Stable isotope systematics of sulfate minerals

Abstract

Stable isotope studies of sulfate minerals are especially useful for unraveling the geochemical history of geological systems. All sulfate minerals can yield sulfur and oxygen isotope data. Hydrous sulfate minerals, such as gypsum, also yield oxygen and hydrogen isotope data for the water of hydration, and more complex sulfate minerals, such as alunite and jarosite also yield oxygen and hydrogen isotope data from hydroxyl sites. Applications of stable isotope data can be divided into two broad categories: geothermometry and tracer studies. The equilibrium partitioning of stable isotopes between two substances, such as the isotopes of sulfur between barite and pyrite, is a function of temperature. Studies can also use stable isotopes as a tracer to fingerprint various sources of hydrogen, oxygen, and sulfur, and to identify physical and chemical processes such as evaporation of water, mixing of waters, and reduction of sulfate to sulfide. Studies of sulfate minerals range from low-temperature surficial processes associated with the evaporation of seawater to form evaporite deposits to high-temperature magmatic-hydrothermal processes associated with the formation of base-and precious-metal deposits. Studies have been conducted on scales from submicroscopic chemical processes associated with the weathering of pyrite to global processes affecting the sulfur budget of the oceans. Sulfate isotope studies provide important information to investigations of energy and mineral resources, environmental geochemistry, paleoclimates, oceanography (past and present), sedimentary, igneous, and metamorphic processes, Earth systems, geomicrobiology, and hydrology. One of the most important aspects of understanding and interpreting the stable isotope characteristics of sulfate minerals is the complex interplay between equilibrium and kinetic chemical and isotopic processes. With few exceptions, sulfate minerals are precipitated from water or have extensively interacted with water at some time in their history. Because of this nearly ubiquitous association with water, the kinetics of isotopic exchange reactions among dissolved species and solids are fundamental in dictating the isotopic composition of sulfate minerals. In general, the heavier isotope of sulfur is enriched in the higher oxidation state, such that under equilibrium conditions, sulfate minerals (e.g. barite, anhydrite) are expected to be enriched in the heavy isotope relative to disulfide minerals (e.g. pyrite, marcasite), which in turn are expected to be enriched relative to monosulfide minerals (e.g. pyrrhotite, sphalerite, galena) ( Sakai 1968 , Bachinski 1969 ). The kinetics of isotopic exchange among minerals with sulfur at the same oxidation state, such as sphalerite, and galena, are such that equilibrium is commonly observed. In contrast, isotopic equilibrium for exchange reactions between minerals of different oxidation states depends on factors such as the pH, time and temperature of reaction, the direction of reaction, fluid composition, and the presence or absence of catalysts ( Ohmoto and Lasaga 1982 ). The kinetics of oxygen isotope exchange between dissolved sulfate and water are extremely sluggish. Extrapolation of the high-temperature (100 to 300°C) isotopic exchange kinetic data of Chiba and Sakai (1985) to ambient temperatures suggests that it would take several billions of years for dissolved sulfate and seawater to reach oxygen isotopic equilibrium. In contrast, the residence time of sulfate in the oceans is only 7.9 million years ( Holland 1978 ). However, at higher temperatures (>200°C), oxygen isotopic exchange is sufficiently rapid to permit application of sulfate isotope geothermometry to geothermal systems and hydrothermal mineral deposits. In general, equilibrium prevails at low pH and high temperatures, whereas kinetic factors preclude equilibrium at low temperatures even at low pH. Thus, the sluggish kinetics of sulfur and oxygen isotope exchange reaction at low temperatures impair the use of these isotopes to understand the conditions of formation of sulfate minerals in these environments. However, because of these slow kinetics, the oxygen and sulfur isotopic compositions of sulfate minerals may preserve a record of the sources and processes that initially produced the dissolved sulfate, because the isotope ratios may not re-equilibrate during fluid transport and mineral precipitation. The first part of this chapter is designed to provide the reader with a basic understanding of the principles that form the foundations of stable isotope geochemistry. Next, an overview of analytical methods used to determine the stable isotope composition of sulfate minerals is presented. This overview is followed by a discussion of geochemical processes that determine the stable isotope characteristics of sulfate minerals and related compounds. The chapter then concludes with an examination of the stable isotope systematics of sulfate minerals in a variety of geochemical environments.