ALBERT

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

Description / Table of Contents: Subsurface aspects of the ore-forming process can be described in terms of standard chemical transport parameters such as T-P gradients, mineral solubilities, solvent chemistry and volume, diffusion parameters and energy flow. These necessary factors are rather easily assessed by geochemical, isotopic and structural studies. If deposition is in the surface environment, a complex array of factors will determine the success of the natural concentration process and the chances of preservation of a deposit. Basically, most large-scale ore-forming processes involve large fluid volumes and energy sources. Many environments where these requirements are met, the modern ocean ridge and the subduction environment, are still not well understood. The need for remote-sensing techniques in the submarine environment is stressed.

Description / Table of Contents: A computer model is described to compute the amount of ice accretion on an object under a variety of initial conditions. Numerical techniques are best applied to these problems because of time dependent effects governing the amount of ice collected and also the variety of initial conditions that can lead to ice accumulation. The helicopter rotor icing problem adds an additional complexity since the velocity along the rotor blade varies over a wide range strongly affecting the amounts of ice collected at different blade positions. The physics of ice accretion is reviewed and the accounting for time-dependence in the computer model is described. Some model results are presented and indicate the dependence of ice accretion on velocity, droplet sizes, cloud liquid water content, and temperature for a cylindrical object of constant size.

Description / Table of Contents: The stress-density relaionships of snow-water mixtures were investigated and are shown as functions of water content, initial snow density, initial snow-water mixture density and rate of deformation. An increase in water content in snow at a particular density or a decrease in the rate of deformation (or strain rate) decreases the stress, but apparently not the specific energy required to reach a specific mixture density.

Description / Table of Contents: Sea ice ridging statistics obtained from a series of laser surface roughnessprofiles are examined. Each set of profiles consists of six 200-km-long flight tracks oriented approximately perpendicular to the coastline of the Chukchi and Beaufort Seas. The landward ends of the profiles were located at Point Lay, Wainwright, Barrow, Lonely, Cross Island and Barter Island. The flights were made in February, April, August, and December 1976, and one additional profile was obtained north of Cross Island during March 1978. It was found that although there is a systematic variation in mean ridge height (h) with season (with the highest values occurring in late winter), there is no systematic spatial variation in h at a given time. The number of ridges/km (micron) is also high during the late winter, with the highest values occurring in the Barter and Cross Island profiles . In most profiles, the ice 20 to 60 km from the coast is more highly deformed (higher micron values) than the ice either nearer the coast or farther seaward. The Wadhams model for the distribution of ridge heights gives better agreement with observed values in the higher ridge categories than does the Hibler model. Estimates of the spatial recurrence frequency of large pressure ridges are made by using the Wadhams model and also by using an extreme value approach. In the latter, the distribution of the lagest ridges per 20 km of laser track was found to be essentially normal

Description / Table of Contents: Nondestructive repetitive plate bearing (RPB) tests were conducted on various test sections in state highways in Maine during 13-15 April 1976. The RPB test consists of making resilient surface deflection measurements during repetitive loadings at various radii from the load plate. The pavement system stiffness was calculated and the resilient modulus values for the various pavement layers were determined with the Chevron computer program for a layered elastic system. A thawed analysis using nondimensional deflection curves for the various sections provided a guide to the susceptibility of the pavement systems to surface failure and pothole development. Some comparisons between stabilized and nonstabilized aggregate and soil were made with calculated stiffness values. The moduli of the various materials were also compared. The residual surface deflections during testing for several pavement systems indicated a linear logarithmic relationship with number of load applications. A relationship between the modulus of the asphalt cement concrete pavement and pavement temperature was developed for the limited temperature range during the testing.

Description / Table of Contents: Tests were conducted to assess the extent of surface degradation resulting from the application of non-chloride deicing chemicals on three types of airfield pavements. The chemicals tested were proprietary mixtures of urea, formamide, and ethylene glycol; sodium chloride, distilled water, and dry specimens were used as controls and for comparison. Pavements included new and old specimens of open-graded asphaltic concrete and old specimens of dense-graded asphaltic concrete. Portland cement concrete specimens used were new and old, with and without air-entrainment. New and old tar rubber concrete specimens were also tested. Samples were subjected to up to 60 freeze-thaw cycles with deicing chemicals flooding their upper surface. Each specimen was rated on a scale of 0-5 after every five freeze-thaw cycles. All PCC specimens showed some surface degradation, whereas the dense- and open-graded asphaltic concretes were largely unaffected.

Description / Table of Contents: This report discusses the relationship between an architect and a behavioral scientist. Some of the discussion applies to this cooperative work for design of buildings. The bulk, however, relates to the cooperation of architect and behavioral scientist while conducting research. Examples from collaborative research at Alaskan military installations are cited which demonstrate the roles and contributions of the two disciplines.

Description / Table of Contents: Results of measurements of salinity, grain size, substructure dimensions and crystal fabrics of the undeformed 2.15-m-thick annual sea ice sheet near Narwhal Island, Alaska, are presented. A notable observation was the formation of a dominant c-axis horizontal structure in all ice below 14 cm, including transformation to a pronounced east-west alignment of the c-axes by a depth of 66 cm. This study confirms earlier reports of the occurrence of very strong horizontal c-axis alignments in arctic fast ice.

Description / Table of Contents: A theory for ice forces acting on inclined wedges has been developed, thus making it possible to predict the magnitude of the intermittent ice forces from knowledge of the physical parameters of the system. The theory has been verified by model tests with artificial and natural ice.

Description / Table of Contents: The spectral reflectance of natural snow in the range of 0.20- to about 0.40-micrometers wavelengths was studied in the laboratory using both continuous spectral scanning and fixed bandpass measurements. White barium sulfate pressed powder was used as a standard for comparison. The reflectance of fresh snow was found to be very high (usually nearly 100%) and only weakly wavelength dependent from 0.24 micrometers to the visible range. In the 0.20- to 0.24-micrometers portion of the spectrum, the reflectance was found to be quite erratic. Possible reasons for the irregularities in reflectance measurements are discussed.

Description / Table of Contents: The report deals with the cutting of rock and similar materials by parallel motion tools. It examines cutting forces and energy requirements, taking into consideration tool geometry, wear, operating conditions, and material properties. After an introductory discussion of terminology, some general principles are outlined, and relevant theoretical ideas on metal cutting and rock cutting are reviewed. The next section, which is the heart of the report, reviews experimental data on the magnitudes and directions of cutting forces. There is a graphical compilation of data, including some from obscure or unpublished sources. The variables covered include chipping depth, rake angle, relief angle, side rake, base angle, tool width, tool compliance, tool speed, tool wear, tool interactions, and material properties. The second major part of the report treats the energetics of cutting. It begins with a short discussion of relevant principles, and continues with a compilation and review of experimental data, covering the same independent variables as the force section. The report ends with a concise summary of general behavior for parallel motion tools.

Description / Table of Contents: Cold weather limits the successful application of built-up roofing, but often a roof installation must be completed late in the fall or in the winter. The loose-laid protected membrane roof with a synthetic sheet membrane can be installed in the middle of the winter with complete reliability. A synthetic membrane is traditionally more expensive than built-up roofing (rising crude oil prices, however, have reversed this condition), but it has two special features besides its suitability for winter installation: it can be placed on a damp deck, if necessary, and, being losse-laid, it does not split because of deck movement. This report documents information on the installation of two roofs in Anchorage, Alaska, during January and February 1972, including a discussion of the necessary snow removal from the bare deck and the use of portable shelters for preparing the lap joints between sheets during very cold weather. The winter installation caused no special construction problems and the advantages of the synthetic membrane make it an attractive alternative to built-up roofing. The cost of loose-laid protected membrane roofs in Alaska was, in 1972, nearly $300 per square ($28/sq.m), including insulation. Prices are rising as labor costs rise and as more insulation is specified.

Description / Table of Contents: Abstract: Models originally developed to describe the arching and the movement of granular materials through hoppers or chutes are applied to the arching and drift of pack ice in straits and gulfs having lengths of 50 to 500 km. Verification of the usefulness of the models is attempted by making comparisons with ice deformation patterns as observed via satellite imagery in the Bering Strait region and in Amundsen Gulf. The results are encouraging in that there is good correspondence between observed arching and lead patterns and those predicted by theory. In addition, values determined via the model for the angle of internal friction (≈ 30° to 35°) and the cohesive strength per unit thickness (≈ 2000 N/m) are similar to values obtained by other approaches. It is estimated that if the wind velocity parallel to the Bering Strait exceeds ≈ 6 m/s, there will be ice flow through the strait.

Description / Table of Contents: A brief discussion is given of the ways an icebreaker breaks ice. Since the icebreaking process is so complex, the solution of a mathematical model does not appear to be feasible. As an alternative, it is suggested that physical models be used to design icebreakers. The appropriate scaling laws for physical models are developed and their practical limitation discussed.

Description / Table of Contents: A literature search was made for information on the accretion of ice on ocean structures and on methods for control. The bulk of the reports were in Russian, with some additional Japanese, British, American, Canadian, and Icelandic sources. Analysis of icing reports indicated that sea spray is the most important cause of ship icing, with lesser amounts due to freezing rain, snow, and fog. Icing is a potential danger whenever air temperatures are below the freezing point of water and the sea temperature is 6 C or lower. Theoretical work on the ice accretion process is discussed, and a method is suggested, based on Russian experiments, for calculating the sea spray accumulation rate for cylindrical and flat surfaces as a function of water source temperature, air temperature, and wind speed. Other factors that influence icing severity are ship size and configuration, angle between ship course and water heading, and ship speed. Icing in the north temperate latitudes generally occurs in the rear of barometric depressions. Maps showing limits of various degrees of icing severity are included. Atmospheric icing measurements on tall land-based structures are presented, and potential maximum accumulations estimated. Control measures are discussed, though no completely effective method is available. Mechanical (impaction) methods are the most common, but experiments have been conducted on heated, icephobic, and deformable surfaces, and with freezing point depressants. No device for the unequivocal measurement of ice accumulation is available, though some experimental methods are suitable for controlled testing; it is recommended that a device be developed.

Description / Table of Contents: A laboratory experimental study was conducted on a scale model of an annular flow ice-water heat sink to be used to store the waste heat produced in a hardened defense installation operating in an isolated mode. The study ex­amined: 1) scaling relationships for predicting the performance of prototype units using data from scale models, 2) the accuracy of a computer prediction technique developed during an earlier study, 3) the heat transfer phenom­enon at the ice-water interface, and 4) some practical aspects related to the operation of a prototype installation. The scaling relationships and the computer program were found to be sufficiently accurate for use in developing a proto­type sink design. During operation the scale model sink provided an almost constant low temperature source of coolant water for approximately one-half its useful life and thereafter behaved like an ordinary stored water reservoir type heat sink. No significant operational problems were discovered.

Description / Table of Contents: Two performance indicators, effectiveness and thermal efficiency, are defined and used to evaluate the year-round performance of three protected membrane roofs in Alaska and New Hampshire. Effectiveness is a measure of the deviations of ceiling temperatures from a yearly average, with large diviations indicating erratic performance in the roofing-insulation system and small departures indicating a thermally stable system. Thermal efficiency, the ratio of calculated heat loss to measured heat loss, is affected by climatic conditions such as rain, snow, solar radiation and wind. Thermal efficiency values of 100% or greater are possible since the calculated heat loss is based only on the inside and outside air temperature differences and the thermal properties of the roof components. Results of the year-round evaluation indicate that the three protected membrane roofs generally have high values of both effectiveness and thermal efficiency.

Description / Table of Contents: This report presents experimental results on the conditions of initiation of an ice jam by a simple surface obstruction, on the equilibrium thickness of an ice jam formed by accumulation and submergence of ice floes, and on the compression strength of floating, fragmented ice cover. In the study on ice jam initiation, it was found that the minimum concentration of floes in the opening of the obstruction at which a jam occurs is nearly independent of the ratio of width of constricted passage to channel width, and is proportional to a negative power of the ratio of floe length to width of constricted passage. From energy analysis of floe submergence, a relationship relating the thickness of a jam formed by accumulation and submergence of floes to the approach flow characteristics was derived and found to fit satisfactorily the experimental data. In experiments on compression strength of floating, fragmented ice cover it was found that the compressive strength is inversely proportional to compression velocity and independent of cover length.

Description / Table of Contents: Three surface elevation and ice thickness profiles obtained during the 1972 Arctic Ice Dynamics Joint Experiment on a multiyear ice floe were analyzed to obtain relationships between surface elevation, thickness and physical properties of the ice. It was found that for ice freeboards from 0.10 m to 1.05 m above sea level a linear relationship between ice density and freeboard could be postulated. The equation for the regression line is: Ice density = -194f' + 974 kg/cu m where f' is the ice freeboard plus snow depth in ice equivalent at the point in question. This statistical relationship is consistent with observed physical properties, which indicate that as the ice freeboard increases, ice salinity decreases and the higher freeboard or thicker ice therefore decreases in density. Using this variable density with freeboard relationship, a model was constructed to predict ice thickness, given ice freeboard and snow depth alone. This prediction is desirable, since snow depth and freeboard are relatively easy to obtain, whereas ice thickness can usually be obtained only by drilling through the ice. The model was compared with two other models. It was found that the variable density prediction model gave the best approximation to observed ice thickness, with a standard error between the measured and predicted value of about 0.4 m, compared with errors from 50 to 100% higher for the other two models.

Description / Table of Contents: The effects of snow temperature and initial density on the stress vs density and stress vs deformation relationships were investigated for shallow compacted snow in the density range of 0.28 to 0.76 g/cu m, for stress range of 0.5 to 72 bars and a temperature range of -1 to -34 C at a deformation rate of 40 cm/s. A decrease in temperature increases the resistance to stress, the effect increasing with applied stress. For any stress, an increase in the initial density results in an increase in the resulting density, the effect decreasing with an increase in stress. The approximate yield envelopes, which define the stress required to initiate any deformation of snow of a particular density and temperature, were determined. Rapid compaction of snow results in extensive recrystallization, significantly different from that of naturally compacted snow. At a stress of 72 bars, transformation to ice occurs only at temperature above -10C.

Description / Table of Contents: Griffith, and later Babel, have previously developed a tensile fracture criterion for a two-dimensional state of stress. This theory is extended to the compression-compression region. From this theory the angle of fracture is developed. The theory is extended conceptually to three dimensions. Triaxial test data by Haynes for snow-ice are shown in this three-dimensional fracture theory. The test data are slightly less than those predicted when the void in the snow-ice is spherical.

Description / Table of Contents: This report covers a series of cantilever beam tests designed to determined the efficacy of adding reinforcement to an ice cover. Tests were run using 1-in.-diam tree branches, 3/16-in.-diam wire rope and 9/16-in. half-round wood dowels as reinforcement for both seawater and freshwater ice. The results show a definite advantage derived from using reinforcement, even when poorly placed. The results also show that reinforced ice carries a load even after it cracks. Thus, after the initial cracks there is time to remove people and equipment before final breakthrough. One must bear in mind, however, that reinforcement has disadvantages. The darker reinforcement absorbs solar radiation and thereby causes earlier weakening of the ice cover. Also, in many cases the time and effort required to place reinforcement may exceed those required to achieve equal strength by additional thickening of the ice sheet. This study has shown that understanding of the failure mechanism of ice under repetitive loading is poor and that future studies should be performed on this problem. Also, this study covered only cantilever beams. The actual field problem is strengthening a three-dimensional sheet. Hence, distribution and orientation of the reinforcement should be addressed in future studies.

Description / Table of Contents: During the past decade a number of methods for measuring the amount of unfrozen water in partially frozen ground have emerged. Means of quickly and simply predicting unfrozen water contents in clay have become increasingly important with the growth of interest in encapsulating clay soils compacted at low water contents to serve as base courses for roads. Unfortunately the measurements require sophisticated equipment and, in most instances, specially trained operators. In an effort to simplify the task of obtaining water-ice phase composition data, methods of calculating phase composition curves from other, simpler measurements on soils have been sought. The paper presents a method of deriving the measurement of unfrozen water contents at various temperatures from liquid limit determinations.

Description / Table of Contents: This volume of Reviews in Mineralogy attempts to synthesize our present understanding of certain aspects of the mineralogy and chemistry of the rock-forming carbonates. Hopefully, it reflects the presently more active areas of research. This review follows, by ten years, a major assessment of (sedimentary) carbonate minerals by Lippmann (1973). There is only minor overlap of subject material, and I hope that this difference reflects fairly how this field has developed. In some respects carbonates are unique, for they are one of the few mineral groups providing an abundant record of biological, physical, and chemical processes throughout much of geologic time. Because of their relative importance in sedimentary rocks, lowtemperature examples are given more emphasis here. Moreover, the obvious correlation with energy resources has been a significant factor contributing to the current resurgence of interest in this area. However, the broader interest in carbonates is also a reflection of their widespread occurrence in vastly different geologic environments, including metamorphic and igneous settings, as well as an appreciation of their role in both atmospheric and oceanic chemistry, both past and present. In this volume, some of the papers are general (i.e., those addressing crystal chemistry and phase relations), and they provide overviews of a fundamental nature and are of interest to many. Others are more specialized in coverage and generally reflect the different approaches used in carbonate geochemistry. The final chapter introduces transmission electron microscopy, a relatively new and powerful technique for mineralogical research that has great potential in carbonate research. Owing to the short time interval between the completion of manuscripts and publication, much of the newer material in this volume is still "fresh." The various reviewers, all gratefully acknowledged, were expeditious in their efforts. A hurried schedule, however, allows for unnoticed errors to persist; these should be brought to my attention.