THE UNTVERSITY OF CHICAGO

I{YDROLOGIC, THERMAL, AND CHEMICAL PROCESSES RELATED TO

FRACTI.JRE CONTROLLED HYDROTTIERMAL WATER-ROCK INTERACTION

A DISSERTATION STJBMITTED TO

THE FACULTY OF TIIE DIVISION OF THE PTIYSICAL SCIENCES

IN CANDIDACY FOR THE DEGREE OF

DOCTOR OF PHILOSOPHY

DEPARTMENT OF THE GEOPHYSICAL SCIENCES

BY

MICHAELEDWARD SHEA

CHICAGO. ILLINOIS

JUNE 1998

Title: Hydrologtc, thermal, and chemical processes related to fracture controlledhydrothermal water-rock interaction

Author: Michael Edward Shea

Advisor: Robert N. Clayton

ABSTRACT

The hydrothermal uranium vein deposits near Marysvale, Utah were studied inorder to elucidate the hydrologic, thermal, and chemical processes that affected thedistribution of elements and oxygen isotopes (as profiles) associated with two distincthydrologic features in the surroundingq\artz monzonite, as well as selected backgroundsamples. These two hydrologic features comprised: l) an open, chloritized joint; and2) asealed, quartz-calcite veinlet. The results of this study are discussed and applied toradwaste isolation concerns, including Kds, retardation factors, and implications for far-field retardation in frachrred granitic rock.

Analytical efforts included: l) mineral chemistry of feldspars, biotite, chlorite, andmagnetite; 2) profiles of the selected elements Na, Mg, Al, Si, K, Ca, Ti, Fe, Rb, Co, Ni,Se,Zr,M, Mo, Cs, Ba, La,Ce,Nd, Sm, Eu, Tb, Tm, yb, Lu, Th, U; and 3) profiles ofoxygen isotope values for quartz, orthoclase, magnetite, calcite, and whole-rock.

Modeling efforts included: l) large-scale finite difference modeling of ttreMarysvale natural hydrothermal system; 2) small-scale analytical modeling of selected

element and oxygen isotope profiles; and 3) interpretation of 6-6 plots of quarz,

orthoclase, and magnetite.

Results include: l) the temperature of the hydrothermal interaction (- 200 to 225

"C);2) evidence of diffusion-dominated transport of the hydrothermal fluid into thequartz monzonite; 3) the determination of apparent diffusivities (D") of the modeledelements, including uranium with a range in Do values of - 10-15 to l0'r7 m2/sec; and 4) thecharacterization of the U diffusion as coupled grain boundary-volume diffirsion, with ananticipated activation energy of - 15 to 95 kJ/mole.

TABLE OF CONTENTS

LIST OF TABLES...LIST OF ILLUSTRATIONS..........ACKNOWLEDGEMENTS................

ChapterI. INTRODUCTION......

l . l Overview ... . . . . . . . . . .1.2 Related Studies.......1.3 Main Components of This Study.........

1.3.1 Sampling and Analysis....1.3.2 Lar ge-Scale Hydrothermal Modeling1.3.3 Small-Scale Analytical Modeling...

GEOLOGIC SETTING. 72.1 Regional Geology. 72.2 Local Geology..... 7

2.2.1 Bullion Canyon Volcanics.. 82.2.2 MowtBelknap Volcanics.. 8

2.3 Study Area Geo1ogy.............. 92.3.1 Central Intrusive Quartz Monzonite. 92.3.2 Hydrothermal Rock Alteration.......... ll2.3.3 Vein Mneralory 14

ANALYTICAL RESI.]LTS................ 203.1 Results of Previous Studies Related To Mass Transport... 203.2 Petrography......... 23

3.2.1 Unaltered Quartz Monzonite. .. 243.2.1.1 Orthoclase, 243.2.1.2 Andesine... 253.2.1.3 Quartz....... 263.2.1.4 Augite........ 263.2.1.5 Biotite....... 273.2.1.6 Magnetite.. 2l

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1I25566

2.

3.

3.3

3.4

3.2.1.7 Chlorite..... 283.2.2 Changes With Distance From Two Hydrologic Features.............. 28

3.2.2.1 MVl70 B Subsample Series..... 293.2.2.2 MVlTl B Subsample Series..... 30

3.2.3 Secondary Mineralory 323.2.3.1 Quartz....... 333.2.3.2 Orttroclase. 343.2.3.3 Magnetite.. 343.2.3.4 Biotite/Ch1orite........... 35

Neutron Activation Chemical Analyses.... 363.3.1 Si Determination by the Method of Difference............... 383.3.2 Oxides Corrected for CaCO3 39

Orygen Isotopic Analyses.... 39

4. MODELING AND DISCUSSION............. 564.1 Introduction.......... 564.2 Large-Scale Finite-Difference Hydrothermal Model.... 56

4.2.1 Physical Model. 584.2.2 Computational Model Code.......... 6l4.2.3 Initial and Boundary Conditions. 62

4.2.3.1 Temperature.... . . . . . . . . . . . . . 624.2.3.2 Permeability 644.2.3.3 Hydrologic F1ow.......... 674.2.3.4 Oxygen Isotopes..... 68

4.3 Results of Large-Scale Hydrothermal Modeling........... 694.3.1 Temperature....... 694.3.2 Hydrologic Flow 7l4.3.3 Integrated Fluid Mass Flux.. ., 724.3.4 Isotopic Alteration.............. 73

4.4 Small-Scale Analytical Mass Transport Models...... 774.4.1 Analytical Elemental Mass Transport Modeling... 78

4.4.1.1 Some Underlying Processes Related to Mass Transport.... 8l4.4.1.1.1 Retardation 8l4.4.1.1.2 Adsorption 824.4.1.1.3 Distribution Coeffrcient (IQ) and Isotherms........... 834.4.1.1.4 Calculated IQs from Concentration Profiles. 84

lu

4.4.1.2 Selected Analytical Equations.. 854.4.1.2.1 One-Dimensional Diffusion... 854.4.1.2.2 One-Dimensional Nonreactive Diffusion-Advection 88

4.4.1.3 Analytical Model Calculations................. 894.4.1.4 Initial and Boundary Conditions. 90

4.4.1.4.1 ElementalConcentrations(f i and G)... . . . . . 9l4.4.1.4.2 Diffusivity (D) .. . 924.4.1.4.3 Time (t).. . . . 924.4.1.4.4 Fluid Velocity (V) ..... 93

4.4.1.5 Results of Analytical Model Calculations................. 944.4.1.5.1 Transport by Diffusion.... . . . . . . . . . . . . 96

4.4.1.5.1.1 MVl70 Elemental hofi les... . . . . . 964.4.1.5.1.2 MVlTl Elemental Profi les... . . . . . 97

4.4.1.5.2 Transport by Coupled Diffusion-Advection............ 994.4.1.5.2.1 MVl70 Elemental Profiles...... 994.4.1.5.2.2 MVlTl Elemental Profiles...... 100

4.5 Orygen Isotopic Exchange... 1004.5.1 6-6 P1ots... . . . . . . . l0l

4.5.1.1 &-6 Plots of Plutonic Rocks From Other Localities 1034.5.1.2 &-6 Plots of Marysvale Quartz Monzonite 1054.5.1.3 Isotopic Equilibrium Mineral-Pair Temperatures................ 107

4.5.2 Interpretation of Marysvale 6-6 P1ots.......... 1084.5.2.1 Primary QM Bulk 6180 Vdue M\m-66 and -63)............. 1094. 5 .2.2 Open-System Rock-B uffered Alterati on (MVF-66, -6 8,

m-scale, and IW-170)... . . . . . . . . . . . . I I I4.5.2.3 Open-System Fluid Dominated Alteration (MV-l7l)........ I 134.5.2.4 Summary of &-6 Plots Interpretations..... ll4

4.5.3 Applicability of Finite Difference Modeling... ll54.5.4 Analytical Isotopic Exchange Modeling... 120

4.5.4.1 Initial and Boundary Conditions. l2l4.5.4.1.1 Temperature (T) .. l2l4.5.4. t .2 6180 0f F1uid. . . . . . . . . . . . . . . . 122

4.5.4.2 Resuls of Isotopic Exchange Analytical Modeling... 123

IV

5. APPLICATION OF RESI]LTS TO RADWASTE ISOLATION......................5. I Introduction..........5.2 Calculation of Retardation Factors (R) . .. . 190

5.2.1 Retardation Factors Based on Fluid/Solute Velocity Ratios.......... l9l5.2.2 Retardation Factors Based on Diffusivity-Derived IQs................. 192

5.3 Application of Marysvale Results to Radwaste Isolation. 1945.3.1 Comparison of Literature D" Values 1945.3.2 Comparison of Literature IQs and Calculated Retardation Factors 199

5.4 Implications for Far-Field Retardation in Fractured Granitic Rock............. 201

208

APPENDIXA. Neutron Activation Analysis.

A. I Sample Preparation. .. . . . . . . . . . . .A.2 Irradiation............. 229A.3 Courtin9.............. 229A.4 DataReduction.. 230A.5 Elements of Interest.............. 233

B. Development of Albite-H2O Isotopic Equilibrium Fractionation Curve...... 238B.l Introduction.......... 238B.2 Wide-Temperature Ab-H2O Fractionation................ 240

B.2.1 Calculation of JtlzO Reduced Partition Function Curves....... 242B. 2. 2 Production offl2O(f,g,l)'s with H2OO-HzO(g)

Fractionation Po1ynomia1................ 247B.2.3 Production of COz-HzO(lg,l) Curves WithTCO2

Reduced Partition Function.... 247B.2.4 Production of AAb-H2O Fractionation Curve..... 249B.2.5 Final Wide-Temperature AAb-H2O Fractionation Curve....... 249

C. Additional 262

190190

226226

LIST OF TABLESTable

3.1 Major element analysis re_sults by XRF for surface quartzmo"nzonite samples from Marysvale, Utah

3.2 Major element analysis rgsylts by XRF for subsurface quafiz- mo"nzonite samplesirom Marysvale, Utah

3.3 Neutron activation analysis results for MVF meter-scale, MYF-66,and MVF-68 qatt" moirzonite samples fromMarysvale, Uta6

3.4 Neutron activation analysis results for MV170 and MVl7lsubsamples series at Marysvale

3.5 Si concentrations for MVl70 subsamples an{ MVFp6 biotiteby the difference method using INAA of bulk powden

3.6 Si concentrations forMVlTl subsample.s an! MVF.68 bulkby the difference method using INAA of butk powders

S.Toxygenisotopecompositionsformineralsep-aratesfromMVF m- and km-scale quartz monzorute at Marysvarc

3.8 Oxygen isotopic comPo_sition of whole-rocks and mineralsepaiates frolir UVtZ0n series subsamples

3.g oxygen and carbon isoto_pic coppositions of whole-rocks andmirieral separates from MVl7lB series subsamples

4.r Diffusional transport parameters for MV170 elemental profiles

Diffusional transport parameters for MV 17 | elemental profiles

Coupled diffusion-advection transport parameters for MV 170elemental profiles

Coupled diffusion-advection transport paritmeters for MV 17 |elemental profiles

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4.2

4.3

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43

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50

51

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126

127

r284.4

5.1 Numerical isocon analysis results for MVF68 and MV l7O

A. I Mass [mg] of samples used in this study

A-2 Element specific neutron activation analysis dua

A.3 Linear correlations between peak areas me:Nured by STRIp3and MURR programs

4.4 Elements and their apploximate concentrations (in ppm)detected in neutron aCtivation analysis blanks

B. 1 H216O vibrational constants

B '2 HzO IR frequency parameters used to calculate reducedpanition functions

8.3 Reduced partition functions for Hzr6O <+ Hzr8O at selectedtemperatures

C alculated i9 oJopic fracti on ation values for /FIz O(g ),ftrzo(l), andfirzo(O at selected temperatures

Calculate{-isotopic fractionation values for CO2-HzO(g) andCOz-HzO(l) at selected temperatures

Calculated values for Ab-/FIzO(f,g,l) at selected temperatures

8.4

206

234

235

236

237

2M

245

8.5

8.6

251

253

255

256

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LIST OF ILLUSTRATIONS

Figure Page

2.1 Simplified distribution of 34 to 17 Maigneous rocks andknown calderas of the Marysvale, San Juan, and Mogollonvolcanic fields in the Great Basin and Colorado Plateau provinces 15

2.2 Schematic geologic history around Marysvale, Utah 16

2.3 Simplified geologic map of Marysvale Area 17

2.4 Modal composition of Marysvale quartz monzonite 18

2.5 Range in occurrence of Marysvale quartz monzonite mineralsrelative to alteration stages 19

3.1 Simplified surface geologic map of the Central Mining area atMarysvale

3.2 Diagrammatic sketch showing the location of m-scale,MVl70 and -l7l samples at the VCA cross-cut terminuswhere it intersects the Freedom #2 veins

3.3 Cut surface of MVlTl showing 5 mm thick subsamples ofB and B' subsample series

3.4 SEMIEDX and electron-microprobe chemistry for Marysvalequartz monzonite alkati and plagioclase feldspars

52

53

54

55

4.1A-N Reconstruction of local Marysvale geologic history 129

4.2 Thermal evolution within the finite difference model systemof the convectively cooling pluton from 0.004 to 50 ka 133

4.3 Superimposedstrearnfunction andtemperaflrrecontourswithinthemodelsystemfrom0.0O4to 100ka 135

4.4 Fluid flow velocities within the model systemfrom 0.004 to 50 ka 136

4.5 Maximum absolute strearnfunction values within the modelsystem during the first 150 ka of convective cooling 138

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4.6 Integrated fluid mass flux within the model systemfrom 0.004 to 50 ka 139

4.7 Maximum integrated fluid mass flux within the modelsystem during the first l50l<a of convective cooling l4l

4.8 Oxygen isotope evolution of the fluid within the modelsystem of the convectively cooling pluton from 0.0(M to 50 ka 142

4.9 Oxygen isotope shift of the rock within the model systemof the convectively cooling pluton from 0.004 to 50 ka 144

4.10 Range of the 6l8Onuio within the model systemduring the first 150 ka ofconvective cooling 146

4.ll Range of the Al8Orocrc within the model systemduringthefirst lsOkaofconvectivecooling 147

4.12 Schematic representation of the physical and analytical conditions usedin the onedimensional diffusion-only transport models 148

4.13 Graphical representations of analytical solutions to selected conditionsfor the diffusion mass tranport equation 149

4.14 Schematic representation of the physical and analytical conditions usedin one-dimensional coupled advectiondiffusion transport models 150

4.15 Graphical representations of analytical solutions to selected conditionsfor coupled advection-diffusion mass tranport l5l

4.164 Graphical results of diffirsion-only transport of Na curve-fitted tomeasured values from the MV170 series subsamples 152

4.168 Graphical results of diffusion-only transport of K curve-fitted tomeasured values from the MVl70 series subsamples 153

4.16C Graphical results of diffusion-only transport of Ba curve-fitted tomeasured values from the MVl70 series subsamples 154

4.16D Graphical results of diffusion-only transport of Nd curve-fitted tomeasured values from the MV170 series subsamples 155

4.16E Graphical results of diffusion-only transport of Lu curve-fitted tomeasurcd values from the MV170 series subsamples 156

4.16F Graphical results of diffusion-only transport of U curve-fitted tomeasured values from the MV170 series subsamples 157

4.16G Graphical results of diffusion-only transport of U curve-fitted tomeasured values from the YVF3A2 thin-section samples 158

u(

4.16H Graphical results of diffusion-only transport of U curve-fitted tomeasured values from the MVF9A9B thin-section samples 159

4.161 Graphical results of diffrrsion-only transport of Mg curve-fitted tomeasurcd values from the MVl70 series subsamples 160

4.16J Graphical results of diffusion-only transport of Ca curve-fitted tomeasurcd values from the MVl70 series subsamples 161

4.16K Graphical results of diffusion-only tnmsport of Cs curve-fitted tomeasurcd values from the MV170 series subsamples 162

4.16L Graphical results of diffusion-only transport of Tb curve-fitted tomeasured values from the MV170 series subsamples 163

4.16M Graphical results of diffusion-only transport of Yb curve-fitted tomeasured values from the MVl70 series subsamples 164

4.17A Graphical results of diffusion-only transport of K curve-fiUed tomeasured values from the MVlTl series subsamples 165

4.178 Graphical results of diffusion-only transport of Ca curve-fitted tomeasured values from the MV171 series subsamples 166

4.17C Graphical results of diffusion-only transport of Rb curve-fitted tomeasured values from the MVl7l series subsamples 167

4.17D Graphical results of diffusion-only transport of Ba curve-fitted tomeasurcd values from the MVlTl series subsamples 168

4.17E. Graphical results of diffusion-only transport of U curve-fitted tomeasured values from the MV171 series subsamples 169

4.17F Graphical results of diffusion-only transport of U curve-fitted tomeasured values from the MVlTl series subsamples 170

4.17G Graphical results of diffirsion-only transport of Na curve-fitted tomeasured values from the MVl7l series subsamples l7l

4.17H Graphical results of diffusion-only transport of Cs curve-fitted tomeasured values from the MVl7l series subsamples 172

4.171 Graphical results of diffusion-only transport of La curve-fitted tomeasured values from the MVl7l series subsamples 173

4.17J Graphical results of diffusion-only transport of Tb curve-fitted tomeasured values from the MVl7l series subsamples 174

4.18A Graphical results of coupled diffusion-advection transport of Kcurve-fitted to measured values from the MVlTl series subsamples 175

4.188 Graphicalresultsofcoupleddiffusion-advectiontransportolP-1,_^ a4.curve-fined to measured values from the MVl7l series subsamples 176

4.!9A 8lSOouartz versus 8lSOorttroctase for Marysvale quartzmonffnite and plutonic rocks from other localities

4198 DlSoquartz ve6us 6lSOma'nerire for Marysvale quartzmonztnite and plutonic rocks from other localities

4.20A 618Oq uartzversus DlSOortrroclase for Marysvale quartzmonzonite

4.208 6180q uwtzversus 6180magnerite for Marysvale quartzmonzorute

4.21 Schematic summary for both fluid-absent closed-systemand fluid-present open-system gxygen isotoqig exchangebetween q-uartz, orthochse, ffid magngtite within theCentral Intrusive quartz monzonite at Marysvale, Utatt

4.ZZ Range of intergrated hydrothermal fluid flux within themodel fracture-ptanes i.t and F2 ata depth of -250 m

4.23 Range of vertical hydrothermal fluid velocities within themodet fracture plaries Fl and F2 at a depth of -250 m

4.24 Range of hydrothermal fluid temperatures within themodit fracture planes Fl and F2-ata depth of -250 m

4.25 Range of 618Onuio values within the model fracture planesFl and F2 at a dePth of -250 m

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180

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185

4.26 Range of shift in 618Qocr values within the model fracture planesFl and F2 at adepth ol?SO * 186

4.27 Correlation with time betrveen modeled 6180 of the fluid exchangingwith rock and the resultant isotopic shift (Al8orocd within the modelfracture planes Fl and F2 atad6pth of -250 m 187

4.28 Graphical results of modeled MVl70 6180 mineral values determinedby ciosed-system equilibrium exchange between feldpar, quartz, and

the independently established water 6180 value at that distance 188

axr

4.29 Graphical results of modeled MV171 6180 mineral values determinedby closed-system equilibrium exchange between feldpar, quartz, andthe independently established water 6180 value at that distance 189

5.1

B. l

8.2

El.3

Anhenius diagram showing representative diffusivities for water,pore water, grain boundary, coupled volume-grain boundaty,volume, and reaction layer diffusion rclative to MVlTl U

Reduced partition functions for oxygen isotope exchangeof H2O using IR vibrational spectra

190

258

B.4 Third-order polynomial fits to high-temperaturcexperimental data and linear equation

C.lA Graphical results of coupled diffrrsion-advection transport of Nacurve-fined to measured values from the MV170 series subsamples

C.1B Graphical results of coupled diffusion-advection transport of Kcurve-fitted to measured values ftom the MVl70 series subsamples

C.lC Graphical results of coupled diffusion-advection transport of Bacurve-fitted to measured values from the MVl70 series subsamples

C.lD Graphical results of coupled diffusion-advection transpoft of Ndcurve-fiued to measured values from the MV170 series subsamples

C.lE Graphical results of coupled diffusion-advection transport of Lucurve-fitted to measured values from the MVl70 series subsamples

C. I F Graphical results of coupled diffusion-advection transport of Ucurve-fitted to measurcd values from the MV170 series subsamples

C.1G Graphical results of coupled diffusion-advection transport of Ucurve-fitted to measured values from the MVF3A2 thin-sections

C.lH Graphical results of coupled diffusion-advection transport of Ucurve-fitted to measured values fromthe MVF9A9B thin-sections

C.lI Graphical results of coupled diffusion-advection transport of Mgcurve-fitted to measured values from the MVl70 series subsamples

Isotopic fractionation curves for both COz-HzO(g) and COz-HzO(l) 259

Third-order polynomial fits to low-temperature Ab-/FI2O(lg,l)calculations and high-temperaturc experinrental data 260

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264

265

266

267

268

269

270

271

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C.lJ Graphical results of coupled diffusion-advection transport of Cacurve-fined to measurcd values from the MVl70 series subsamples 272

C.lK Graphical results of coupled diffusion-advection transport of Cscurve-fitted to measured values from the MVl70 series subsamples 273

C.lL Graphical results of coupled diffusion-advection transport of Tbcurve-fitted to measurcd values from the MVl70 series subsamples 274

C.lM Graphical results of coupled diffusion-advection transport of Ybcurve-fitted to measured values from the MVl70 series subsamples 215

C.2A Graphical results of coupled diffusion-advection transport of Cacurve-fitted to measurcd values from the MV171 series subsamples 276

C.2B Graphical results of coupled diffrrsion-advection transport of Rbcurve-fitted to measured values from the MVlTl series subsamples 277

C.zC Graphical results of coupled diffusion-advection transport of Ucurve-fitted to measured values from the MVl7l series subsamples 278

C.zD Graphical results of coupled diffusion-advection uansport of Ucurve-fitted to measured values from the MVlTl series subsamples 279

C.zE Graphical results of coupled difftrsion-advection transport of Nacurve-fined to measurcd values from the MVITl series subsamples 280

C.2F Graphical results of coupled diffusion-advection transport of Cscurve-fitted to measured values from the MVITl series subsamples 281

C.2G Graphical results of coupled diffusion-advection transpon of Lacurve-fitted to measured values from the MVITl series subsamples 282

C.2H Graphical results of coupled diffusion-advection transport of Tbcurve-fitted to measured values from the MVlTl series subsamples 283

xiii

ACKNOWLEDGMENTS

I thank my fellow students in the Deparunent of Geophysical Sciences, including

Eriks Puris, Mark Peters, Jeff Sweeney, and in particular Nadja Aquino who became a

close friend and confidante. Also, I thank my fellow graduate students in Professor Bob

Clayton's group Munir Humayun, Roberto Santos, Lin Huang, Hal Karlsson, and in

particular Mark Sund who left our group too soon.

Many of the Deparbnent professional and research staff members were a valuable

asset. Marilyn Bowie was exfemely helpful and always had an encouraging word. Andy

Davis assisted me greatly by granting me access to his superior Mac computer systems and

teaching me how to use the microprobe. Roy Lewis lent me his color printer.

Obviously I am very thanHul to the members of my committee Frank Richter, Fred

Anderson, I-affy Grossman, and my advisor Bob Clayton. Words cannot adequately

express the gratitude I feel nor the debt I owe to Bob for his unflagging support, thorough

and thoughfful review of my dissertation, and high scientific standards. I am also very

grateful to Tosh Mayeda, who cared so deeply and helped so much on a very human and

heart-felt level.

Other academic and professional colleagues and mentors helped and encouraged me

greatly during the time that I both worked on the Ph.D. and pursued a professional career,

including Ken Foland, Larry Cathles, Neil Chapman,Ian McKinley, John Smellie, Walt

Newcomb, Bob Laughon, Dave Curtis, Gerry Stirewalt" Dan Melchior, and Bob trvich.

My warmest thanks go to my family members and many friends who were always

kind enough to ask how things were going, and kinder still to at least appear to care,

including Larry Gaber, Dave Brown, L€o Gentile, and especially Fonest Manhew Frame-

Butthe single person to whom I am by far the most grateful is my wife Canie.

Without her boundless support, unquestioned love, and remindful sense of reality,I could

not have completed this dissertation.axlv