ALBERT

Description / Table of Contents: The review chapters in this volume were the basis for a short course on molecular modeling theory jointly sponsored by the Geochemical Society (GS) and the Mineralogical Society of America (MSA) May 18-20, 2001 in Roanoke, Virginia which was held prior to the 2001 Goldschmidt Conference in nearby Hot Springs, Virginia. Dr. William C. Luth has had a long and distinguished career in research, education and in the government. He was a leader in experimental petrology and in training graduate students at Stanford University. His efforts at Sandia National Laboratory and at the Department of Energy's headquarters resulted in the initiation and long-term support of many of the cutting edge research projects whose results form the foundations of these short courses. Bill's broad interest in understanding fundamental geochemical processes and their applications to national problems is a continuous thread through both his university and government career. He retired in 1996, but his efforts to foster excellent basic research, and to promote the development of advanced analytical capabilities gave a unique focus to the basic research portfolio in Geosciences at the Department of Energy. He has been, and continues to be, a friend and mentor to many of us. It is appropriate to celebrate his career in education and government service with this series of courses in cutting-edge geochemistry that have particular focus on Department of Energy-related science, at a time when he can still enjoy the recognition of his contributions. Molecular modeling methods have become important tools in many areas of geochemical and mineralogical research. Theoretical methods describing atomistic and molecular-based processes are now commonplace in the geosciences literature and have helped in the interpretation of numerous experimental, spectroscopic, and field observations. Dramatic increases in computer power-involving personal computers, workstations, and massively parallel supercomputers-have helped to increase our knowledge of the fundamental processes in geochemistry and mineralogy. All researchers can now have access to the basic computer hardware and molecular modeling codes needed to evaluate these processes. The purpose of this volume of Reviews in Mineralogy and Geochemistry is to provide the student and professional with a general introduction to molecular modeling methods and a review of various applications of the theory to problems in the geosciences. Molecular mechanics methods that are reviewed include energy minimization, lattice dynamics, Monte Carlo methods, and molecular dynamics. Important concepts of quantum mechanics and electronic structure calculations, including both molecular orbital and density functional theories, are also presented. Applications cover a broad range of mineralogy and geochemistry topics-from atmospheric reactions to fluid-rock interactions to properties of mantle and core phases. Emphasis is placed on the comparison of molecular simulations with experimental data and the synergy that can be generated by using both approaches in tandem. We hope the content of this review volume will help the interested reader to quickly develop an appreciation for the fundamental theories behind the molecular modeling tools and to become aware of the limits in applying these state-of-the-art methods to solve geosciences problems.

Description / Table of Contents: PREFACE Sulfate is an abundant and ubiquitous component of Earth’s lithosphere and hydrosphere. Sulfate minerals represent an important component of our mineral economy, the pollution problems in our air and water, the technology for alleviating pollution, and the natural processes that affect the land we utilize. Vast quantities of gypsum are consumed in the manufacture of wallboard, and calcium sulfates are also used in sculpture in the forms of alabaster (gypsum) and papier-mâché (bassanite). For centuries, Al-sulfate minerals, or “alums,” have been used in the tanning and dyeing industries, and these sulfate minerals have also been a minor source of aluminum metal. Barite is used extensively in the petroleum industry as a weighting agent during drilling, and celestine (also known as “celestite”) is a primary source of strontium for the ceramics, metallurgical, glass, and television face-plate industries. Jarosite is a major waste product of the hydrometallurgical processing of zinc ores and is used in agriculture to reduce alkalinity in soils. At many mining sites, the extraction and processing of coal or metal-sulfide ores (largely for gold, silver, copper, lead, and zinc) produce waste materials that generate acid-sulfate waters rich in heavy metals, commonly leading to contamination of water and sediment. Concentrated waters associated with mine wastes may precipitate a variety of metal-sulfate minerals upon evaporation, oxidation, or neutralization. Some of these sulfate minerals are soluble and store metals and acidity only temporarily, whereas others are insoluble and improve water quality by removing metals from the water column. There is considerable scientific interest in the mineralogy and geochemistry of sulfate minerals in both high-temperature (igneous and hydrothermal) and low-temperature (weathering and evaporite) environments. The physical scale of processes affected by aqueous sulfate and associated minerals spans from submicroscopic reactions at mineral-water interfaces to global issues of oceanic cycling and mass balance, and even to extraterrestrial applications in the exploration of other planets and their satellites. In mineral exploration, minerals of the alunite-jarosite supergroup are recognized as key components of the advanced argillic (acid-sulfate) hydrothermal alteration assemblage, and supergene sulfate minerals can be useful guides to primary sulfide deposits. The role of soluble sulfate minerals formed from acid mine drainage (and its natural equivalent, acid rock drainage) in the storage and release of potentially toxic metals associated with wet-dry climatic cycles (on annual or other time scales) is increasingly appreciated in environmental studies of mineral deposits and of waste materials from mining and mineral processing. This volume compiles and synthesizes current information on sulfate minerals from a variety of perspectives, including crystallography, geochemical properties, geological environments of formation, thermodynamic stability relations, kinetics of formation and dissolution, and environmental aspects. The first two chapters cover crystallography (Chapter 1) and spectroscopy (Chapter 2). Environments with alkali and alkaline earth sulfates are described in the next three chapters, on evaporites (Chapter 3). barite-celestine deposits (Chapter 4), and the kinetics of precipitation and dissolution of gypsum, barite, and celestine (Chapter 5). Acidic environments are the theme for the next four chapters, which cover soluble metal salts from sulfide oxidation (Chapter 6), iron and aluminum hydroxysulfates (Chapter 7), jarosites in hydrometallugy (Chapter 8), and alunite-jarosite crystallography, thermodynamics, and geochronology (Chapter 9). The next two chapters discuss thermodynamic modeling of sulfate systems from the perspectives of predicting sulfate-mineral solubilities in waters covering a wide range in composition and concentration (Chapter 10) and predicting interactions between sulfate solid solutions and aqueous solutions (Chapter 11). The concluding chapter on stable-isotope systematics (Chapter 12) discusses the utility of sulfate minerals in understanding the geological and geochemical processes in both high-and low-temperature environments, and in unraveling the past evolution of natural systems through paleoclimate studies. We thank the authors for their comprehensive and timely efforts, and for their cooperation with our various requests regarding consistency of format and nomenclature. Special thanks are due to the numerous scientists who provided peer reviews, which substantially improved the content of the chapters. This volume would not have been possible without the usual magic touch and extreme patience of Paul H. Ribbe, Series Editor for Reviews in Mineralogy and Geochemistry. Finally, we thank our families for their support and understanding during the past several months.

Description / Table of Contents: Several years ago, John Rakovan and John Hughes (colleagues at Miami of Ohio), and later Matt Kohn (at South Carolina), separately proposed short courses on phosphate minerals to the Council of the Mineralogical Society of America (MSA). Council suggested that they join forces. Thus this volume, Phosphates: Geochemical, Geobiological, and Materials Importance, was organized. It was prepared in advance of a short course of the same title, sponsored by MSA and presented at Golden, Colorado, October 25-27. We are pleased to present this volume entitled Phosphates: Geochemical, Geobiological and Materials Importance. Phosphate minerals are an integral component of geological and biological systems. They are found in virtually all rocks, are the major structural component of vertebrates, and when dissolved are critical for biological activity. This volume represents the work of many authors whose research illustrates how the unique chemical and physical behavior of phosphate minerals permits a wide range of applications that encompasses phosphate mineralogy, petrology, biomineralization, geochronology, and materials science. While diverse, these fields are all linked structurally, crystal-chemically and geochemically. As geoscientists turn their attention to the intersection of the biological, geological, and material science realms, there is no group of compounds more germane than the phosphates. The chapters of this book are grouped into five topics: Mineralogy and Crystal Chemistry, Petrology, Biomineralization, Geochronology, and Materials Applications. In the first section, three chapters are devoted to mineralogical aspects of apatite, a phase with both inorganic and organic origins, the most abundant phosphate mineral on earth, and the main mineral phase in the human body. Monazite and xenotime are highlighted in a fourth chapter, which includes their potential use as solid-state radioactive waste repositories. The Mineralogy and Crystal Chemistry section concludes with a detailed examination of the crystal chemistry of 244 other naturally-occurring phosphate phases and a listing of an additional 126 minerals. In the Petrology section, three chapters detail the igneous, metamorphic, and sedimentary aspects of phosphate minerals. A fourth chapter provides a close look at analyzing phosphates for major, minor, and trace elements using the electron microprobe. A final chapter treats the global geochemical cycling of phosphate, a topic of intense, current geochemical interest. The Biomineralization section begins with a summary of the current state of research on bone, dentin and enamel phosphates, a topic that crosses disciplines that include mineralogical, medical, and dental research. The following two chapters treat the stable isotope and trace element compositions of modern and fossil biogenic phosphates, with applications to paleontology, paleoclimatology, and paleoecology. The Geochronology section focuses principally on apatite and monazite for U-ThPb, (U- Th)/He, and fission-track age determinations; it covers both classical geochronologic techniques as well as recent developments. The final section-Materials Applications-highlights how phosphate phases play key roles in fields such as optics, luminescence, medical engineering and prosthetics, and engineering of radionuclide repositories. These chapters provide a glimpse of the use of natural phases in engineering and biomedical applications and illustrate fruitful areas of future research in geochemical, geobiological and materials science. We hope all chapters in this volume encourage researchers to expand their work on all aspects of natural and synthetic phosphate compounds.

Description / Table of Contents: Exactly 100 years before the publication of this volume, the first paper which calculated the half-life for the newly discovered radioactive substance U-X (now called 234Th), was published. Now, in this volume, the editors Bernard Bourdon, Gideon Henderson, Craig Lundstrom and Simon Turner have integrated a group of contributors who update our knowledge of U-series geochemistry, offer an opportunity for non-specialists to understand its basic principles, and give us a view of the future of this active field of research. In this volume, for the first time, all the methods for determining the uranium and thorium decay chain nuclides in Earth materials are discussed. It was prepared in advance of a two-day short course (April 3-4, 2003) on U-series geochemistry, jointly sponsored by GS and MSA and presented in Paris, France prior to the joint EGS/AGU/EUG meeting in Nice. The discovery of the 238U decay chain, of course, started with the seminal work of Marie Curie in identifying and separating 226Ra. Through the work of the Curies and others, all the members of the 238U decay chain were identified. An important milestone for geochronometrists was the discovery of 230Th (called Ionium) by Bertram Boltwood, the Yale scientist who also made the first age determinations on minerals using the U-Pb dating method (Boltwood in 1906 established the antiquity of rocks and even identified a mineral from Sri Lanka-then Ceylon as having an age of 2.1 billion years!) The application of the 238U decay chain to the dating of deep sea sediments was by Piggott and Urry in 1942 using the "Ionium" method of dating. Actually they measured 222Ra (itself through 222Rn) assuming secular equilibrium had been established between 230Th and 226Ra. Although 230Th was measured in deep sea sediments by Picciotto and Gilvain in 1954 using photographic emulsions, it was not until alpha spectrometry was developed in the late 1950's that 20Th was routinely measured in marine deposits. Alpha spectrometry and gamma spectrometry became the work horses for the study of the uranium and thorium decay chains in a variety of Earth materials. These ranged from 222Rn and its daughters in the atmosphere, to the uranium decay chain nuclides in the oceanic water column, and volcanic rocks and many other systems in which either chronometry or element partitioning, were explored. Much of what we learned about the 238U, 235U and 232Th decay chain nuclides as chronometers and process indicators we owe to these seminal studies based on the measurement of radioactivity. The discovery that mass spectrometry would soon usurp many of the tasks performed by radioactive counting was in itself serendipitous. It came about because a fundamental issue in cosmochemistry was at stake. Although variation in 235U/238U had been reported for meteorites the results were easily discredited as due to analytical difficulties. One set of results, however, was published by a credible laboratory long involved in quality measurements of high mass isotopes such as the lead isotopes. The purported discovery of 235U/238U variations in meteorites, if true, would have consequences in defining the early history of the formation of the elements and the development of inhomogeneity of uranium isotopes in the accumulation of the protoplanetary materials of the Solar System. Clearly the result was too important to escape the scrutiny of falsification implicit in the way we do science. The Lunatic Asylum at Caltech under the leadership of Jerry Wasserburg took on that task. Jerry Wasserburg and Jim Chen clearly established the constancy and Earth-likeness of 235U/238U in the samplable universe. In the hands of another member of the Lunatic Asylum, Larry Edwards, the methodology was transformed into a tool for the study of the 238U decay chain in marine systems. Thus the mass spectrometric techniques developed provided an approach to measuring the U and Th isotopes in geological materials as well as cosmic materials with the same refinement and accommodation for small sample size. Soon after this discovery the harnessing of the technique to the measurement of all the U isotopes and all the Th isotopes with great precision immediately opened up the entire field of uranium and thorium decay chain studies. This area of study was formerly the poaching ground for radioactive measurements alone but now became part of the wonderful world of mass spectrometric measurements. (The same transformation took place for radiocarbon from the various radioactive counting schemes to accelerator mass spectrometry.) No Earth material was protected from this assault. The refinement of dating corals, analyzing volcanic rocks for partitioning and chronometer studies and extensions far and wide into ground waters and ocean bottom dwelling organisms has been the consequence of this innovation. Although Ra isotopes, 210Pb and 210Po remain an active pursuit of those doing radioactive measurements, many of these nuclides have also become subject to the mass spectrometric approach. In this volume, for the first time, all the methods for determining the uranium and thorium decay chain nuclides in Earth materials are discussed. The range of problems solvable with this approach is remarkable-a fitting, tribute to the Curies and the early workers who discovered them for us to use.

Description / Table of Contents: Since the dawn of life on earth, organisms have played roles in mineral formation in processes broadly known as biomineralization. This biologically-mediated organization of aqueous ions into amorphous and crystalline materials results in materials that are as simple as adventitious precipitates or as complex as exquisitely fabricated structures that meet specialized functionalities. The purpose of this volume of Reviews in Mineralogy and Geochemistry is to provide students and professionals in the earth sciences with a review that focuses upon the various processes by which organisms direct the formation of minerals. Our framework of examining biominerals from the viewpoints of major mineralization strategies distinguishes this volume from most previous reviews. The review begins by introducing the reader to over-arching principles that are needed to investigate biomineralization phenomena and shows the current state of knowledge regarding the major approaches to mineralization that organisms have developed over the course of Earth history. By exploring the complexities that underlie the "synthesis" of biogenic materials, and therefore the basis for how compositions and structures of biominerals are mediated (or not), we believe this volume will be instrumental in propelling studies of biomineralization to a new level of research questions that are grounded in an understanding of the underlying biological phenomena.

Description / Table of Contents: In the two decades since J. Alexander Speer's Zircon chapter in Orthosilicates (Reviews in Mineralogy, Vol. 5), much has been learned about the internal textures, trace-element and isotope geochemistry (both radiogenic and stable) and chemical and mechanical stability of zircon. The application of this knowledge and the use of zircon in geologic studies have become widespread. Today, the study of zircon exists as the pseudo-discipline of "zirconology" that involves materials scientists and geoscientists from across a range of sub-disciplines including stable and radiogenic isotopes, sedimentology, petrology, trace elements and experimental mineralogy. Zirconology has become an important field of research, so much so that coverage of the mineral zircon in a review volume that included zircon as one of many accessory minerals would not meet the needs or interests of the zirconology community in terms of depth or breadth of coverage. The sixteen chapters in this volume cover the most important aspects of zircon-related research over the past twenty-years and highlight possible future research avenues. Finch and Hanchar (Chapter 1) review the structure of zircon and other mineral (and synthetic) phases with the zircon structure. In most rock types where zircon occurs it is a significant host of the rare-earth elements, Th and U. The abundances of these elements and the form of chondrite-normalized rare-earth element patterns may provide significant information on the processes that generate igneous and metamorphic rocks. The minor and trace element compositions of igneous, metamorphic and hydrothermal zircons are reviewed by Hoskin and Schaltegger in Chapter 2. The investigation of melt inclusions in zircon is an exciting line of new research. Trapped melt inclusions can provide direct information of the trace element and isotopic composition of the melt from which the crystal formed as a function of time throughout the growth of the crystal. Thomas et a!. (Chapter 3) review the study of melt inclusions in zircon. Hanchar and Watson (Chapter 4) review experimental and natural studies of zircon saturation and the use of zircon saturation thermometry for natural rocks. Cation diffusion and oxygen diffusion in zircon is discussed by Cherniak and Watson (Chapter 5). Diffusion studies are essential for providing constraints on the quality of trace element and isotope data and for providing estimates of temperature exposure in geological environments. Zircon remains the most widely utilized accessory mineral for U- Th-Pb isotope geochronology. Significant instrumental and analytical developments over the past thirty years mean that zircon has an essential role in early Achaean studies, magma genesis, and astrobiology. Four chapters are devoted to different aspects of zircon geochronology. The first of these four, Chapter 6 by Davis et a!., reviews the historical development of zircon geochronology from the mid-1950s to the present; the following three chapters focus on particular techniques for zircon geochronology, namely ID-TIMS (Parrish and Noble, Chapter 7), SIMS (Ireland and Williams, Chapter 8) and ICP-MS (Kosier and Sylvester, Chapter 9). The application of zircon chronology in constraining sediment provenance.and the calibration ofthe geologic time-scale are reviewed by Fedo et al. (Chapter 10) and Bowring and Schmitz (Chapter 11), respectively. Other isotopic systematics are reviewed for zircon by Kinny and Maas (Chapter 12), who discuss the application of Nd-Sm and Lu-Hf isotopes in zircon to petrogenetic studies, and by Valley (Chapter 13), who discusses the importance of oxygen isotopic studies in traditional and emerging fields of geologic study. As a host of U and Th, zircon is subject to radiation damage. Radiation damage is likely responsible for isotopic disturbance and promotes mechanical instability. There is increasing interest in both the effect of radiation damage on the zircon crystal structure and mechanisms of damage and recrystallization, as well as the structure of the damaged phase. These studies contribute to an overall understanding of how zircon may behave as a waste-form for safe disposal of radioactive waste and are discussed by Ewing et a!. (Chapter 14). The spectroscopy of zircon, both crystalline and metamict is reviewed by Nadsala et a!. (Chapter 15). The final chapter, by Corfu et al. (Chapter 16), is an atlas of internal textures of zircon. The imaging of internal textures in zircon is essential for directing the acquisition of geochemical data and to the integrity of conclusions reached once data has been collected and interpreted. This chapter, for the first time, brings into one place textural images that represent common and not so common textures reported in the literature, along with brief interpretations of their significance. There is presently no comparable atlas. It is intended that this chapter will become a reference point for future workers to compare and contrast their own images against. The chapters in this volume of Reviews in Mineralogy and Geochemistry were prepared for presentation at a Short Course, sponsored by the Mineralogical Society of America (MSA) in Freiburg, Germany, April 3-4, 2003. This preceded a joint meeting of the European Union of Geology, the American Geophysical Union and the European Geophysical Society held in Nice, France, April 6-11, 2003.

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: Until only a few years ago, I would never have imagined that a volume on the stable isotope geochemistry of elements like Mg, Fe or Cu would be written. In fact, a comic book of blank pages entitled The Stable Isotope Geochemistry of Fluorine would have been a more likely prospect. In volume 16 of this series, published in 1986, I wrote: Isotopic variations have been looked for but not found for heavy elements like Cu, Sn, and Fe .... Natural variations in isotopic ratios of terrestrial materials have been reported for other light elements like Mg and K, but such variations usually turn out to be laboratory artifacts. I am about ready to eat those words. We have known for many years that large isotopic fractionations of heavy elements like Pb develop in the source regions of TIMS machines. Nonetheless, most of us held fast to the conventional wisdom that no significant mass-dependent isotopic fractionations were likely to occur in natural or laboratory systems for elements that are either heavy or engaged in bonds with a dominant ionic character. With the relatively recent appearance of new instrumentation like MC-ICP-MS and heroic methods development in TIMS analyses, it became possible to make very precise measurements of the isotopic ratios of some of these non-traditional elements, particularly if they comprise three or more isotopes. It was eminently reasonable to reexamine these systems in this new light. Perhaps atomic weights could be refined, or maybe there were some unexpected isotopic variations to discover. There were around the turn of the present century, reports began appearing of biological fractionations of about 2-3 per mil for heavy elements like Fe and Cr and attempts were made to determine the magnitude of equilibrium isotope effects in these systems, both by experiment and semi-empirical calculations. Interest emerged in applying these effects to the study of environmental problems. Even the most recalcitrant skeptic now accepts the fact that measurable and meaningful variations in the isotopic ratios of heavy elements occur as a result of chemical, biological and physical processes. Most of the work discussed in this volume was published after the year 2000 and thus the chapters are more like progress reports rather than reviews. Skepticism now focuses on whether isotopic variations as small as 0.1 per mil are indeed as meaningful as some think, and the fact that measured isotopic fractionations of these non-traditional elements are frequently much smaller than predicted from theoretical considerations. In fact the large fractionations suggested by the calculations provide much of the stimulus for working in this discipline. Clearly some carefully designed experiments could shed light on some of the ambiguity. My optimism for the future of this burgeoning new field remains high because it is in very good hands indeed.

Description / Table of Contents: This volume was produced in response to the need for a comprehensive introduction to the continually evolving state of the art of synchrotron radiation applications in low-temperature geochemistry and environmental science. It owes much to the hard work and imagination of the devoted cadre of sleep-deprived individuals who blazed a trail that many others are beginning to follow. Synchrotron radiation methods have opened new scientific vistas in the earth and environmental sciences, and progress in this direction will undoubtedly continue. The organization of this volume is as follows. Chapter 1 (Brown and Sturchio) gives a fairly comprehensive overview of synchrotron radiation applications in low temperature geochemistry and environmental science. The presentation is organized by synchrotron methods and scientific issues. It also has an extensive reference list that should prove valuable as a starting point for further research. Chapter 2 (Sham and Rivers) describes the ways that synchrotron radiation is generated, including a history of synchrotrons and a discussion of aspects of synchrotron radiation that are important to the experimentalist. The remaining chapters of the volume are organized into two groups. Chapters 3 through 6 describe specific synchrotron methods that are most useful for single-crystal surface and mineral-fluid interface studies. Chapters 7 through 9 describe methods that can be used more generally for investigating complex polyphase fine-grained or amorphous materials, including soils, rocks, and organic matter. Chapter 3 (Fenter) presents the elementary theory of synchrotron X-ray reflectivity along with examples of recent applications, with emphasis on in situ studies of mineral-fluid interfaces. Chapter 4 (Bedzyk and Cheng) summarizes the theory of X-ray standing waves (XSW), the various methods for using XSW in surface and interfaces studies, and gives a brief review of recent applications in geochemistry and mineralogy. Chapter 5 (Waychunas) covers the theory and applications of grazing-incidence X-ray absorption and emission spectroscopy, with recent examples of studies at mineral surfaces. Chapter 6 (Hirschmugl) describes the theory and applications of synchrotron infrared microspectroscopy. Chapter 7 (Manceau, Marcus, and Tamura) gives background and examples of the combined application of synchrotron X-ray microfluorescence, microdiffraction, and microabsorption spectroscopy in characterizing the distribution and speciation of metals in soils and sediments. Chapter 8 (Sutton, Newville, Rivers, Lanzirotti, Eng, and Bertsch) demonstrates a wide variety of applications of synchrotron X-ray microspectroscopy and microtomography in characterizing earth and environmental materials and processes. Finally, Chapter 9 (Myneni) presents a review of the principles and applications of soft X-ray microspectroscopic studies of natural organic materials. All of these chapters review the state of the art of synchrotron radiation applications in low temperature geochemistry and environmental science, and offer speculations on future developments. The reader of this volume will acquire an appreciation of the theory and applications of synchrotron radiation in low temperature geochemistry and environmental science, as well as the significant advances that have been made in this area in the past two decades (especially since the advent of the third-generation synchrotron sources). We hope that this volume will inspire new users to "see the light" and pursue their research using the potent tool of synchrotron radiation.

Description / Table of Contents: This volume highlights some of the frontiers in the study of plastic deformation of minerals and rocks. The research into the plastic properties of minerals and rocks had a major peak in late 1960s to early 1970s, largely stimulated by research in the laboratory of D. T. Griggs and his students and associates. It is the same time when the theory of plate tectonics was established and provided a first quantitative theoretical framework for understanding geological processes. The theory of plate tectonics stimulated the study of deformation properties of Earth materials, both in the brittle and the ductile regimes. Many of the foundations of plastic deformation of minerals and rocks were established during this period. Also, new experimental techniques were developed, including deformation apparatus for high-pressure and high-temperature conditions, electron micros-copy study of defects in minerals, and the X-ray technique of deformation fabric analysis. The field benefited greatly from materials science concepts of deformation that were introduced, including the models of point defects and their interaction with dislocations. A summary of progress is given by the volume Flow and Fracture of Rocks: The Griggs Volume, published in 1972 by the American Geophysical Union. Since then, the scope of Earth sciences has greatly expanded. Geodynamics became concerned with the Earth's deep interior where seismologists discovered heterogeneities and anisotropy at all scales that were previously thought to be typical of the crust and the upper mantle. Investigations of the solar system documented new mineral phases and rocks far beyond the Earth. Both domains have received a lot of attention from mineralogists (e.g., summarized in MSA's Reviews in Mineralogy, Volume 36, Planetary Materials and Volume 37, Ultra-High Pressure Mineralogy). Most attention was directed towards crystal chemistry and phase relations, yet an understanding of the deformation behavior is essential for interpreting the dynamic geological processes from geological and geophysical observations. This was largely the reason for a rebirth of the study of rock plasticity, leading to new approaches that include experiments at extreme conditions and modeling of deformation behavior based on physical principles. A wide spectrum of communities emerged that need to use information about mineral plasticity, including mineralogy, petrology, structural geology, seismology, geodynamics and engineering. This was the motivation to organize a workshop, in December 2002 in Emeryville, California, to bridge the very diverse disciplines and facilitate communication. This volume written for this workshop should help one to become familiar with a notoriously difficult subject, and the various contributions represent some of the important progress that has been achieved. The spectrum is broad. High-resolution tomographic images of Earth's interior obtained from seismology need to be interpreted on the bases of materials properties to understand their geodynamic significance. Key issues include the influence of deformation on seismic signatures, such as attenuation and anisotropy, and a new generation of experimental and theoretical studies on rock plasticity has contributed to a better understanding. Extensive space exploration has revealed a variety of tectonic styles on planets and their satellites, underlining the uniqueness of the Earth. To understand why plate tectonics is unique to Earth, one needs to understand the physical mechanisms of localization of deformation at various scales and under different physical conditions. Also here important theoretical and experimental studies have been conducted. In both fields, studies on anisotropy and shear localization, large-strain deformation experiments and quantitative modeling are critical, and these have become available only recently. Complicated interplay among chemical reactions (including partial melting) is a key to understand the evolution of Earth. This book contains two chapters on the developments of new techniques of experimental studies: one is large-strain shear deformation (Chapter 1 by Mackwell and Paterson) and another is deformation experiments under ultrahigh pressures (Chapter 2 by Durham et al.). Both technical developments are the results of years of efforts that are opening up new avenues of research along which rich new results are expected to be obtained. Details of physical and chemical processes of deformation in the crust and the upper mantle are much better understood through the combination of well controlled laboratory experiments with observations on "real" rocks deformed in Earth. Chapter 3 by Tullis and Chapter 4 by Hirth address the issues of deformation of crustal rocks and the upper mantle, respectively. In Chapter 5 Kohlstedt reviews the interplay of partial melting and deformation, an important subject in understanding the chemical evolution of Earth. Cordier presents in Chapter 6 an overview of the new results of ultrahigh pressure deformation of deep mantle minerals and discusses microscopic mechanisms controlling the variation of deformation mechanisms with minerals in the deep mantle. Green and Marone review in Chapter 7 the stability of deformation under deep mantle conditions with special reference to phase transformations and their relationship to the origin of intermediate depth and deep-focus earthquakes. In Chapter 8 Schulson provides a detailed description of fracture mechanisms of ice, including the critical brittle-ductile transition that is relevant not only for glaciology, planetology and engineering, but for structural geology as well. In Chapter 9 Cooper provides a review of experimental and theoretical studies on seismic wave attenuation, which is a critical element in interpreting distribution of seismic wave velocities and attenuation. Chapter 10 by Wenk reviews the relationship between crystal preferred orientation and macroscopic anisotropy, illustrating it with case studies. In Chapter 11 Dawson presents recent progress in poly-crystal plasticity to model the development of anisotropic fabrics both at the microscopic and macroscopic scale. Such studies form the basis for geodynamic interpretation of seismic anisotropy. Finally, in Chapter 12 Montagner and Guillot present a thorough review of seismic anisotropy of the upper mantle covering the vast regions of geodynamic interests, using a global surface wave data set. In Chapter 13 Bercovici and Karato summarize the theoretical aspects of shear localization. All chapters contain extensive reference lists to guide readers to the more specialized literature. Obviously this book does not cover all the areas related to plastic deformation of minerals and rocks. Important topics that are not fully covered in this book include mechanisms of semi-brittle deformation and the interplay between microstructure evolution and deformation at different levels, such as dislocation substructures and grain-size evolution ("self-organization"). However, we hope that this volume provides a good introduction for graduate students in Earth science or materials science as well as the researchers in these areas to enter this multidisciplinary field.