PNL-2776 UC-70 3 3679 00049 3611 ,. NATURALLY OCCURRING GLASSES: ANALOGUES FOR RADIOACTIVE WASTE FOR~1S • Rodney C. Ewing Richard F. Haaker Department of Geology University of New Mexico Albuquerque, ~ew Mexico 87131 April 1979 Prepared for the U.S. Department of Energy under Contract EY-76-C-06-1830 Pacifi c i'lorthwest Laboratory Richland, Washington 99352 TABLE OF CONTENTS List of Tables. i i List of Figures iii Acknowledgements. Introduction. 3 Natural Glasses 5 Volcanic Glasses 9 Physical Properties 10 Compos i ti on . 10 Age Distributions 10 Alteration. 27 Devitrification 29 Hydration 32 Tekti tes. 37 Physical Properties 38 Composition . 38 Age Distributions . 38 Alteration, Hydration 44 and Devitrification Lunar Glasses 44 Summary . 49 Applications to Radioactive Waste Disposal. 51 Recommenda ti ons 59 References 61 Glossary 65 i LIST OF TABLES 1. Petrographic Properties of Natural Glasses 6 2. Average Densities of Natural Glasses 11 3. Density of Crystalline Rock and Corresponding Glass 11 4. Glass and Glassy Rocks: Compressibility 12 5. Glass and Glassy Rocks: Elastic Constants 13 6. Glass: Effect of Temperature on Elastic Constants 13 7. Strength of Hollow Cylinders of Glass Under External 14 Hydrostatic Pressure 8. Shearing Strength Under High Confining Pressure 14 9. Conductivity of Glass 15 10. Viscosity of Miscellaneous Glasses 16 11. Typical Compositions for Volcanic Glasses 18 12. Selected Physical Properties of Tektites 39 13. Elastic Constants 40 14. Average Composition of Tektites 41 15. K-Ar and Fission-Track Ages of Tektite Strewn Fields 42 16. Microprobe Analyses of Various Apollo 11 Glasses 46 17. Comparison of Composition of Waste Glass To Volcanic 53 Glass 18. Assumed Waste Repository Conditions 54 19. Average Chemical Analyses of Igneous Rocks 66 i i LIST OF FIGURES 1. Silica content of 159 volcanic glasses. 19 2. Age distribution of volcanic glasses. 20 3. Age distribution for rhyolite and obsidian glasses. 23 4. Age distribution for rhyolites. 24 5. Age distribution for tuff, ash flows and pumice 25 6. Age distribution for andesite and diorite. 26 7. Minimum time for thermal reconstruction of natural 30 glass plotted against temperature. 8. Time for hydrothermal reconstruction of perlite. 31 9. Experimental hydration rate curve for obsidian at 100oe. 33 10. Relationship between chemical composition of obsidian 34 and hydration rate. 11. Hydration rate curves for obsidian artifacts. 35 12. Activation energy of hydration curve. 36 13. Expected thermal history of waste canister 55 14. Mineralogical constituents of igneous rocks. 67 .. iii ACKNOWLEDGEMENTS This report has benefitted from the efforts of Ms. Kathleen Affholter. As this report is necessarily a compilation of the work of others, the authors are particularly indebted to Dr. John A. O'Keefe for the data available in Tektites and Their Origin and to Dr. Sydney P. Clark, editor of Geological Society of America Memoir 97: Handbook of Physical Constants. , , I NTRODUCTI ON Glass, primarily the borosilicate type, has received major considera­ tion as the primary waste form for the disposal of high level radioactive wastes (Grover and Chidley, 1962; Grover, 1972; Blasewitz and others, 1972; Mendel and McElroy, 1972; Platt and McElroy, 1973-1974; Mendel, 1977). One criteria in selecting glass as a waste form, in preference to other ceramic or glass-ceramic waste forms, is the evaluation of its long-term "geologic ll stability. The waste form is considered unstable should physical changes occur which cause significant increased radionuclide mobility. These transformations may include devitrification of the glass, alteration effects or radiation damage which produce new, and perhaps, unexpected phases of undetermined physical and chemical properties. Work presently in progress is designed to predict the appearance of such phases (e.g. Turcotte and Wald, 1978) The long-term effects of alteration and radiation damage on the waste glass form as a result of interaction with the geologic environment are dif­ ficult to assess in time-limited laboratory experiments. Therefore, it becomes important to look at naturally occurring analogues of waste forms to evaluate their long-term stability. Age distributions and alteration effects observed in natural glasses in different geologic environments pro­ vide insight into variables controlling the rates of devitrification, alteration and radiation damage. This report describes the properties and occurrence of natural glasses (volcanic glasses, tektites, and lunar glasses). Much of the data on the 3 physical and chemical properties of glasses are taken from Clark (1966), an excellent reference for geologic materials. Particular attention is paid to the compositional variations, age distributions and alteration effects of these natural glasses in different geologic environments. Radia­ tion damage effects are difficult to evaluate in natural glasses as uranium and thorium concentrations are quite low (1-30 ppm). A description of radiation effects in natural glasses and the metamict state will be the subject of a later report. Although the compositions of the synthetic waste glass form are quite different from those of naturally occurring glasses, these natural materials provide excellent benchmark standards for comparison to the synthetic glasses, and they may serve as checks on the data of time-limited laboratory experiments that must be extrapolated to estimate long-term stability. A discussion of experimental studies of natural glasses is included. Since much of the appropriate data are taken from the geologic and mineralogic literature, certain terms may be unfamiliar. A glossary is therefore provided at the end of this report. 4 NATURAL GLASSES Naturally occurring silicate glasses are of three main types: (1) volcanic glasses, (2) tektites and (3) lunar glasses. A less important category of natural glasses are fulgurites, an irregular, glassy, often -' tabular or rod-like structure or crust produced by the fusion of loose sand by lightning. Petrographic properties of each of these glass types are summarized in Table 1. Volcanic glasses (see Table 11 for typical compositions) are associated with extrusive volcanic rocks that have been undercooled so quickly that crystalline phases have not had an opportunity to fOnTI. These "chilled" zones may be as much as 10 to 20 meters thick and are a common feature of the volcanic belts that circle the earth. Tektites are natural silicate glasses ranging in size from fractions of a millimeter to tens of centimeters in size. Their shape may be irregular and blocky, but the majority occur as spheres or dumbbell and lense shaped buttons. They seldom occur as isolated objects but rather, are found as members of large associations, strewn fields, which may cover areas up to 10,000 km wide. Their origin, terrestrial or extraterrestrial, is still the subject of much debate. Lunar glasses occur as a common constituent of the lunar microbreccias and fines. The individual glass bodies may be perfectly spherical, oblate spherules, or dumbbell shaped. Aside from the small amount of residual glass in the lunar basalts, all lunar glasses have been ascribed to shock­ induced melting of preexisting rocks due to meteorite impacts, possibly at 5 Table 1: Petrographic Properties of Natural Glasses Range of Bulk Range of Type of Specific Index of Glass Color Gravitt Refraction Homogeneitt Structure Obsidians Black, grey 2.30- 1.47-1.53 Crystallites are commonly Banded or lamellar structure to red 2.46 present but contain no generally due to bands of glass inclusions of com- oriented crysta11 ites. position different from Strain birefringence the bulk glass, generally generally not pronounced. dense. Tekti tes Bl ac k, dark 2.21- 1.4798- Contain no crystallites but Pronounced flow structure brown, to 2.80 1.51 inclusions of siliceous consisting of schlieren of bottle green glass are nearly ubiquitous; glasses of slightly dif- generally dense to slightly ferent composition, accom- vesicular. panied by strain birefrin- gence. Lunar Varies from 2.5-3.0 1.56-1.70 Generally very homogeneous Flow structure may be well Glasses colorless to with only minor streaking. developed. Streaks of green or deep Inclusions are rare, but gl ass of different refrac- red brown metallic spheres of iron tive indices are not and spherulites of clino- uncommon. pyroxenes and plagioclase may be present. Fu1 gurites Light gray Generally 1.46 Crystallites locally pre- Generally tubular-shaped to green- less than sent; siliceous inclusions with adhered sand grains. ish gray 2.2 are also present. Sand Flow structure present grains or mineral fragments but only locally developed. can usually be detected; highly vesicular. I. --- . '-r " pressures in the megabar range. This splattering effect is responsible for the common glass crusts found on both Apollo 11 and Apollo 12 samples. The physical properties, compositional variations, age distributions and alteration, devitrification and hydration effects for each of these natural glass types are discussed separately in the following sections. J 7 ,," VOLCANIC GLASSES: Volcanic glass is a common and highly characteristic constituent of volcanic rocks. In basic rocks (S;02 = 47 wt. %), the parent magma of which has a relatively low viscosity, glass is typically present in sub­ -' ordinate amounts in the groundmass or is altogether lacking. In acidic lavas (Si02 = 72 Wt. %), glass is an important constituent material. These acidic lavas are granitic (compositionally equivalent