ALBERT

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 publication of this volume occurs at the one-hundredth anniversary of 1905, which has been called the annus mirabilus because it was the year of a number of enormous scientific advances. Among them are four papers by Albert Einstein explaining (among other things) Brownian motion, the photoelectric effect, the special theory of relativity, and the equation E = mc2. Also of significance in 1905 was the first application of another major advance in physics, which dramatically changed the fields of Earth and planetary science. In March of 1905 (and published the following year), Ernest Rutherford presented the following in the Silliman Lectures at Yale: "The helium observed in the radioactive minerals is almost certainly due to its production from the radium and other radioactive substances contained therein. If the rate of production of helium from known weights of the different radioelements were experimentally known, it should thus be possible to determine the interval required for the production of the amount of helium observed in radioactive minerals, or, in other words, to determine the age of the mineral." Rutherford E (1906) Radioactive Transformations. Charles Scriber's Sons, NY Thus radioisotopic geochronology was born, almost immediately shattering centuries of speculative conjectures and estimates and laying the foundation for establishment of the geologic timescale, the age of the Earth and meteorites, and a quantitative understanding of the rates of processes ranging from nebular condensation to Quaternary glaciations. There is an important subplot to the historical development of radioisotopic dating over the last hundred years, which, ironically, arises directly from the subsequent history of the U-He dating method Rutherford described in 1905. Almost as soon as radioisotopic dating was invented, it was recognized that the U-He [or later the (U-Th)/He method], provided ages that were often far younger than those allowed by stratigraphic correlations or other techniques such as U/Pb dating. Clearly, as R.J. Strutt noted in 1910, He ages only provided "minimum values, because helium leaks out from the mineral, to what extent it is impossible to say" (Strutt, 1910, Proc Roy Soc Lond, Ser A 84:379-388). For several decades most attention was diverted to U/Pb and other techniques better suited to measurement of crystallization ages and establishment of the geologic timescale. Gradually it became clear that other radioisotopic systems such as K/Ar and later fission-track also provided ages that were clearly younger than formation ages. In 1910 it may have been impossible to say the extent to which He (or most other elements) leaked out of minerals, but eventually a growing understanding of thermally-activated diffusion and annealing began to shed light on the significance of such ages. The recognition that some systems can provide cooling, rather than formation, ages, was gradual and diachronous across radioisotopic systems. Most of the heavy lifting in this regard was accomplished by researchers working on the interpretation of K/Ar and fission-track ages. Ironically, Rutherfordπs He-based radioisotopic system was one of the last to be quantitatively interpreted as a thermochronometer, and has been added to K/Ar (including 40Ar/39Ar) and fission-track methods as important for constraining the medium- to low-temperature thermal histories of rocks and minerals. Thermochronology has had a slow and sometimes fitful maturation from what were once troubling age discrepancies and poorly-understood open-system behaviors, into a powerful branch of geochronology applied by Earth scientists from diverse fields. Cooling ages, coupled with quantitative understanding of crystal-scale kinetic phenomena and crustal- or landscape-scale interpretational models now provide an enormous range of insights into tectonics, geomorphology, and subjects of other fields. At the same time, blossoming of lower temperature thermochronometric approaches has inspired new perspectives into the detailed behavior of higher temperature systems that previously may have been primarily used for establishing formation ages. Increased recognition of the importance of thermal histories, combined with improved analytical precision, has motivated progress in understanding the thermochronologic behavior of U/Pb, Sm/Nd, Lu/Hf, and other systems in a wide range of minerals, filling out the temperature range accessible by thermochronologic approaches. Thus the maturation of low- and medium-temperature thermochronology has led to a fuller understanding of the significance of radioisotopic ages in general, and to one degree or another has permeated most of geochronology. Except in rare cases, the goal of thermochronology is not thermal histories themselves, but rather the geologic processes responsible for them. Thermochronometers are now routinely used for quantifying exhumation histories (tectonic or erosional), magmatism, or landscape evolution. As thermochronology has matured, so have model and interpretational approaches used to convert thermal histories into these more useful geologic histories. Low-temperature thermochronology has been especially important in this regard, as knowledge of thermal processes in the uppermost few kilometers of the crust require consideration of coupled interactions of tectonic, geodynamic, and surface processes. Exciting new developments in these fields in turn drive improved thermochronologic methods and innovative sampling approaches. The chapters This volume presents 22 chapters covering many of the important modern aspects of thermochronology. The coverage of the chapters ranges widely, including historical perspective, analytical techniques, kinetics and calibrations, modeling approaches, and interpretational methods. In general, the chapters focus on intermediate- to low-temperature thermochronometry, though some chapters cover higher temperature methods such as monazite U/Pb closure profiles, and the same theory and approaches used in low-temperature thermochronometry are generally applicable to higher temperature systems. The widely used low- to medium-temperature thermochronometric systems are reviewed in detail in these chapters, but while there are numerous chapters reviewing various aspects of the apatite (U-Th)/He system, there is no chapter singularly devoted to it, partly because of several previous reviews recently published on this topic. Chapter 1 by Reiners, Ehlers, and Zeitler provides a perspective on the history of thermochronology, comments on modern work in this field and general lessons on the potential for noise to be turned into signal. This chapter also provides a summary of the current challenges, unresolved issues, and most exciting prospects in the field. Much of the modern understanding of kinetic controls on apparent ages, thermal histories, and sampling approaches comes from decades of progress in fission-track dating, a method that remains as essential as ever, partly because of the power of track-length measurements and the depth of (at least empirical) understanding of the kinetics of track annealing. Tagami, Donelick and OπSullivan review the fundamentals of modern fission-track dating (Chapter 2). Two of the most commonly dated, well-understood, and powerful minerals dated by fission-track methods are apatite and zircon, and the specifics of modern methods for these systems and their kinetics are reviewed by Donelick, OπSullivan, and Ketcham (Chapter 3), and Tagami (Chapter 4). Although 40Ar/39Ar and (U-Th)/He dating methods followed somewhat different paths to their modern thermochronologic incarnations, they have many features in common, especially in the kinetics of diffusion and closure. Zeitler and Harrison review the concepts underlying both 40Ar/39Ar and (U-Th)/He methods (Chapter 5). Zircon was one of the first minerals dated by the (U-Th)/He method, but has only just begun to be used for thermochronometry of both bedrock and detrital samples, as reviewed by Reiners (Chapter 6). Continuous time-temperature paths from intracrystalline variations of radiogenic Ar proven perhaps the most powerful of all thermochronologic approaches, and an innovative analogous approach in He dating (4He/3He thermochronometry) is revealing remarkably powerful constraints on the extreme low temperature end of thermal histories, as reviewed by Shuster and Farley (Chapter 7). Thermochronology of detrital minerals provides unique constraints on the long-term evolution of orogens, sediment provenance, and depositional age constraints, to name a few. Bernet and Garver (Chapter 8) review the essentials of detrital zircon fission-track dating, one of the most venerable and robust of detrital thermochronometers, and in Chapter 9, Hodges, Ruhl, Wobus, and Pringle review the use of 40Ar/39Ar dating of detrital minerals, demonstrating the power of detrital muscovite ages in illuminating variations in exhumation rates in catchments over broad landscapes. (U-Th)/He thermochronometry presents several unique interpretational challenges besides new kinetics and low temperature sensitivity. One of these is long-alpha stopping distances, and its coupling with diffusion and U-Th zonation in age corrections. Dunai reviews modeling approaches to deal with these issues in interpreting low-temperature thermal histories (Chapter 10). Ketcham (Chapter 11) reviews the theory and calibration of both forward and inverse models of thermal histories from fission-track and (U-Th)/He data, and makes some important points about the interpretations of such models. Translating thermal histories into exhumational histories and their tectonic or geomorphic significance across a landscape requires quantitative understanding of the thermal structure of the crust and how it is perturbed, a review of which is presented by Ehlers (Chapter 12). Braun (Chapter 13) illustrates the power of low-temperature thermochronometry to constrain topographic evolution of landscapes over time, using PECUBE. Gallagher, Stephenson, Brown, Holmes, and Ballester present a novel method of inverse modeling of fission-track and (U-Th)/He data for thermal histories over landscapes (Chapter 14). Continuous time-temperature paths from closure profiles or their step-heating-derived equivalents are, to some degree, the holy grail of thermochronology. Harrison, Zeitler, Grove, and Lovera (Chapter 15) provide a review of the theory, measurement, and interpretation of continuous thermal histories at both intermediate and high temperatures, derived from both K-feldspar 40Ar/39Ar and monazite U/Pb dating. Extensional orogens provide a special challenge and opportunity for thermochronometry because tectonic exhumation by footwall unroofing often outstrips erosional exhumation, and often occurs at high rates. As Stockli shows (Chapter 16) thermochronology in these setting provides opportunities to measure rates of a number of important processes, as well as obtain a snapshot of crustal thermal structure and its imprint on thermochronometers with varying closure temperatures. Spotila (Chapter 17) reviews the use of thermochronology applied to tectonic geomorphology in a wide range of orogenic settings, introducing the concept of denudational maturity. Thermochronology has found great utility in economic geology, and newly developed approaches pose great potential in this area, and shown by McInnes, Evans, Fu, and Garwin in their review of the use and modeling of thermochronology of hydrothermal ore deposits (Chapter 18). The thermal histories of sedimentary basins are also critical to understanding thermal maturation of hydrocarbons, but are also critical for understanding basin formation, erosional histories of source regions, fluid flow, and climate change and other temporal signals preserved in sedimentary rocks. Armstrong (Chapter 19) reviews these issues and the use of thermochronology in deducing the thermal histories of sedimentary basins. Drawing on large datasets of bedrock apatite fission-track dates, Kohn, Gleadow, Brown, Gallagher, Lorencak, and Noble demonstrate the power of modeling, and, importantly, effectively visualizing, integrated thermotectonic and denudational histories over large regions (Chapter 20). Thermal histories of meteorites provide constraints on a wide range of fundamentally important processes, including nebular condensation and early solar-system metamorphic histories, and the dynamics of interplanetary collisions and shock metamorphism. Min reviews thermochronologic approaches to understanding meteorite thermal histories (Chapter 21), including new methods and approaches. Finally, the importance of robust models with which to interpret thermochronologic data is underscored by the review of the Software for Interpretation and Analysis of Thermochronologic Data (Chapter 22), summarized and compiled by Ehlers, for programs associated with the work of authors in this volume and others.