ALBERT

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.

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: A new experimental method for measuring the soil-water diffusivity of frozen soil under isothermal conditions is introduced. The theoretical justification of the method is presented and the feasibility of the method is demonstrated by experiments conducted using marine-deposited clay. The measured values of the soil-water diffusivity are found comparable to reported experimental data.

Description / Table of Contents: An analysis of ice fracture that incorporates dislocation mechanics and linear elastic fracture mechanics is discussed. The derived relationships predict a brittle to ductile transition in polycrystalline ice under tension with a Hall-Petch type dependence of brittle fracture strength on grain size. A uniaxial tensile testing technique, including specimen preparation and loading system design was developed and employed to verify the model. The tensile strength of ice in purely brittle fracture was found to vary with the square root of the reciprocal of grain size, supporting the relationship that the theory suggests. The inherent strength of the ice lattice and the Hall-Petch slope are evaluated and findings discussed in relation to previous results. Monitoring of acoustic emissions was incorporated in the tests, providing insights into the process of microfracture during ice deformation.

Description / Table of Contents: Investigations of ground radar performance over thawed and seasonally frozen silts, and sands and gravels containing artificial and natural reflectors were carried out in Alaska. The radar emitted 5-10 ns pulses, the center frequency of which was approximately 150 MHz. The artificial reflectors were metal sheets and discs and the natural reflectors were the groundwater table and interfaces between frozen and thawed material. The water table was profiled at three sites where the subsurface material was coarse-grained alluvium. Dielectric constants of 16 to 18 were measured for the thawed silts, 6 to 7 for the frozen silts and 3 to 9 for the sands and gravels. Signal penetration in the thawed high moisture content silts may be achieved only by use of a lower frequency radar, whereas in the sands and gravels greater depths may be detected with more sophisticated signal processing.

Description / Table of Contents: A sea ice model was applied to the East Greenland Sea to examine a 60-day ice advance period beginning 1 October 1979. This investigation compares model results using driving geostrophic wind fields derived from three sources. Winds calculated from sea-level pressures obtained from the National Weather Service's operational analysis system resulted in strong velocities concentrated in a narrow band adjacent to the Greenland coast, with moderate velocities elsewhere. The model showed excessive ice transport and thickness build-ups in the coastal region. The extreme pressure gradient parallel to the coast resulted partially from a pressure reduction procedure that was applied to the terrain-following sigma coordinate system to obtain sea-level pressures. Additional sea-level pressure fields were obtained from an independent optimal interpolation analysis that merged FGGE buoys drifting in the Arctic basin with high latitude land stations and from manual digitization of the NWS hand-analyzed Northern Hemisphere Surface Charts. Modeling results using winds from both of these fields agreed favorably.

Description / Table of Contents: Ice action on two cylindrical and conical structures, located side by side, was investigated in a small-scale experimental study to determine the interference on the ice forces generated during ice-structure interaction. The proximity of the two structures changes the mode of ice failure, the magnitude and direction of ice forces on the individual structure, and the dominant frequency of ice force variations. Interference effects were determined by comparing the experimental results of tests at different structure spacings.

Description / Table of Contents: Ice accreted on high-speed rotors operating in supercooled fog can be thrown off by centrifugal force, creating severe unbalance and dangerous projectiles. A simple force balance analysis indicates that the strength of accreted ice and its adhesive strength can be obtained by measuring the thickness of the accretion, the location of the separation, the rotor speed, and the density. Such an analysis was applied to field and laboratory observations of self-shedding events. The results agree reasonably well with other observations.

Description / Table of Contents: Ice sheets are formed and retained in several ways in nature, and an understanding of these factors is needed before most structures can be successfully applied. Many ice sheet retention structures float and are somewhat flexible; others are fixed and rigid or semirigid. An example of the former is the Lake Erie ice boom and of the latter, the Montreal ice control structure. Ice sheet retention technology is changing. The use of timber cribs is gradually but not totally giving way to sheet steel pilings and concrete cells. New structures and applications are being tried but with caution. Ice-hydraulic analyses are helpful in predicting the effects of structures and channel modifications on ice cover formation and retention. Often, varying the flow rate in a particular system at the proper time will make the difference between whether a structure will or will not retain ice. The structure, however, invariably adds reliability to the sheet ice retention process.

Description / Table of Contents: A literature review indicated that the effects or permafrost on streambank erodibility and stability are not yet understood because systematic and quantitative measurements are seriously lacking. Consequently, general controversy exists as to whether perennially frozen ground inhibits lateral erosion and bankline recession, or whether it increases bank recession rates. Perennially frozen streambanks erode because of modification of the bank's thermal regime by exposure to air and water, and because of various erosional processes. Factors that determine rates and locations of erosion include physical, thermal and structural properties of bank sediments, stream hydraulics and climate. Thermal and physical modification of streambanks may also induce accelerated erosion within permafrost terrain removed from the immediate river environment. Bankline or bluffline recession rates are highly variable, ranging from less than 1 m/year to over 30 m/year and, exceptionally, to over 60 m/year. Long-term observations of the physical and thermal erosion processes and systematic ground surveys and measurements of bankline-bluffline recession rates are needed.

Description / Table of Contents: A mathematical model is described that is used to determine the maximum ice conveyance capacity of a river channel. Based upon this model, computer programs were developed that enable the ice discharge to be calculated for steady-state flow conditions. For rivers that have uniform flow, the maximum ice-conveying capacity can be described with a simple function expressed in terms of the size of the ice fragments, channel geometry, and the flow of water in the river. For nonuniform flows, the computer program determines the elevation profile of the surface layer in addition to other flow characteristics, such as the velocity and surface concentration of the ice fragments. The location along this surface profile where the ice conveyance capacity becomes less than the upstream supply is determined and is considered to be the position where a surface ice jam or ice bridge will be formed.

Description / Table of Contents: Ice forces on a bridge pier in the Ottauquechee River, in Quechee, Vermont, were measured by installing fourpanels-each capable of measuring forces in the normal and tangential direction - on both sides of a vertical V-shaped pier nose. The measured forces are presented for a short period during an ice run. After the ice run, the thickness and sizes of the ice floes were measured and the compressive strength of the ice was determined in the laboratory from the ice samples collected along the river banks. The water level measurements made at several locations along theriver are also presented for the period of the ice run.

Description / Table of Contents: A thermodynamic model has been developed that for the first time describes the entire creep process, including primary, secondary, and tertiary creep, and failure for both constant stress (CSR) tests (σ= const.) and constant strain rate (CSR) tests (ϵ = const.), in the form of a unified constitutive equation and unified failure criteria. Deformation and failure areconsidered as a single thermoactivated process in which the dominant role belongs to the change of entropy. Failure occurs when the entropy change is zero. At that moment the strain rates in CS tests reach the minima and stress in CSR tests reaches the maximum (peak) values. Families of creep (ϵ vs τ) and stress-strain (σ vs ϵ) curves, obtained from uni-axial compression CS and CSR tests of frozen soil, respectively (both presented in dimensionless coordinates), are plotted as straight lines and are superposed, confirming the unity of the deformation and failure process and the validity of the model. A method is developed for determining the parameters of the model, so that creep deformation and the stress-strain relationship of ductile materials such as soils can be predicted based upon information obtained from either type of test.

Description / Table of Contents: During the austral summers of 1976-77 and 1978-79, several ice cores were taken from the McMurdo Ice Shelf brine zone to investigate its thermal, physical and chemical properties. This brine zone consists of a series of super-imposed brine layers (waves) that originate at the seaward edge of the ice shelf and migrate at various rates, depending upon their age and position in the ice shelf. The brine in these layers becomes increasingly concentrated as the waves migrate inland through the permeable ice shelf firn. Chemical analyses of brine samples from the youngest (uppermost) brine wave show that it contains sea salts in normal seawater proportions. Further inland, deeper and older brine layers, though highly saline (S 〉 200 ‰), are severely depleted in SO2-4 with the SO2-4/Na+ ratio being an order of magnitude less than that of normal seawater. Analyses of Na+, K+, Ca2+, Mg2+, SO2-4 and CI-, together with solubility and temperature considerations, show that the sulfate depletion is due to selective precipitation of mirabilite, Na2SO4*10H2O. The location of the inland boundary of brine penetration is closely related to the depth at which the brine en-counters the firn/ice transition. However, a small but measurable migration of brine is still occurring in otherwise impermeable ice; this is attributed to eutectic dissolution of the ice by concentrated brine as it moves into deeper and warmer parts of the McMurdo Ice Shelf.

Description / Table of Contents: This report presents the results of dynamic ice-structure interaction model tests conducted at the CRREL Ice Engineering Facility. A flexible, single-pile, bottom-founded offshore structure was simulated by a test pile with about a one-to-ten scale ratio. Urea (instead of sodium chloride) was used as dopant to scale down the ice properties, resulting in good model ice properties. Six ice fields were frozen and 18 tests carried out. In all cases distinctive dynamic ice structure interaction vibrations appeared, from which abundant data were collected. In tests with linear ice velocity sweep, sawtooth-shaped ice force fluctuations occurred first. With increasing velocity the natural modes of the test pile were excited, and shifts from one mode to another occurred. The maximum ice force values appeared mostly with low loading rates, but high forces appeared random'y at high ice velocities. As a general trend, ice force maximums, averages and standard deviations decreased with increasing ice velocities. The aspect ratio effect of the ice force in continuous crushing follows the same dependence as in static loadings. The frequency of observed ice forces is strongly dominated by the natural modes of the structure. Dynamically unstable natural modes tend to make the developing ice force frequencies the same as the natural frequencies. Otherwise the resulting frequency depends directly on structural stiffness and ice velocity and inversely on the ice force range. During vibrations the displacement rates of the structure overcome the velocity of ice, making low loading rates and hence high ice forces possible. During crushing, ice induces both positive and negative damping.

Description / Table of Contents: A numerical model of rime ice accretion on an arbitrary two-dimensional airfoil is presented. The physics of the model are described and results are presented that demonstrate, by comparison with other theoretical data and experimental data, that the model predictions are believable. Results are also presented that illustrate the capability of the model to handle time-dependent rime ice accretion, taking into account the feedback between the ice accretion and the airflow and droplet trajectory fields.

Description / Table of Contents: Measurements and analysis of seasonal ice growth and decay on Post Pond, New Hampshire, for the period 1973-1982 are presented. Observations included ice thickness measurements, examination of the various ice types contributing to the ice cover, and measurements of meteorological parameters for correlation with and modeling of the ice growth process. The overall nature of ice growth and decay (ice loss) on the Post Pond has been ascertained, the seasonal variability in the timing of freeze-up and ice-out and the duration of the ice cover have been determined, and the relationship of ice growth to freezing-degree-day (deg C) records evaluated on the basis of a Stefan conduction equation modified to deal with ice sheets covered with or free of snow. Ice growth occurs predominantly by the direct freezing of lake water, but snow ice may compose as much as 50% of the ice cover in winters with higher than average snowfall. Freeze-up leading to the establishment of a stable ice cover occurs during the 4-week period from the end of November to the end of December. Maximum seasonal ice thicknesses were from 45 to 67 cm and are generally attained during the first two weeks of March; ice-out, marking the final disappearance of ice from Post Pond, usually occurs by the third week of April. The overall rate of the ice loss is three to four times that of ice growth, and is dominated initially by melting from the top. As much as 50% of the ice may be lost in this way before the onset of any bottom melting. Final dissipation of the ice cover is usually expedited by candling resulting from preferential melting and disintegration of the ice at crystal boundaries.

Description / Table of Contents: The probability density function of the gouge depths into the sediment is represented by a simple negative exponential over four decades of gouge frequency. The exceedance probability function is, therefore, e to the -lambda d, where d is the gouge depth in meters and lambda is a constant. The value of lambda shows a general decrease with increasing water depth, from 9/m in shallow water to less than 3/m in water 30 to 35 m deep. The deepest gouge observed was 3.6 m, from a sample of 20,354 gouges that have depths greater than or equal to 0.2 m. The dominant gouge orientations are usually unimodal and reasonably clustered, with the most frequent alignments roughly parallel to the general trend to the coastline. The value of N(bar) sub 1, the mean number of gouges (deeper than 0.2 m) per kilometer measured normal to the trend of the gouges, varies from 0.2 for protected lagoons to 80 in water between 20 and 38 m deep in unprotected offshore regions. The distribution of the spacings between gouges as measured along a sampling track is a negative exponential. The form of the frequency distribution of N sub 1 varies with water depth and is exponential for lagoons and shallow offshore areas, previously skewed for 10 to 20 m depths off the barrier islands, and near-normal for deeper water. As a Poisson distribution gives a reasonable fit to the N sub 1 distributions for all water depths, it is suggested that gouging can be taken as approximating a Poisson process in both space and time. The distributions of the largest values per kilometer of gouge depths, gouge widths, and the heights of the lateral embankment of sediments plowed from the gouges are also investigated.

Description / Table of Contents: Small-scale laboratory experiments were conducted on model bridge piers in the CRREL test basin. The experiments were performed by pushing model ice sheets against structures and monitoring the ice forces during the ice/structure interaction. The parameters, varied during the test program, were the geometry of the bridge piers and the velocity, thickness, and flexural strength of the ice. The results are presented in the form of ice forces on sloping and vertical structures with different geometries. During ice action on sloping structures, a phenomenon of transition of failure mode from bending to crushing was observed as the ice velocity was steadily increased.