ALBERT

Description / Table of Contents: PREFACE The application of thermal analysis to earth science has a long history. This is evidenced by the extensive coverages by Mackenzie (1957, 1970), Langier-Kuzniarowa (1967), Schultze (1971), Liptay (t973), Smykatz- Kloss (1974), Todor (1976) and Heide (1982). The chief thermal method has been differential thermal analysis (DTA). Additionally, thermogravimetry (TG; Duval, 1963; Keattch, 1969; Earnest, 1988) and thermodilatometry (Schomburg & Strörr, 1984) have gained some importance. All these methods are still widely ltsed. But recently several new techniques have gained attention, such as thermomagnetometry, thermomechanical analysis and thermosonimetry. Improved equipment made possible the application of thermal methods to problems in thermodynamics and kinetics (e.g. by means of differential scanning calorimetry, DSC). This progress in the construction of new instruments as well as the combination of existing methods to enable simultaneous determinations (e.g. TG/DTA; TG/IR spectroscopy; DTA/mass spectrometry; DTA/microscopy; high-pressure DTA) have led to a resurgence in the use and application of thermal analysis in the earth sciences. Here the applications cover such diverse areas as the examination of individual minerals, mineral mixtures, rocks, soils, ceramics, cements, raw materials as well as their industrial evaluation, performance assessment and quality control. In the field of solid fossil fuels thermal determinations range from proximate analysis of inorganic constituents and the measurement of calorific values to the assessment of the environmental aspects of fly ashes and mineral residues. To support this tendency, the International Confederation for Thermal Analysis (ICTA) has recently founded a "Committee for Thermal Analysis in Geosciences". The aim of this committee shall be to discuss, improve and distribute the knowledge about the possibilities of solving geoscientific questions by means of thermal analytic methods...

Description / Table of Contents: PREFACE Some of the major ecological and social problems of the present and future are the production, treatment, and disposal of anthropogenic wastes. Iaais is equally true for sparsely and densely populated industrial areas, including large countries in which sites for waste disposal would seem to be readily available. Especially nonradioactive hazardous wastes with their long-term toxicity need to be isolated from the biosphere just as effectively as radioactive substances. The long-term safety required of waste disposal sites can only be assured under specific geological and mineralogical conditions in certain parts of the lithosphere (underground repositories). The subjects related to the production, avoidance, treatment, and disposal of anthropogenic wastes cover a range of knowledge encompassing the natural sciences, engineering, medicine, and law. This work presents some fundamental situations and problems conceming the disposal of toxic hazardous wastes which have been dealt with in several research projects. The individual chapters are related scientifically. Long-term, effective solutions to our waste problems can only be found when interrelationships and possible future developments are considered. Only the current status of this rapidly developing field can be discussed here. The individual chapters contain scientifically founded data and observations. Other aspects for which there are still controversial opinions and arguments are also discussed, which should stimulate further thought. Further developments and scientific advances can only be achieved by constantly challenging previous theories, and not through static observation and narrow-mindedness. The most extensive quantification possible of the problems related to disposal of hazardous wastes is an essential aim of our work. This not only involves calculating the volume of waste and available repository space, but also compiling data on the long-term effects and the safe, long-term isolation of anthropogenic wastes from the biosphere. A simple description of conditions and processes without using concrete data, which is still widespread, is rejected since it frequently leads to pure speculation. The scientific fundamentals and results presented in this work are of general validity for many questions concerning waste disposal. One example is the amount of waste produced annually in Germany, in which toxic, hazardous wastes play a major role. FoIlowing this train of thought, available data are used to show how limited the possibilities are for the long-term safe underground deposition of hazardous wastes with respect to the current quantities of waste. Of utmost importance is information on the 10ng-term effects of toxic wastes, as well as criteria which have to be considered with respect to the long-term safe deposition of hazardous waste. The natural chemical cycles and material transport in the various zones of the earth are the focus of interest here. They are the scientific basis for assessing every repository for anthropogenic wastes in geological systems. Therefore the significance of material transport and geochemical cycles is emphasized regarding all questions concerning the long-term safety of repositories on the earth's surface and in the lithosphere. Thus, our concept for the scientific evaluation of the long-term safety of underground repositories in geological systems differs from all other models presently under discussion in Germany. In this work, marine evaporites are discussed with respect to the underground deposition of hazardous wastes and the long-term safety of underground repositories in salt rocks. The isolation of hazardous materials from the biosphere can above all be influenced by fluid phases. Fluid phases can mobilize and transport hazardous materials through rocks in the biosphere. This is true, without exception, for all magmatic, sedimentary, and metamorphic rocks, and for marine evaporites, too! In Germany evaporites have commonly been considered to be completely impermeable with respect to fluid phases (solutions and gases). This erroneous view stems from a complete lack of knowledge or misestimation of the dynamic evolution of the composition of evaporite bodies. Unfortunately, this is still true today for parts of some state agencies which deal with repositories. However, all observations of evaporite bodies made over the last more than 100 years have clearly shown that under certain conditions fluid and gaseous components are mobile in evaporites as well. Solutions in marine evaporites have been the object of personal interest and scientific research of A.G. Herrmann for 40 years. The occurrence and formation of salt solutions in the various salt mining districts of Germany are presently being restudied and reevaluated on an extended scientific basis (e.g., v. BORSTEL 1992). A presentation of the current knowledge on salt solutions is beyond the scope of this publication. However, in the interest of continuing research a research project proposed by A.G. Herrmann (1987b) will be introduced here. The direct quantitative analysis of the chemical composition (quatemary and quinary systems) of small fluid inclusions in rocks of the salt deposits of Hessen and Niedersachsen are the primary focus of this project. Information important to fundamental research on the formation and alteration of salt rocks and on the long-term safety of underground repositories should be gained from these studies (e.g., HERRMANN & v. BORSTEL 1991). In addition to salt solutions, gases are also fluid components which occur in practically all marine evaporite deposits. Hence, both salt solutions and gases must be carefully considered when planning underground repositories in an evaporite body and evaluating their long-term safety. This publication contains an up-to-date overview of the gas occurrences in the marine evaporites of Central Europe. Despite previous studies, there is still a considerable deficit in scientific information regarding the distribution and formation of gases in the evaporites occurring in Germany. A detailed research program on the geochemical relationships involving the formation of evaporites and gases will draw attention to this situation. One aspect must be emphasized in the planning and construction of repositories for anthropogenic wastes: their long-term safety. This publication deals precisely with this subject, and in Part III of this work we will present the concept that we have developed. This concept is based on the fact that evaporite bodies are subject to a dynamic evolution and that the chemical and mineralogical composition provides important information on the effect of fluid phases on salt rocks. Previous works contain the testing of methods and presented initial results using the Gorleben salt dome as an example. However, we are just at the beginning of our research project on the long-term safety of underground repositories (e.g., HERRMANN & KNIPPING 1989, HERRMANN 1992). The information contained in this publication is based on years of experience in evaporite research and underground repositories for anthropogenic wastes. Examples are presented which can be applied to similar situations and problems in other countries. Waste disposal is not just a national problem, it has long become an international one for all types of anthropogenic wastes...

Description / Table of Contents: PREFACE The search for tin dates back to the earliest days of civilization. For about 40 years, world tin mining has oscillated at a level of 150,000-250,000 t Sn/year, with a mine output in 1989 of 210,000 t Sn (MCS 1990). This figure corresponds to a current annual value of about US$1.5 billion and places tin ninth on the metal market behind iron, gold, uranium, copper, zinc, silver, platinum and nickel. Tin deposits belong to the granite-related ore deposit spectrum which includes many metals vital to current and future technologies such as Cu, W, Mo, U, Nb, Ta, Ag, Au, Sb, Bi, As, Pb, Zn, REE, Be, Ga and Li. The granitic rocks associated with tin and tin-tungsten deposits have long been identified as a special group of granites, the so-called tin granites. These rocks provide a unique opportunity to study the magmatic and hydrothermal history of tin ore formation. Tin granites are more easily identifiable as parent rocks for tin (and tungsten) mineralization than is the case for other mineralized granitic rocks such as molybdenum and copper porphyries. The magmatic molybdenum and copper distribution patterns are more complex (control by sulfide solubilities), and commonly obliterated by fluid interaction. The relatively simple situation of tin granites provides therefore an invaluable opportunity to study some metallogenic aspects of magmatic-hydrothermal ore deposits in general. The present study attempts to develop a general metallogenic model for tin in identifying the essential or relevant processes in tin ore formation. The methodological principle is based, on an interplay between a background of some basic petrogenetic concepts and a number of specific local and regional data on tin deposits and tin provinces, with particular reference to those areas with which the author is most familiar with (Bolivia, SE Asia, Europe). This inductive approach condenses the many apparently specific complexities encountered in individual ore deposits to a few major processes of general importance. The inherent reductionism may have a personal bias which is probably inevitable in any simple and broad-scale picture ("Apr6s tout, la raison est bien I'esclave des passions"; Feyerabend 1979:210). The critical problem of the relevance of those factors chosen for our model can be judged by its degree of consistency and predictive capability for new and analogous cases...

Description / Table of Contents: INTRODUCTION The International Summer School of Theoretical Geodesy on Satellite Altimetry in Geodesy and Oceanography was held in Trieste (Italy) from May 25 to June 6, igg2. It was organized by Prof. R. Rummel of the Delft University of Technology and by Prof. F. Sansò of the Politecnico di Milano and was attended by 63 participants and 7 lecturers from 17 countries. The School was hosted by the International Centre of Theoretical Physics of Trieste. Satellite altimetry provides a lot of data that require more and more sophisticated models in order to be interpreted and exploited. One of the main problems related to the practical treatment of the data can be summarized as follows: oceanographers would like to ask geodesists to compute precise orbits and a precise geoid in order to put into evidence the Sea Surface Topography that can be interpreted as an oceanographic signal related to currents and to several physical parameters; on the other hand, geodesists would like to ask oceanographers to a-priori determine the Sea Surface Topography, in order to be able to extract from the altimeter data the geoid and the orbit errors to be used in the gravity field modelling. The solution to this dilemma can only be found in a cooperative frame. An integrated model to be used for a single-step treatment of altimetry is probably far to be defined, so at present geodesists and oceanographers must cooperate to obtain step-wise and iterative modelling of the gravity field and of the oceanographic phenomena. This is precisely the reason why the school on Satellite Altimetry was organized on an interdisciplinary basis...

Description / Table of Contents: INTRODUCTION "The geological history, as expressed by the stratigraphic column, is basically composed of cycles of sedimentation, stratification and magmatism which correlate with relative changes in sea level determined in turn by different types of crustal movements. The classical sequence of stages "transgression - inundation - differentiation - regression - emergence" is believed to reflect the deformation phases of a geotectonic cycle" (Wezel,1988: p.37). The concept of geotectonic cycle is fundamental in geology because it links tectonics with sedimentary processes. According to Wezel (1988) the geotectonic cycle is an expression of cyclic variations in the behavior of the crust; more precisely,it is a geodynamic response to the Earth's variations in the rate of rotation (Mörner,19869 Whyte,1977~ Carey,1976).Based on a global analysis of geotectonic data, synchronous episodes of intense global swelling, governed by cyclically ordered diastrophic processes, were identified (Wezel,1985;1988). The process leading to these swells was termed krikogenesis (Wezel, 1988).It basically consists of not steady, localized, migratory vertical movements linked to mantle diapirism and concentrated in single zones.The overlying crust adjusts itself to mantle motions induced by krikogenesis, with the formation of transient troughs and swells ('touche-de-piano' tectonics).This mechanism was individuated in several areas (Wezel,1988). The history of the Earth is described by six episodes that repeat in the same way in the course of geological time.Their duration progressively decreases:the first cycle has a duration of about 200 million years, the following,younger cycles lasted 150, 115, 65, A5 and 20 m.y. ...

Description / Table of Contents: INTRODUCTION The study is essentially empirical, since it portrays and appraises two different water management systems, and relates them to one another. Yet the analysis has also been made with definite research aims in mind. Its focus has been narrowed down to the environmental assessment of urban water management systems in arid and semi-arid regions, especially with an eye to deal with information problems in the Developing World. The study addresses a set of very critical issues of global concern, and, thus, delineates a crucial topic for international research. The fact that a wide range of critical issues usually complicates and aggravates the given problem setting provides the comparative analysis with a special practical incentive to explore the opportunities for joint strategies and comprehensive solutions. However, the complexities involved between water management and the environment and the relative lack of a joint theory in that field pose certain difficulties to such an undertaking. In order to fully appreciate the underlying purpose of the study and the scope of its implications, the various facets of the problem setting and the essential ingredients of the general line of approach have first to be unravelled and expounded at some length. Above all, it needs to be shown how these facets combine to produce the complex, burning issues which in turn seem to, both in theory and practice, require correspondingly intricate, strategic approaches for their solutions...

Description / Table of Contents: PREFACE Turbidity currents have been comprehensively studied in the past although much remains unknown about both their flow characteristics and resultant sedimentary deposits. Much of this uncertainty arises from the catastrophic nature of their formation which makes them difficult to study in the environment, and has resulted in the majority of studies being experimental or theoretical. Experiments have shown that reversals in the flow of density currents can be associated with the generation of internal solitary waves. This is in contrast to the belief held by many workers that the reversal of a turbidity current simply generates an identical flow travelling in the opposite direction. This book arose from the need for a detailed experimental study to examine the effects and to consider the consequences of density current reversals from a variety of obstructions to their flow. The first part of this book comprises a detailed review of literature covering the fluid dynamics and sedimentology relevant to the experimental study (chapter one). Chapter two presents the results from the comprehensive experimental programme which are discussed and compared with appropiate theoretical hypotheses. This permits the synthesis of a model for the general features of flows that result from the incidence of density currents upon obstructions to the flow. The application of this model to both modern and ancient turbidite systems is then discussed in chapter three. This book is suitable for earth scientists with an interest in the dynamics of turbidity currents. In addition, workers from other fields such as applied maths, meteorology and engineering who have an interest in density currents and bores in practical situations may find it useful...

Description / Table of Contents: Starting from a more general discussion of mechanisms controlling organic carbon deposition in marine environments and indicators useful for paleoenvironmental reconstructions, this study concentrates on detailed organic-geochemical and sedimentological investigations of late Cenozoic deep-sea sediments from (1) the Baffin Bay and the Labrador Sea (ODP-Leg 105), (2) the upwelling area off Northwest Africa (ODP-Leg 108), and (3) the Sea of Japan (ODP-Leg 128). Of major interest are shortas well as long-term changes in organic carbon accumulation during the past 20 m.y. As shown in the data from ODP-Legs 105, 108, and 128, sediments characterized by similar high organic carbon contents can be deposited in very different environments. Thus, simple total organic carbon data do not allow (i) to distinguish between different factors controlling organic carbon enrichment and (ii) to reconstruct the depositional history of these sediments. Data on both quantity and composition of the organic matter, however, provide important informations about the depositional environment and allow detailed reconstructions of the evolution of paleoclimate, paleoceanic circulation, and paleoproductivity in these areas. The results have significant implications for quantitative models of the mechanisms of climatic change. Furthermore, the data may also help to explain the formation of fossil black shales, i.e., hydrocarbon source rocks. (1) BAFFIN BAY AND LABRADOR SEA The Miocene to Quaternary sediments at Baffin Bay Site 645 are characterized by relatively high organic carbon contents, most of which range from 0.5% to almost 3%. This organic carbon enrichment was mainly controlled by increased supply .of terrigenous organic matter throughout the entire time interval. Two distinct maxima were identified: (i) a middle Miocene maximum, possibly reflecting a dense vegetation cover and fluvial sediment supply from adjacent islands, that decreased during late Miocene and early Pliocene time because of expansion of tundra vegetation due to global climatic deterioration; (ii) a late Pliocene-Pleistocene maximum possibly caused by glacial erosion and meltwater outwash. Significant amounts of marine organic carbon were accumulated in western Baffin Bay during middle Miocene time, indicating higher surface-water productivity (up to about 150 gC m -2 y-l) resulted from the inflow of cold and nutrient-rich Arctic water masses. The decrease in average surface-water productivity to values similar to those of the modern Baffin Bay was recorded during the late Miocene and was probably caused by the development of a seasonal sea-ice cover. At Labrador Sea Sites 646 and 647, organic carbon contents are low varying between 0.10% and 0.75%; the origin of most of the organic matter probably is marine. A major increase in organic carbon accumulation at Site 646 at about 7.2 Ma may indicate increased surface-water productivity triggered by the onset of the cold East-Greeniand Current system. Near 2.4 Ma, i.e., parallel to the development of major Northern Hemisphere Glaciation, accumulation rates of both organic carbon and biogenic opal decreased, suggesting a reduced surface-water productivity because of the development of dosed seasonal sea-ice cover in the northern Labrador Sea. The influence of varying sea-ice cover on surface-water productivity is also documented in the short-term glacial/interglacial fluctuations in organic carbon deposition at Sites 646 and 647. (2) UPWELLING AREAS OFF NORTHWEST AFRICA The upper Pliocene-Quaternary sediments at coastal-upwelling Site 658 are characterized by high organic carbon contents of 4%; the organic matter is a mixture of marine and terrigenous material with a dominance of the marine proportion. The upper Miocene to Quaternary pelagic sediments from close-by non-upwelling Sites 657 and 659, on the other hand, display low organic carbon values of less than 0.5%. Only in turbidites and slumps occasionally intercalated at the latter two sites, high organic carbon values of up to 3% occur. The high accumulation rates of marine organic carbon recorded at Site 658 reflect the high-productivity upwelling environment. Paleoproductivity varies between 100 and 400 gC m "2 y-1 during the past 3.6 m.y. and is clearly triggered by changes in global climate. However, there is no simple relationship between climate and organic carbon supply, i.e., it is not possble to postulate that productivity was generally higher at Site 658 during glacials than during interglacials or vice versa. Changes in the relative importance between upwelling activity (which was increased during glacial intervals) and fluvial nutrient supply (which was increased during interglacial intervals) may have caused the complex productivity record at Site 658. Most of the maximum productivity values, for example, were recorded at peak interglacials and at terminations indicating the importance of local fluvial nutrient supply at Site 658. Near 0.5 Ma, a long-term decrease in paleoproductivity occurs, probably indicating a decrease in fluvial nutrient supply and/or a change in nutrient "content of the upwelled waters. The former explanation is supported by the contemporaneous decrease in terrigenous organic carbon and (river-borne) clay supply suggesting an increase in long-term aridity in the Central Sahara. At Site 660, underneath the Northern Equatorial Divergence Zone, (marine) organic carbon values of up to 1.5% were recorded in upper Pliocene-Quaternary sediments. During the last 2.5 Ma, the glacial sediments are carbonate-lean and enriched in organic carbon probably caused by the influence of a carbonate-dissolving and oxygen-poor deep-water mass. (3) SEA OF JAPAN Based on preliminary results of organic-geochemical investigations, the Miocene to Quaternary sediments from ODP-Sites 798 (Oki Ridge) and 799 (Kita-Yamato-Trough) are characterized by high organic carbon contents of up to 6%; the organic matter is a mixture between marine and terrigenous material. Dominant mechanisms controlling (marine) organic carbon enrichments are probably high-surface water productivity and increased preservations rates under anoxic deep-water conditions. In the lower Pliocene sediments at Site 798 and the Miocene to Quaternary sediments at Site 799, rapid burial of organic carbon in turbidites may have occurred episodically. Distinct cycles of dark laminated sediments with organic carbon values of more than 5% and light bioturbated to homogenous sediments with lower organic carbon contents indicate dramatic shortterm paleoceanographic variations. More detailed records of accumulation rates of marine and terrigenous organic carbon and biogenic opal as well as a detailed oxygen isotope stratigraphy are required for a more precise reconstruction of the environmental history of the Sea of Japan through late Cenozoic time.

Description / Table of Contents: PREFACE There are problems, when applying statistical inference to the analysis of data, which are not readily solved by the inferential methods of the standard statistical techniques. One example is the computation of confidence intervals for variance components or for functions of variance components. Another example is the statistical inference on the random parameters of the mixed model of the standard statistical techniques or the inference on parameters of nonlinear models. Bayesian analysis gives answers to these problems. The advantage of the Bayesian approach is its conceptual simplicity. It is based on Bayes' theorem only. In general, the posterior distribution for the unknown parameters following from Bayes' theorem can be readily written down. The statistical inference is then solved by this distribution. Often the posterior distribution cannot be integrated analytically. However, this is not a serious drawback, since efficient methods exist for the numerical integration. The results of the standard statistical techniques concerning the linear models can also be derived by the Bayesian inference. These techniques may therefore be considered as special cases of the Bayesian analysis. Thus, the Bayesian inference is more general. Linear models and models closely related to linear models will be assumed for the analysis of the observations which contain the information on the unknown parameters of the models. The models, which are presented, are well suited for a variety of tasks connected with the evaluation of data. When applications are considered, data will be analyzed which have been taken to solve problems of surveying engineering. This does not mean, of course, that the applications are restricted to geodesy. Bayesian statistics may be applied wherever data need to be evaluated, for instance in geophysics. After an introduction the basic concepts of Bayesian inference are presented in Chapter 2. Bayes' theorem is derived and the introduction of prior information for the unknown parameters is discussed. Estimates of the unknown parameters, of confidence regions and the testing of hypotheses are derived and the predictive analysis is treated. Finally techniques for the numerical integration of the integrals are presented which have to be solved for the statistical inference. Chapter 3 introduces models to analyze data for the statistical inference on the unknown parameters and deals with special applications. First the linear model is presented with noninformative and informative priors for the unknown parameters. The agreement with the results of the standard statistical techniques is pointed out. Furthermore, the prediction of data and the linear model not of full rank are discussed. A method for identifying a model is presented and a less sensitive hypothesis test for the standard statistical techniques is derived. The Kalman-Bucy filter for estimating unknown parameters of linear dynamic systems is also given. Nonlinear models are introduced and as an example the fit of a straight line is treated. The resulting posterior distribution for the unknown parameters is analytically not tractable, so that numerical methods have to be applied for the statistical inference. In contrast to the standard statistical techniques, the Bayesian analysis for mixed models does not discriminate between fixed and random parameters, it distinguishes the parameters according to their prior information. The Bayesian inference on the parameters, which correspond to the random parameters of the mixed model of the standard statistical techniques, is therefore readily accomplished. Noninformafive priors of the variance and covariance components are derived for the linear model with unknown variance and covariance components. In addition, informative priors are given. Again, the resulting posterior distributions are analytically not tractable, so that numerical methods have to be applied for the Bayesian inference. The problem of classification is solved by applying the Bayes rule, i.e. the posterior expected loss computed by the predictive density function of the observations is minimized. Robust estimates of the standard statistical techniques, which are maximum likelihood type estimates, the so-called M-estimates, may also be derived by Bayesian inference. But this approach not only leads to the M-estimates, but also any inferential problem for the parameters may be solved. Finally, the reconstruction of digital images is discussed. Numerous methods exist for the analysis of digital images. The Bayesian approach unites some of them and gives them a common theoretical foundation. This is due to the flexibility by which prior information for the unknown parameters can be introduced. It is assumed that the reader has a basic knowledge of the standard statistical techniques. Whenever these results are needed, for easy reference the appropriate page of the book "Parameter Estimation and Hypothesis Testing in Linear Models" by the author (Koch 1988a) is cited. Of course, any other textbook on statistical techniques can serve this purpose. To easily recognize the end of an example or a proof, it is marked by a A or a t~, respectively. I want to thank all colleagues and students who contributed to this book. In particular, I thank Mr. Andreas Busch, Dipl.-Ing., for his suggestions. I also convey my thanks to Mrs. Karin Bauer, who prepared the copy of the book. The assistance of the Springer- Verlag in checking the English text is gratefully acknowledged. The responsibility of errors, of course, remains with the author.