ALBERT

Beschreibung / Inhaltsverzeichnis: Geochemistry is a science that is based on an understanding of chemical processes in the earth. One of the principal tools available to the chemist for understanding systems at equilibrium is thermodynamics. The awareness and application of thermodynamic techniques has increased at a very fast pace in geosciences; in fact, one may be so bold as to say that thermodynamics in geology has reached the "mature" stage, although much future thermodynamic research is certainly needed. However, the natural processes in the earth are often sluggish enough that a particular system may not reach equilibrium. This observation is being supported constantly by new experimental and field data available to the geochemist e.g. the non-applicability of the phase rule in some assemblages, the compositional inhomogeneities of mineral grains, the partial reaction rims surrounding original minerals, the lack of isotopic equilibration or the absence of minerals (e.g. dolomite), which should be present according to thermodynamics. The need to apply kinetics has produced a large number of papers dealing with kinetics in geochemistry. As an initial response to this growing field, a conference on geochemical transport and kinetics was conducted at Airlie House, VA, in 1973, sponsored by the Carnegie Institution of Washington. The papers there dealt with several kinetic topics including diffusion, exsolution, metasomatism and metamorphic layering. Since 1973 the number of kinetic papers has continued to increase greatly. Therefore, the time is ripe for a Short Course in Kinetics, which brings together the fundamentals needed to explain field observations using kinetic data. It is hoped that this book may serve, not only as a reference for researchers dealing with the rates of geochemical processes, but also as a text in courses on geochemical kinetics. One of us has found this need of a text in teaching a graduate course on geochemical kinetics at Harvard and at Penn State during the past several years. Finally, it is our hope that the book may itself further even more research into the rates of geochemical processes and into the quantification of geochemical observations. The book is organized with a rough temperature gradient in mind, i.e. low temperature kinetics at the beginning and igneous kinetics at the end (no prejudices are intended with this scheme!). However, the topics in each chapter are general enough that they can be applied often to any geochemical domain: sedimentary, metamorphic or igneous. The theory of kinetics operates at two complementary levels: the phenomenological and the atomistic. The former relies on macroscopic variables (e.g. temperature or concentrations) to describe the rates of reactions or the rates of transport; the latter relates the rates to the basic forces operating between the particular atomic or molecular species of any system. This book deals with both descriptions of the kinetics of geochemical processes. Chapter one sets the framework for the phenomenological theory of reaction rates. If any geochemical reaction is to be described quantitatively, the rate law must be experimentally obtained in a kinetically sound manner and the reaction mechanism must be understood. This applies to heterogeneous fluid-rock reactions such as those occurring during metamorphism, hydrothermal alteration or weathering as well as to homogeneous reactions. Chapter 2 extends the theory to the global kinetics of geochemical cycles. This enables the kinetic concepts of stability and feedback to be applied to the cycling of elements in the many reservoirs of the earth. Chapter 3 applies the phenomenological treatment of chapter 1 to diagenesis and weathering. The rate of dissolution of minerals as well as the chemical evolution of pore waters are discussed. The atomistic basis of rates of reaction, transition state theory, is introduced in Chapter 4. Transition state theory can be applied to relate the rate constants of geochemical reactions to the atomic processes taking place. This includes not only homogeneous reactions but also reactions that occur at the surface of minerals. Chapter 5 discusses the theory of irreversible thermodynamics and its application to petrology. The use of the second law of thermodynamics along with the expressions for the rate of entropy production in a system have been used successfully since 1935 to describe kinetic phenomena. The chapter applies the concepts to the growth of minerals during metamorphism as well as to the formation of differentiated layers (banding) in petrology. Chapter 6 describes the phenomenological theory of diffusion both in aqueous solutions and in minerals. In particular, the multicomponent nature of diffusion and its consequence in natural systems is elaborated. Chapter 7 provides the atomistic basis for the rates of reactions in minerals. Understanding of the rates of diffusion, conduction, order-disorder reactions or exsolution in minerals depends on proper description of the defects in the various mineral structures. Chapter 8 provides the kinetic theory of crystal nucleation and growth. While many of the concepts in the chapter can be applied to aqueous systems, the emphasis is on igneous processes occurring during crystallization of a melt. To fully understand both the mineral composition as well as the texture of igneous rocks, the processes whereby new crystals form and grow must be quantified by using kinetic theory. Due to space and time limitations (kinetics!) some topics have not been covered in detail. In particular, the mathematical solution of diffusion or conduction equations is discussed very well by Crank in his book, Mathematics of Diffusion, and so is not covered to a great extent here. The treatment of fluid flow (e.g. convection) is also not covered in the text.

Beschreibung / Inhaltsverzeichnis: When Van't Hoff calculated the effect of solution composition on the gypsum-anhydrite transition a century ago, he solved a significant geochemical problem (Hardie, 1967). Other well known examples of the early use of chemical thermodynamics in geology are Bowen's calculations of the plagioclase melting loop and the diopside-anorthite eutectic (Bowen, 1913, 1928). Except for a few specialists, however, these techniques were largely ignored by earth scientists during the first half of the 20th century. The situation changed dramatically by the 1950's when more and better thermodynamic data on geologic materials became available, and when thermodynamic arguments of increasing sophistication began to permeate the petrologic and geochemical literature. This rejuvenation was spearheaded by D.S. Korzhinskii, H. Ramberg, J.B. Thompson, J. Verhoogen and others. Today a graduating petrologist or geochemist can be expected to have a thorough grounding in geological thermodynamics. Rapid intellectual growth in a field brings with it the difficulty of keeping abreast of parallel and diverging specialties. In order to alleviate this problem, we asked a group of active researchers to contribute up-to-date summaries relating to their specialties in the thermodynamic modeling of geological materials, in particular minerals, fluids and melts. Whereas each of these topics could fill a book, by covering the whole range we hope to emphasize similarities as much as differences in the treatment of various materials. For instance, there are useful parallels to be noted between Margules parameters and Pitzer coefficients. The emphasis here is on modeling, after the required data have been collected, and the approach ranges form theoretical to empirical. We deliberately imposed few restrictions on the authors. Some chose to interpret modeling in the rigorous thermodynamic sense, while others approached their topics from more general geochemical viewpoints. We hope that any lack of unity and balance is compensated for by a collection of lively and idiosyncratic essays in which students and professionals will find new ideas and helpful hints. If the selection appears tilted towards fluids, it is because other recent summaries have emphasized minerals and melts. The editors and authors of this volume presented a short course, entitled "Thermodynamic Modeling of Geological Materials: Minerals, Fluids amd Melts," October 22-25, 1987, at the Wickenburg Inn near Phoenix, Arizona.

Beschreibung / Inhaltsverzeichnis: This book provides a synthesis of Archaean and Proterozoic crustal evolution in the North Atlantic Region. There is particular reference to Proterozoic collisional tectonics. The main topics include: Archaean crustal growth; Proterozoic crustal growth; orogenic processes during the Proterozic; geochronology of Proterozoic tectono-thermal processes; and provenance of Proterozoic sediments.

Beschreibung / Inhaltsverzeichnis: This book presents a series of review articles on nine important ancient orogens on Earth. Comparison of these mountain belts provides a wealth of information for the debate on whether there has been a change in mountain-building processes through the history of the Earth. As a precursor to these papers, the rheology of the Earth’s lithosphere through time is reviewed. Theoretical analysis and insight into the behaviour of the lithosphere of other planets constrain mechanical considerations of the Earth’s lithosphere. It is clear from these overviews that geodynamic concepts and modelling, and new techniques such as deep seismic profiling and geochronology are having a profound impact on orogenic studies. It is also clear that orogenesis must not be equated with the Wilson cycle, culminating in continent-continent collision. Subduction-related orogens and intraplate orogens are also significant.

Beschreibung / Inhaltsverzeichnis: This volume represents a review of the key topics that are important to the continuing successful exploitation of gas from one of Europe's oldest hydrocarbon provinces. In a mature hydrocarbon province such as the southern North Sea, advanced techniques are needed for stratigraphic correlation and for improving the efficiency of production. Exploration in the SNS now aims for subtle traps and satellite structures. Explorers are re-evaluating the economic value of marginal and existing fields, and they are continually searching for, and applying, new techniques and technologies for enhanced productivity. Detailed techniques in diagenesis play an important role. Re-evaluation also includes examination of old plays, using detailed knowledge of the connectivity, spatial extent and correlation of known prospective strata to make reliable predictions.

Beschreibung / Inhaltsverzeichnis: 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.