ALBERT

Description / Table of Contents: Volatile components, by which we mean those magma constituents which typically prefer to occur in the gaseous or super-critical fluid state, may influence virtually every aspect of igneous petrology. The study of volatile-bearing systems, both in nature and in the laboratory, has far exceeded the relative abundances of these components in igneous rocks, yet in many ways the words of Bowen (1928) are still broadly applicable: " ... to many petrologists a volatile component is exactly like a Maxwell demon; it does just what one may wish it to do." (Bowen, 1928, p. 282) What we hope to show in this volume are some areas of progress in understanding the behavior of magmatic volatiles and their influence on a wide variety of geological phenomena; in doing this it also becomes apparent that there remain many questions outstanding. The range of topics we have tried to cover is broad, going from atomisticscale aspects of volatile solubility mechanisms and attendant effects on melt physical properties, to the chemistry of volcanic gases and the concentrations of volatiles in magmas, to the global geochemical cycles of volatiles. The reader should quickly see that much progress has been made since Bowen voiced his concerns about Maxwell demons, but like much scientific progress, answers to old questions have prompted even greater numbers of new questions. The Voltiles in Magmas course was organized and transpired at the Napa Valley Sheraton Hotel in California, December 2-4, 1994, just prior to the Fall Meetings of the American Geophysical Union in San Francisco.

Description / Table of Contents: The Mineralogical Society of America sponsored a short course for which this was the text at Stanford University December 9 and 10, 1995, preceding the Fall Meeting of the American Geophysical Union and MSA in San Fransisco, with about 100 professionals and graduate students in attendance. A silicate melt phase is the essential component of nearly all igneous processes, with dramatic consequences for the properties of the Earth's interior. Throughout Earth history and continuing to the present day, silicate melts have acted as transport agents in the chemical and physical differentiation of the Earth into core, mantle and crust. The occurrence of such magmatic processes leads to the definition of our planet as "active," and the resulting volcanism has a profound impact on the Earth's atmosphere, hydrosphere and biosphere. Although near-surface melts are observed directly during volcanic eruptions, the properties of magmas deep within the Earth must be characterized and constrained by laboratory experiments. Many of these experiments are designed to aid in developing an atomic level understanding of the structure and dynamics of silicate melts under the P- T conditions of the Earth's crust and mantle, which will make extrapolation from the laboratory results to the behavior of natural magmas as reliable as possible. Silicate melts are also the archetypal glass-forming materials. Because of the ready availability of raw materials, and the ease with which molten silicates can be vitrified, commercial "glass" has necessarily implied a silicate composition, over most of the history of glass technology. The properties of the melt, or "slag" in metallurgical extractions, determine the nature of the glass formed, and the needs of the glass industry have provided much of the impetus for understanding the structure-property relations of molten silicates as well as for the glasses themselves. It is now recognized that any liquid might become glassy, if cooled rapidly enough, and understanding the thermodynamic and kinetic aspects of the glass transition, or passage between the liquid and glassy states of matter, has become a subject of intense interest in fundamental physics and chemistry. Glasses have also been studied in many geochemical investigations, often as substitutes for the high temperature melts, with the results being extrapolated to the liquid state. In many cases, in situ techniques for direct investigation of these refractory systems have only recently become available. Much valuable information concerning the melt structure has been gleaned from such studies. Nevertheless, there are fundamental differences between the liquid and glassy states. In liquids, the structure becomes progressively more disordered with increasing temperature, which usually gives rise to major changes in all thermodynamic properties and processes. These changes must, in general, be investigated directly by in situ studies at high temperature. Studies of glass only represent a starting point, which reflect a frozen image of the melt "structure" at the glass transition temperature. This is generally hundreds of degrees below the near-liquidus temperatures of greatest interest to petrologists. Since the early 1980s, a much deeper understanding of the structure, dynamics, and properties of molten silicates has been developed within the geochemical community, applying techniques and concepts developed within glass science, extractive metallurgy and liquid state physics. Some of these developments have far-reaching implications for igneous petrology. The purpose of this Short Course and volume is to introduce the basic concepts of melt physics and relaxation theory as applied to silicate melts, then to describe the current state of experimental and computer simulation techniques for exploring the detailed atomic structure and dynamic processes which occur at high temperature, and finally to consider the relationships between melt structure, thermodynamic properties and rheology within these liquids. These fundamental relations serve to bridge the extrapolation from often highly simplified melt compositions studied in the laboratory to the multicomponent systems found in nature. This volume focuses on the properties of simple model silicate systems, which are usually volatile-free. The behavior of natural magmas has been summarized in a previous Short Course volume (Nicholls and Russell, editors, 1990: Reviews in Mineralogy, Vol. 24), and the effect of volatiles on magmatic properties in yet another (Carroll and Holloway, editors, 1994: Vol. 30). In the chapters by Moynihan, by Webb and Dingwell, and by Richet and Bottinga, the concepts of relaxation and the glass transition are introduced, along with techniques for studying the rheology of silicate liquids, and theories for understanding the transport and relaxation behavior in terms of the structure and thermodynamic properties of the liquid. The chapter by Dingwell presents applications of relaxation-based studies of melts in the characterization of their properties. Chapters by Stebbins, by Brown, Farges and Calas, and by McMillan and Wolf present the principal techniques for studying the melt structure and atomic scale dynamics by a variety of spectroscopic and diffraction methods. Wolf and McMillan summarize our current understanding of the effects of pressure on silicate glass and melt structure. Chapters by Navrotsky and by Hess consider the thermodynamic properties and mixing relations in simple and multicomponent aluminosilicate melts, both from a fundamental structural point of view and empirical chemical models which can be conveniently extrapolated to natural systems. The chapter by Chakraborty describes the diffusivity of chemical species in silicate melts and glasses, and the chapter by Poole, McMillan and Wolf discusses the application of computer simulation methods to understanding the structure and dynamics of molten silicates. The emphasis in this volume is on reviewing the current state of knowledge of the structure, dynamics and physical properties of silicate melts, along with present capabilities for studying the molten state under conditions relevant to melting within the Earth, with the intention that these techniques and results can then be applied to understanding and modeling both the nature of silicate melts and the role of silicate melts in nature.

Description / Table of Contents: Although phyllosilicates are common in almost all types of rocks, their detailed study has not advanced in proportion to their importance. Books and reviews on this subject have been restricted primarily to the areas of clay mineralogy and soils. Such treatments understandably restrict coverage of the occurrences of the macroscopic-size species as well as much of their mineralogical and petrological nature. It was decided at the outset that not all phyllosilicates could be covered in a single book, and the size of this volume addressed only to the micas justifies the original decision. Kaolins, serpentines, chlorites, etc. will have to wait until some later date. This volume attempts to gather together much of our knowledge of micas, the most abundant phyllosilicate, and to indicate promising areas of future research. Chapters 1-3 lay the foundations of the classification, structures, and crystal chemistry of micas. Chapter 4 treats bonding and electrostatic modeling of micas. Chapters 5 and 6 cover spectroscopic and optical properties. Chapters 7-13, the bulk of the volume, are devoted to geochemistry and petrology. These include phase equilibria and the occurrences, chemistry, and petrology of micas in igneous, metamorphic, and sedimentary rocks, pegmatites, and certain ore deposits. Some treatments are exhaustive. All are at the forefront of our present knowledge, and indicate clearly the practical applications'of the study of micas to ascertaining various parameters of origin and crystallization history, as well as the many problems that still exist. The aim of this type of treatment is twofold -- to provide a handy reference volume for teachers and students and to enable researchers to pick more easily those directions and problems for which future research is most needed or is apt to be most productive or most challenging. X-ray powder patterns of micas in the literature are of surprisingly poor quality. The best are collated and supplemented with additional new patterns in the Appendix as an aid to identification.

Description / Table of Contents: Microorganisms cause mineral precipitation and dissolution and control the distribution of elements in diverse environments at and below the surface of the Earth. Conversely, mineralogical and geochemical factors exert important controls on microbial evolution and the structure of microbial communities. This was the rationale for the Short Course on Geomicrobiology presented by the Mineralogical Society of America on October 18 and 19, 1997, at the Alta Peruvian Lodge in Alta, Utah. Minerals have been known and honored since humans realized their essential contributions to the "terra firma" and stone tools thrust our species on the path of cultural evolution. Microbes are the oldest living creatures, probably inhabiting at least a few salubrious environments on the earth as early as 3.8 billion years ago. At this moment in history we are only beginning to appreciate the intimate juxtaposition and interdependence of minerals and microbes. We have been nudged into this position by the realization that our earth is finite, and the recognition of many global environmental problems that minerals and microbes contribute to, both positively and negatively. In addition, our globe may not be the only site in the solar system where 'life' arose, or may persist. What all of these concerns enunciate is that we as scientists only dimly comprehend our own dynamic "terrestrial halls." This short course and volume have been generated with great enthusiasm for grasping as much as possible of the whole panorama of possibilities that involve both the inorganic and biologic realms . Over 3600 mineral species have been defined and their relationships to each other and the environments in which they form have been documented. This vast data base, collected over the past several hundred years and constantly added to and upgraded, is a monument to the research efforts of many geoscientists focused on the inorganic realm. Much of this data has come from investigators intrigued by the novelty, beauty, and versatility of minerals, direct expressions of the chemistry and physics of geologic processes. We are now adding a new dimension to questions of mineral formation, dissolution, and distribution: what were, are, and will be the contributions of microbes to these basic components of the environment. Microbes have also been known for hundreds of years. However, their small size (0.5 to 5 µm in diameter) and the difficulties associated with identifying a species unless it was grown in the laboratory (cultured), precluded thorough analysis. The advent of molecular biology has only recently made it possible to evaluate microbial evolutionary relatedness (phylogeny) and physiological diversity. These techniques are now being applied to study of microbial populations in natural environments. It is becoming very clear that the surface of Earth is populated by far more species of microbes than there are types of minerals. We are now exploring every portion of the globe and finding the relationships under the rubric "geomicrobiology." The ocean deeps are characterized by a diversity of microorganisms, including those associated with manganese nodules. The profusion and concentration of minerals created at ocean ridges and vents matches the variety of microorganisms, large animals, and plants there. The snowy tops of mountain ranges and glaciers of Antarctica harbor not just ice but whole bacterial communities whose cellular types and activities need elucidation. The equatorial jungles and the deserts, with their enormous diversity of ecological niches, further challenge us. The diversity of geographic, geologic, and biologic environments, including some contributed by humans (e.g. mines, air-conditioning equipment), can now also be explored in detail. Modern studies use protocols developed to preserve or measure in situ chemical and physical characteristics. Electron microscopes allow direct characterization of mineral and biological morphology and internal structures. Spectroscopic techniques permit complimentary chemical analysis, including determination of oxidation states, with very high spatial resolution. Other studies quantitatively measure isotopic abudances. These data serve to distinguish biologically mediated, or biologically controlled formation of the mineral from an abiotic process and mechanism. Each ecological niche requires accurate characterization of the mineralogic and biologic entities in order for us to begin to understand the range of dynamic relationships. We can pose many questions. Is the mineral only a substrate, or is its occurrence and stability impacted by microbiologic activity and metabolic requirements? Which minerals are of microbiological rather than inorganic origin and what are the mechanisms by which organisms dictate the morphology and structure of the solid phase formed? How do organic metabolic products bind metals and change their form and distribution, with implications for metal toxicity and geochemical cycles? How do inorganic reactions such as mineral dissolution and precipitation impact microbial populations through control of their physical and chemical environments? Clearly, new and excitingly research areas exist for all varieties of scientists. Although published by the Mineralogical Society of America, the authors of this volume include microbiologists, molecular biologists, biochemists, biophysicists, bioengineers as well as biomineralogists. Here, they bring together their respective expertise and perspectives to provide disciplinary and interdisciplinary background needed to define and further explore the topic of geomicrobiology. The volume is organized so as to first introduce the nature, diversity, and metabolic impact of microorganisms and the types of solid phases they interact with. This is followed by a discussion of processes that occur at cell surfaces, interfaces between microbes and minerals, and within cells, and the resulting mineral precipitation, dissolution, and changes in aqueous geochemistry. The volume concludes with a discussion of the carbon cycle over geologic time. In detail: Nealson and Stahl acquaint us with the basic properties of prokaryotes, including their size and structure. They define the types and ranges of microorganisms and their metabolisms and describe their impacts on some important biogeochemical cycles. Barns and Nierzwicki-Bauer document the phylogenetic relationships and evolution of microorganisms, begging some fundamental questions that might be now just beyond our grasp: What was the 'last common ancestor'? The physiology, biochemistry and ecology of hyperthermophilic, and the many diverse geologically important microbial species from the lithosphere and hydrosphere, as well as some of the techniques employed, are presented. Banfield and Hamers describe and integrate the processes acting on minerals and at surfaces relevant to microorganisms, examining the factors that control mineralogy, mineral forms, and the stability of phases. Surface properties and reaction rates for dissolution, precipitation, and growth of important classes of minerals are discussed. The possible role of mineral surfaces in formation of prebiotic molecules needed to explain the origin of life is examined. Little, Wagner and Lewandowski describe biofilms, an essential interface between microbes and minerals. They demonstrate that these membranes, with their unique morphological and structural attributes, are sites where much activity related to dissolution and/or formation of minerals takes place. Biology makes it possible to move molecules and elements against a gradient. Many questions regarding the transfer of elements from minerals to microbes at this important heterogeneous interface remain. Fortin, Ferris and Beveridge review surface-mediated mineral development by bacteria. Fresh or oceanic waters, anaerobic or aerobic environments provide discretely different ecologies, bacterial entities, and resulting mineralogies. It is obvious from this presentation that investigators have just scratched the surface of microbial mineralization processes. Bazlinski and Moskowitz review the magnetic biominerals and provide insights into the environmental and biological significance of these few tens of nanometer-sized mineral products. The magnetosome chemistry and biochemistry is probably the best understood of any biologically precipitated mineral. Their formation and unique properties underscore the roles these biomaterials play in the rock magnetic record and in geochemical cycles. Tebo, Ghiorse, van Waasbergen, Siering and Caspi contribute data on the roles of Mnminerals and Mn(II) oxidation in geologic environments. Their chapter encompasses molecular genetic and biochemical investigations. Manganese oxides and oxyhydroxides are notoriously difficult to identify and the crystal chemistry of these phases is a research effort on its own. The prospect of learning how microbes utilize the multiple oxidation states of Mn (2+, 3+ and 4+) as a source of energy sharpens the motivation for interdisciplinary study. Manganese is also known as a cofactor in the production and activation of the enzymes that digest large biomolecules that must be the source of the smaller molecular species and ultimately the building blocks of C, N, 0, H required by all species. How have the mechanisms identified in the bacterial systems been transferred up the phylogenetic tree to plants and humans? This is an expanding and intriguing area for further investigation. DeVrind-de Jong and de Vrind address silicate and carbonate deposition by algae (eukaryotic photosynthetic microorganisms). This chapter documents the mechanisms of biomineralization of diatoms and coccoliths. These abundant aquatic organisms are responsible for huge volumes of siliceous sediments and calcium carbonate deposits world wide. The implications of algal biomineralization for climatic variation throughout much of the Earth's history may be quite significant. Stone leads us though a quantitative approach to evaluating reactions between organic molecules and cations. He considers available extracellular organic ligands and the roles these play in uptake of metals. He documents the basic chemical speciation and complexation for several elements, making metal to metal comparisons. Remaining challenges involve coordinating the organic and inorganic results of biologic activity. Following the discussion of biomineralization and interactions between organic compounds and cations, Silver discusses the strategies microorganisms have evolved to deal with toxic metal concentrations in solution. Beyond the fundamental biological significance, this has important implications for understanding microbial populations in contaminated environments. The impact on the geochemical form (speciation) and distribution of elements is also discussed. Nordstrom and Southam summarize sulfide mineral oxidation and dissolution kinetics and devote considerable effort to describing the specific contributions of microorganisms, mostly bacteria. Despite the vast amount of accumulated information, many unanswered questions remain. Barker, Welch and Banfield address weathering of silicate minerals. This topic encompasses not only mineralogy but geomorphology, microbiology, and geochemistry. The necessary interdisciplinary mode of these investigations is highlighted by discussion of the role(s) of bacterial nutrition, groundwater chemistry, and biochemistry. There are obvious implications for hazardous waste storage, a currently daunting and politicized topic that requires predictions over thousands to millions of years. Finally, Des Marais treats the long term evolution of the carbon cycle, adopting a biogeochemical view. He discusses the sources, sinks and the transfer of the element over geologic time. Consideration of such a basic series of questions relating to the partitioning of carbon necessitate interdisciplinary crossovers. It is a fitting conclusion to a dialogue in progress.