High Pressure and Low Temperature Equations of State for Aqueous Magnesium Sulfate: Applications to the Search for Life in Extraterrestrial Oceans, with Particular Reference to Europa. Steven Vance A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy University of Washington 2007 Program Authorized to Offer Degree: Department of Earth and Space Sciences University of Washington Graduate School This is to certify that I have examined this copy of a doctoral dissertation by Steven Vance and have found that it is complete and satisfactory in all respects, and that any and all revisions required by the final examining committee have been made. Chair of the Supervisory Committee: J. Michael Brown Reading Committee: J. Michael Brown Evan Abramson John Baross Date: In presenting this dissertation in partial fulfillment of the requirements for the doctoral degree at the University of Washington, I agree that the Library shall make its copies freely available for inspection. I further agree that extensive copying of this dissertation is allowable only for scholarly purposes, consistent with \fair use" as prescribed in the U.S. Copyright Law. Requests for copying or reproduction of this dissertation may be referred to Proquest Information and Learning, 300 North Zeeb Road, Ann Arbor, MI 48106-1346, 1-800-521-0600, or to the author. Signature Date University of Washington Abstract High Pressure and Low Temperature Equations of State for Aqueous Magnesium Sulfate: Applications to the Search for Life in Extraterrestrial Oceans, with Particular Reference to Europa. Steven Vance Chair of the Supervisory Committee: Professor J. Michael Brown Department of Earth and Space Sciences A prevalence of cold, high pressure (P > 100 MPa) environments in the Solar Sys- tem, and beyond, is discussed in the context of contemporary efforts to understand the origin and abundance of life in the Universe. Constraints on the depths of fluid circu- lation in extraterrestrial seafloors are explored through a model for the development of microfractures in olivine through cooling. For the example of Europa, we estimate a factor of four in per-unit-area hydrogen flux from serpentinization as compared with calculations for Earth's seafloor. Uptake of seafloor salt by an incipient thermal plume is suggested as a stay on buoyancy and a driver for stratification in the Europa's ocean. An apparatus for optical measurements in deep-ocean analogue materials is described. Laser-induced phonon spectroscopy is applied to the determination of the velocity of sound in water and in aqueous solutions of MgSO4. The equation of state is deduced for concentrations from 0 to 2.0137 m for temperatures from -20 to 100 oC and pressures as high as 700 MPa. Debye H¨uckel theory is employed for calculating partial molal volume at infinite dilution. The volumetric contribution of MgSO4 is less than expected above 200 MPa and at the extremes of temperature, indicating a change in ion-water interaction due to increased confinement under these conditions. TABLE OF CONTENTS Page List of Tables . .v List of Figures . vi Chapter 1: Introduction: The Deep Cold Biosphere? Cold, High Pressure Environments as Abodes for Life . .1 1.1 A Prevalence of Cold and Deep Aqueous Environments in the Solar System and Beyond . .2 1.1.1 Mars . .3 1.1.2 Icy Jovian Satellites . .4 1.1.3 Icy Kronian Satellites . .4 1.1.4 Uranus and Neptune . .6 1.2 Prebiotic Chemistry in the Solar System . .6 1.3 Pressure's Role in Planetary Processes as Revealed by the Present Con- tribution . .7 Chapter 2: Deep Hydrothermal Systems in Small Ocean Planets . .9 2.1 Introduction . 10 2.2 Ocean Planets in the Solar System . 11 2.3 Depth of Fluid Circulation Below an Extraterrestrial Seafloor . 12 2.3.1 Constraints Based on the Permeability of Earth's Oceanic Crust 13 2.3.2 Constraints Based on Thermal Cracking in Olivine . 14 2.4 Sources of Hydrothermal Energy . 21 2.4.1 Tidal Heating . 21 2.4.2 Serpentinization . 32 2.4.3 Longevity of Serpentinizing Systems . 35 2.4.4 Serpentinization as a Source of Nutrients and Metabolites . 36 i 2.5 Implications for Life in Ocean Planets . 38 2.5.1 Organics in the Solar System . 38 2.5.2 Potential Extraterrestrial Biomass . 40 2.6 Conclusion . 41 Chapter 3: Stratification and Double-Diffusive Convection in Europa's Ocean 45 3.1 The Influence of Pressure Thermochemistry on Buoyancy in Europa's Ocean . 47 3.1.1 Results . 48 3.1.2 Double-Diffusive Convection in Europa's Ocean . 50 3.1.3 Feasibility of Double-Diffusive Convection in Europa's Ocean . 52 3.1.4 Double-Diffusive Convection in Earth's Waters . 53 3.2 Implications for Europa's Geologic History . 54 3.3 Conclusion . 55 Chapter 4: Setup and Operation of the Icy Satellite Interior Simulator . 57 4.1 A Description of ISIS . 57 4.1.1 Hydraulic Component . 57 4.1.2 Fluid Component . 61 4.1.3 High-Pressure Plumbing . 64 4.2 Operating Instructions for the High Pressure System . 64 Chapter 5: Sound Velocities in Water to 700 MPa and -20 to 100 oC.... 77 5.1 Introduction . 77 5.2 Equipment and Methods . 77 5.2.1 The Icy Satellite Interior Simulator: An Apparatus with Op- tical Access for In-Situ Measurements to 700 MPa from -20 to 100 oC............................... 78 5.2.2 Control and Measurement of Pressure . 79 5.2.3 Control and Measurement of Temperature . 79 5.3 Results . 80 5.4 Discussion . 80 5.5 Conclusion . 81 ii Chapter 6: Equation of State for Concentrated Aqueous MgSO4 to 700 MPa at Temperatures from -20 to 100 oC from Measured Sound Ve- locities . 84 6.1 Introduction . 84 6.2 Equipment and Methods . 85 6.2.1 The Icy Satellite Interior Simulator: An Apparatus with Op- tical Access for In-Situ Measurements to 700 MPa from -20 to 100 oC............................... 86 6.2.2 Control and Measurement of Pressure . 87 6.2.3 Control and Measurement of Temperature . 87 6.3 Results . 88 6.3.1 Velocities . 88 6.3.2 Volumetric Properties . 89 6.3.3 Excess Volumes . 90 6.4 Discussion . 91 6.4.1 Evaluation of Velocity Measurements . 91 6.4.2 Calculation of Densities . 92 6.4.3 Densities . 92 6.4.4 Apparent Molal Volumes . 93 6.4.5 Partial Molal Volumes at Infinite Dilution . 93 6.4.6 Excess Volumes . 94 6.5 Conclusion . 95 Chapter 7: Conclusion: A Deeper Understanding of the Prospects for Life in Ocean Planets . 112 7.1 The Propects for Life in Europa and Elsewhere as Revealed by the Present Contribution . 113 7.2 Future Work . 114 7.2.1 Extended Simulations of Ocean Chemistry . 114 7.2.2 Some Like it Cold . 115 Bibliography . 118 Appendix A: Measurement of Independent Parameters . 139 A.0.3 Assessing Precisions Needed for the ISS Experiment . 139 iii A.0.4 Calibration of the Instruments . 139 Appendix B: ISS Velocity Data . 143 Appendix C: Revised Heat Flow Estimates for Europa's Ocean . 185 iv LIST OF TABLES Table Number Page 2.1 Physical properties used in the prediction of thermal cracking in ex- traterrestrial seafloors . 18 2.2 Hydrothermally relevant properties in extraterrestrial seafloors . 22 2.3 Tidal dissipation rate (Htidal) and maximum radial displacement at the surface (ur) for possible ocean-bearing satellites . 29 3.1 Depth of neutral buoyancy for a saline-enriched upwelling in Europa's ocean.................................... 49 v LIST OF FIGURES Figure Number Page 2.1 Stress intensity KI in olivine . 19 2.2 Pressure-temperature profiles in planetary seafloors . 26 2.3 Near-surface pressure, temperature, and cracking depth profiles for Earth and Mars . 27 2.4 Pressure, temperature, and cracking depth profiles for Europa and Enceladus. 28 2.5 tidal energy input (W m−2) from viscous dissipation . 43 2.6 Viscously dissipated energy Hvis ..................... 44 3.1 Density anomaly in a Europan ocean for a plume with thermal anomaly of 0.2 mK . 50 3.2 Partial molal volumes for Na2SO4 and MgSO4 ............. 51 4.1 Schematic of the apparatus for obtaining high hydraulic pressure in aqueous solutions . 58 4.2 Separator assembly . 62 4.3 Detail of separator connector tube . 71 4.4 Exploded view of separator connector tube . 72 4.5 Assembled separator connector . 73 4.6 Exploded view of separator piston plug . 74 4.7 Exploded wireframe view of separator piston plug . 75 4.8 Assembled separator piston plug . 76 5.1 Sound velocities in water to 700 MPa from 0 to 95 oC. 82 5.2 Comparison of sound velocities from this study with previously pub- lished values. 83 6.1 Pressure and temperatures at which densities have been measured for aqueous MgSO4 .............................. 97 vi 6.2 Sound velocities in 0.5103 molal MgSO4 (aq) to 700 MPa from -17 to 95 oC.................................... 98 6.3 Residuals of velocity measurements, along isotherms, with polynomial fits in pressure for 0.0800 m MgSO4................... 99 6.4 Residuals of velocity measurements, along isotherms, with polynomial fits in pressure for 0.5103 m MgSO4................... 100 6.5 Residuals of velocity measurements, along isotherms, with polynomial fits in pressure for 0.9965 m MgSO4................... 101 6.6 Fits to inverse velocity squared vs the inverse of velocity, Ptx = 1=(P + b), for 0.0800 m MgSO4 (aq) . 102 6.7 Residuals of velocity surfaces used to calculate density . 103 6.8 Distribution of residuals of velocity surfaces used to calculate density 104 o 6.9 Densities of MgSO4 (aq) at 30 C versus pressure to 400 MPa . 105 6.10 Densities in aqueous MgSO4 (aq) from measured sound velocities .