

A =5.46325(9) B =5.46325(9) C =5.46325(9) Alpha =90 Beta =90 Gamma =90

Volume = 163.062(8)

115 Table A-5 MP CrystalSleuth unit cell refinement output.

MP Cubic 1.541838 1.540562 1.544390 28.3450 1 1 1 2 47.0645 2 2 0 2 55.8151 3 1 1 2 58.5312 2 2 2 2 68.6979 4 0 0 2 75.8787 3 3 1 2 87.4081 4 2 2 2 94.2575 5 1 1 2 105.8396 4 4 0 2 113.0933 5 3 1 2 115.5965 6 0 0 2 126.2110 6 2 0 2 135.2500 5 3 3 2 ***************************************************************************** **Program REFINE Version 3.0** Kurt Bartelmehs and Bob Downs, 1998 ***************************************************************************** MP

Symmetry constraint is: CUBIC

Wavelength #1 = 1.541838 Wavelength #2 = 1.540562 Wavelength #3 = 1.544390

Refinement after correcting for machine error

MACHINE ERROR: -0.052

OBSERVED CALCULATED DIFFERENCE 2theta d h k l Wave# 2theta d 2theta d 28.3450 3.151662 1 1 1 2 28.3199 3.154399 -0.0251 -0.002737 47.0645 1.931247 2 2 0 2 47.0537 1.931667 -0.0108 -0.000420 55.8151 1.647140 3 1 1 2 55.8081 1.647331 -0.0070 -0.000191 58.5312 1.576941 2 2 2 2 58.5207 1.577199 -0.0105 -0.000258 68.6979 1.366088 4 0 0 2 68.7089 1.365895 0.0110 0.000193 75.8787 1.253567 3 3 1 2 75.8884 1.253431 0.0097 0.000136 87.4081 1.115367 4 2 2 2 87.4198 1.115248 0.0117 0.000119 94.2575 1.051467 5 1 1 2 94.2576 1.051466 0.0001 0.000001 105.8396 0.965845 4 4 0 2 105.8414 0.965833 0.0018 0.000012 113.0933 0.923503 5 3 1 2 113.0913 0.923513 -0.0020 -0.000011 115.5965 0.910566 6 0 0 2 115.5904 0.910597 -0.0061 -0.000030 126.2110 0.863895 6 2 0 2 126.2182 0.863868 0.0072 0.000028 135.2500 0.833150 5 3 3 2 135.2374 0.833188 -0.0126 -0.000038

rmse = 0.00011995277

A =5.4636(1) B =5.4636(1) C =5.4636(1) Alpha =90 Beta =90 Gamma =90

Volume = 163.092(9)

116 Table A-6 MX CrystalSleuth unit cell refinement output.

MX Cubic 1.541838 1.540562 1.544390 28.3647 1 1 1 2 47.0880 2 2 0 2 55.8360 3 1 1 2 58.5546 2 2 2 2 68.7293 4 0 0 2 75.9112 3 3 1 2 87.4411 4 2 2 2 94.2878 5 1 1 2 105.8741 4 4 0 2 113.1251 5 3 1 2 115.6252 6 0 0 2 126.2589 6 2 0 2 135.2846 5 3 3 2 ***************************************************************************** **Program REFINE Version 3.0** Kurt Bartelmehs and Bob Downs, 1998 ***************************************************************************** MX

Symmetry constraint is: CUBIC

Wavelength #1 = 1.541838 Wavelength #2 = 1.540562 Wavelength #3 = 1.544390

Refinement after correcting for machine error

MACHINE ERROR: -0.074

OBSERVED CALCULATED DIFFERENCE 2theta d h k l Wave# 2theta d 2theta d 28.3647 3.151916 1 1 1 2 28.3440 3.154178 -0.0207 -0.002261 47.0880 1.931190 2 2 0 2 47.0792 1.931531 -0.0088 -0.000341 55.8360 1.647171 3 1 1 2 55.8343 1.647216 -0.0017 -0.000045 58.5546 1.576908 2 2 2 2 58.5472 1.577089 -0.0074 -0.000181 68.7293 1.365924 4 0 0 2 68.7365 1.365799 0.0072 0.000125 75.9112 1.253420 3 3 1 2 75.9167 1.253343 0.0055 0.000077 87.4411 1.115256 4 2 2 2 87.4495 1.115170 0.0084 0.000086 94.2878 1.051397 5 1 1 2 94.2883 1.051393 0.0005 0.000004 105.8741 0.965766 4 4 0 2 105.8741 0.965766 0.0000 0.000000 113.1251 0.923451 5 3 1 2 113.1255 0.923449 0.0004 0.000002 115.6252 0.910533 6 0 0 2 115.6252 0.910533 0.0000 0.000000 126.2589 0.863796 6 2 0 2 126.2561 0.863807 -0.0028 -0.000011 135.2846 0.833113 5 3 3 2 135.2789 0.833130 -0.0057 -0.000017

rmse = 0.00007872665

A =5.46320(7) B =5.46320(7) C =5.46320(7) Alpha =90 Beta =90 Gamma =90

Volume = 163.057(6)

117 Table A-7 NGB CrystalSleuth unit cell refinement output.

NGB Cubic 1.541838 1.540562 1.544390 28.3067 1 1 1 2 47.0343 2 2 0 2 55.7840 3 1 1 2 68.6819 4 0 0 2 75.8580 3 3 1 2 87.4010 4 2 2 2 94.2491 5 1 1 2 105.8260 4 4 0 2 113.0955 5 3 1 2 126.2337 6 2 0 2 135.2664 5 3 3 2

NGB

Symmetry constraint is: CUBIC

Wavelength #1 = 1.541838 Wavelength #2 = 1.540562 Wavelength #3 = 1.544390

Refinement after correcting for machine error

MACHINE ERROR: -0.010

OBSERVED CALCULATED DIFFERENCE 2theta d h k l Wave# 2theta d 2theta d 28.3067 3.151281 1 1 1 2 28.2850 3.153646 -0.0217 -0.002366 47.0343 1.930798 2 2 0 2 47.0238 1.931206 -0.0105 -0.000408 55.7840 1.646849 3 1 1 2 55.7807 1.646938 -0.0033 -0.000089 68.6819 1.365637 4 0 0 2 68.6858 1.365569 0.0039 0.000069 75.8580 1.253271 3 3 1 2 75.8679 1.253132 0.0099 0.000139 87.4010 1.115014 4 2 2 2 87.4041 1.114982 0.0031 0.000032 94.2491 1.051182 5 1 1 2 94.2452 1.051215 -0.0039 -0.000033 105.8260 0.965665 4 4 0 2 105.8358 0.965603 0.0098 0.000062 113.0955 0.923269 5 3 1 2 113.0909 0.923293 -0.0046 -0.000025 126.2337 0.863649 6 2 0 2 126.2304 0.863662 -0.0033 -0.000013 135.2664 0.832976 5 3 3 2 135.2620 0.832989 -0.0044 -0.000013

rmse = 0.00009601684

A =5.46228(9) B =5.46228(9) C =5.46228(9) Alpha =90 Beta =90 Gamma =90

Volume = 162.975(8)

118 Table A-8 NGY CrystalSleuth unit cell refinement output.

NGY Cubic 1.541838 1.540562 1.544390 28.3676 1 1 1 2 47.0907 2 2 0 2 55.8375 3 1 1 2 58.5539 2 2 2 2 68.7279 4 0 0 2 75.9049 3 3 1 2 87.4323 4 2 2 2 94.2769 5 1 1 2 105.8651 4 4 0 2 113.1148 5 3 1 2 115.6082 6 0 0 2 126.2416 6 2 0 2 135.2538 5 3 3 2 ***************************************************************************** **Program REFINE Version 3.0** Kurt Bartelmehs and Bob Downs, 1998 NGY

Symmetry constraint is: CUBIC

Wavelength #1 = 1.541838 Wavelength #2 = 1.540562 Wavelength #3 = 1.544390

Refinement after correcting for machine error

MACHINE ERROR: -0.081

OBSERVED CALCULATED DIFFERENCE 2theta d h k l Wave# 2theta d 2theta d 28.3676 3.152370 1 1 1 2 28.3475 3.154564 -0.0201 -0.002194 47.0907 1.931359 2 2 0 2 47.0801 1.931768 -0.0106 -0.000409 55.8375 1.647322 3 1 1 2 55.8340 1.647417 -0.0035 -0.000096 58.5539 1.577098 2 2 2 2 58.5464 1.577282 -0.0075 -0.000184 68.7279 1.366072 4 0 0 2 68.7339 1.365966 0.0060 0.000105 75.9049 1.253608 3 3 1 2 75.9128 1.253497 0.0079 0.000111 87.4323 1.115417 4 2 2 2 87.4431 1.115307 0.0108 0.000110 94.2769 1.051550 5 1 1 2 94.2802 1.051521 0.0033 0.000028 105.8651 0.965868 4 4 0 2 105.8626 0.965884 -0.0025 -0.000016 113.1148 0.923543 5 3 1 2 113.1113 0.923562 -0.0035 -0.000018 115.6082 0.910653 6 0 0 2 115.6100 0.910644 0.0018 0.000009 126.2416 0.863890 6 2 0 2 126.2355 0.863913 -0.0061 -0.000023 135.2538 0.833226 5 3 3 2 135.2519 0.833232 -0.0019 -0.000006

rmse = 0.00009130658

A =5.46387(8) B =5.46387(8) C =5.46387(8) Alpha =90 Beta =90 Gamma =90

Volume = 163.117(7)

119 Table A-9 SPD CrystalSleuth unit cell refinement output.

SPD Cubic 1.541838 1.540562 1.544390 28.3303 1 1 1 2 47.0525 2 2 0 2 55.8024 3 1 1 2 68.6889 4 0 0 2 75.8648 3 3 1 2 87.4044 4 2 2 2 94.2409 5 1 1 2 105.8273 4 4 0 2 113.0788 5 3 1 2 115.5765 6 0 0 2 126.2098 6 2 0 2 135.2458 5 3 3 2 ***************************************************************************** **Program REFINE Version 3.0** Kurt Bartelmehs and Bob Downs, 1998 ***************************************************************************** SPD

Symmetry constraint is: CUBIC

Wavelength #1 = 1.541838 Wavelength #2 = 1.540562 Wavelength #3 = 1.544390

Refinement after correcting for machine error

MACHINE ERROR: -0.035

OBSERVED CALCULATED DIFFERENCE 2theta d h k l Wave# 2theta d 2theta d 28.3303 3.151425 1 1 1 2 28.3041 3.154288 -0.0262 -0.002862 47.0525 1.931059 2 2 0 2 47.0386 1.931599 -0.0139 -0.000540 55.8024 1.647027 3 1 1 2 55.7933 1.647273 -0.0091 -0.000247 68.6889 1.365950 4 0 0 2 68.6948 1.365847 0.0059 0.000104 75.8648 1.253526 3 3 1 2 75.8747 1.253387 0.0099 0.000139 87.4044 1.115233 4 2 2 2 87.4068 1.115209 0.0024 0.000024 94.2409 1.051465 5 1 1 2 94.2451 1.051429 0.0042 0.000035 105.8273 0.965816 4 4 0 2 105.8299 0.965799 0.0026 0.000016 113.0788 0.923490 5 3 1 2 113.0806 0.923481 0.0018 0.000009 115.5765 0.910582 6 0 0 2 115.5799 0.910564 0.0034 0.000017 126.2098 0.863835 6 2 0 2 126.2093 0.863837 -0.0005 -0.000002 135.2458 0.833112 5 3 3 2 135.2303 0.833159 -0.0155 -0.000046

rmse = 0.00010841306

A =5.46339(9) B =5.46339(9) C =5.46339(9) Alpha =90 Beta =90 Gamma =90

Volume = 163.074(8)

120 Table A-10 SY CrystalSleuth unit cell refinement output.

SY Cubic 1.541838 1.540562 1.544390 28.3121 1 1 1 2 32.7888 2 0 0 2 47.0491 2 2 0 2 55.8048 3 1 1 2 58.5193 2 2 2 2 68.7087 4 0 0 2 75.8938 3 3 1 2 87.4389 4 2 2 2 94.2859 5 1 1 2 105.8907 4 4 0 2 113.1575 5 3 1 2 115.6536 6 0 0 2 126.3118 6 2 0 2 135.3568 5 3 3 2 ***************************************************************************** **Program REFINE Version 3.0** Kurt Bartelmehs and Bob Downs, 1998 ***************************************************************************** SY Symmetry constraint is: CUBIC

Wavelength #1 = 1.541838 Wavelength #2 = 1.540562 Wavelength #3 = 1.544390

Refinement after correcting for machine error

MACHINE ERROR: -0.012

OBSERVED CALCULATED DIFFERENCE 2theta d h k l Wave# 2theta d 2theta d 28.3121 3.150881 1 1 1 2 28.2965 3.152579 -0.0156 -0.001699 32.7888 2.730037 2 0 0 2 32.7866 2.730214 -0.0022 -0.000176 47.0491 1.930292 2 2 0 2 47.0424 1.930553 -0.0067 -0.000261 55.8048 1.646332 3 1 1 2 55.8030 1.646381 -0.0018 -0.000049 58.5193 1.576249 2 2 2 2 58.5177 1.576290 -0.0016 -0.000040 68.7087 1.365200 4 0 0 2 68.7141 1.365107 0.0054 0.000093 75.8938 1.252793 3 3 1 2 75.8999 1.252708 0.0061 0.000085 87.4389 1.114646 4 2 2 2 87.4429 1.114605 0.0040 0.000041 94.2859 1.050884 5 1 1 2 94.2887 1.050860 0.0028 0.000024 105.8907 0.965264 4 4 0 2 105.8888 0.965276 -0.0019 -0.000012 113.1575 0.922948 5 3 1 2 113.1513 0.922981 -0.0062 -0.000033 115.6536 0.910080 6 0 0 2 115.6553 0.910071 0.0017 0.000009 126.3118 0.863357 6 2 0 2 126.3086 0.863369 -0.0032 -0.000012 135.3568 0.832711 5 3 3 2 135.3580 0.832707 0.0012 0.000004

rmse = 0.00005955433

A =5.46043(5) B =5.46043(5) C =5.46043(5) Alpha =90 Beta =90 Gamma =90 Volume = 162.810(5)

121 APPENDIX B

LABORATORY ANALYTICAL RESULTS

122 Table B-1 Laboratory analytical results for this study.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 1 BCP-05U-01 7 5 0.0005 7.4 6.9 2 BCP-05U-02 7 5 0.0005 7.4 6.8 3 BCP-05U-03 7 5 0.0005 7.4 6.8 4 BCP-05U-11 6.79 5 0.1 11.5 10.5 5 BCP-05U-12 6.79 5 0.1 11.4 10.4 6 BCP-05U-13 6.79 5 0.1 11.3 10.4 7 BCP-05U-21 6.56 5 0.2 12.7 11.7 8 BCP-05U-22 6.56 5 0.2 12.8 11.7 9 BCP-05U-23 6.56 5 0.2 12.6 11.6 10 BCP-05U-31 6.54 5 0.3 13.4 12.4 11 BCP-05U-32 6.54 5 0.3 13.5 12.4 12 BCP-05U-33 6.54 5 0.3 13.5 12.5 13 BCP-05U-51 6.14 5 0.5 14.7 13.5 14 BCP-05U-52 6.14 5 0.5 14.8 13.6 15 BCP-05U-53 6.14 5 0.5 14.8 13.5 16 BCP-05U-71 6.16 5 0.72 15.4 14.1 17 BCP-05U-72 6.16 5 0.72 15.3 14.0 18 BCP-05U-73 6.16 5 0.72 15.1 14.0 19 BCP-25U-01 7 25 0.0005 9.0 8.2 20 BCP-25U-02 7 25 0.0005 8.9 8.2 21 BCP-25U-03 7 25 0.0005 9.0 8.2 22 BCP-25U-11 6.79 25 0.1 14.2 12.8 23 BCP-25U-12 6.79 25 0.1 14.0 12.8 24 BCP-25U-13 6.79 25 0.1 14.1 12.7

123 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 25 BCP-25U-21 6.56 25 0.2 15.5 14.1 26 BCP-25U-22 6.56 25 0.2 15.1 13.9 27 BCP-25U-23 6.56 25 0.2 15.3 13.9 28 BCP-25U-31 6.54 25 0.3 16.4 14.9 29 BCP-25U-32 6.54 25 0.3 16.4 14.8 30 BCP-25U-33 6.54 25 0.3 16.3 14.8 31 BCP-25U-51 6.14 25 0.5 17.7 16.0 32 BCP-25U-52 6.14 25 0.5 17.1 15.9 33 BCP-25U-53 6.14 25 0.5 17.4 15.9 34 BCP-25U-71 6.16 25 0.72 17.5 16.9 35 BCP-25U-72 6.16 25 0.72 17.9 16.9 36 BCP-25U-73 6.16 25 0.72 17.3 16.9 37 BCP-50U-01 7 50 0.0005 9.2 8.7 38 BCP-50U-02 7 50 0.0005 9.4 8.9 39 BCP-50U-03 7 50 0.0005 9.1 8.9 40 BCP-50U-11 6.79 50 0.1 14.9 13.4 41 BCP-50U-12 6.79 50 0.1 14.4 13.4 42 BCP-50U-13 6.79 50 0.1 14.8 13.4 43 BCP-50U-21 6.56 50 0.2 16.7 15.2 44 BCP-50U-22 6.56 50 0.2 16.4 15.2 45 BCP-50U-23 6.56 50 0.2 16.5 15.0 46 BCP-50U-31 6.54 50 0.3 17.8 16.5 47 BCP-50U-32 6.54 50 0.3 17.4 16.4 48 BCP-50U-33 6.54 50 0.3 17.5 16.3

124 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 49 BCP-50U-51 6.14 50 0.5 19.7 17.8 50 BCP-50U-52 6.14 50 0.5 19.5 17.9 51 BCP-50U-53 6.14 50 0.5 19.6 17.8 52 BCP-50U-71 6.16 50 0.72 21.5 18.8 53 BCP-50U-72 6.16 50 0.72 21.1 18.8 54 BCP-50U-73 6.16 50 0.72 21.2 18.7 55 BCW-05U-01 7 5 0.0005 7.3 6.5 56 BCW-05U-02 7 5 0.0005 7.2 6.5 57 BCW-05U-03 7 5 0.0005 7.2 6.5 58 BCW-05U-11 6.79 5 0.1 10.6 9.7 59 BCW-05U-12 6.79 5 0.1 10.4 9.6 60 BCW-05U-13 6.79 5 0.1 10.7 9.6 61 BCW-05U-21 6.56 5 0.2 11.4 11.1 62 BCW-05U-22 6.56 5 0.2 11.6 11.2 63 BCW-05U-23 6.56 5 0.2 11.9 11.2 64 BCW-05U-31 6.54 5 0.3 12.9 12.1 65 BCW-05U-32 6.54 5 0.3 13.1 12.1 66 BCW-05U-33 6.54 5 0.3 13.1 12.0 67 BCW-05U-51 6.14 5 0.5 13.7 13.0 68 BCW-05U-52 6.14 5 0.5 13.8 13.0 69 BCW-05U-53 6.14 5 0.5 13.8 12.9 70 BCW-05U-71 6.16 5 0.72 14.5 13.5 71 BCW-05U-72 6.16 5 0.72 15.0 13.6 72 BCW-05U-73 6.16 5 0.72 14.5 13.5

125 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 73 BCW-25U-01 7 25 0.0005 8.6 7.8 74 BCW-25U-02 7 25 0.0005 8.6 7.8 75 BCW-25U-03 7 25 0.0005 8.4 7.8 76 BCW-25U-11 6.79 25 0.1 12.5 12.0 77 BCW-25U-12 6.79 25 0.1 12.8 12.0 78 BCW-25U-13 6.79 25 0.1 12.5 12.0 79 BCW-25U-21 6.56 25 0.2 14.5 13.5 80 BCW-25U-22 6.56 25 0.2 14.4 13.5 81 BCW-25U-23 6.56 25 0.2 14.1 13.5 82 BCW-25U-31 6.54 25 0.3 15.5 14.4 83 BCW-25U-32 6.54 25 0.3 15.3 14.4 84 BCW-25U-33 6.54 25 0.3 15.6 14.3 85 BCW-25U-51 6.14 25 0.5 16.4 15.4 86 BCW-25U-52 6.14 25 0.5 16.2 15.4 87 BCW-25U-53 6.14 25 0.5 16.1 15.3 88 BCW-25U-71 6.16 25 0.72 17.0 15.9 89 BCW-25U-72 6.16 25 0.72 16.7 15.9 90 BCW-25U-73 6.16 25 0.72 16.8 15.9 91 BCW-50U-01 7 50 0.0005 9.0 8.6 92 BCW-50U-02 7 50 0.0005 8.7 8.5 93 BCW-50U-03 7 50 0.0005 8.8 8.6 94 BCW-50U-11 6.79 50 0.1 14.2 13.8 95 BCW-50U-12 6.79 50 0.1 14.2 13.7 96 BCW-50U-13 6.79 50 0.1 14.0 13.7

126 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 97 BCW-50U-21 6.56 50 0.2 16.3 15.3 98 BCW-50U-22 6.56 50 0.2 16.5 15.4 99 BCW-50U-23 6.56 50 0.2 16.4 15.5 100 BCW-50U-31 6.54 50 0.3 17.7 16.5 101 BCW-50U-32 6.54 50 0.3 17.3 16.5 102 BCW-50U-33 6.54 50 0.3 17.6 16.5 103 BCW-50U-51 6.14 50 0.5 18.6 17.7 104 BCW-50U-52 6.14 50 0.5 18.5 17.8 105 BCW-50U-53 6.14 50 0.5 18.5 17.7 106 BCW-50U-71 6.16 50 0.72 20.0 18.4 107 BCW-50U-72 6.16 50 0.72 19.8 18.5 108 BCW-50U-73 6.16 50 0.72 19.7 18.4 109 CH-05U-01 7 5 0.0005 6.8 6.3 110 CH-05U-02 7 5 0.0005 6.9 6.3 111 CH-05U-03 7 5 0.0005 6.7 6.3 112 CH-05U-11 6.79 5 0.1 10.1 9.3 113 CH-05U-12 6.79 5 0.1 10.2 9.3 114 CH-05U-13 6.79 5 0.1 10.0 9.3 115 CH-05U-21 6.56 5 0.2 11.1 10.6 116 CH-05U-22 6.56 5 0.2 11.2 10.6 117 CH-05U-23 6.56 5 0.2 11.3 10.7 118 CH-05U-31 6.54 5 0.3 12.4 11.3 119 CH-05U-32 6.54 5 0.3 12.0 11.2 120 CH-05U-33 6.54 5 0.3 12.3 11.3

127 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 121 CH-05U-51 6.14 5 0.5 13.1 12.1 122 CH-05U-52 6.14 5 0.5 13.3 12.1 123 CH-05U-53 6.14 5 0.5 12.9 12.1 124 CH-05U-71 6.16 5 0.72 13.6 12.8 125 CH-05U-72 6.16 5 0.72 13.7 12.7 126 CH-05U-73 6.16 5 0.72 13.9 12.8 127 CH-25U-01 7 25 0.0005 7.8 7.2 128 CH-25U-02 7 25 0.0005 7.7 7.3 129 CH-25U-03 7 25 0.0005 7.8 7.2 130 CH-25U-11 6.79 25 0.1 11.9 11.1 131 CH-25U-12 6.79 25 0.1 11.6 11.1 132 CH-25U-13 6.79 25 0.1 11.5 11.1 133 CH-25U-21 6.56 25 0.2 13.3 12.7 134 CH-25U-22 6.56 25 0.2 13.6 12.7 135 CH-25U-23 6.56 25 0.2 13.0 12.7 136 CH-25U-31 6.54 25 0.3 14.0 13.4 137 CH-25U-32 6.54 25 0.3 14.5 13.4 138 CH-25U-33 6.54 25 0.3 14.4 13.4 139 CH-25U-51 6.14 25 0.5 15.1 14.3 140 CH-25U-52 6.14 25 0.5 15.3 14.2 141 CH-25U-53 6.14 25 0.5 15.2 14.3 142 CH-25U-71 6.16 25 0.72 15.7 14.9 143 CH-25U-72 6.16 25 0.72 15.3 14.9 144 CH-25U-73 6.16 25 0.72 15.6 14.9

128 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 145 CH-50U-01 7 50 0.0005 9.2 8.5 146 CH-50U-02 7 50 0.0005 9.1 8.4 147 CH-50U-03 7 50 0.0005 8.9 8.4 148 CH-50U-11 6.79 50 0.1 12.9 12.3 149 CH-50U-12 6.79 50 0.1 13.4 12.4 150 CH-50U-13 6.79 50 0.1 13.0 12.4 151 CH-50U-21 6.56 50 0.2 14.3 13.7 152 CH-50U-22 6.56 50 0.2 14.3 13.8 153 CH-50U-23 6.56 50 0.2 14.1 13.7 154 CH-50U-31 6.54 50 0.3 15.3 14.8 155 CH-50U-32 6.54 50 0.3 15.3 14.8 156 CH-50U-33 6.54 50 0.3 15.1 14.9 157 CH-50U-51 6.14 50 0.5 17.1 16.5 158 CH-50U-52 6.14 50 0.5 16.9 16.5 159 CH-50U-53 6.14 50 0.5 17.2 16.6 160 CH-50U-71 6.16 50 0.72 18.6 17.3 161 CH-50U-72 6.16 50 0.72 17.8 17.3 162 CH-50U-73 6.16 50 0.72 17.9 17.4 163 IY-05U-01 7 5 0.0005 6.4 6.2 164 IY-05U-02 7 5 0.0005 6.4 6.2 165 IY-05U-03 7 5 0.0005 6.5 6.2 166 IY-05U-11 6.79 5 0.1 10.0 9.1 167 IY-05U-12 6.79 5 0.1 9.9 9.2 168 IY-05U-13 6.79 5 0.1 9.8 9.0

129 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 169 IY-05U-21 6.56 5 0.2 10.8 10.1 170 IY-05U-22 6.56 5 0.2 10.9 10.2 171 IY-05U-23 6.56 5 0.2 10.7 10.1 172 IY-05U-31 6.54 5 0.3 11.9 11.0 173 IY-05U-32 6.54 5 0.3 11.8 10.8 174 IY-05U-33 6.54 5 0.3 12.0 10.9 175 IY-05U-51 6.14 5 0.5 12.7 11.8 176 IY-05U-52 6.14 5 0.5 12.6 11.8 177 IY-05U-53 6.14 5 0.5 12.5 11.9 178 IY-05U-71 6.16 5 0.72 13.0 12.3 179 IY-05U-72 6.16 5 0.72 13.2 12.4 180 IY-05U-73 6.16 5 0.72 13.0 12.4 181 IY-25U-01 7 25 0.0005 7.6 7.1 182 IY-25U-02 7 25 0.0005 7.4 7.1 183 IY-25U-03 7 25 0.0005 7.5 7.1 184 IY-25U-11 6.79 25 0.1 11.4 10.5 185 IY-25U-12 6.79 25 0.1 11.2 10.5 186 IY-25U-13 6.79 25 0.1 11.4 10.6 187 IY-25U-21 6.56 25 0.2 13.4 12.4 188 IY-25U-22 6.56 25 0.2 13.1 12.4 189 IY-25U-23 6.56 25 0.2 12.9 12.4 190 IY-25U-31 6.54 25 0.3 14.5 13.4 191 IY-25U-32 6.54 25 0.3 14.4 13.4 192 IY-25U-33 6.54 25 0.3 13.9 13.4

130 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 193 IY-25U-51 6.14 25 0.5 14.9 14.4 194 IY-25U-52 6.14 25 0.5 15.0 14.3 195 IY-25U-53 6.14 25 0.5 15.1 14.4 196 IY-25U-71 6.16 25 0.72 15.3 14.8 197 IY-25U-72 6.16 25 0.72 15.2 14.8 198 IY-25U-73 6.16 25 0.72 15.5 14.8 199 IY-50U-01 7 50 0.0005 8.7 8.1 200 IY-50U-02 7 50 0.0005 8.7 8.1 201 IY-50U-03 7 50 0.0005 8.6 8.1 202 IY-50U-11 6.79 50 0.1 12.5 11.6 203 IY-50U-12 6.79 50 0.1 12.4 11.5 204 IY-50U-13 6.79 50 0.1 12.4 11.5 205 IY-50U-21 6.56 50 0.2 14.5 14.0 206 IY-50U-22 6.56 50 0.2 14.5 13.9 207 IY-50U-23 6.56 50 0.2 14.6 13.8 208 IY-50U-31 6.54 50 0.3 15.6 15.1 209 IY-50U-32 6.54 50 0.3 15.7 15.2 210 IY-50U-33 6.54 50 0.3 16.0 15.2 211 IY-50U-51 6.14 50 0.5 16.5 16.1 212 IY-50U-52 6.14 50 0.5 16.7 16.0 213 IY-50U-53 6.14 50 0.5 16.6 16.1 214 IY-50U-71 6.16 50 0.72 17.7 16.8 215 IY-50U-72 6.16 50 0.72 17.5 16.7 216 IY-50U-73 6.16 50 0.72 17.6 16.7

131 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 217 MP-05U-01 7 5 0.0005 6.7 6.3 218 MP-05U-02 7 5 0.0005 6.6 6.3 219 MP-05U-03 7 5 0.0005 6.6 6.3 220 MP-05U-11 6.79 5 0.1 10.4 9.6 221 MP-05U-12 6.79 5 0.1 10.5 9.6 222 MP-05U-13 6.79 5 0.1 10.4 9.6 223 MP-05U-21 6.56 5 0.2 11.3 10.7 224 MP-05U-22 6.56 5 0.2 11.3 10.8 225 MP-05U-23 6.56 5 0.2 11.2 10.8 226 MP-05U-31 6.54 5 0.3 12.3 11.5 227 MP-05U-32 6.54 5 0.3 12.2 11.4 228 MP-05U-33 6.54 5 0.3 12.3 11.5 229 MP-05U-51 6.14 5 0.5 12.9 12.2 230 MP-05U-52 6.14 5 0.5 13.0 12.1 231 MP-05U-53 6.14 5 0.5 13.0 12.3 232 MP-05U-71 6.16 5 0.72 13.4 12.8 233 MP-05U-72 6.16 5 0.72 13.3 12.8 234 MP-05U-73 6.16 5 0.72 13.2 12.7 235 MP-25U-01 7 25 0.0005 7.9 7.3 236 MP-25U-02 7 25 0.0005 7.8 7.3 237 MP-25U-03 7 25 0.0005 8.0 7.3 238 MP-25U-11 6.79 25 0.1 12.2 11.3 239 MP-25U-12 6.79 25 0.1 12.0 11.3 240 MP-25U-13 6.79 25 0.1 12.1 11.4

132 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 241 MP-25U-21 6.56 25 0.2 13.8 12.7 242 MP-25U-22 6.56 25 0.2 13.3 12.7 243 MP-25U-23 6.56 25 0.2 13.5 12.7 244 MP-25U-31 6.54 25 0.3 14.6 13.5 245 MP-25U-32 6.54 25 0.3 14.6 13.5 246 MP-25U-33 6.54 25 0.3 14.5 13.5 247 MP-25U-51 6.14 25 0.5 15.1 14.2 248 MP-25U-52 6.14 25 0.5 14.8 14.2 249 MP-25U-53 6.14 25 0.5 14.8 14.2 250 MP-25U-71 6.16 25 0.72 15.4 14.9 251 MP-25U-72 6.16 25 0.72 15.5 14.9 252 MP-25U-73 6.16 25 0.72 15.6 15.0 253 MP-50U-01 7 50 0.0005 9.0 8.2 254 MP-50U-02 7 50 0.0005 9.0 8.2 255 MP-50U-03 7 50 0.0005 9.0 8.2 256 MP-50U-11 6.79 50 0.1 13.4 13.1 257 MP-50U-12 6.79 50 0.1 13.5 13.0 258 MP-50U-13 6.79 50 0.1 13.6 13.0 259 MP-50U-21 6.56 50 0.2 14.8 14.3 260 MP-50U-22 6.56 50 0.2 14.9 14.3 261 MP-50U-23 6.56 50 0.2 15.0 14.2 262 MP-50U-31 6.54 50 0.3 16.0 15.3 263 MP-50U-32 6.54 50 0.3 16.2 15.2 264 MP-50U-33 6.54 50 0.3 16.0 15.2

133 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 265 MP-50U-51 6.14 50 0.5 17.5 16.9 266 MP-50U-52 6.14 50 0.5 17.7 17.0 267 MP-50U-53 6.14 50 0.5 17.4 16.9 268 MP-50U-71 6.16 50 0.72 18.7 17.7 269 MP-50U-72 6.16 50 0.72 19.0 17.5 270 MP-50U-73 6.16 50 0.72 18.5 17.5 271 MX-05U-01 7 5 0.0005 6.3 6.0 272 MX-05U-02 7 5 0.0005 6.5 6.1 273 MX-05U-03 7 5 0.0005 6.2 6.1 274 MX-05U-11 6.79 5 0.1 10.5 9.5 275 MX-05U-12 6.79 5 0.1 10.4 9.5 276 MX-05U-13 6.79 5 0.1 10.2 9.5 277 MX-05U-21 6.56 5 0.2 10.9 10.5 278 MX-05U-22 6.56 5 0.2 11.0 10.6 279 MX-05U-23 6.56 5 0.2 11.2 10.5 280 MX-05U-31 6.54 5 0.3 12.0 11.3 281 MX-05U-32 6.54 5 0.3 11.8 11.2 282 MX-05U-33 6.54 5 0.3 11.8 11.3 283 MX-05U-51 6.14 5 0.5 12.5 12.2 284 MX-05U-52 6.14 5 0.5 12.5 12.2 285 MX-05U-53 6.14 5 0.5 12.6 12.2 286 MX-05U-71 6.16 5 0.72 13.0 12.6 287 MX-05U-72 6.16 5 0.72 12.9 12.5 288 MX-05U-73 6.16 5 0.72 13.2 12.6

134 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 289 MX-25U-01 7 25 0.0005 7.6 7.0 290 MX-25U-02 7 25 0.0005 7.6 7.0 291 MX-25U-03 7 25 0.0005 7.5 7.0 292 MX-25U-11 6.79 25 0.1 12.1 11.1 293 MX-25U-12 6.79 25 0.1 11.5 11.1 294 MX-25U-13 6.79 25 0.1 11.3 11.1 295 MX-25U-21 6.56 25 0.2 13.4 12.5 296 MX-25U-22 6.56 25 0.2 13.2 12.5 297 MX-25U-23 6.56 25 0.2 13.8 12.6 298 MX-25U-31 6.54 25 0.3 14.2 13.2 299 MX-25U-32 6.54 25 0.3 14.3 13.2 300 MX-25U-33 6.54 25 0.3 14.2 13.2 301 MX-25U-51 6.14 25 0.5 14.4 14.1 302 MX-25U-52 6.14 25 0.5 14.5 14.1 303 MX-25U-53 6.14 25 0.5 14.3 14.1 304 MX-25U-71 6.16 25 0.72 15.5 14.7 305 MX-25U-72 6.16 25 0.72 15.8 14.7 306 MX-25U-73 6.16 25 0.72 15.8 14.7 307 MX-50U-01 7 50 0.0005 8.6 8.0 308 MX-50U-02 7 50 0.0005 8.6 8.0 309 MX-50U-03 7 50 0.0005 8.5 8.0 310 MX-50U-11 6.79 50 0.1 13.1 12.7 311 MX-50U-12 6.79 50 0.1 13.6 12.9 312 MX-50U-13 6.79 50 0.1 13.2 12.7

135 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 313 MX-50U-21 6.56 50 0.2 14.8 14.5 314 MX-50U-22 6.56 50 0.2 14.5 14.3 315 MX-50U-23 6.56 50 0.2 14.6 14.3 316 MX-50U-31 6.54 50 0.3 16.0 15.2 317 MX-50U-32 6.54 50 0.3 16.0 15.0 318 MX-50U-33 6.54 50 0.3 16.1 15.0 319 MX-50U-51 6.14 50 0.5 16.7 16.3 320 MX-50U-52 6.14 50 0.5 16.6 16.3 321 MX-50U-53 6.14 50 0.5 16.8 16.3 322 MX-50U-71 6.16 50 0.72 17.3 16.9 323 MX-50U-72 6.16 50 0.72 17.2 16.7 324 MX-50U-73 6.16 50 0.72 17.8 16.7 325 NGB-05U-01 7 5 0.0005 6.5 6.2 326 NGB-05U-02 7 5 0.0005 6.6 6.3 327 NGB-05U-03 7 5 0.0005 6.4 6.3 328 NGB-05U-11 6.79 5 0.1 9.9 9.2 329 NGB-05U-12 6.79 5 0.1 9.7 9.2 330 NGB-05U-13 6.79 5 0.1 10.0 9.1 331 NGB-05U-21 6.56 5 0.2 11.4 10.7 332 NGB-05U-22 6.56 5 0.2 11.2 10.8 333 NGB-05U-23 6.56 5 0.2 11.6 10.7 334 NGB-05U-31 6.54 5 0.3 12.1 11.5 335 NGB-05U-32 6.54 5 0.3 12.4 11.5 336 NGB-05U-33 6.54 5 0.3 11.9 11.5

136 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 337 NGB-05U-51 6.14 5 0.5 12.9 12.2 338 NGB-05U-52 6.14 5 0.5 12.7 12.1 339 NGB-05U-53 6.14 5 0.5 12.4 12.1 340 NGB-05U-71 6.16 5 0.72 13.2 12.8 341 NGB-05U-72 6.16 5 0.72 13.3 12.8 342 NGB-05U-73 6.16 5 0.72 13.4 12.8 343 NGB-25U-01 7 25 0.0005 7.4 7.3 344 NGB-25U-02 7 25 0.0005 7.6 7.4 345 NGB-25U-03 7 25 0.0005 7.5 7.4 346 NGB-25U-11 6.79 25 0.1 11.4 10.4 347 NGB-25U-12 6.79 25 0.1 11.1 10.4 348 NGB-25U-13 6.79 25 0.1 11.2 10.4 349 NGB-25U-21 6.56 25 0.2 13.1 12.0 350 NGB-25U-22 6.56 25 0.2 13.0 12.0 351 NGB-25U-23 6.56 25 0.2 13.0 12.0 352 NGB-25U-31 6.54 25 0.3 14.2 13.3 353 NGB-25U-32 6.54 25 0.3 14.4 13.2 354 NGB-25U-33 6.54 25 0.3 14.3 13.2 355 NGB-25U-51 6.14 25 0.5 15.3 14.1 356 NGB-25U-52 6.14 25 0.5 14.5 14.1 357 NGB-25U-53 6.14 25 0.5 14.8 14.2 358 NGB-25U-71 6.16 25 0.72 15.3 14.9 359 NGB-25U-72 6.16 25 0.72 15.1 14.9 360 NGB-25U-73 6.16 25 0.72 15.4 14.9

137 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 361 NGB-50U-01 7 50 0.0005 8.3 8.1 362 NGB-50U-02 7 50 0.0005 8.6 8.1 363 NGB-50U-03 7 50 0.0005 8.4 8.2 364 NGB-50U-11 6.79 50 0.1 12.2 11.4 365 NGB-50U-12 6.79 50 0.1 12.2 11.2 366 NGB-50U-13 6.79 50 0.1 12.3 11.2 367 NGB-50U-21 6.56 50 0.2 13.3 12.9 368 NGB-50U-22 6.56 50 0.2 13.2 12.9 369 NGB-50U-23 6.56 50 0.2 13.6 13.0 370 NGB-50U-31 6.54 50 0.3 15.1 14.7 371 NGB-50U-32 6.54 50 0.3 15.2 14.8 372 NGB-50U-33 6.54 50 0.3 15.5 14.8 373 NGB-50U-51 6.14 50 0.5 16.9 16.2 374 NGB-50U-52 6.14 50 0.5 16.6 16.2 375 NGB-50U-53 6.14 50 0.5 16.5 16.1 376 NGB-50U-71 6.16 50 0.72 18.2 17.0 377 NGB-50U-72 6.16 50 0.72 17.7 16.9 378 NGB-50U-73 6.16 50 0.72 17.9 16.9 379 NGY-05U-01 7 5 0.0005 6.5 6.4 380 NGY-05U-02 7 5 0.0005 6.7 6.4 381 NGY-05U-03 7 5 0.0005 6.8 6.4 382 NGY-05U-11 6.79 5 0.1 10.4 9.9 383 NGY-05U-12 6.79 5 0.1 10.5 9.9 384 NGY-05U-13 6.79 5 0.1 10.6 9.9

138 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 385 NGY-05U-21 6.56 5 0.2 12.0 11.1 386 NGY-05U-22 6.56 5 0.2 11.9 11.2 387 NGY-05U-23 6.56 5 0.2 11.5 11.1 388 NGY-05U-31 6.54 5 0.3 12.3 12.0 389 NGY-05U-32 6.54 5 0.3 12.8 12.0 390 NGY-05U-33 6.54 5 0.3 12.5 12.0 391 NGY-05U-51 6.14 5 0.5 13.1 12.8 392 NGY-05U-52 6.14 5 0.5 13.0 12.8 393 NGY-05U-53 6.14 5 0.5 13.0 12.8 394 NGY-05U-71 6.16 5 0.72 13.6 13.1 395 NGY-05U-72 6.16 5 0.72 13.8 13.3 396 NGY-05U-73 6.16 5 0.72 14.2 13.1 397 NGY-25U-01 7 25 0.0005 8.2 7.5 398 NGY-25U-02 7 25 0.0005 8.2 7.5 399 NGY-25U-03 7 25 0.0005 8.1 7.5 400 NGY-25U-11 6.79 25 0.1 12.8 11.8 401 NGY-25U-12 6.79 25 0.1 12.5 11.7 402 NGY-25U-13 6.79 25 0.1 12.3 11.7 403 NGY-25U-21 6.56 25 0.2 13.4 13.0 404 NGY-25U-22 6.56 25 0.2 13.4 13.0 405 NGY-25U-23 6.56 25 0.2 13.8 13.0 406 NGY-25U-31 6.54 25 0.3 15.0 14.1 407 NGY-25U-32 6.54 25 0.3 15.2 14.1 408 NGY-25U-33 6.54 25 0.3 14.7 14.1

139 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 409 NGY-25U-51 6.14 25 0.5 15.8 14.8 410 NGY-25U-52 6.14 25 0.5 15.4 14.8 411 NGY-25U-53 6.14 25 0.5 15.9 14.8 412 NGY-25U-71 6.16 25 0.72 15.9 15.4 413 NGY-25U-72 6.16 25 0.72 16.1 15.4 414 NGY-25U-73 6.16 25 0.72 16.5 15.4 415 NGY-50U-01 7 50 0.0005 8.8 8.1 416 NGY-50U-02 7 50 0.0005 8.6 8.0 417 NGY-50U-03 7 50 0.0005 8.3 8.0 418 NGY-50U-11 6.79 50 0.1 13.6 13.0 419 NGY-50U-12 6.79 50 0.1 13.7 13.0 420 NGY-50U-13 6.79 50 0.1 13.8 13.0 421 NGY-50U-21 6.56 50 0.2 15.8 14.5 422 NGY-50U-22 6.56 50 0.2 15.1 14.6 423 NGY-50U-23 6.56 50 0.2 15.6 14.5 424 NGY-50U-31 6.54 50 0.3 16.7 15.6 425 NGY-50U-32 6.54 50 0.3 16.8 15.5 426 NGY-50U-33 6.54 50 0.3 16.8 15.5 427 NGY-50U-51 6.14 50 0.5 18.2 17.0 428 NGY-50U-52 6.14 50 0.5 18.5 17.0 429 NGY-50U-53 6.14 50 0.5 18.0 17.0 430 NGY-50U-71 6.16 50 0.72 18.6 17.7 431 NGY-50U-72 6.16 50 0.72 18.9 17.7 432 NGY-50U-73 6.16 50 0.72 19.0 17.6

140 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 433 SPD-05U-01 7 5 0.0005 6.9 6.5 434 SPD-05U-02 7 5 0.0005 6.9 6.5 435 SPD-05U-03 7 5 0.0005 6.7 6.5 436 SPD-05U-11 6.79 5 0.1 9.5 8.8 437 SPD-05U-12 6.79 5 0.1 9.6 8.8 438 SPD-05U-13 6.79 5 0.1 9.6 8.8 439 SPD-05U-21 6.56 5 0.2 11.4 10.5 440 SPD-05U-22 6.56 5 0.2 11.2 10.5 441 SPD-05U-23 6.56 5 0.2 11.0 10.5 442 SPD-05U-31 6.54 5 0.3 12.2 11.8 443 SPD-05U-32 6.54 5 0.3 12.7 11.8 444 SPD-05U-33 6.54 5 0.3 12.6 11.7 445 SPD-05U-51 6.14 5 0.5 13.3 13.0 446 SPD-05U-52 6.14 5 0.5 13.2 12.9 447 SPD-05U-53 6.14 5 0.5 13.1 12.8 448 SPD-05U-71 6.16 5 0.72 14.6 13.5 449 SPD-05U-72 6.16 5 0.72 14.6 13.6 450 SPD-05U-73 6.16 5 0.72 14.0 13.6 451 SPD-25U-01 7 25 0.0005 8.5 7.7 452 SPD-25U-02 7 25 0.0005 8.1 7.7 453 SPD-25U-03 7 25 0.0005 8.4 7.8 454 SPD-25U-11 6.79 25 0.1 10.9 10.5 455 SPD-25U-12 6.79 25 0.1 11.4 10.5 456 SPD-25U-13 6.79 25 0.1 11.2 10.5

141 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 457 SPD-25U-21 6.56 25 0.2 13.4 12.7 458 SPD-25U-22 6.56 25 0.2 13.8 12.7 459 SPD-25U-23 6.56 25 0.2 13.3 12.7 460 SPD-25U-31 6.54 25 0.3 15.3 14.0 461 SPD-25U-32 6.54 25 0.3 15.2 14.0 462 SPD-25U-33 6.54 25 0.3 14.5 14.0 463 SPD-25U-51 6.14 25 0.5 15.7 15.2 464 SPD-25U-52 6.14 25 0.5 15.8 15.2 465 SPD-25U-53 6.14 25 0.5 16.3 15.1 466 SPD-25U-71 6.16 25 0.72 14.1 16.0 467 SPD-25U-72 6.16 25 0.72 15.0 15.9 468 SPD-25U-73 6.16 25 0.72 15.0 15.9 469 SPD-50U-01 7 50 0.0005 8.4 8.1 470 SPD-50U-02 7 50 0.0005 8.8 8.1 471 SPD-50U-03 7 50 0.0005 8.6 8.1 472 SPD-50U-11 6.79 50 0.1 12.8 11.8 473 SPD-50U-12 6.79 50 0.1 12.1 11.7 474 SPD-50U-13 6.79 50 0.1 12.5 11.7 475 SPD-50U-21 6.56 50 0.2 15.4 14.5 476 SPD-50U-22 6.56 50 0.2 15.7 14.5 477 SPD-50U-23 6.56 50 0.2 15.6 14.4 478 SPD-50U-31 6.54 50 0.3 16.2 15.8 479 SPD-50U-32 6.54 50 0.3 16.9 15.7 480 SPD-50U-33 6.54 50 0.3 17.2 15.8

142 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 481 SPD-50U-51 6.14 50 0.5 17.8 17.0 482 SPD-50U-52 6.14 50 0.5 17.5 17.0 483 SPD-50U-53 6.14 50 0.5 18.2 17.0 484 SPD-50U-71 6.16 50 0.72 18.8 17.6 485 SPD-50U-72 6.16 50 0.72 18.9 17.6 486 SPD-50U-73 6.16 50 0.72 19.0 17.4 487 SY-05U-01 7 5 0.0005 6.5 6.0 488 SY-05U-02 7 5 0.0005 6.6 6.0 489 SY-05U-03 7 5 0.0005 6.4 6.0 490 SY-05U-11 6.79 5 0.1 9.8 9.0 491 SY-05U-12 6.79 5 0.1 9.7 9.0 492 SY-05U-13 6.79 5 0.1 9.5 9.0 493 SY-05U-21 6.56 5 0.2 10.6 10.2 494 SY-05U-22 6.56 5 0.2 10.8 10.2 495 SY-05U-23 6.56 5 0.2 11.1 10.2 496 SY-05U-31 6.54 5 0.3 11.3 10.9 497 SY-05U-32 6.54 5 0.3 11.0 10.8 498 SY-05U-33 6.54 5 0.3 11.3 10.8 499 SY-05U-51 6.14 5 0.5 12.5 11.9 500 SY-05U-52 6.14 5 0.5 12.0 11.8 501 SY-05U-53 6.14 5 0.5 12.0 11.7 502 SY-05U-71 6.16 5 0.72 13.6 12.6 503 SY-05U-72 6.16 5 0.72 13.6 12.7 504 SY-05U-73 6.16 5 0.72 13.7 12.6

143 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 505 SY-25U-01 7 25 0.0005 7.9 7.2 506 SY-25U-02 7 25 0.0005 7.5 7.2 507 SY-25U-03 7 25 0.0005 7.8 7.1 508 SY-25U-11 6.79 25 0.1 12.4 11.5 509 SY-25U-12 6.79 25 0.1 11.8 11.5 510 SY-25U-13 6.79 25 0.1 11.7 11.5 511 SY-25U-21 6.56 25 0.2 13.9 12.9 512 SY-25U-22 6.56 25 0.2 14.1 12.9 513 SY-25U-23 6.56 25 0.2 13.8 12.8 514 SY-25U-31 6.54 25 0.3 14.2 13.7 515 SY-25U-32 6.54 25 0.3 14.5 13.7 516 SY-25U-33 6.54 25 0.3 14.2 13.6 517 SY-25U-51 6.14 25 0.5 15.5 14.4 518 SY-25U-52 6.14 25 0.5 15.2 14.5 519 SY-25U-53 6.14 25 0.5 15.4 14.5 520 SY-25U-71 6.16 25 0.72 16.2 15.4 521 SY-25U-72 6.16 25 0.72 16.6 15.4 522 SY-25U-73 6.16 25 0.72 16.7 15.5 523 SY-50U-01 7 50 0.0005 8.7 8.4 524 SY-50U-02 7 50 0.0005 9.0 8.4 525 SY-50U-03 7 50 0.0005 8.6 8.4 526 SY-50U-11 6.79 50 0.1 14.6 13.5 527 SY-50U-12 6.79 50 0.1 14.3 13.5 528 SY-50U-13 6.79 50 0.1 14.6 13.5

144 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 529 SY-50U-21 6.56 50 0.2 15.8 14.7 530 SY-50U-22 6.56 50 0.2 15.7 14.7 531 SY-50U-23 6.56 50 0.2 15.9 14.6 532 SY-50U-31 6.54 50 0.3 16.3 15.5 533 SY-50U-32 6.54 50 0.3 16.8 15.5 534 SY-50U-33 6.54 50 0.3 16.5 15.6 535 SY-50U-51 6.14 50 0.5 17.2 16.5 536 SY-50U-52 6.14 50 0.5 17.9 16.5 537 SY-50U-53 6.14 50 0.5 17.8 16.5 538 SY-50U-71 6.16 50 0.72 18.8 17.6 539 SY-50U-72 6.16 50 0.72 19.0 17.6 540 SY-50U-73 6.16 50 0.72 18.4 17.6

800 IY-25S-01 7 25 0.0005 7.9 7.3 801 IY-25S-11 6.79 25 0.1 10.8 10.4 802 IY-25S-21 6.56 25 0.2 14.1 12.6 803 IY-25S-31 6.54 25 0.3 15.7 13.6 804 IY-25S-51 6.14 25 0.5 16.9 14.7 805 IY-25S-71 6.16 25 0.72 18.2 15.0 806 MX-25S-01 7 25 0.0005 8.0 7.3 807 MX-25S-11 6.79 25 0.1 11.7 11.3 808 MX-25S-21 6.56 25 0.2 13.7 12.6 809 MX-25S-31 6.54 25 0.3 15.7 13.6 810 MX-25S-51 6.14 25 0.5 16.8 14.4 811 MX-25S-71 6.16 25 0.72 17.6 14.9

145 Table B-1 continued.

Solution Temperature I Ca F Description pH Number (oC) (M) (mg/L) (mg/L) 812 SY-25S-01 7 25 0.0005 7.8 7.3 813 SY-25S-11 6.79 25 0.1 12.6 11.7 814 SY-25S-21 6.56 25 0.2 14.3 13.2 815 SY-25S-31 6.54 25 0.3 16.2 13.9 816 SY-25S-51 6.14 25 0.5 16.9 15.0 817 SY-25S-71 6.16 25 0.72 19.0 15.8 Notes: I = ionic strength; mg/L = milligrams per liter Description Interpretation: The initial 2 or 3 letter code is the sample identifier (e.g., BCP = Browns Canyon Porcelain fluorite sample) The 25U or 25S designation is the experiment temperature and whether equilibrium was approached from a U (undersaturated) or S (supersaturated) condition The last two digits refer to the ionic strength of the solution and the solution replicate number (e.g., 51 = an ionic strength of 0.5M and solution replicate 1)

146 APPENDIX C

PHREEQC INPUT FILES

147 Table C-1 PHREEQC input file for historical literature solubility data.

#Historical Literature Ksp Calculations

SOLUTION 1 Aumeras (1927) Precipitated Calcium Fluoride units ppm temp 25.0 Ca 9.2 F 8.8 END

SOLUTION 2 Gutierrez and Navarro (1981) Average Calcium Fluoride Reagent temp 22.5 Ca 1.81e-1 F 4.11e-1 END

SOLUTION 3 Gutierrez and Navarro (1981) Calcium Fluoride Reagent temp 22.5 Ca 2.16e-1 F 4.55e-1 END

SOLUTION 4 Gutierrez and Navarro (1981) Calcium Fluoride Reagent temp 22.5 Ca 2.15e-1 F 4.38e-1 END

SOLUTION 5 Kazakov and Sokolova (1950) Natural Fluorite units ppm temp 0.0 Ca 11.59 F 11.01 END

SOLUTION 6 Kazakov and Sokolova (1950) Natural Fluorite units ppm temp 10 Ca 13.69 F 13.00 END

SOLUTION 7 Kazakov and Sokolova (1950) Natural Fluorite units ppm

148 Table C-1 continued.

temp 20.0 Ca 15.79 F 15.00 END

SOLUTION 8 Kazakov and Sokolova (1950) Natural Fluorite units ppm temp 100.0 Ca 31.59 F 30.01 END

SOLUTION 9 Kohlrausch (1904) Natural Fluorite units ppm temp 18.0 Ca 7.69 F 7.31 END

SOLUTION 10 Kohlrausch (1904) Precipitated Calcium Fluoride units ppm temp 18.0 Ca 8.21 F 7.79 END

SOLUTION 11 Wilson (1850) Natural Fluorite units ppm temp 18.0 Ca 18.26 F 17.35 END

SOLUTION 12 Wilson (1850) Natural Fluorite units ppm temp 18.0 Ca 18.26 F 17.35 END

SOLUTION 13 Wilson (1850) Natural Fluorite units ppm temp 18.0 Ca 17.67

149 Table C-1 continued.

F 16.79 END

SOLUTION 14 Kohlrausch (1908) Natural Fluorite units ppm temp 0.05 Ca 6.68 F 6.35 END

SOLUTION 15 Kohlrausch (1908) Natural Fluorite units ppm temp 16.08 Ca 7.58 F 7.20 END

SOLUTION 16 Kohlrausch (1908) Natural Fluorite units ppm temp 17.28 Ca 7.68 F 7.30 END

SOLUTION 17 Kohlrausch (1908) Natural Fluorite units ppm temp 26.59 Ca 8.20 F 7.79 END

SOLUTION 18 Kohlrausch (1908) Natural Fluorite units ppm temp 40.0 Ca 8.52 F 8.09 END

SOLUTION 19 Kohlrausch (1908) Natural Fluorite units ppm temp 18.0 Ca 7.72 F 7.33 END

150 Table C-1 continued.

SOLUTION 20 Kohlrausch (1908) Precipitated Calcium Fluoride units ppm temp 17.47 Ca 8.32 F 7.90 END

SOLUTION 21 Kohlrausch (1908) Precipitated Calcium Fluoride units ppm temp 26.11 Ca 8.78 F 8.34 END

SOLUTION 22 Kohlrausch (1908) Precipitated Calcium Fluoride units ppm temp 18.0 Ca 8.34 F 7.92 END

SOLUTION 23 Kohlrausch and Rose (1893) Natural Fluorite units ppm temp 18.0 #CaF2 14 mg/L Ca 7.18 F 6.82 END

SOLUTION 24 Kohlrausch and Rose (1893) Natural Fluorite units ppm temp 18.0 #CaF2 14 mg/L; converted to 13.65 mg/L using C=10^6/A Ca 7.00 F 6.65 END

SOLUTION 25 Jensen (1937) Dissolution units ppm temp 18.0 Ca 7.33 F 6.97 END

151 Table C-1 continued.

SOLUTION 26 Jensen (1937) Crystallization units ppm temp 18.0 Ca 8.41 F 7.99 END

SOLUTION 27 Carter (1928) Dissolution units ppm pH 6.4 temp 25.0 Ca 20.51 F 19.49 END

SOLUTION 28 Ikrami et al (1971) Dissolution CaF2 Precipitate units ppm temp 10.0 Ca 8.72 F 8.28 END

SOLUTION 29 Ikrami et al (1971) Dissolution CaF2 Precipitate units ppm temp 20.0 #same CaF2 concentrations for 30oC Ca 9.23 F 8.77 END

SOLUTION 30 Lingane (1971) Titration/Precipitation temp 24.0 Ca 1.1 F 2.2 END

SOLUTION 31 Strubel (1965) Dissolution in Water units ppm temp 23.0 Ca 4.49 F 4.27 END

SOLUTION 32 Strubel (1965) Dissolution in Water units ppm

152 Table C-1 continued.

temp 25.0 Ca 4.68 F 4.45 END

SOLUTION 33 Strubel (1965) Dissolution in Water units ppm temp 26.5 Ca 4.74 F 4.50 END

SOLUTION 34 Strubel (1965) Dissolution in Water units ppm temp 39.0 Ca 5.86 F 5.57 END

SOLUTION 35 Strubel (1965) Dissolution in Water units ppm temp 50.0 Ca 7.03 F 6.67 END

SOLUTION 36 Strubel (1965) Dissolution in 0.1 moles NaCl/kg H2O temp 20.0 Ca 2.48E-1 F 4.96E-1 Na 100 Cl 100 END

SOLUTION 37 Strubel (1965) Dissolution in 0.5 moles NaCl/kg H2O temp 20.0 Ca 3.06E-1 F 6.12E-1 Na 500 Cl 500 END

SOLUTION 38 Strubel (1965) Dissolution in 1.0 moles NaCl/kg H2O temp 20.0

153 Table C-1 continued.

Ca 3.15e-1 F 6.30E-1 Na 1000 Cl 1000 END

SOLUTION 39 Strubel (1965) Dissolution in 2.0 moles NaCl/kg H2O temp 20.0 Ca 3.23e-1 F 6.46e-1 Na 2000 Cl 2000 END

SOLUTION 40 Strubel (1965) Dissolution in 0.1 moles NaCl/kg H2O temp 30.0 Ca 3.07E-1 F 6.14E-1 Na 100 Cl 100 END

SOLUTION 41 Strubel (1965) Dissolution in 0.5 moles NaCl/kg H2O temp 30.0 Ca 3.70E-1 F 7.39E-1 Na 500 Cl 500 END

SOLUTION 42 Strubel (1965) Dissolution in 1.0 moles NaCl/kg H2O temp 30.0 Ca 3.80E-1 F 7.60E-1 Na 1000 Cl 1000 END

SOLUTION 43 Strubel (1965) Dissolution in 2.0 moles NaCl/kg H2O temp 30.0 Ca 3.83E-1 F 7.66E-1 Na 2000 Cl 2000

154 Table C-1 continued.

END

SOLUTION 44 Strubel (1965) Dissolution in 0.1 moles NaCl/kg H2O temp 40.0 Ca 3.48E-1 F 6.96E-1 Na 100 Cl 100 END

SOLUTION 45 Strubel (1965) Dissolution in 0.5 moles NaCl/kg H2O temp 40.0 Ca 4.28E-1 F 8.55E-1 Na 500 Cl 500 END

SOLUTION 46 Strubel (1965) Dissolution in 1.0 moles NaCl/kg H2O temp 40.0 Ca 4.33E-1 F 8.67E-1 Na 1000 Cl 1000 END

SOLUTION 47 Strubel (1965) Dissolution in 2.0 moles NaCl/kg H2O temp 40.0 Ca 4.44E-1 F 8.89E-1 Na 2000 Cl 2000 END

SOLUTION 48 Strubel (1965) Dissolution in 0.1 moles NaCl/kg H2O temp 50.0 Ca 3.78E-1 F 7.57E-1 Na 100 Cl 100 END

SOLUTION 49 Strubel (1965) Dissolution in 0.5 moles NaCl/kg H2O temp 50.0

155 Table C-1 continued.

Ca 4.63E-1 F 9.25E-1 Na 500 Cl 500 END

SOLUTION 50 Strubel (1965) Dissolution in 1.0 moles NaCl/kg H2O temp 50.0 Ca 4.77E-1 F 9.53E-1 Na 1000 Cl 1000 END

SOLUTION 51 Strubel (1965) Dissolution in 2.0 moles NaCl/kg H2O temp 50.0 Ca 4.96E-1 F 9.91E-1 Na 2000 Cl 2000 END

SOLUTION 52 Gardner and Nancollas (1976) Dissolution units ppm temp 5.0 Ca 0.4703 F 0.9405 END

SOLUTION 53 Street and Elwali (1983) Dissolution units ppm temp 25.0 Ca 7.98 F 7.56 END

SOLUTION 54 Garand and Mucci Dissolution Nanopure pH 7.7 temp 25.0 Ca 0.276 F 0.36 END

156 Table C-1 continued.

SOLUTION 55 Garand and Mucci Dissolution 0.1006 M NaCl pH 7.7 temp 25.0 Ca 0.42 F 0.58 Na 100.6 Cl 100.6 END

SOLUTION 56 Garand and Mucci Dissolution 0.4096 M NaCl pH 7.7 temp 25.0 Ca 0.512 F 0.71 Na 409.6 Cl 409.6 END

SOLUTION 57 Garand and Mucci Dissolution 0.7299 M NaCl pH 7.7 temp 25.0 Ca 0.503 F 0.85 Na 729.6 Cl 729.6 END

SOLUTION 58 Zhang et al 2017 0.1 M NaCl units ppm pH 7 temp 30.0 Ca 3.05 F 8.15 END

SOLUTION 59 Zhang et al 2017 0.1 M NaCl units ppm pH 7 temp 50.0 Ca 3.81 F 8.57

END

157 Table C-2 PHREEQC input file for this study’s solubility data.

Title Thesis Log Ksp* Calculation SOLUTION_SPREAD units mg/L

Number Description pH temp pe Ca F K Cl 1 BCP-05U-01 7 5 8 7.4 6.9 0 0 2 BCP-05U-02 7 5 8 7.4 6.8 0 0 3 BCP-05U-03 7 5 8 7.4 6.8 0 0 4 BCP-05U-11 6.79 5 8 11.5 10.5 3910 3545 5 BCP-05U-12 6.79 5 8 11.4 10.4 3910 3545 6 BCP-05U-13 6.79 5 8 11.3 10.4 3910 3545 7 BCP-05U-21 6.56 5 8 12.7 11.7 7820 7091 8 BCP-05U-22 6.56 5 8 12.8 11.7 7820 7091 9 BCP-05U-23 6.56 5 8 12.6 11.6 7820 7091 10 BCP-05U-31 6.54 5 8 13.4 12.4 11729 10636 11 BCP-05U-32 6.54 5 8 13.5 12.4 11729 10636 12 BCP-05U-33 6.54 5 8 13.5 12.5 11729 10636 13 BCP-05U-51 6.14 5 8 14.7 13.5 19549 17726 14 BCP-05U-52 6.14 5 8 14.8 13.6 19549 17726 15 BCP-05U-53 6.14 5 8 14.8 13.5 19549 17726 16 BCP-05U-71 6.16 5 8 15.4 14.1 28151 25526 17 BCP-05U-72 6.16 5 8 15.3 14.0 28151 25526 18 BCP-05U-73 6.16 5 8 15.1 14.0 28151 25526 19 BCP-25U-01 7 25 8 9.0 8.2 0 0 20 BCP-25U-02 7 25 8 8.9 8.2 0 0 21 BCP-25U-03 7 25 8 9.0 8.2 0 0 22 BCP-25U-11 6.79 25 8 14.2 12.8 3910 3545 23 BCP-25U-12 6.79 25 8 14.0 12.8 3910 3545 24 BCP-25U-13 6.79 25 8 14.1 12.7 3910 3545 25 BCP-25U-21 6.56 25 8 15.5 14.1 7820 7091 26 BCP-25U-22 6.56 25 8 15.1 13.9 7820 7091 27 BCP-25U-23 6.56 25 8 15.3 13.9 7820 7091 28 BCP-25U-31 6.54 25 8 16.4 14.9 11729 10636 29 BCP-25U-32 6.54 25 8 16.4 14.8 11729 10636 30 BCP-25U-33 6.54 25 8 16.3 14.8 11729 10636 31 BCP-25U-51 6.14 25 8 17.7 16.0 19549 17726 32 BCP-25U-52 6.14 25 8 17.1 15.9 19549 17726 33 BCP-25U-53 6.14 25 8 17.4 15.9 19549 17726 34 BCP-25U-71 6.16 25 8 17.5 16.9 28151 25526 35 BCP-25U-72 6.16 25 8 17.9 16.9 28151 25526 36 BCP-25U-73 6.16 25 8 17.3 16.9 28151 25526 37 BCP-50U-01 7 50 8 9.2 8.7 0 0 38 BCP-50U-02 7 50 8 9.4 8.9 0 0

158 Table C-2 continued.

39 BCP-50U-03 7 50 8 9.1 8.9 0 0 40 BCP-50U-11 6.79 50 8 14.9 13.4 3910 3545 41 BCP-50U-12 6.79 50 8 14.4 13.4 3910 3545 42 BCP-50U-13 6.79 50 8 14.8 13.4 3910 3545 43 BCP-50U-21 6.56 50 8 16.7 15.2 7820 7091 44 BCP-50U-22 6.56 50 8 16.4 15.2 7820 7091 45 BCP-50U-23 6.56 50 8 16.5 15.0 7820 7091 46 BCP-50U-31 6.54 50 8 17.8 16.5 11729 10636 47 BCP-50U-32 6.54 50 8 17.4 16.4 11729 10636 48 BCP-50U-33 6.54 50 8 17.5 16.3 11729 10636 49 BCP-50U-51 6.14 50 8 19.7 17.8 19549 17726 50 BCP-50U-52 6.14 50 8 19.5 17.9 19549 17726 51 BCP-50U-53 6.14 50 8 19.6 17.8 19549 17726 52 BCP-50U-71 6.16 50 8 21.5 18.8 28151 25526 53 BCP-50U-72 6.16 50 8 21.1 18.8 28151 25526 54 BCP-50U-73 6.16 50 8 21.2 18.7 28151 25526 55 BCW-05U-01 7 5 8 7.3 6.5 0 0 56 BCW-05U-02 7 5 8 7.2 6.5 0 0 57 BCW-05U-03 7 5 8 7.2 6.5 0 0 58 BCW-05U-11 6.79 5 8 10.6 9.7 3910 3545 59 BCW-05U-12 6.79 5 8 10.4 9.6 3910 3545 60 BCW-05U-13 6.79 5 8 10.7 9.6 3910 3545 61 BCW-05U-21 6.56 5 8 11.4 11.1 7820 7091 62 BCW-05U-22 6.56 5 8 11.6 11.2 7820 7091 63 BCW-05U-23 6.56 5 8 11.9 11.2 7820 7091 64 BCW-05U-31 6.54 5 8 12.9 12.1 11729 10636 65 BCW-05U-32 6.54 5 8 13.1 12.1 11729 10636 66 BCW-05U-33 6.54 5 8 13.1 12.0 11729 10636 67 BCW-05U-51 6.14 5 8 13.7 13.0 19549 17726 68 BCW-05U-52 6.14 5 8 13.8 13.0 19549 17726 69 BCW-05U-53 6.14 5 8 13.8 12.9 19549 17726 70 BCW-05U-71 6.16 5 8 14.5 13.5 28151 25526 71 BCW-05U-72 6.16 5 8 15.0 13.6 28151 25526 72 BCW-05U-73 6.16 5 8 14.5 13.5 28151 25526 73 BCW-25U-01 7 25 8 8.6 7.8 0 0 74 BCW-25U-02 7 25 8 8.6 7.8 0 0 75 BCW-25U-03 7 25 8 8.4 7.8 0 0 76 BCW-25U-11 6.79 25 8 12.5 12.0 3910 3545 77 BCW-25U-12 6.79 25 8 12.8 12.0 3910 3545 78 BCW-25U-13 6.79 25 8 12.5 12.0 3910 3545 79 BCW-25U-21 6.56 25 8 14.5 13.5 7820 7091 80 BCW-25U-22 6.56 25 8 14.4 13.5 7820 7091 81 BCW-25U-23 6.56 25 8 14.1 13.5 7820 7091 82 BCW-25U-31 6.54 25 8 15.5 14.4 11729 10636

159 Table C-2 continued.

83 BCW-25U-32 6.54 25 8 15.3 14.4 11729 10636 84 BCW-25U-33 6.54 25 8 15.6 14.3 11729 10636 85 BCW-25U-51 6.14 25 8 16.4 15.4 19549 17726 86 BCW-25U-52 6.14 25 8 16.2 15.4 19549 17726 87 BCW-25U-53 6.14 25 8 16.1 15.3 19549 17726 88 BCW-25U-71 6.16 25 8 17.0 15.9 28151 25526 89 BCW-25U-72 6.16 25 8 16.7 15.9 28151 25526 90 BCW-25U-73 6.16 25 8 16.8 15.9 28151 25526 91 BCW-50U-01 7 50 8 9.0 8.6 0 0 92 BCW-50U-02 7 50 8 8.7 8.5 0 0 93 BCW-50U-03 7 50 8 8.8 8.6 0 0 94 BCW-50U-11 6.79 50 8 14.2 13.8 3910 3545 95 BCW-50U-12 6.79 50 8 14.2 13.7 3910 3545 96 BCW-50U-13 6.79 50 8 14.0 13.7 3910 3545 97 BCW-50U-21 6.56 50 8 16.3 15.3 7820 7091 98 BCW-50U-22 6.56 50 8 16.5 15.4 7820 7091 99 BCW-50U-23 6.56 50 8 16.4 15.5 7820 7091 100 BCW-50U-31 6.54 50 8 17.7 16.5 11729 10636 101 BCW-50U-32 6.54 50 8 17.3 16.5 11729 10636 102 BCW-50U-33 6.54 50 8 17.6 16.5 11729 10636 103 BCW-50U-51 6.14 50 8 18.6 17.7 19549 17726 104 BCW-50U-52 6.14 50 8 18.5 17.8 19549 17726 105 BCW-50U-53 6.14 50 8 18.5 17.7 19549 17726 106 BCW-50U-71 6.16 50 8 20.0 18.4 28151 25526 107 BCW-50U-72 6.16 50 8 19.8 18.5 28151 25526 108 BCW-50U-73 6.16 50 8 19.7 18.4 28151 25526 109 CH-05U-01 7 5 8 6.8 6.3 0 0 110 CH-05U-02 7 5 8 6.9 6.3 0 0 111 CH-05U-03 7 5 8 6.7 6.3 0 0 112 CH-05U-11 6.79 5 8 10.1 9.3 3910 3545 113 CH-05U-12 6.79 5 8 10.2 9.3 3910 3545 114 CH-05U-13 6.79 5 8 10.0 9.3 3910 3545 115 CH-05U-21 6.56 5 8 11.1 10.6 7820 7091 116 CH-05U-22 6.56 5 8 11.2 10.6 7820 7091 117 CH-05U-23 6.56 5 8 11.3 10.7 7820 7091 118 CH-05U-31 6.54 5 8 12.4 11.3 11729 10636 119 CH-05U-32 6.54 5 8 12.0 11.2 11729 10636 120 CH-05U-33 6.54 5 8 12.3 11.3 11729 10636 121 CH-05U-51 6.14 5 8 13.1 12.1 19549 17726 122 CH-05U-52 6.14 5 8 13.3 12.1 19549 17726 123 CH-05U-53 6.14 5 8 12.9 12.1 19549 17726 124 CH-05U-71 6.16 5 8 13.6 12.8 28151 25526 125 CH-05U-72 6.16 5 8 13.7 12.7 28151 25526 126 CH-05U-73 6.16 5 8 13.9 12.8 28151 25526

160 Table C-2 continued.

127 CH-25U-01 7 25 8 7.8 7.2 0 0 128 CH-25U-02 7 25 8 7.7 7.3 0 0 129 CH-25U-03 7 25 8 7.8 7.2 0 0 130 CH-25U-11 6.79 25 8 11.9 11.1 3910 3545 131 CH-25U-12 6.79 25 8 11.6 11.1 3910 3545 132 CH-25U-13 6.79 25 8 11.5 11.1 3910 3545 133 CH-25U-21 6.56 25 8 13.3 12.7 7820 7091 134 CH-25U-22 6.56 25 8 13.6 12.7 7820 7091 135 CH-25U-23 6.56 25 8 13.0 12.7 7820 7091 136 CH-25U-31 6.54 25 8 14.0 13.4 11729 10636 137 CH-25U-32 6.54 25 8 14.5 13.4 11729 10636 138 CH-25U-33 6.54 25 8 14.4 13.4 11729 10636 139 CH-25U-51 6.14 25 8 15.1 14.3 19549 17726 140 CH-25U-52 6.14 25 8 15.3 14.2 19549 17726 141 CH-25U-53 6.14 25 8 15.2 14.3 19549 17726 142 CH-25U-71 6.16 25 8 15.7 14.9 28151 25526 143 CH-25U-72 6.16 25 8 15.3 14.9 28151 25526 144 CH-25U-73 6.16 25 8 15.6 14.9 28151 25526 145 CH-50U-01 7 50 8 9.2 8.5 0 0 146 CH-50U-02 7 50 8 9.1 8.4 0 0 147 CH-50U-03 7 50 8 8.9 8.4 0 0 148 CH-50U-11 6.79 50 8 12.9 12.3 3910 3545 149 CH-50U-12 6.79 50 8 13.4 12.4 3910 3545 150 CH-50U-13 6.79 50 8 13.0 12.4 3910 3545 151 CH-50U-21 6.56 50 8 14.3 13.7 7820 7091 152 CH-50U-22 6.56 50 8 14.3 13.8 7820 7091 153 CH-50U-23 6.56 50 8 14.1 13.7 7820 7091 154 CH-50U-31 6.54 50 8 15.3 14.8 11729 10636 155 CH-50U-32 6.54 50 8 15.3 14.8 11729 10636 156 CH-50U-33 6.54 50 8 15.1 14.9 11729 10636 157 CH-50U-51 6.14 50 8 17.1 16.5 19549 17726 158 CH-50U-52 6.14 50 8 16.9 16.5 19549 17726 159 CH-50U-53 6.14 50 8 17.2 16.6 19549 17726 160 CH-50U-71 6.16 50 8 18.6 17.3 28151 25526 161 CH-50U-72 6.16 50 8 17.8 17.3 28151 25526 162 CH-50U-73 6.16 50 8 17.9 17.4 28151 25526 163 IY-05U-01 7 5 8 6.4 6.2 0 0 164 IY-05U-02 7 5 8 6.4 6.2 0 0 165 IY-05U-03 7 5 8 6.5 6.2 0 0 166 IY-05U-11 6.79 5 8 10.0 9.1 3910 3545 167 IY-05U-12 6.79 5 8 9.9 9.2 3910 3545 168 IY-05U-13 6.79 5 8 9.8 9.0 3910 3545 169 IY-05U-21 6.56 5 8 10.8 10.1 7820 7091 170 IY-05U-22 6.56 5 8 10.9 10.2 7820 7091

161 Table C-2 continued.

171 IY-05U-23 6.56 5 8 10.7 10.1 7820 7091 172 IY-05U-31 6.54 5 8 11.9 11.0 11729 10636 173 IY-05U-32 6.54 5 8 11.8 10.8 11729 10636 174 IY-05U-33 6.54 5 8 12.0 10.9 11729 10636 175 IY-05U-51 6.14 5 8 12.7 11.8 19549 17726 176 IY-05U-52 6.14 5 8 12.6 11.8 19549 17726 177 IY-05U-53 6.14 5 8 12.5 11.9 19549 17726 178 IY-05U-71 6.16 5 8 13.0 12.3 28151 25526 179 IY-05U-72 6.16 5 8 13.2 12.4 28151 25526 180 IY-05U-73 6.16 5 8 13.0 12.4 28151 25526 181 IY-25U-01 7 25 8 7.6 7.1 0 0 182 IY-25U-02 7 25 8 7.4 7.1 0 0 183 IY-25U-03 7 25 8 7.5 7.1 0 0 184 IY-25U-11 6.79 25 8 11.4 10.5 3910 3545 185 IY-25U-12 6.79 25 8 11.2 10.5 3910 3545 186 IY-25U-13 6.79 25 8 11.4 10.6 3910 3545 187 IY-25U-21 6.56 25 8 13.4 12.4 7820 7091 188 IY-25U-22 6.56 25 8 13.1 12.4 7820 7091 189 IY-25U-23 6.56 25 8 12.9 12.4 7820 7091 190 IY-25U-31 6.54 25 8 14.5 13.4 11729 10636 191 IY-25U-32 6.54 25 8 14.4 13.4 11729 10636 192 IY-25U-33 6.54 25 8 13.9 13.4 11729 10636 193 IY-25U-51 6.14 25 8 14.9 14.4 19549 17726 194 IY-25U-52 6.14 25 8 15.0 14.3 19549 17726 195 IY-25U-53 6.14 25 8 15.1 14.4 19549 17726 196 IY-25U-71 6.16 25 8 15.3 14.8 28151 25526 197 IY-25U-72 6.16 25 8 15.2 14.8 28151 25526 198 IY-25U-73 6.16 25 8 15.5 14.8 28151 25526 199 IY-50U-01 7 50 8 8.7 8.1 0 0 200 IY-50U-02 7 50 8 8.7 8.1 0 0 201 IY-50U-03 7 50 8 8.6 8.1 0 0 202 IY-50U-11 6.79 50 8 12.5 11.6 3910 3545 203 IY-50U-12 6.79 50 8 12.4 11.5 3910 3545 204 IY-50U-13 6.79 50 8 12.4 11.5 3910 3545 205 IY-50U-21 6.56 50 8 14.5 14.0 7820 7091 206 IY-50U-22 6.56 50 8 14.5 13.9 7820 7091 207 IY-50U-23 6.56 50 8 14.6 13.8 7820 7091 208 IY-50U-31 6.54 50 8 15.6 15.1 11729 10636 209 IY-50U-32 6.54 50 8 15.7 15.2 11729 10636 210 IY-50U-33 6.54 50 8 16.0 15.2 11729 10636 211 IY-50U-51 6.14 50 8 16.5 16.1 19549 17726 212 IY-50U-52 6.14 50 8 16.7 16.0 19549 17726 213 IY-50U-53 6.14 50 8 16.6 16.1 19549 17726 214 IY-50U-71 6.16 50 8 17.7 16.8 28151 25526

162 Table C-2 continued.

215 IY-50U-72 6.16 50 8 17.5 16.7 28151 25526 216 IY-50U-73 6.16 50 8 17.6 16.7 28151 25526 217 MP-05U-01 7 5 8 6.7 6.3 0 0 218 MP-05U-02 7 5 8 6.6 6.3 0 0 219 MP-05U-03 7 5 8 6.6 6.3 0 0 220 MP-05U-11 6.79 5 8 10.4 9.6 3910 3545 221 MP-05U-12 6.79 5 8 10.5 9.6 3910 3545 222 MP-05U-13 6.79 5 8 10.4 9.6 3910 3545 223 MP-05U-21 6.56 5 8 11.3 10.7 7820 7091 224 MP-05U-22 6.56 5 8 11.3 10.8 7820 7091 225 MP-05U-23 6.56 5 8 11.2 10.8 7820 7091 226 MP-05U-31 6.54 5 8 12.3 11.5 11729 10636 227 MP-05U-32 6.54 5 8 12.2 11.4 11729 10636 228 MP-05U-33 6.54 5 8 12.3 11.5 11729 10636 229 MP-05U-51 6.14 5 8 12.9 12.2 19549 17726 230 MP-05U-52 6.14 5 8 13.0 12.1 19549 17726 231 MP-05U-53 6.14 5 8 13.0 12.3 19549 17726 232 MP-05U-71 6.16 5 8 13.4 12.8 28151 25526 233 MP-05U-72 6.16 5 8 13.3 12.8 28151 25526 234 MP-05U-73 6.16 5 8 13.2 12.7 28151 25526 235 MP-25U-01 7 25 8 7.9 7.3 0 0 236 MP-25U-02 7 25 8 7.8 7.3 0 0 237 MP-25U-03 7 25 8 8.0 7.3 0 0 238 MP-25U-11 6.79 25 8 12.2 11.3 3910 3545 239 MP-25U-12 6.79 25 8 12.0 11.3 3910 3545 240 MP-25U-13 6.79 25 8 12.1 11.4 3910 3545 241 MP-25U-21 6.56 25 8 13.8 12.7 7820 7091 242 MP-25U-22 6.56 25 8 13.3 12.7 7820 7091 243 MP-25U-23 6.56 25 8 13.5 12.7 7820 7091 244 MP-25U-31 6.54 25 8 14.6 13.5 11729 10636 245 MP-25U-32 6.54 25 8 14.6 13.5 11729 10636 246 MP-25U-33 6.54 25 8 14.5 13.5 11729 10636 247 MP-25U-51 6.14 25 8 15.1 14.2 19549 17726 248 MP-25U-52 6.14 25 8 14.8 14.2 19549 17726 249 MP-25U-53 6.14 25 8 14.8 14.2 19549 17726 250 MP-25U-71 6.16 25 8 15.4 14.9 28151 25526 251 MP-25U-72 6.16 25 8 15.5 14.9 28151 25526 252 MP-25U-73 6.16 25 8 15.6 15.0 28151 25526 253 MP-50U-01 7 50 8 9.0 8.2 0 0 254 MP-50U-02 7 50 8 9.0 8.2 0 0 255 MP-50U-03 7 50 8 9.0 8.2 0 0 256 MP-50U-11 6.79 50 8 13.4 13.1 3910 3545 257 MP-50U-12 6.79 50 8 13.5 13.0 3910 3545 258 MP-50U-13 6.79 50 8 13.6 13.0 3910 3545

163 Table C-2 continued.

259 MP-50U-21 6.56 50 8 14.8 14.3 7820 7091 260 MP-50U-22 6.56 50 8 14.9 14.3 7820 7091 261 MP-50U-23 6.56 50 8 15.0 14.2 7820 7091 262 MP-50U-31 6.54 50 8 16.0 15.3 11729 10636 263 MP-50U-32 6.54 50 8 16.2 15.2 11729 10636 264 MP-50U-33 6.54 50 8 16.0 15.2 11729 10636 265 MP-50U-51 6.14 50 8 17.5 16.9 19549 17726 266 MP-50U-52 6.14 50 8 17.7 17.0 19549 17726 267 MP-50U-53 6.14 50 8 17.4 16.9 19549 17726 268 MP-50U-71 6.16 50 8 18.7 17.7 28151 25526 269 MP-50U-72 6.16 50 8 19.0 17.5 28151 25526 270 MP-50U-73 6.16 50 8 18.5 17.5 28151 25526 271 MX-05U-01 7 5 8 6.3 6.0 0 0 272 MX-05U-02 7 5 8 6.5 6.1 0 0 273 MX-05U-03 7 5 8 6.2 6.1 0 0 274 MX-05U-11 6.79 5 8 10.5 9.5 3910 3545 275 MX-05U-12 6.79 5 8 10.4 9.5 3910 3545 276 MX-05U-13 6.79 5 8 10.2 9.5 3910 3545 277 MX-05U-21 6.56 5 8 10.9 10.5 7820 7091 278 MX-05U-22 6.56 5 8 11.0 10.6 7820 7091 279 MX-05U-23 6.56 5 8 11.2 10.5 7820 7091 280 MX-05U-31 6.54 5 8 12.0 11.3 11729 10636 281 MX-05U-32 6.54 5 8 11.8 11.2 11729 10636 282 MX-05U-33 6.54 5 8 11.8 11.3 11729 10636 283 MX-05U-51 6.14 5 8 12.5 12.2 19549 17726 284 MX-05U-52 6.14 5 8 12.5 12.2 19549 17726 285 MX-05U-53 6.14 5 8 12.6 12.2 19549 17726 286 MX-05U-71 6.16 5 8 13.0 12.6 28151 25526 287 MX-05U-72 6.16 5 8 12.9 12.5 28151 25526 288 MX-05U-73 6.16 5 8 13.2 12.6 28151 25526 289 MX-25U-01 7 25 8 7.6 7.0 0 0 290 MX-25U-02 7 25 8 7.6 7.0 0 0 291 MX-25U-03 7 25 8 7.5 7.0 0 0 292 MX-25U-11 6.79 25 8 12.1 11.1 3910 3545 293 MX-25U-12 6.79 25 8 11.5 11.1 3910 3545 294 MX-25U-13 6.79 25 8 11.3 11.1 3910 3545 295 MX-25U-21 6.56 25 8 13.4 12.5 7820 7091 296 MX-25U-22 6.56 25 8 13.2 12.5 7820 7091 297 MX-25U-23 6.56 25 8 13.8 12.6 7820 7091 298 MX-25U-31 6.54 25 8 14.2 13.2 11729 10636 299 MX-25U-32 6.54 25 8 14.3 13.2 11729 10636 300 MX-25U-33 6.54 25 8 14.2 13.2 11729 10636 301 MX-25U-51 6.14 25 8 14.4 14.1 19549 17726 302 MX-25U-52 6.14 25 8 14.5 14.1 19549 17726

164 Table C-2 continued.

303 MX-25U-53 6.14 25 8 14.3 14.1 19549 17726 304 MX-25U-71 6.16 25 8 15.5 14.7 28151 25526 305 MX-25U-72 6.16 25 8 15.8 14.7 28151 25526 306 MX-25U-73 6.16 25 8 15.8 14.7 28151 25526 307 MX-50U-01 7 50 8 8.6 8.0 0 0 308 MX-50U-02 7 50 8 8.6 8.0 0 0 309 MX-50U-03 7 50 8 8.5 8.0 0 0 310 MX-50U-11 6.79 50 8 13.1 12.7 3910 3545 311 MX-50U-12 6.79 50 8 13.6 12.9 3910 3545 312 MX-50U-13 6.79 50 8 13.2 12.7 3910 3545 313 MX-50U-21 6.56 50 8 14.8 14.5 7820 7091 314 MX-50U-22 6.56 50 8 14.5 14.3 7820 7091 315 MX-50U-23 6.56 50 8 14.6 14.3 7820 7091 316 MX-50U-31 6.54 50 8 16.0 15.2 11729 10636 317 MX-50U-32 6.54 50 8 16.0 15.0 11729 10636 318 MX-50U-33 6.54 50 8 16.1 15.0 11729 10636 319 MX-50U-51 6.14 50 8 16.7 16.3 19549 17726 320 MX-50U-52 6.14 50 8 16.6 16.3 19549 17726 321 MX-50U-53 6.14 50 8 16.8 16.3 19549 17726 322 MX-50U-71 6.16 50 8 17.3 16.9 28151 25526 323 MX-50U-72 6.16 50 8 17.2 16.7 28151 25526 324 MX-50U-73 6.16 50 8 17.8 16.7 28151 25526 325 NGB-05U-01 7 5 8 6.5 6.2 0 0 326 NGB-05U-02 7 5 8 6.6 6.3 0 0 327 NGB-05U-03 7 5 8 6.4 6.3 0 0 328 NGB-05U-11 6.79 5 8 9.9 9.2 3910 3545 329 NGB-05U-12 6.79 5 8 9.7 9.2 3910 3545 330 NGB-05U-13 6.79 5 8 10.0 9.1 3910 3545 331 NGB-05U-21 6.56 5 8 11.4 10.7 7820 7091 332 NGB-05U-22 6.56 5 8 11.2 10.8 7820 7091 333 NGB-05U-23 6.56 5 8 11.6 10.7 7820 7091 334 NGB-05U-31 6.54 5 8 12.1 11.5 11729 10636 335 NGB-05U-32 6.54 5 8 12.4 11.5 11729 10636 336 NGB-05U-33 6.54 5 8 11.9 11.5 11729 10636 337 NGB-05U-51 6.14 5 8 12.9 12.2 19549 17726 338 NGB-05U-52 6.14 5 8 12.7 12.1 19549 17726 339 NGB-05U-53 6.14 5 8 12.4 12.1 19549 17726 340 NGB-05U-71 6.16 5 8 13.2 12.8 28151 25526 341 NGB-05U-72 6.16 5 8 13.3 12.8 28151 25526 342 NGB-05U-73 6.16 5 8 13.4 12.8 28151 25526 343 NGB-25U-01 7 25 8 7.4 7.3 0 0 344 NGB-25U-02 7 25 8 7.6 7.4 0 0 345 NGB-25U-03 7 25 8 7.5 7.4 0 0 346 NGB-25U-11 6.79 25 8 11.4 10.4 3910 3545

165 Table C-2 continued.

347 NGB-25U-12 6.79 25 8 11.1 10.4 3910 3545 348 NGB-25U-13 6.79 25 8 11.2 10.4 3910 3545 349 NGB-25U-21 6.56 25 8 13.1 12.0 7820 7091 350 NGB-25U-22 6.56 25 8 13.0 12.0 7820 7091 351 NGB-25U-23 6.56 25 8 13.0 12.0 7820 7091 352 NGB-25U-31 6.54 25 8 14.2 13.3 11729 10636 353 NGB-25U-32 6.54 25 8 14.4 13.2 11729 10636 354 NGB-25U-33 6.54 25 8 14.3 13.2 11729 10636 355 NGB-25U-51 6.14 25 8 15.3 14.1 19549 17726 356 NGB-25U-52 6.14 25 8 14.5 14.1 19549 17726 357 NGB-25U-53 6.14 25 8 14.8 14.2 19549 17726 358 NGB-25U-71 6.16 25 8 15.3 14.9 28151 25526 359 NGB-25U-72 6.16 25 8 15.1 14.9 28151 25526 360 NGB-25U-73 6.16 25 8 15.4 14.9 28151 25526 361 NGB-50U-01 7 50 8 8.3 8.1 0 0 362 NGB-50U-02 7 50 8 8.6 8.1 0 0 363 NGB-50U-03 7 50 8 8.4 8.2 0 0 364 NGB-50U-11 6.79 50 8 12.2 11.4 3910 3545 365 NGB-50U-12 6.79 50 8 12.2 11.2 3910 3545 366 NGB-50U-13 6.79 50 8 12.3 11.2 3910 3545 367 NGB-50U-21 6.56 50 8 13.3 12.9 7820 7091 368 NGB-50U-22 6.56 50 8 13.2 12.9 7820 7091 369 NGB-50U-23 6.56 50 8 13.6 13.0 7820 7091 370 NGB-50U-31 6.54 50 8 15.1 14.7 11729 10636 371 NGB-50U-32 6.54 50 8 15.2 14.8 11729 10636 372 NGB-50U-33 6.54 50 8 15.5 14.8 11729 10636 373 NGB-50U-51 6.14 50 8 16.9 16.2 19549 17726 374 NGB-50U-52 6.14 50 8 16.6 16.2 19549 17726 375 NGB-50U-53 6.14 50 8 16.5 16.1 19549 17726 376 NGB-50U-71 6.16 50 8 18.2 17.0 28151 25526 377 NGB-50U-72 6.16 50 8 17.7 16.9 28151 25526 378 NGB-50U-73 6.16 50 8 17.9 16.9 28151 25526 379 NGY-05U-01 7 5 8 6.5 6.4 0 0 380 NGY-05U-02 7 5 8 6.7 6.4 0 0 381 NGY-05U-03 7 5 8 6.8 6.4 0 0 382 NGY-05U-11 6.79 5 8 10.4 9.9 3910 3545 383 NGY-05U-12 6.79 5 8 10.5 9.9 3910 3545 384 NGY-05U-13 6.79 5 8 10.6 9.9 3910 3545 385 NGY-05U-21 6.56 5 8 12.0 11.1 7820 7091 386 NGY-05U-22 6.56 5 8 11.9 11.2 7820 7091 387 NGY-05U-23 6.56 5 8 11.5 11.1 7820 7091 388 NGY-05U-31 6.54 5 8 12.3 12.0 11729 10636 389 NGY-05U-32 6.54 5 8 12.8 12.0 11729 10636 390 NGY-05U-33 6.54 5 8 12.5 12.0 11729 10636

166 Table C-2 continued.

391 NGY-05U-51 6.14 5 8 13.1 12.8 19549 17726 392 NGY-05U-52 6.14 5 8 13.0 12.8 19549 17726 393 NGY-05U-53 6.14 5 8 13.0 12.8 19549 17726 394 NGY-05U-71 6.16 5 8 13.6 13.1 28151 25526 395 NGY-05U-72 6.16 5 8 13.8 13.3 28151 25526 396 NGY-05U-73 6.16 5 8 14.2 13.1 28151 25526 397 NGY-25U-01 7 25 8 8.2 7.5 0 0 398 NGY-25U-02 7 25 8 8.2 7.5 0 0 399 NGY-25U-03 7 25 8 8.1 7.5 0 0 400 NGY-25U-11 6.79 25 8 12.8 11.8 3910 3545 401 NGY-25U-12 6.79 25 8 12.5 11.7 3910 3545 402 NGY-25U-13 6.79 25 8 12.3 11.7 3910 3545 403 NGY-25U-21 6.56 25 8 13.4 13.0 7820 7091 404 NGY-25U-22 6.56 25 8 13.4 13.0 7820 7091 405 NGY-25U-23 6.56 25 8 13.8 13.0 7820 7091 406 NGY-25U-31 6.54 25 8 15.0 14.1 11729 10636 407 NGY-25U-32 6.54 25 8 15.2 14.1 11729 10636 408 NGY-25U-33 6.54 25 8 14.7 14.1 11729 10636 409 NGY-25U-51 6.14 25 8 15.8 14.8 19549 17726 410 NGY-25U-52 6.14 25 8 15.4 14.8 19549 17726 411 NGY-25U-53 6.14 25 8 15.9 14.8 19549 17726 412 NGY-25U-71 6.16 25 8 15.9 15.4 28151 25526 413 NGY-25U-72 6.16 25 8 16.1 15.4 28151 25526 414 NGY-25U-73 6.16 25 8 16.5 15.4 28151 25526 415 NGY-50U-01 7 50 8 8.8 8.1 0 0 416 NGY-50U-02 7 50 8 8.6 8.0 0 0 417 NGY-50U-03 7 50 8 8.3 8.0 0 0 418 NGY-50U-11 6.79 50 8 13.6 13.0 3910 3545 419 NGY-50U-12 6.79 50 8 13.7 13.0 3910 3545 420 NGY-50U-13 6.79 50 8 13.8 13.0 3910 3545 421 NGY-50U-21 6.56 50 8 15.8 14.5 7820 7091 422 NGY-50U-22 6.56 50 8 15.1 14.6 7820 7091 423 NGY-50U-23 6.56 50 8 15.6 14.5 7820 7091 424 NGY-50U-31 6.54 50 8 16.7 15.6 11729 10636 425 NGY-50U-32 6.54 50 8 16.8 15.5 11729 10636 426 NGY-50U-33 6.54 50 8 16.8 15.5 11729 10636 427 NGY-50U-51 6.14 50 8 18.2 17.0 19549 17726 428 NGY-50U-52 6.14 50 8 18.5 17.0 19549 17726 429 NGY-50U-53 6.14 50 8 18.0 17.0 19549 17726 430 NGY-50U-71 6.16 50 8 18.6 17.7 28151 25526 431 NGY-50U-72 6.16 50 8 18.9 17.7 28151 25526 432 NGY-50U-73 6.16 50 8 19.0 17.6 28151 25526 433 SPD-05U-01 7 5 8 6.9 6.5 0 0 434 SPD-05U-02 7 5 8 6.9 6.5 0 0

167 Table C-2 continued.

435 SPD-05U-03 7 5 8 6.7 6.5 0 0 436 SPD-05U-11 6.79 5 8 9.5 8.8 3910 3545 437 SPD-05U-12 6.79 5 8 9.6 8.8 3910 3545 438 SPD-05U-13 6.79 5 8 9.6 8.8 3910 3545 439 SPD-05U-21 6.56 5 8 11.4 10.5 7820 7091 440 SPD-05U-22 6.56 5 8 11.2 10.5 7820 7091 441 SPD-05U-23 6.56 5 8 11.0 10.5 7820 7091 442 SPD-05U-31 6.54 5 8 12.2 11.8 11729 10636 443 SPD-05U-32 6.54 5 8 12.7 11.8 11729 10636 444 SPD-05U-33 6.54 5 8 12.6 11.7 11729 10636 445 SPD-05U-51 6.14 5 8 13.3 13.0 19549 17726 446 SPD-05U-52 6.14 5 8 13.2 12.9 19549 17726 447 SPD-05U-53 6.14 5 8 13.1 12.8 19549 17726 448 SPD-05U-71 6.16 5 8 14.6 13.5 28151 25526 449 SPD-05U-72 6.16 5 8 14.6 13.6 28151 25526 450 SPD-05U-73 6.16 5 8 14.0 13.6 28151 25526 451 SPD-25U-01 7 25 8 8.5 7.7 0 0 452 SPD-25U-02 7 25 8 8.1 7.7 0 0 453 SPD-25U-03 7 25 8 8.4 7.8 0 0 454 SPD-25U-11 6.79 25 8 10.9 10.5 3910 3545 455 SPD-25U-12 6.79 25 8 11.4 10.5 3910 3545 456 SPD-25U-13 6.79 25 8 11.2 10.5 3910 3545 457 SPD-25U-21 6.56 25 8 13.4 12.7 7820 7091 458 SPD-25U-22 6.56 25 8 13.8 12.7 7820 7091 459 SPD-25U-23 6.56 25 8 13.3 12.7 7820 7091 460 SPD-25U-31 6.54 25 8 15.3 14.0 11729 10636 461 SPD-25U-32 6.54 25 8 15.2 14.0 11729 10636 462 SPD-25U-33 6.54 25 8 14.5 14.0 11729 10636 463 SPD-25U-51 6.14 25 8 15.7 15.2 19549 17726 464 SPD-25U-52 6.14 25 8 15.8 15.2 19549 17726 465 SPD-25U-53 6.14 25 8 16.3 15.1 19549 17726 466 SPD-25U-71 6.16 25 8 14.1 16.0 28151 25526 467 SPD-25U-72 6.16 25 8 15.0 15.9 28151 25526 468 SPD-25U-73 6.16 25 8 15.0 15.9 28151 25526 469 SPD-50U-01 7 50 8 8.4 8.1 0 0 470 SPD-50U-02 7 50 8 8.8 8.1 0 0 471 SPD-50U-03 7 50 8 8.6 8.1 0 0 472 SPD-50U-11 6.79 50 8 12.8 11.8 3910 3545 473 SPD-50U-12 6.79 50 8 12.1 11.7 3910 3545 474 SPD-50U-13 6.79 50 8 12.5 11.7 3910 3545 475 SPD-50U-21 6.56 50 8 15.4 14.5 7820 7091 476 SPD-50U-22 6.56 50 8 15.7 14.5 7820 7091 477 SPD-50U-23 6.56 50 8 15.6 14.4 7820 7091 478 SPD-50U-31 6.54 50 8 16.2 15.8 11729 10636

168 Table C-2 continued.

479 SPD-50U-32 6.54 50 8 16.9 15.7 11729 10636 480 SPD-50U-33 6.54 50 8 17.2 15.8 11729 10636 481 SPD-50U-51 6.14 50 8 17.8 17.0 19549 17726 482 SPD-50U-52 6.14 50 8 17.5 17.0 19549 17726 483 SPD-50U-53 6.14 50 8 18.2 17.0 19549 17726 484 SPD-50U-71 6.16 50 8 18.8 17.6 28151 25526 485 SPD-50U-72 6.16 50 8 18.9 17.6 28151 25526 486 SPD-50U-73 6.16 50 8 19.0 17.4 28151 25526 487 SY-05U-01 7 5 8 6.5 6.0 0 0 488 SY-05U-02 7 5 8 6.6 6.0 0 0 489 SY-05U-03 7 5 8 6.4 6.0 0 0 490 SY-05U-11 6.79 5 8 9.8 9.0 3910 3545 491 SY-05U-12 6.79 5 8 9.7 9.0 3910 3545 492 SY-05U-13 6.79 5 8 9.5 9.0 3910 3545 493 SY-05U-21 6.56 5 8 10.6 10.2 7820 7091 494 SY-05U-22 6.56 5 8 10.8 10.2 7820 7091 495 SY-05U-23 6.56 5 8 11.1 10.2 7820 7091 496 SY-05U-31 6.54 5 8 11.3 10.9 11729 10636 497 SY-05U-32 6.54 5 8 11.0 10.8 11729 10636 498 SY-05U-33 6.54 5 8 11.3 10.8 11729 10636 499 SY-05U-51 6.14 5 8 12.5 11.9 19549 17726 500 SY-05U-52 6.14 5 8 12.0 11.8 19549 17726 501 SY-05U-53 6.14 5 8 12.0 11.7 19549 17726 502 SY-05U-71 6.16 5 8 13.6 12.6 28151 25526 503 SY-05U-72 6.16 5 8 13.6 12.7 28151 25526 504 SY-05U-73 6.16 5 8 13.7 12.6 28151 25526 505 SY-25U-01 7 25 8 7.9 7.2 0 0 506 SY-25U-02 7 25 8 7.5 7.2 0 0 507 SY-25U-03 7 25 8 7.8 7.1 0 0 508 SY-25U-11 6.79 25 8 12.4 11.5 3910 3545 509 SY-25U-12 6.79 25 8 11.8 11.5 3910 3545 510 SY-25U-13 6.79 25 8 11.7 11.5 3910 3545 511 SY-25U-21 6.56 25 8 13.9 12.9 7820 7091 512 SY-25U-22 6.56 25 8 14.1 12.9 7820 7091 513 SY-25U-23 6.56 25 8 13.8 12.8 7820 7091 514 SY-25U-31 6.54 25 8 14.2 13.7 11729 10636 515 SY-25U-32 6.54 25 8 14.5 13.7 11729 10636 516 SY-25U-33 6.54 25 8 14.2 13.6 11729 10636 517 SY-25U-51 6.14 25 8 15.5 14.4 19549 17726 518 SY-25U-52 6.14 25 8 15.2 14.5 19549 17726 519 SY-25U-53 6.14 25 8 15.4 14.5 19549 17726 520 SY-25U-71 6.16 25 8 16.2 15.4 28151 25526 521 SY-25U-72 6.16 25 8 16.6 15.4 28151 25526 522 SY-25U-73 6.16 25 8 16.7 15.5 28151 25526

169 Table C-2 continued.

523 SY-50U-01 7 50 8 8.7 8.4 0 0 524 SY-50U-02 7 50 8 9.0 8.4 0 0 525 SY-50U-03 7 50 8 8.6 8.4 0 0 526 SY-50U-11 6.79 50 8 14.6 13.5 3910 3545 527 SY-50U-12 6.79 50 8 14.3 13.5 3910 3545 528 SY-50U-13 6.79 50 8 14.6 13.5 3910 3545 529 SY-50U-21 6.56 50 8 15.8 14.7 7820 7091 530 SY-50U-22 6.56 50 8 15.7 14.7 7820 7091 531 SY-50U-23 6.56 50 8 15.9 14.6 7820 7091 532 SY-50U-31 6.54 50 8 16.3 15.5 11729 10636 533 SY-50U-32 6.54 50 8 16.8 15.5 11729 10636 534 SY-50U-33 6.54 50 8 16.5 15.6 11729 10636 535 SY-50U-51 6.14 50 8 17.2 16.5 19549 17726 536 SY-50U-52 6.14 50 8 17.9 16.5 19549 17726 537 SY-50U-53 6.14 50 8 17.8 16.5 19549 17726 538 SY-50U-71 6.16 50 8 18.8 17.6 28151 25526 539 SY-50U-72 6.16 50 8 19.0 17.6 28151 25526 540 SY-50U-73 6.16 50 8 18.4 17.6 28151 25526 800 IY-25S-01 7 50 8 7.9 7.3 0 0 801 IY-25S-11 6.79 50 8 10.8 10.4 3910 3545 802 IY-25S-21 6.56 50 8 14.1 12.6 7820 7091 803 IY-25S-31 6.54 50 8 15.7 13.6 11729 10636 804 IY-25S-51 6.14 50 8 16.9 14.7 19549 17726 805 IY-25S-71 6.16 50 8 18.2 15.0 28151 25526 806 MX-25S-01 7 50 8 8.0 7.3 0 0 807 MX-25S-11 6.79 50 8 11.7 11.3 3910 3545 808 MX-25S-21 6.56 50 8 13.7 12.6 7820 7091 809 MX-25S-31 6.54 50 8 15.7 13.6 11729 10636 810 MX-25S-51 6.14 50 8 16.8 14.4 19549 17726 811 MX-25S-71 6.16 50 8 17.6 14.9 28151 25526 812 SY-25S-01 7 50 8 7.8 7.3 0 0 813 SY-25S-11 6.79 50 8 12.6 11.7 3910 3545 814 SY-25S-21 6.56 50 8 14.3 13.2 7820 7091 815 SY-25S-31 6.54 50 8 16.2 13.9 11729 10636 816 SY-25S-51 6.14 50 8 16.9 15.0 19549 17726 817 SY-25S-71 6.16 50 8 19.0 15.8 28151 25526

SELECTED_OUTPUT -file c:\thesis\thesis_charge_balance_output_Ksp-I_wateq.txt -user_punch -solution -ionic_strength true -percent_error

170 Table C-2 continued.

-charge_balance false -distance false -time false #-mu false -state false -step false -temp -pH -pe false -alkalinity false -molalities Ca+2 F- -activities Ca+2 F-

USER_PUNCH headings Ca(mg/L) F(mg/L) 10 Ca_ppm = TOT("Ca")*40.078*1000 20 F_ppm = TOT("F")*18.9984*1000

30 PUNCH Ca_ppm 40 PUNCH F_ppm END

171 APPENDIX D

LOG KSP CALCULATION RESULTS

172 Table D-1 Summary of this study's log Ksp* minimum, maximum, median, and mean values.

Log Ksp* Log Ksp* Log Ksp* Log Ksp* Log Ksp* Log Ksp* 95.0% Lower 95.0% Upper Sample N of Cases Minimum Maximum Median Mean Confidence Confidence Limit Limit BCP-05U-0 3 -10.70 -10.68 -10.70 -10.69 -10.71 -10.67 BCP-05U-1 3 -10.16 -10.14 -10.16 -10.15 -10.17 -10.13 BCP-05U-2 3 -10.02 -10.01 -10.01 -10.01 -10.03 -10.00 BCP-05U-3 3 -9.94 -9.93 -9.94 -9.94 -9.95 -9.92 BCP-05U-5 3 -9.83 -9.82 -9.83 -9.83 -9.84 -9.82 BCP-05U-7 3 -9.79 -9.77 -9.78 -9.78 -9.80 -9.76 BCP-25U-0 3 -10.46 -10.46 -10.46 -10.46 -10.47 -10.45 BCP-25U-1 3 -9.90 -9.89 -9.90 -9.90 -9.91 -9.89 BCP-25U-2 3 -9.80 -9.78 -9.79 -9.79 -9.82 -9.76 BCP-25U-3 3 -9.72 -9.71 -9.71 -9.71 -9.72 -9.70 BCP-25U-5 3 -9.64 -9.62 -9.63 -9.63 -9.65 -9.60 BCP-25U-7 3 -9.58 -9.57 -9.57 -9.57 -9.59 -9.56 BCP-50U-0 3 -10.41 -10.38 -10.39 -10.39 -10.43 -10.36 BCP-50U-1 3 -9.86 -9.84 -9.85 -9.85 -9.87 -9.83 BCP-50U-2 3 -9.71 -9.69 -9.70 -9.70 -9.72 -9.68 BCP-50U-3 3 -9.61 -9.60 -9.61 -9.61 -9.63 -9.59 BCP-50U-5 3 -9.50 -9.49 -9.49 -9.49 -9.50 -9.49 BCP-50U-7 3 -9.42 -9.41 -9.42 -9.42 -9.43 -9.41

BCW-05U-0 3 -10.75 -10.74 -10.75 -10.74 -10.75 -10.74 BCW-05U-1 3 -10.26 -10.24 -10.25 -10.25 -10.27 -10.23 BCW-05U-2 3 -10.10 -10.08 -10.09 -10.09 -10.12 -10.06 BCW-05U-3 3 -9.98 -9.97 -9.98 -9.97 -9.98 -9.97 BCW-05U-5 3 -9.89 -9.89 -9.89 -9.89 -9.90 -9.88 BCW-05U-7 3 -9.84 -9.82 -9.84 -9.83 -9.86 -9.80 BCW-25U-0 3 -10.53 -10.52 -10.52 -10.52 -10.54 -10.51 BCW-25U-1 3 -10.00 -9.99 -10.00 -10.00 -10.01 -9.98 BCW-25U-2 3 -9.85 -9.84 -9.84 -9.85 -9.86 -9.83 BCW-25U-3 3 -9.76 -9.76 -9.76 -9.76 -9.77 -9.76 BCW-25U-5 3 -9.69 -9.68 -9.68 -9.69 -9.70 -9.67 BCW-25U-7 3 -9.65 -9.64 -9.64 -9.64 -9.65 -9.63 BCW-50U-0 3 -10.45 -10.42 -10.43 -10.44 -10.46 -10.41 BCW-50U-1 3 -9.85 -9.84 -9.84 -9.84 -9.86 -9.83 BCW-50U-2 3 -9.70 -9.68 -9.69 -9.69 -9.70 -9.67 BCW-50U-3 3 -9.61 -9.60 -9.60 -9.60 -9.61 -9.59 BCW-50U-5 3 -9.52 -9.52 -9.52 -9.52 -9.53 -9.51 BCW-50U-7 3 -9.47 -9.46 -9.46 -9.46 -9.47 -9.45

173 Table D-1 continued.

Log Ksp* Log Ksp* Log Ksp* Log Ksp* Log Ksp* Log Ksp* 95.0% Lower 95.0% Upper Sample N of Cases Minimum Maximum Median Mean Confidence Confidence Limit Limit CH-05U-0 3 -10.80 -10.79 -10.80 -10.80 -10.81 -10.78 CH-05U-1 3 -10.30 -10.30 -10.30 -10.30 -10.31 -10.29 CH-05U-2 3 -10.15 -10.14 -10.15 -10.14 -10.16 -10.12 CH-05U-3 3 -10.07 -10.05 -10.05 -10.06 -10.09 -10.03 CH-05U-5 3 -9.98 -9.96 -9.97 -9.97 -9.99 -9.96 CH-05U-7 3 -9.91 -9.90 -9.91 -9.91 -9.92 -9.89 CH-25U-0 3 -10.63 -10.62 -10.63 -10.63 -10.64 -10.62 CH-25U-1 3 -10.10 -10.09 -10.10 -10.10 -10.11 -10.08 CH-25U-2 3 -9.94 -9.92 -9.93 -9.93 -9.95 -9.91 CH-25U-3 3 -9.86 -9.85 -9.85 -9.85 -9.87 -9.83 CH-25U-5 3 -9.78 -9.77 -9.78 -9.78 -9.78 -9.77 CH-25U-7 3 -9.74 -9.73 -9.73 -9.73 -9.74 -9.72 CH-50U-0 3 -10.45 -10.43 -10.44 -10.44 -10.47 -10.41 CH-50U-1 3 -9.97 -9.95 -9.96 -9.96 -9.99 -9.94 CH-50U-2 3 -9.85 -9.84 -9.84 -9.84 -9.86 -9.83 CH-50U-3 3 -9.75 -9.75 -9.75 -9.75 -9.75 -9.75 CH-50U-5 3 -9.62 -9.61 -9.61 -9.61 -9.63 -9.60 CH-50U-7 3 -9.56 -9.54 -9.55 -9.55 -9.57 -9.53

IY-05U-0 3 -10.84 -10.83 -10.84 -10.83 -10.84 -10.82 IY-05U-1 3 -10.34 -10.32 -10.32 -10.33 -10.36 -10.30 IY-05U-2 3 -10.21 -10.19 -10.20 -10.20 -10.22 -10.18 IY-05U-3 3 -10.11 -10.09 -10.09 -10.10 -10.12 -10.07 IY-05U-5 3 -10.01 -10.00 -10.00 -10.01 -10.01 -10.00 IY-05U-7 3 -9.96 -9.95 -9.95 -9.95 -9.97 -9.94 IY-25U-0 3 -10.66 -10.65 -10.66 -10.66 -10.67 -10.64 IY-25U-1 3 -10.16 -10.14 -10.15 -10.15 -10.17 -10.13 IY-25U-2 3 -9.96 -9.94 -9.95 -9.95 -9.97 -9.93 IY-25U-3 3 -9.86 -9.85 -9.85 -9.85 -9.88 -9.83 IY-25U-5 3 -9.78 -9.77 -9.78 -9.77 -9.79 -9.76 IY-25U-7 3 -9.74 -9.74 -9.74 -9.74 -9.75 -9.73 IY-50U-0 3 -10.49 -10.49 -10.49 -10.49 -10.50 -10.48 IY-50U-1 3 -10.05 -10.04 -10.05 -10.04 -10.06 -10.03 IY-50U-2 3 -9.83 -9.82 -9.82 -9.82 -9.84 -9.81 IY-50U-3 3 -9.72 -9.71 -9.72 -9.72 -9.74 -9.70 IY-50U-5 3 -9.65 -9.65 -9.65 -9.65 -9.65 -9.64 IY-50U-7 3 -9.59 -9.58 -9.59 -9.59 -9.60 -9.58

174 Table D-1 continued.

Log Ksp* Log Ksp* Log Ksp* Log Ksp* Log Ksp* Log Ksp* 95.0% Lower 95.0% Upper Sample N of Cases Minimum Maximum Median Mean Confidence Confidence Limit Limit MP-05U-0 3 -10.81 -10.80 -10.81 -10.81 -10.82 -10.80 MP-05U-1 3 -10.26 -10.26 -10.26 -10.26 -10.27 -10.25 MP-05U-2 3 -10.14 -10.13 -10.13 -10.13 -10.14 -10.12 MP-05U-3 3 -10.05 -10.04 -10.04 -10.04 -10.06 -10.03 MP-05U-5 3 -9.97 -9.96 -9.97 -9.97 -9.99 -9.95 MP-05U-7 3 -9.93 -9.91 -9.92 -9.92 -9.93 -9.90 MP-25U-0 3 -10.62 -10.61 -10.61 -10.61 -10.62 -10.60 MP-25U-1 3 -10.07 -10.06 -10.06 -10.06 -10.08 -10.05 MP-25U-2 3 -9.93 -9.91 -9.92 -9.92 -9.94 -9.90 MP-25U-3 3 -9.84 -9.84 -9.84 -9.84 -9.84 -9.84 MP-25U-5 3 -9.79 -9.78 -9.79 -9.79 -9.80 -9.78 MP-25U-7 3 -9.73 -9.72 -9.73 -9.73 -9.74 -9.72 MP-50U-0 3 -10.46 -10.46 -10.46 -10.46 -10.46 -10.46 MP-50U-1 3 -9.91 -9.91 -9.91 -9.91 -9.91 -9.90 MP-50U-2 3 -9.79 -9.79 -9.79 -9.79 -9.80 -9.79 MP-50U-3 3 -9.71 -9.70 -9.70 -9.71 -9.71 -9.70 MP-50U-5 3 -9.59 -9.57 -9.58 -9.58 -9.60 -9.57 MP-50U-7 3 -9.53 -9.52 -9.52 -9.52 -9.54 -9.51

MX-05U-0 3 -10.87 -10.84 -10.86 -10.86 -10.89 -10.82 MX-05U-1 3 -10.28 -10.27 -10.27 -10.27 -10.29 -10.26 MX-05U-2 3 -10.17 -10.15 -10.15 -10.16 -10.17 -10.14 MX-05U-3 3 -10.08 -10.06 -10.07 -10.07 -10.09 -10.05 MX-05U-5 3 -9.98 -9.98 -9.98 -9.98 -9.99 -9.98 MX-05U-7 3 -9.95 -9.93 -9.94 -9.94 -9.96 -9.92 MX-25U-0 3 -10.67 -10.66 -10.66 -10.67 -10.67 -10.66 MX-25U-1 3 -10.11 -10.08 -10.10 -10.10 -10.13 -10.06 MX-25U-2 3 -9.94 -9.92 -9.94 -9.93 -9.97 -9.90 MX-25U-3 3 -9.87 -9.87 -9.87 -9.87 -9.87 -9.86 MX-25U-5 3 -9.81 -9.80 -9.81 -9.81 -9.81 -9.80 MX-25U-7 3 -9.74 -9.73 -9.73 -9.74 -9.75 -9.73 MX-50U-0 3 -10.51 -10.50 -10.50 -10.51 -10.51 -10.50 MX-50U-1 3 -9.94 -9.91 -9.94 -9.93 -9.97 -9.89 MX-50U-2 3 -9.80 -9.78 -9.80 -9.79 -9.82 -9.77 MX-50U-3 3 -9.72 -9.71 -9.72 -9.72 -9.73 -9.70 MX-50U-5 3 -9.64 -9.63 -9.63 -9.63 -9.64 -9.63 MX-50U-7 3 -9.60 -9.59 -9.59 -9.59 -9.61 -9.57

175 Table D-1 continued.

Log Ksp* Log Ksp* Log Ksp* Log Ksp* Log Ksp* Log Ksp* 95.0% Lower 95.0% Upper Sample N of Cases Minimum Maximum Median Mean Confidence Confidence Limit Limit NGB-05U-0 3 -10.83 -10.81 -10.82 -10.82 -10.84 -10.79 NGB-05U-1 3 -10.33 -10.32 -10.32 -10.32 -10.33 -10.31 NGB-05U-2 3 -10.13 -10.12 -10.13 -10.13 -10.14 -10.12 NGB-05U-3 3 -10.05 -10.04 -10.05 -10.04 -10.07 -10.02 NGB-05U-5 3 -9.99 -9.97 -9.98 -9.98 -10.01 -9.95 NGB-05U-7 3 -9.92 -9.91 -9.92 -9.92 -9.92 -9.91 NGB-25U-0 3 -10.64 -10.62 -10.62 -10.63 -10.65 -10.60 NGB-25U-1 3 -10.17 -10.16 -10.17 -10.17 -10.18 -10.15 NGB-25U-2 3 -9.99 -9.98 -9.99 -9.98 -9.99 -9.98 NGB-25U-3 3 -9.87 -9.86 -9.86 -9.86 -9.87 -9.86 NGB-25U-5 3 -9.80 -9.78 -9.79 -9.79 -9.82 -9.77 NGB-25U-7 3 -9.74 -9.73 -9.74 -9.74 -9.75 -9.73 NGB-50U-0 3 -10.51 -10.49 -10.49 -10.50 -10.52 -10.48 NGB-50U-1 3 -10.08 -10.06 -10.07 -10.07 -10.09 -10.05 NGB-50U-2 3 -9.92 -9.91 -9.92 -9.92 -9.94 -9.89 NGB-50U-3 3 -9.76 -9.74 -9.75 -9.75 -9.77 -9.73 NGB-50U-5 3 -9.65 -9.63 -9.64 -9.64 -9.66 -9.62 NGB-50U-7 3 -9.58 -9.56 -9.57 -9.57 -9.59 -9.55

NGY-05U-0 3 -10.80 -10.78 -10.79 -10.79 -10.81 -10.77 NGY-05U-1 3 -10.24 -10.23 -10.23 -10.23 -10.24 -10.22 NGY-05U-2 3 -10.10 -10.08 -10.08 -10.08 -10.11 -10.06 NGY-05U-3 3 -10.00 -9.99 -10.00 -10.00 -10.02 -9.98 NGY-05U-5 3 -9.93 -9.92 -9.93 -9.92 -9.93 -9.92 NGY-05U-7 3 -9.89 -9.87 -9.87 -9.88 -9.90 -9.85 NGY-25U-0 3 -10.58 -10.57 -10.57 -10.58 -10.58 -10.57 NGY-25U-1 3 -10.03 -10.01 -10.02 -10.02 -10.05 -9.99 NGY-25U-2 3 -9.90 -9.89 -9.90 -9.90 -9.92 -9.88 NGY-25U-3 3 -9.80 -9.79 -9.79 -9.79 -9.81 -9.78 NGY-25U-5 3 -9.74 -9.73 -9.73 -9.73 -9.75 -9.71 NGY-25U-7 3 -9.69 -9.68 -9.69 -9.69 -9.70 -9.67 NGY-50U-0 3 -10.52 -10.48 -10.50 -10.50 -10.54 -10.46 NGY-50U-1 3 -9.91 -9.90 -9.90 -9.90 -9.91 -9.90 NGY-50U-2 3 -9.77 -9.75 -9.76 -9.76 -9.77 -9.74 NGY-50U-3 3 -9.67 -9.67 -9.67 -9.67 -9.68 -9.67 NGY-50U-5 3 -9.57 -9.56 -9.56 -9.56 -9.58 -9.55 NGY-50U-7 3 -9.52 -9.51 -9.52 -9.52 -9.52 -9.51

176 Table D-1 continued.

Log Ksp* Log Ksp* Log Ksp* Log Ksp* Log Ksp* Log Ksp* 95.0% Lower 95.0% Upper Sample N of Cases Minimum Maximum Median Mean Confidence Confidence Limit Limit SPD-05U-0 3 -10.78 -10.76 -10.76 -10.77 -10.78 -10.75 SPD-05U-1 3 -10.37 -10.37 -10.37 -10.37 -10.38 -10.36 SPD-05U-2 3 -10.16 -10.15 -10.15 -10.15 -10.17 -10.14 SPD-05U-3 3 -10.02 -10.00 -10.01 -10.01 -10.03 -9.99 SPD-05U-5 3 -9.92 -9.90 -9.91 -9.91 -9.94 -9.89 SPD-05U-7 3 -9.84 -9.83 -9.83 -9.83 -9.86 -9.81 SPD-25U-0 3 -10.56 -10.53 -10.54 -10.54 -10.57 -10.51 SPD-25U-1 3 -10.17 -10.15 -10.16 -10.16 -10.18 -10.14 SPD-25U-2 3 -9.93 -9.91 -9.92 -9.92 -9.94 -9.90 SPD-25U-3 3 -9.81 -9.79 -9.79 -9.80 -9.82 -9.77 SPD-25U-5 3 -9.71 -9.70 -9.71 -9.70 -9.72 -9.69 SPD-25U-7 3 -9.71 -9.69 -9.69 -9.69 -9.72 -9.67 SPD-50U-0 3 -10.50 -10.48 -10.49 -10.49 -10.52 -10.47 SPD-50U-1 3 -10.04 -10.01 -10.03 -10.03 -10.07 -9.99 SPD-50U-2 3 -9.76 -9.76 -9.76 -9.76 -9.77 -9.75 SPD-50U-3 3 -9.67 -9.65 -9.66 -9.66 -9.69 -9.63 SPD-50U-5 3 -9.58 -9.56 -9.57 -9.57 -9.59 -9.55 SPD-50U-7 3 -9.53 -9.52 -9.52 -9.52 -9.53 -9.51

SY-05U-0 3 -10.86 -10.85 -10.86 -10.86 -10.87 -10.84 SY-05U-1 3 -10.35 -10.34 -10.35 -10.35 -10.36 -10.33 SY-05U-2 3 -10.20 -10.18 -10.19 -10.19 -10.22 -10.17 SY-05U-3 3 -10.14 -10.12 -10.13 -10.13 -10.15 -10.10 SY-05U-5 3 -10.03 -10.00 -10.03 -10.02 -10.06 -9.98 SY-05U-7 3 -9.92 -9.91 -9.92 -9.92 -9.93 -9.91 SY-25U-0 3 -10.64 -10.62 -10.64 -10.64 -10.66 -10.61 SY-25U-1 3 -10.06 -10.04 -10.06 -10.05 -10.09 -10.02 SY-25U-2 3 -9.91 -9.89 -9.90 -9.90 -9.92 -9.88 SY-25U-3 3 -9.84 -9.83 -9.84 -9.84 -9.85 -9.82 SY-25U-5 3 -9.76 -9.76 -9.76 -9.76 -9.77 -9.75 SY-25U-7 3 -9.68 -9.67 -9.67 -9.68 -9.70 -9.65 SY-50U-0 3 -10.46 -10.44 -10.46 -10.45 -10.48 -10.43 SY-50U-1 3 -9.85 -9.85 -9.85 -9.85 -9.86 -9.84 SY-50U-2 3 -9.75 -9.74 -9.74 -9.74 -9.75 -9.74 SY-50U-3 3 -9.68 -9.67 -9.67 -9.68 -9.69 -9.66 SY-50U-5 3 -9.61 -9.60 -9.60 -9.60 -9.62 -9.58 SY-50U-7 3 -9.53 -9.52 -9.52 -9.52 -9.54 -9.51

177 Figure D- 1 Nonlinear curve fitting results for Browns Canyon Porcelain (BCP) fluorite at 5oC.

178 Figure D-2 Nonlinear curve fitting results for Browns Canyon Porcelain (BCP) fluorite at 25oC.

179 Figure D-3 Nonlinear curve fitting results for Browns Canyon Porcelain (BCP) fluorite at 50oC.

180 Figure D-4 Nonlinear curve fitting results for Browns Canyon White (BCW) fluorite at 5oC.

181 Figure D-5 Nonlinear curve fitting results for Browns Canyon White (BCW) fluorite at 25oC.

182 Figure D-6 Nonlinear curve fitting results for Browns Canyon White (BCW) fluorite at 50oC.

183 Figure D-7 Nonlinear curve fitting results for China Green (CH) fluorite at 5oC.

184 Figure D-8 Nonlinear curve fitting results for China Green (CH) fluorite at 25oC.

185 Figure D-9 Nonlinear curve fitting results for China Green (CH) fluorite at 50oC.

186 Figure D-10 Nonlinear curve fitting results for Illinois Yellow (IY) fluorite at 5oC.

187 Figure D-11 Nonlinear curve fitting results for Illinois Yellow (IY) fluorite at 25oC.

188 Figure D-12 Nonlinear curve fitting results for Illinois Yellow (IY) fluorite at 50oC.

189 Figure D-13 Nonlinear curve fitting results for Mexican Purple (MP) fluorite at 5oC.

190 Figure D-14 Nonlinear curve fitting results for Mexican Purple (MP) fluorite at 25oC.

191 Figure D-15 Nonlinear curve fitting results for Mexican Purple (MP) fluorite at 50oC.

192 Figure D-16 Nonlinear curve fitting results for Mexican Lilac (MX) fluorite at 5oC.

193 Figure D-17 Nonlinear curve fitting results for Mexican Lilac (MX) fluorite at 25oC.

194 Figure D-18 Nonlinear curve fitting results for Mexican Lilac (MX) fluorite at 50oC.

195 Figure D-19 Nonlinear curve fitting results for Northgate Blue (NGB) fluorite at 5oC.

196 Figure D-20 Nonlinear curve fitting results for Northgate Blue (NGB) fluorite at 25oC.

197 Figure D-21 Nonlinear curve fitting results for Northgate Blue (NGB) fluorite at 50oC.

198 Figure D-22 Nonlinear curve fitting results for Northgate Yellow (NGY) fluorite at 5oC.

199 Figure D-23 Nonlinear curve fitting results for Northgate Yellow (NGY) fluorite at 25oC.

200 Figure D-24 Nonlinear curve fitting results for Northgate Yellow (NGY) fluorite at 50oC.

201 Figure D-25 Nonlinear curve fitting results for St. Peter’s Dome (SPD) fluorite at 5oC.

202 Figure D-26 Nonlinear curve fitting results for St. Peter’s Dome (SPD) fluorite at 25oC.

203 Figure D-27 Nonlinear curve fitting results for St. Peter’s Dome (SPD) fluorite at 50oC.

204 Figure D-28 Nonlinear curve fitting results for Synthetic (SY) fluorite at 5oC.

205 Figure D-29 Nonlinear curve fitting results for Synthetic (SY) fluorite at 25oC.

206 Figure D-30 Nonlinear curve fitting results for Synthetic (SY) fluorite at 50oC.

207