Isotopic Analyses of Helium from Wells Located in the Four Corners Area, Southwestern, Us
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ISOTOPIC ANALYSES OF HELIUM FROM WELLS LOCATED IN THE FOUR CORNERS AREA, SOUTHWESTERN, US By Daniel Thomas Halford Copyright by Daniel Halford (2018) All Rights Reserved A thesis submitted to the Faculty and the Board of Trustees of the Colorado School of Mines in partial fulfillment of the requirements for the degree of Master of Science (Geology). Golden, Colorado Date: ______________________________ Signed: ______________________________ Daniel Halford Signed: ______________________________ Dr. Stephen Sonnenberg Thesis Advisor Golden, Colorado Date: ______________________________ Signed: ______________________________ Dr. Steve Enders Professor and Head Department of Geology ii ABSTRACT Helium, the lightest noble gas, is a valuable resource located on the Colorado Plateau southwestern US. Helium, a proven, useful noble gas, has many applications in modern technology for its chemical, physical, and thermodynamic properties. As of this writing, the price of crude helium is ~40% greater than CH4, rendering the economic grade for direct and secondary extraction at 0.3% helium. The helium systems in the Four Corners area (i.e., the study area) are characterized utilizing the geochemistry of noble gases, hydrocarbons, and non- hydrocarbons (compositional and isotopic), as well as geologic mapping. The geochemistry delineates sources of gases, migration pathways, and potential trapping/sealing mechanisms of the helium system, which is a slight deviation from the petroleum system. Economic helium (>0.3%) is primarily found in Paleozoic intervals structurally trapped on the Four Corners Platform, the edge of the Defiance Uplift, and the edge of the Holbrook Basin. Thirty-one gas samples, isotopically analyzed, are from actively producing Paleozoic formations within five fields: Tocito Dome, Dineh-Bi-Keyah, Ratherford, Pinta Dome, and Navajo Springs. Helium concentrations range from 0.01% to >6.0% and incorporates a spectrum of other gas values associated with relatively similar Paleozoic formations. Noble gases along with hydrocarbon and non-hydrocarbon gas geochemistry are successfully used in genetically fingerprinting gas families. The source of helium is determined to be from the shallow crust, i.e., Precambrian granitic basement. Noted faults and attendant fracture systems serve as primary migration conduits (via fluid flow from advection). Observed gas-water reactions indicate groundwater involvement in the concentration of helium and extreme solubility fractionation (i.e., long secondary migration pathways). By investigating iii migration pathways, N2 and CO2 are recognized as major, helium carrier gases, whereas CH4 is a helium dilutant. Geologic mapping illustrates dominant structural, stratigraphic, and combination structural-stratigraphic traps. The helium system definition is updated, as well as criteria developed to successfully explore for helium. Proper isotopic and geological analyses can improve helium system models that involve generation, migration, and trapping/sealing mechanisms. Improvements in the understanding of the helium system model are critical for more effective helium exploration. Native Americans Tribes of the Southwest and other economic sectors stand to benefit (economically and socially) from a more enhanced scientific knowledge of the helium system in the study area. iv TABLE OF CONTENTS ABSTRACT ................................................................................................................................... iii LIST OF FIGURES ...................................................................................................................... xii LIST OF TABLES ....................................................................................................................... xix ACKNOWLEDGEMENTS ......................................................................................................... xxi CHAPTER 1 INTRODUCTION .....................................................................................................1 1.1 Objectives and Thesis Outline .......................................................................................1 1.2 Brief History of Helium .................................................................................................3 1.3 Helium Applications ......................................................................................................4 1.4 Helium Supply and Demand ..........................................................................................6 1.5 Helium’s Processing and Transport ...............................................................................9 1.6.1 Helium’s Policies ........................................................................................................9 1.6.2 Policy Summary ........................................................................................................13 1.7 Helium’s Price .............................................................................................................14 1.8.1 Helium’s Reservoirs..................................................................................................16 1.8.2 N2-Rich Fields ...........................................................................................................17 1.8.3 CH4-Rich Fields ........................................................................................................18 1.8.4 CO2-Rich Fields ........................................................................................................19 CHAPTER 2 NOBLE GAS GEOCHEMISTRY ...........................................................................21 2.1 Review of Noble Gases ................................................................................................21 2.2.1 Origins of Noble Gases and Their Isotopes ..............................................................23 2.2.2 Helium.......................................................................................................................23 v 2.2.3 Formation of Helium Isotopes ..................................................................................24 2.2.4 Neon ..........................................................................................................................25 2.2.5 Argon ........................................................................................................................26 2.2.6 Krypton and Xenon ...................................................................................................27 2.3.1 Noble Gases as Tracers .............................................................................................29 2.3.2 Sources of Noble Gases ............................................................................................30 2.3.3 Air Saturated Water ..................................................................................................33 2.3.4 Crust ..........................................................................................................................35 2.3.5 Mantle .......................................................................................................................37 2.4.1 Noble Gas Recharge Processes .................................................................................38 2.4.2 Phase Exchanges .......................................................................................................39 2.4.3 Sorption Processes ....................................................................................................41 2.4.4 Diffusion ...................................................................................................................42 2.5 Noble Gas Applications ...............................................................................................43 CHAPTER 3 LITERATURE REVIEW ........................................................................................46 3.1 Generation of 4He ........................................................................................................46 3.2 Primary Migration of 4He ............................................................................................52 3.3 Secondary Migration of 4He ........................................................................................56 3.4 Trapping and Sealing of 4He ........................................................................................61 3.5 Generation Model Summary ........................................................................................66 3.6.1 Variables to the Helium System ...............................................................................66 3.6.2 Helium Saturation .....................................................................................................66 3.6.3 Porosity .....................................................................................................................68 vi 3.6.4 Depth .........................................................................................................................70 3.6.5 Age ............................................................................................................................75 3.6.6 Tectonic Activity (Volcanism and Faulting) ............................................................76 3.6.7 Hydrocarbons ............................................................................................................81 3.6.8 Basement High ..........................................................................................................85