Trace Hydrogen in Minerals

Citation

Aines, Roger Deane (1984) Trace Hydrogen in Minerals. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/n7vk-f724. https://resolver.caltech.edu/CaltechTHESIS:11092018-122937399

Abstract

Trace hydrogen in minerals most frequently occurs bonded to oxygen. The resulting water and hydroxyl (OH^-) affect and play a role in a variety of mineral properties and reactions. This thesis examines the occurrence of trace hydrogen in nominally anhydrous minerals, the mechanisms by which trace hydrogen participates in reactions and controls properties, and the changes that occur in hydrogen speciation and siting as a function of temperature. The principal tool used in this study is infrared (IR) spectroscopy because of its sensitivity to the highly polar O-H bond, yielding quantitative information on concentration, and symmetry, speciation, and siting information.

The speciation of trace hydrogen in garnet and low temperature natural and synthetic quartz is examined in detail. In garnet hydrogen occurs as the hydrogarnet substitution, four hydroxyl groups replacing a silicate tetrahedron. This substitution is extremely common among natural garnets. Concentrations range from 0.05 to 0.20 wt. % (as H₂O) in garnets from most occurrences, including garnets from the mantle. This trace hydrogen is truly dissolved. The hydrogen found in natural and synthetic quartz formed at low temperature can occur as either hydroxyl or molecular water. The molecular water is the active participant in hydrolytic weakening of quartz, but it is not truly dissolved. It occurs as small groups of molecules (approximately 5 to 200) which were trapped during rapid growth.

Two properties of minerals affected by trace hydrogen are strength and radiation response. Molecular water may be responsible for weakening of other minerals as well as quartz. Both water and hydroxyl participate in radiation response of minerals. In metamict zircon, water stabilizes local charge imbalance formed when bonds are broken. Water enters the crystal after a threshold of damage occurs, and reacts with broken bonds to form hydroxyl groups. These must reform molecular water and be expelled before recrystallization occurs during heating. In quartz, molecular water is strongly correlated with the formation of citrine color during irradiation, but inhibits the formation of the amethyst color center Fe⁴⁺. Apparently molecular hydrogen forms during radiolysis of the water, and reduces the Fe⁴⁺. Several hydroxyl sites in topaz are strongly correlated with the formation of brown color upon irradiation. The unifying theme in all these reactions is the extreme mobility of hydrogen and the ease with which different oxygen-hydrogen species may be formed in silicates.

The behavior of trace hydrogen at temperatures of geologic interest has been examined using high temperature infrared spectroscopy. Direct observations of speciation, concentration, and properties have been made up to 1200°C. In muscovite there is no change in hydrogen speciation or site up to the dehydration point, as expected. However, in cordierite and beryl water reversibly partitions into a gas-like state above 400°C, and the formation of this new state controls the dehydration behavior. In topaz, hydroxyl groups have been observed converting to new sites at temperatures above 500°C. In orthoclase feldspar, one type of molecular water dehydrates at 200°C, while a second type converts irreversibly to a new hydrous species above 600°C.

There is no evidence for the existence of hydrogen species other than hydroxyl and water in silicate minerals. The hydrogarnet substitution (four hydroxyl groups in a tetrahedral configuration) is common in garnets and may be important in other orthosilicates. The most common hydrous species in nominally anhydrous silicates (aside from fluid inclusions and alteration) are: small groups of trapped water molecules; individual water molecules occupying voids in the structure of minerals; hydroxyl occurring in a charge balancing role such as AlO₃OH substituting for SiO₄; hydroxyl neutralizing substitutional atoms, e.g., LiOH; and hydroxyl groups formed from the reaction of broken bonds with water as in radiation damaged minerals. There is no evidence for the presence of the oxonium ion, H₃O⁺, in common minerals, and the existing evidence for the occurrence of molecular hydrogen may better be explained by the presence of water or hydroxyl groups.

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