ALBERT

Description / Table of Contents: Medical Mineralogy and Geochemistry is an emergent, highly interdisciplinary field of study. The disciplines of mineralogy and geochemistry are integral components of cross-disciplinary investigations that aim to understand the interactions between geomaterials and humans as well as the normal and pathological formation of inorganic solid precipitates in vivo. Research strategies and methods include but are not limited to: stability and solubility studies of earth materials and biomaterials in biofluids or their proxies (i.e., equilibrium thermodynamic studies), kinetic studies of pertinent reactions under conditions relevant to the human body, molecular modeling studies, and geospatial and statistical studies aimed at evaluating environmental factors as causes for activating certain chronic diseases in genetically predisposed individuals or populations. Despite its importance, the area of Medical Mineralogy and Geochemistry has received limited attention by scientists, administrators, and the public. The objectives of this volume are to highlight some of the existing research opportunities and challenges, and to invigorate exchange of ideas between mineralogists and geochemists working on medical problems and medical scientists working on problems involving geomaterials and biominerals. Examples presented in this volume (Table of contents below) include the effects of inhaled dust particles in the lung (Huang et al. 2006; Schoonen et al. 2006), biomineralization of bones and teeth (Glimcher et al. 2006), the formation of kidney-stones, the calcification of arteries, the speciation exposure pathways and pathological effects of heavy metal contaminants (Reeder et al. 2006; Plumlee et al. 2006), the transport and fate of prions and pathological viruses in the environment (Schramm et al. 2006), the possible environmental-genetic link in the occurrence of neurodegenerative diseases (Perl and Moalem 2006), the design of biocompatible, bioactive ceramics for use as orthopaedic and dental implants and related tissue engineering applications (Cerruti and Sahai 2006) and the use of oxide-encapsulated living cells for the development of biosensors (Livage and Coradin 2006).

Description / Table of Contents: For over half a century neutron scattering has added valuable information about the structure of materials. Unlike X-rays that have quickly become a standard laboratory technique and are available to all modern researchers in physics, chemistry, materials and earth sciences, neutrons have been elusive and reserved for specialists. A primary reason is that neutron beams, at least so far, are only produced at large dedicated facilities with nuclear reactors and accelerators and access to those has been limited. Yet there are a substantial number of experiments that use neutron scattering. While earth science users are still a small minority, neutron scattering has nevertheless contributed valuable information on geological materials for well over half a century. Important applications have been in crystallography (e.g. atomic positions of hydrogen and Al-Si ordering in feldspars and zeolites, Mn-Fe-Ti distribution in oxides), magnetic structures, mineral physics at non-ambient conditions and investigations of anisotropy and residual strain in structural geology and rock mechanics. Applications range from structure determinations of large single crystals, to powder refinements and short-range order determination in amorphous materials. Zeolites, feldspars, magnetite, carbonates, ice, clathrates are just some of the minerals where knowledge has greatly been augmented by neutron scattering experiments. Yet relatively few researchers in earth sciences are taking advantage of the unique opportunities provided by modern neutron facilities. The goal of this volume, and the associated short course by the Mineralogical Society of America held December 7-9 in Emeryville/Berkeley CA, is to attract new users to this field and introduce them to the wide range of applications. As the following chapters will illustrate, neutron scattering offers unique opportunities to quantify properties of earth materials and processes. Focus of this volume is on scientific applications but issues of instrumental availabilities and methods of data processing are also covered to help scientists from such diverse fields as crystallography, mineral physics, geochemistry, rock mechanics, materials science, biomineralogy become familiar with neutron scattering. A few years ago European mineralogists spearheaded a similar initiative that resulted in a special issue of the European Journal of Mineralogy (Volume 14, 2002). Since then the field has much advanced and a review volume that is widely available is highly desirable. At present there is really no easy access for earth scientists to this field and a more focused treatise can complement Bacon's (1955) book, now in its third edition, which is still a classic. The purpose of this volume is to provide an introduction for those not yet familiar with neutrons by describing basic features of neutrons and their interaction with matter as well illustrating important applications. The volume is divided into 17 Chapters. The first two chapters introduce properties of neutrons and neutron facilities, setting the stage for applications. Some applications rely on single crystals (Chapter 3) but mostly powders (Chapters 4-5) and bulk polycrystals (Chapters 15-16) are analyzed, at ambient conditions as well as low and high temperature and high pressure (Chapters 7-9). Characterization of magnetic structures remains a core application of neutron scattering (Chapter 6). The analysis of neutron data is not trivial and crystallographic methods have been modified to take account of the complexities, such as the Rietveld technique (Chapter 4) and the pair distribution function (Chapter 11). Information is not only obtained about solids but about liquids, melts and aqueous solutions as well (Chapters 11-13). In fact this field, approached with inelastic scattering (Chapter 10) and small angle scattering (Chapter 13) is opening unprecedented opportunities for earth sciences. Small angle scattering also contributes information about microstructures (Chapter 14). Neutron diffraction has become a favorite method to quantify residual stresses in deformed materials (Chapter 16) as well as preferred orientation patterns (Chapter 15). The volume concludes with a short introduction into neutron tomography and radiography that may well emerge as a principal application of neutron scattering in the future (Chapter 17).

Description / Table of Contents: Fluids rich in water, carbon and sulfur species and a variety of dissolved salts are a ubiquitous transport medium for heat and matter in the Earth’s interior. Fluid transport through the upper mantle and crust controls the origin of magmatism above subduction zones and results in natural risks of explosive volcanism. Fluids passing through rocks affect the chemical and heat budget of the global oceans, and can be utilized as a source of geothermal energy on land. Fluid transport is a key to the formation and the practical utilization of natural resources, from the origin of hydrothermal mineral deposits, through the exploitation of gaseous and liquid hydrocarbons as sources of energy and essential raw materials, to the subsurface storage of waste materials such as CO2. Different sources of fluids and variable paths of recycling volatile components from the hydrosphere and atmosphere through the solid interior of the Earth lead to a broad range of fluid compositions, from aqueous liquids and gases through water-rich silicate or salt melts to carbon-rich endmember compositions. Different rock regimes in the crust and mantle generate characteristic ranges of fluid composition, which depending on pressure, temperature and composition are miscible to greatly variable degrees. For example, aqueous liquids and vapors are increasingly miscible at elevated pressure and temperature. The degree of this miscibility is, however, greatly influenced by the presence of additional carbonic or salt components. A wide range of fluid–fluid interactions results from this partial miscibility of crustal fluids. Vastly different chemical and physical properties of variably miscible fluids, combined with fluid flow from one pressure – temperature regime to another, therefore have major consequences for the chemical and physical evolution of the crust and mantle. Several recent textbooks and review articles have addressed the role and diverse aspects of fluids in crustal processes. However, immiscibility of fluids and the associated phenomena of m ultiphase fluid flow are generally dealt with only in subsections with respect to specific environments and aspects of fluid mediated processes. This volume of Reviews in Mineralogy and Geochemistry attempts to fill this gap and to explicitly focus on the role that co-existing fluids play in the diverse geologic environments. It brings together the previously somewhat detached literature on fluid–fluid interactions in continental, volcanic, submarine and subduction zone environments. It emphasizes that fluid mixing and unmixing are widespread processes that may occur in all geologic environments of the entire crust and upper mantle. Despite different P-T conditions, the fundamental processes are analogous in the different settings.

Description / Table of Contents: The idea for this book was conceived in early June, 2005 at a paleoaltimetry workshop held at Lehigh University, Lehigh, Pennsyalvania and organized by Dork Sahagian. The workshop was funded by the tectonics program at NSF, and was designed to bring together researchers in paleoaltimetry to discuss different techniques and focus the community on ways of improving paleoelevation estimates and consequent interpretations of geodynamics and tectonics. At this meeting, some commented that a comprehensive volume describing the different methods could help advance the field. I offered to contact the Mineralogical Society of America and the Geochemical Society about publishing a RiMG volume on paleoaltimetry. Because many of the techniques used to infer paleoelevations are geochemically-based or deal with thermodynamic principles, the GS and MSA agreed to the project. Two years and roughly 1000 e-mails later, our book has arrived. The book is organized into 4 sections: Geodynamic and geomorphologic rationale (Clark). This chapter provides the broad rationale behind paleoaltimetry, i.e., why we study it. Stable isotope proxies. These 4 chapters cover theory of stable isotopes in precipitation and their response to altitudinal gradients (Rowley), and stable isotopes sytematics in paleosols (Quade, Garzione and Eiler), silicates (Mulch and Chamberlain) and fossils (Kohn and Dettman). Proxies of atmospheric properties. These 4 chapters cover temperature lapse rates (Meyer), entropy (Forest), and atmospheric pressure proxies, including total atmospheric pressure from gas bubbles in basalt (Sahagian and Proussevitch), and the partial pressure of CO2 (Kouwenberg, Kürshner, and McElwain). Note that clumped isotope thermometry (Quade, Garzione and Eiler) also provides direct estimates of temperature. Radiogenic and cosmogenic nuclides. These 2 chapters cover low-temperature thermochronologic approaches (Reiners) and cosmogenic isotopes (Riihimaki and Libarkin). Some chapters overlap in general content (e.g., basic principles of stable isotopes in precipitation are covered to different degrees in all stable isotope chapters), but no attempt was made to limit authors' discussion of principles, or somehow attempt to arrive at a "consensus view" on any specific topic. Because science advances by critical discussion of concepts, such restrictions were viewed as counterproductive. This does mean that different chapters may present different views on reliability of paleoelevation estimates, and readers are advised to read other chapters in the book on related topics – they may be more closely linked than they might at first appear! I hope readers of this book will discover and appreciate the synergy among paleoaltimetry, climate change, and tectonic geomorphology. These interrelationships create a complex, yet rich field of scientific enquiry that in turn offers insights into climate and geodynamics.

Description / Table of Contents: The very successful orbital missions of the 1990's, Clementine and Lunar Prospector, provided key mineralogical, geochemical, and geophysical data sets that extended our view of the Moon beyond what we knew from Apollo and Luna exploration to a truly global perspective. These new data sets have been integrated with information gained from three preceding decades of study of lunar samples and older, less complete remotely sensed data sets. Although there have been no new lunar sample-return missions since Apollo and Luna, new samples are available in the form of meteorites, recognized to be pieces of the Moon. These, too, play a role in improved knowledge of the Moon and in helping to couple information obtained by remote sensing with information obtained from rock and soil samples. As we stand on the edge of a new era of lunar and planetary exploration, including new missions to the Moon, Mars, and other planets and moons, we find it essential to examine in depth how the wide variety of data sets obtained during the course of lunar exploration can be used together to better understand the formation of the Moon and how it evolved to its present state. Such an understanding holds important lessons for the new era of lunar exploration as well as the exploration of other planets in the Solar System. This will ultimately lead to better knowledge of how our own planet Earth - with its unique environment suitable for the origin and evolution of life - originated and changed with time. This book assesses the current state of knowledge of lunar geoscience, given the data sets provided by missions of the 1990's, and lists remaining key questions as well as new ones for future exploration to address. It documents how a planet or moon other than the world on which we live can be studied and understood in light of integrated suites of specific kinds of information. The Moon is the only body other than Earth for which we have material samples of known geologic context for study. This book seeks to show how the different kinds of information gained about the Moon relate to each other and also to learn from this experience, thus allowing more efficient planning for the exploration of other worlds.

Description / Table of Contents: As geomicrobiologists, we seek to understand how some of nature's most complex systems work, yet the very complexity we seek to understand has placed many of the insights out of reach. Recent advances in cultivation methodologies, the development of ultrahigh throughput DNA sequencing capabilities, and new methods to assay gene expression and protein function open the way for rapid progress. In the eight years since the first Geomicrobiology volume (Geomicrobiology: Interactions between microbes and minerals; volume 35 in this series) we have transformed into scientists working hand in hand with biochemists, molecular biologists, genome scientists, analytical chemists, and even physicists to reveal the most fundamental molecular-scale underpinnings of biogeochemical systems. Through synthesis achieved by integration of diverse perspectives, skills, and interests, we have begun to learn how organisms mediate chemical transformations, the ways in which the environment determines the architecture of microbial communities, and the interplay between evolution and selection that shapes the biodiversity of the planet. This volume presents chapters written by leaders in the rapidly maturing field we refer to as molecular geomicrobiology. Most of them are relatively young researchers who share their approaches and insights and provide pointers to exciting areas ripe for new advances. This volume ties together themes common to environmental microbiology, earth science, and astrobiology. The resesarch presented here, the associated short course, and the volume production were supported by funding from many sources, notably the Mineralogical Society of America, the Geochemical Society, the US Department of Energy Chemical Sciences Program and the NASA Astrobiology Institute.

Description / Table of Contents: Earth is a water planet. Oceans of liquid water dominate the surface processes of the planet. On the surface, water controls weathering as well as transport and deposition of sediments. Liquid water is necessary for life. In the interior, water fluxes melting and controls the solid-state viscosity of the convecting mantle and so controls volcanism and tectonics. Oceans cover more than 70% of the surface but make up only about 0.025% of the planet's mass. Hydrogen is the most abundant element in the cosmos, but in the bulk Earth, it is one of the most poorly constrained chemical compositional variables. Almost all of the nominally anhydrous minerals that compose the Earth's crust and mantle can incorporate measurable amounts of hydrogen. Because these are minerals that contain oxygen as the principal anion, the major incorporation mechanism is as hydroxyl, OH-, and the chemical component is equivalent to water, H2O. Although the hydrogen proton can be considered a monovalent cation, it does not occupy same structural position as a typical cation in a mineral structure, but rather forms a hydrogen bond with the oxygens on the edge of the coordination polyhedron. The amount incorporated is thus quite sensitive to pressure and the amount of H that can be incorporated in these phases generally increases with pressure and sometimes with temperature. Hydrogen solubility in nominally anhydrous minerals is thus much more sensitive to temperature and pressure than that of other elements. Because the mass of rock in the mantle is so large relative to ocean mass, the amount that is incorporated the nominally anhydrous phases of the interior may constitute the largest reservoir of water in the planet. Understanding the behavior and chemistry of hydrogen in minerals at the atomic scale is thus central to understanding the geology of the planet. There have been significant recent advances in the detection, measurement, and location of H in the nominally anhydrous silicate and oxide minerals that compose the planet. There have also been advances in experimental methods for measurement of H diffusion and the effects of H on the phase boundaries and physical properties whereby the presence of H in the interior may be inferred from seismic or other geophysical studies. It is the objective of this volume to consolidate these advances with reviews of recent research in the geochemistry and mineral physics of hydrogen in the principal mineral phases of the Earth's crust and mantle. The Chapters We begin with a review of analytical methods for measuring and calibrating water contents in nominally anhydrous minerals by George Rossman. While infrared spectroscopy is still the most sensitive and most convenient method for detecting water in minerals, it is not intrinsically quantitative but requires calibration by some other, independent analytical method, such as nuclear reaction analysis, hydrogen manometry, or SIMS. A particular advantage of infrared spectroscopy, however, is the fact that it does not only probe the concentration, but also the structure of hydrous species in a mineral and in many cases the precise location of a proton in a mineral structure can be worked out based on infrared spectra alone. The methods and principles behind this are reviewed by Eugen Libowitzky and Anton Beran, with many illustrative examples. Compared to infrared spectroscopy, NMR is much less used in studying hydrogen in minerals, mostly due to its lower sensitivity, the requirement of samples free of paramagnetic ions such as Fe2+ and because of the more complicated instrumentation required for NMR measurements. However, NMR could be very useful under some circumstances. It could detect any hydrogen species in a sample, including such species as H2 that would be invisible with infrared. Potential applications of NMR to the study of hydrogen in minerals are reviewed by Simon Kohn. While structural models of "water" in minerals have already been deduced from infrared spectra several decades ago, in recent years atomistic modeling has become a powerful tool for predicting potential sites for hydrogen in minerals. The review by Kate Wright gives an overview over both quantum mechanical methods and classical methods based on interatomic potentials. Joseph Smyth then summarizes the crystal chemistry of hydrogen in high-pressure silicate and oxide minerals. As a general rule, the incorporation of hydrogen is not controlled by the size of potential sites in the crystal lattice; rather, the protons will preferentially attach to oxygen atoms that are electrostatically underbonded, such as the non-silicate oxygen atoms in some high-pressure phases. Moreover, heterovalent substitutions, e.g., the substitution of Al3+ for Si4+, can have a major effect on the incorporation of hydrogen. Data on water in natural minerals from crust and mantle are compiled and discussed in three reviews by Elisabeth Johnson, Henrik Skogby and by Anton Beran and Eugen Libowitzky. Among the major mantle minerals, clinopyroxenes usually retain the highest water contents, followed by orthopyroxenes and olivine, while the water contents in garnets are generally low. Most of these water contents need to be considered as minimum values, as many of the mantle xenoliths may have lost water during ascent. However, there are some cases where the correlation between the water contents and other geochemical parameters suggest that the measured water concentrations reflect the true original water content in the mantle. The basic thermodynamics as well as experimental data on water solubility and partitioning are reviewed by Hans Keppler and Nathalie Bolfan Casanova. Water solubility in minerals depends in a complicated way on pressure, temperature, water fugacity and bulk composition. For example, water solubility in the same mineral can increase or decrease with temperature, depending on the pressure of the experiments. Nevertheless, the pressure and temperature dependence of water solubility can be described by a rather simple thermodynamic formalism and for most minerals of the upper mantle, the relevant thermodynamic parameters are known. The highest water solubilities are reached in the minerals wadsleyite and ringwoodite stable in the transition zone, while the minerals of the lower mantle are probably mostly dry. The rather limited experimental data on water partitioning between silicate melts and minerals are reviewed by Simon Kohn and Kevin Grant. One important observation here is that comparing the compatibility of hydrogen with that of some rare earth element is misleading, as such correlations are always limited to a small range of pressure and temperature for a given mineral. The stabilities of hydrous phases in the peridotite mantle and in subducted slabs are reviewed by Daniel Frost and by Tatsuhiko Kawamoto. While most of the water in the mantle is certainly stored in the nominally anhydrous minerals, hydrous phases can be important storage sites of water in certain environments. Amphibole and phlogopite require a significant metasomatic enrichment of Na and K in order to be stabilized in the upper mantle, but serpentine may be an important carrier of water in cold subducted slabs. The diffusion of hydrogen in minerals is reviewed by Jannick Ingrin and Marc Blanchard. An important general observation here is that natural minerals usually do not loose hydrogen as water, but as H2 generated by redox reaction of OH with Fe2+. Moreover, diffusion coefficients of different mantle minerals can vary by orders of magnitude, often with significant anisotropy. While some minerals in a mantle xenolith may therefore have lost virtually all of their water during ascent, other minerals may still preserve the original water content and in general, the apparent partition coefficients of water between the minerals of the same xenolith can be totally out of equilibrium. Accordingly, it would be highly desirable to directly deduce the water content in the mantle from geophysical data. One strategy, based on seismic velocities and therefore ultimately on the effect of water on the equation of state of minerals, is outlined by Steve Jacobsen. The dissolution of water in minerals usually increases the number of cation vacancies, yielding reduced bulk and shear moduli and seismic velocities. Particularly, the effect on shear velocities is strong and probably larger than the effect expected from local temperature variations. Accordingly, the vs/vp ratio could be a sensitive indicator of mantle hydration. A more general approach towards remote sensing of hydrogen in the Earth's mantle, including effects of seismic anisotropy due to lattice preferred orientation and the use of electrical conductivity data is presented by Shun-ichiro Karato. Probably the most important effect of water on geodynamics is related to the fact that even traces of water dramatically reduce the mechanical strength of rocks during deformation. The physics behind this effect is discussed by David Kohlstedt. Interestingly, it appears that the main mechanism behind "hydrolytic weakening" is related to the effect of water on the concentration and mobility of Si vacancies, rather than to the protons themselves. Water may have major effects on the location of mantle discontinuities, as reviewed by Eiji Ohtani and Konstantin Litasov. Most of these effects can be rationalized as being due to the expansion of the stability fields of those phases (e.g., wadsleyite) that preferentially incorporate water. Together with other geophysical data, the changes in the depths of discontinuities are a promising tool for the remote sensing of water contents in the mantle. The global effects of water on the evolution of our planet are reviewed in the last two chapters by Bernard Marty, Reika Yokochi and Klaus Regenauer-Lieb. By combining hydrogen und nitrogen isotope data, Marty and Yokochi demonstrate convincingly that most of the Earth's water very likely originated from a chondritic source. Water may have had a profound effect on the early evolution of our planet, since a water-rich dense atmosphere could have favored melting by a thermal blanketing effect. However, Marty and Yokochi also show very clearly that it is pretty much impossible to derive reliable estimates of the Earth's present-day water content from cosmochemical arguments, since many factors affecting the loss of water during and after accretion are poorly constrained or not constrained at all. In the last chapter, Klaus Regenauer-Lieb investigates the effect of water on the style of global tectonics. He demonstrates that plate tectonics as we know it is only possible if the water content of the mantle is above a threshold value. The different tectonic style observed on Mars and Venus may therefore be directly related to differences in mantle water content. Earth is the water planet — not just because of it's oceans, but also because of its tectonic evolution.

Description / Table of Contents: In Materials Science, investigations aiming to prepare new types of molecular sieves (porous materials) have opened a productive field of research inspired by the crystal structures of minerals. These new molecular sieves are distinct from zeolites in that they have different kinds of polyhedra that build up their structures. Of particular interest are the new molecular sieves characterized by a mixed "octahedral"-tetrahedral framework (heteropolyhedral frameworks), instead of a purely tetrahedral framework as in zeolites. Heteropolyhedral compounds have been extensively studied since the early 1990's, with particular attention having been focused on titanosilicates, such as ETS-4 (synthetic analog of the mineral zorite) and ETS-10. However, titanosilicates are not the only representatives of novel microporous mineral phases. The search for "octahedral"-tetrahedral silicates was extended to metals other than titanium, for instance, the zirconosilicates with the preparation of synthetic counterparts of the minerals gaidonnayite, petarasite and umbite. Many microporous heteropolyhedral compounds containing metals such as Nb, V, Sn, Ca and lanthanides, have been reported and a wide number of distinct structural types (e.g., rhodesite-delhayelite and tobermorite) have been synthesized and structurally characterized. Moreover, the potential applications of these novel materials have been evaluated, particularly in the areas of catalysis, separation of molecular species, ion exchange and optical and magnetic properties. A comprehensive review of the mineralogical, structural, chemical and crystal-chemical studies carried on natural phases may be extremely useful to inspire and favor investigations on analogs or related synthetic materials. A similar synergy between mineralogists and materials scientists already occurred in the "classical" case of zeolites, in which the wide and deep structural and crystal-chemical knowledge accumulated in the study of the natural phases was extraordinarily useful to the chemists who are active in the field of molecular sieves. In particular, the structural investigation of the natural phases may be extremely rewarding and helpful in orienting the work of synthesis and in understanding the nature of the synthetic products, for the following reasons: Whereas rarely the crystalline synthetic products are suitable for single-crystal structural investigations, the natural counterparts are often well crystallized. Crystallization in nature occurs from chemical systems characterized by a wide compositional range, thus producing compounds with a very rich and variable crystal chemistry, which may provide precious information, suggesting possible substituting elements and addressing the synthetic work in a very productive way. The present volume follows a meeting on "Micro- and mesoporous mineral phases" (Rome, December 6-7, 2004) that was jointly organized by the Accademia Nazionale dei Lincei (ANL) and the International Union of Crystallography (IUCr) via its Commission on Inorganic and Mineral Structures (CIMS). The meeting was convened by Fausto Calderazzo, Giovanni Ferraris, Stefano Merlino and Annibale Mottana and financially supported by several other organizations representing both Mineralogy (e.g., the International Mineralogical Association and the European Mineralogical Union) and Crystallography (e.g., the European Crystallographic Association and the Italian Association of Crystallography). To participants, ANL staff, organizations, and, in general, all involved persons, our sincere acknowledgments; in particular, we are grateful to Annibale Mottana who was able to convince the ANL Academicians to schedule and support the meeting. This volume of the RiMG series highlights the present knowledge on micro- and mesoporous mineral phases, with focus on their crystal-chemical aspects, occurrence and porous activity in nature and experiments. As zeolites are the matter of numerous ad hoc meetings and books - including two volumes in this series - they do not specifically appear in the present volume. The phases of the sodalite and cancrinite-davyne groups, which mineralogists consider distinct from zeolites, are instead considered (in the order, chapter 7 by W. Depmeier and part of chapter 8 by E. Bonaccorsi and S. Merlino, respectively). The first two chapters of the volume cover general aspects of porous materials. This includes the application of the IUPAC nomenclature developed for ordered porous materials to non-zeolite mineral phases (L.B. McCusker, chapter 1) and the extension to heteropolyhedral structures of a topological description by using nodes representing the coordination polyhedra (S.V. Krivovichev, chapter 2). Chapters from 3 to 7 are dedicated to various groups of heteropolyhedral porous structures for which the authors emphasize some of the more general aspects according to their research specialization. G. Ferraris and A. Gula (chapter 3) put the emphasis on the modular aspects of well-known porous phases (such as sepiolite, palygorskite and rhodesite-related structures) as well as on heterophyllosilicates that may be not strictly porous phases (according to the definition given in chapter 1) but could be the starting basis for pillared materials. The porous mineral phases typical of hyperalkaline rocks (such as eudialytes and labuntsovites) are discussed by N.V. Chukanov and I.V. Pekov under their crystal-chemical (chapter 4) and minerogenetic (chapter 5) aspects showing the role of ion exchange during the geological evolution from primary to later phases, with experimental cation exchange data also being reported. J. Rocha and Z. Lin (chapter 6) emphasize how research on the synthesis of octahedral-pentahedral-tetrahedral framework silicates has been inspired and motivated by the many examples of such materials provided by nature; synthesis, structure and possible technological applications of a wide number of these materials are also described. Following chapters 7 and 8 - which besides the cancrinite-davyne group, presents the crystallographic features of the minerals in the tobermorite and gyrolite groups - M. Pasero (chapter 9) illustrates the topological and polysomatic aspects of the "tunnel oxides," a historical name applied to porous oxides related to MnO2, and reviews their main technological applications. The next two chapters (10 and 11) draw attention to "unexpected" porous materials like apatite and sulfides. T.J. White and his team (chapter 10) convincingly show that the apatite structure type displays porous properties, some of which are already exploited. Chapter 10 also contains two appendices that report crystal and synthesis data for hundreds of synthetic apatites, a number that demonstrates how wide the interest is for this class of compounds. E. Makovicky (chapter 11) analyzes the structures of natural and synthetic sulfides and selenides showing that, even if experimental work proving porous activity is practically still missing, several structure types display promising channels. Chapter 12, by M. Mellini, is the only one dedicated to mesoporous mineral phases - which are crystalline compounds with pores wider than 2 nm. Examples discussed are carbon nanotubes, fullerenes - which occur also in nature - chrysotile, opal and, moving from channels to cages, clathrates.

Description / Table of Contents: The importance of sulfide minerals in ores has long been, and continues to be, a major reason for the interest of mineralogists and geochemists in these materials. Determining the fundamental chemistry of sulfides is key to understanding their conditions of formation and, hence, the geological processes by which certain ore deposits have formed. This, in turn, may inform the strategies used in exploration for such deposits and their subsequent exploitation. In this context, knowledge of structures, stabilities, phase relations and transformations, together with the relevant thermodynamic and kinetic data, is critical. As with many geochemical systems, much can also be learned from isotopic studies. The practical contributions of mineralogists and geochemists to sulfide studies extend beyond areas related to geological applications. The mining of sulfide ores, to satisfy ever increasing world demand for metals, now involves extracting very large volumes of rock that contains a few percent at most (and commonly less than one percent) of the metal being mined. This is true of relatively low value metals such as copper; for the precious metals commonly occurring as sulfides, or associated with them, the mineable concentrations (grades) are very much lower. The "as-mined" ores therefore require extensive processing in order to produce a concentrate with a much higher percentage content of the metal being extracted. Such mineral processing (beneficiation) involves crushing and grinding of the ores to a very fine grain size in order to liberate the valuable metal-bearing (sulfide) minerals which can then be concentrated. In some cases, the metalliferous (sulfide) minerals may have specific electrical or magnetic properties that can be exploited to enable separation and, hence, concentration. More commonly, froth flotation is used, whereby the surfaces of particles of a particular mineral phase are rendered water repellent by the addition of chemical reagents and hence are attracted to air bubbles pulsed through a mineral particle-water-reagent pulp. An understanding of the surface chemistry and surface reactivity of sulfide minerals is central to this major industrial process and, of course, knowledge of electrical and magnetic properties is very important in cases where those particular properties can be utilized. In the years since the publication of the first ever Reviews in Mineralogy volume (1974, at that time called MSA "Short Course Notes") which was entitled Sulfide Mineralogy, sulfides have become a focus of research interest for reasons centering on at least two other areas in addition to their key role in ore deposit studies and mineral processing technology. It is in these two new areas that much of the research on sulfides has been concentrated in recent years. The first of these areas relates to the capacity of sulfides to react with natural waters and acidify them; the resulting Acid Rock Drainage (ARD), or Acid Mine Drainage (AMD) where the sulfides are the waste products of mining, has the capacity to damage or destroy vegetation, fish and other aquatic life forms. These acid waters may also accelerate the dissolution of associated minerals containing potentially toxic elements (e.g., As, Pb, Cd, Hg, etc.) and these may, in turn, cause environmental damage. The much greater public awareness of the need to prevent or control AMD and toxic metal pollution has led to regulation and legislation in many parts of the world, and to the funding of research programs aimed at a greater understanding of the factors controlling the breakdown of sulfide minerals. We begin with a review of analytical methods for measuring and calibrating water contents in nominally anhydrous minerals by George Rossman. While infrared spectroscopy is still the most sensitive and most convenient method for detecting water in minerals, it is not intrinsically quantitative but requires calibration by some other, independent analytical method, such as nuclear reaction analysis, hydrogen manometry, or SIMS. A particular advantage of infrared spectroscopy, however, is the fact that it does not only probe the concentration, but also the structure of hydrous species in a mineral and in many cases the precise location of a proton in a mineral structure can be worked out based on infrared spectra alone. The methods and principles behind this are reviewed by Eugen Libowitzky and Anton Beran, with many illustrative examples. Compared to infrared spectroscopy, NMR is much less used in studying hydrogen in minerals, mostly due to its lower sensitivity, the requirement of samples free of paramagnetic ions such as Fe2+ and because of the more complicated instrumentation required for NMR measurements. However, NMR could be very useful under some circumstances. It could detect any hydrogen species in a sample, including such species as H2 that would be invisible with infrared. Potential applications of NMR to the study of hydrogen in minerals are reviewed by Simon Kohn. While structural models of "water" in minerals have already been deduced from infrared spectra several decades ago, in recent years atomistic modeling has become a powerful tool for predicting potential sites for hydrogen in minerals. The review by Kate Wright gives an overview over both quantum mechanical methods and classical methods based on interatomic potentials. Joseph Smyth then summarizes the crystal chemistry of hydrogen in high-pressure silicate and oxide minerals. As a general rule, the incorporation of hydrogen is not controlled by the size of potential sites in the crystal lattice; rather, the protons will preferentially attach to oxygen atoms that are electrostatically underbonded, such as the non-silicate oxygen atoms in some high-pressure phases. Moreover, heterovalent substitutions, e.g., the substitution of Al3+ for Si4+, can have a major effect on the incorporation of hydrogen. The second reason for even greater research interest in sulfide minerals arose initially from the discoveries of active hydrothermal systems in the deep oceans. The presence of life forms that have chemical rather than photosynthetic metabolisms, and that occur in association with newly-forming sulfides, has encouraged research on the potential of sulfide surfaces in catalyzing the reactions leading to assembling of the complex molecules needed for life on Earth. These developments have been associated with a great upsurge of interest in the interactions between microbes and minerals, and in the role that minerals can play in biological systems. In the rapidly growing field of geomicrobiology, metal sulfides are of major interest. This interest is related to a variety of processes including, for example, those where bacteria interact with sulfides as part of their metabolic activity and cause chemical changes such as oxidation or reduction, or those in which biogenic sulfide minerals perform a specific function, such as that of navigation in magnetotactic bacteria. The development of research in areas such as geomicrobiology and environmental mineralogy and geochemistry, is also leading to a greater appreciation of the role of sulfides (particularly the iron sulfides) in the geochemical cycling of the elements at or near the surface of the Earth. For example, the iron sulfides precipitated in the reducing environments beneath the surface of modern sediments in many estuarine areas may play a key role in the trapping of toxic metals and other pollutants. In our understanding of "Earth Systems," geochemical processes involving metal sulfides are an important part of the story. The main objective of the present text is to provide an up-to-date review of sulfide mineralogy and geochemistry. The emphasis is, therefore, on such topics as crystal structure and classification, electrical and magnetic properties, spectroscopic studies, chemical bonding, high and low temperature phase relations, thermochemistry, and stable isotope systematics. In the context of this book, emphasis is on metal sulfides sensu stricto where only the compounds of sulfur with one or more metals are considered. Where it is appropriate for comparison, there is brief discussion of the selenide or telluride analogs of the metal sulfides. When discussing crystal structures and structural relationships, the sulfosalt minerals as well as the sulfides are considered in some detail (see Chapter 2; also for definition of the term "sulfosalt"). However, in other chapters there is only limited discussion of sulfosalts, in part because there is little information available beyond knowledge of chemical composition and crystal structure. Given the dramatic developments in areas of research that were virtually non-existent at the time of the earlier reviews, major sections have been added here on sulfide mineral surface chemistry and reactivity, formation and transformation of metal-sulfur clusters and nanoparticles, modeling of hydrothermal precipitation, and on sulfides in biosystems. However, it should be emphasized that the growth in the literature on certain aspects of sulfide mineralogy over the past 20 years or so has been such that comprehensive coverage is not possible in a single volume. Thus, the general area of "sulfides in biosystems" is probably worthy of a volume in itself, and "environmental sulfide geochemistry" (including topics such as oxidative breakdown of sulfides) is another area where far more could have been written. In selecting areas for detailed coverage in this volume, we have been mindful of the existence of other relatively recent review volumes, including those in the RiMG series. It has also been our intention not to cover any aspects of the natural occurrence, textural or paragenetic relationships involving sulfides. This is published information that, although it may be supplemented by new observations, is likely to remain useful for a long period and largely not be superceded by later work. In the following chapters, the crystal structures, electrical and magnetic properties, spectroscopic studies, chemical bonding, thermochemistry, phase relations, solution chemistry, surface structure and chemistry, hydrothermal precipitation processes, sulfur isotope geochemistry and geobiology of metal sulfides are reviewed. Makovicky (Chapter 2) discusses the crystal structures and structural classification of sulfides and other chalcogenides (including the sulfosalts) in terms of the relationships between structural units. This very comprehensive survey, using a rather different and complementary approach to that used in previous review volumes, shows the great diversity of sulfide structures and the wealth of materials that remain to be characterized in detail. These materials include rare minerals, and synthetic sulfides that may represent as yet undescribed minerals. Pearce, Pattrick and Vaughan (Chapter 3) review the electrical and magnetic properties of sulfides, discussing the importance of this aspect of the sulfides to any understanding of their electronic structures (chemical bonding) and to applications ranging from geophysical prospecting and mineral extraction to geomagnetic and palaeomagnetic studies. Rapidly developing new areas of interest discussed include studies of the distinctive properties of sulfide nanoparticles. Wincott and Vaughan (Chapter 4) then outline the spectroscopic methods employed to study the crystal chemistry and electronic structures of sulfides. These range from UV-visible through infrared and Raman spectroscopies, to X-ray emission, photoemission and absorption, and to nuclear spectroscopies. Chemical bonding (electronic structure) in sulfides is the subject of the following chapter by Vaughan and Rosso (Chapter 5), a topic which draws on knowledge of electrical and magnetic properties and spectroscopic data as experimental input, as well as on a range of rapidly developing computational methods. Attention then turns to the thermochemistry of sulfides in a chapter by Sack and Ebel (Chapter 6) which is followed by discussion of phase equilibria at high temperatures in the review by Fleet (Chapter 7). Sulfides in aqueous systems, with emphasis on solution complexes and clusters, forms the subject matter of the chapter written by Rickard and Luther (Chapter 8). Sulfide mineral surfaces are the focus of the next two chapters, both by Rosso and Vaughan. The first of these chapters (Chapter 9) addresses characterization of the pristine sulfide surface, its structure and chemistry; the second (Chapter 10) concerns surface reactivity, including redox reactions, sorption phenomena, and the catalytic activity of sulfide surfaces. Reed and Palandri (Chapter 11) show in the next chapter how much can now be achieved in attempting to predict processes of sulfide precipitation in hydrothermal systems. The final chapters deal with two distinctive areas of sulfide mineralogy and geochemistry. Seal (Chapter 12) presents a comprehensive account of the theory and applications of sulfur isotope geochemistry; sulfur isotope fractionation can provide the key to understanding the natural processes of formation of sulfide deposits. In the final chapter, Posfai and Dunin-Borkowski (Chapter 13) review the rapidly developing area of sulfides in biosystems, discussing aspects of both sulfide mineral-microbe interactions and biomineralization processes involving sulfides.