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Note: TABLE OF CONTENTS FOREWORD 1 INTRODUCTION AND SURVEY OF RADIOANALYSIS 1.1 Introduction 1.2 Principles of radioanalysis 1.2.1 General 1.2.2 Glossary of basic terms and concepts 1.3 Scope and contents References 2 SAMPLING AND PRECONCENTRATION 2.1 Survey and principles 2.1.1 Sampling 2.1.2 From sample to aliquot 2.1.2 .1 General 2.1.2.2 Granular material 2.1.2.3 Water 2.2 Sampling procedures 2.2.1 Rocks 2.2.2 Sediments and pore water 2.2.2.1 Sediments 2.2.2.2 Pore water 2.2.3 Fresh and ground water and related particulate matter 2.2.3.1 Fresh water 2.2.3.2 Ground water 2.2.4 Sea- and estuarine water and related particulate matter and sediments 2.2.4.1 Water 2.2.4.2 Particulate matter 2.2.4.3 Sediment cores 2.2.5 Rainwater and dry deposition 2.2.5.1 Rainwater 2.2.5.2 Dry deposition 2.3 Preconcentration 2.3.1 General 2.3.2 Fresh water and rainwater 2.3.3 Seawater 2.3.3.1 Survey 2.3.3.2 Scavenging procedures 2.3.3.3 Ion-exchange and solvent extraction procedures for Th, U and Pu 2.4 Reference materials 2.4.1 Principle 2.4.2 Survey of reference materials and SRM's 2.4.3 Use of reference materials and SRM's 2.4.3.1 Reference materials 2.4.3.2 SRM's 2.4.4 Reference materials for environmental radioactivity and isotopic ratio measurements References 3 INSTRUMENTAL RADIOANALYSIS OF GEOLOGICAL MATERIALS 3.1 Survey 3.1.1 Activation analysis 3.1.2 Photon activation analysis 3.1.3 Charged particle activation analysis (CPAA and HIAA) 3.1.4 Prompt techniques 3.1.4.1 Neutron induced prompt capture y-ray measurement (PGAA) 3.1.4.2 Proton induced X-ray emission (PIXE) 3.2 Principles 3.2.1 Principles of instrumental neutron activation analysis (INAA) 3.2.1.1 Activation 3.2.1.2 Standardization and flux monitoring 3.2.1.3 Count rate 3.2.1.4 Counting result 3.2.1.5 Sensitivity 3.2.1.6 Characteristic parameters of the three types of neutron activation 3.2.2 Delayed neutron counting 3.2.3 Activation analysis with high-energy photons 3.2.4 Principles of charged particle activation analysis (CPAA) 3.2.5 Principles of prompt techniques 3.2.5.1 Prompt capture gamma-ray measurements (PGAA) 3.2.5.2 Proton induced X-ray emission (PIXE) 3.3 Practical aspects of INAA, IPAA and PIXE 3.3.1 The radioanalytical laboratory 3.3.2 Irradiation facilities for NAA 3.3.2.1 Nuclear reactors 3.3.2.2 Rabbit systems 3.3.2.3 Epithermal activation 3.3.2.4 Neutron generators 3.3.2.5 Delayed neutron counting 3.3.3 Routing of INAA 3.3.4 Practical aspects of IPAA 3.3.5 Practical aspects of CPAA 3.3.6 Practical aspects of PGAA 3.3.7 Practical aspects of PIXE and PIGE 3.3.7.1 Proton induced X-ray emission (PIXE) 3.3.7.2 Proton induced prompt gamma emission (PIGE) 3.3.8 The error-budget 3.4 Multielement determination by INAA based on gamma-ray spectrometry 3.4.1 General 3.4.2 A practical procedure for INAA of silicates based on thermal neutrons 3.4.2.1 Preparation of sample and standards for irradiation 3.4.2.2 Irradiation and measurements 3.4.2.3 Conclusion 3.4.3 Rocks and ores 3.4.4 Meteorites 3.4.5 Sediments 3.4.6 Air-dust 3.4.7 Coal and ash 3.5 Instrumental neutron activation analysis of the lanthanides 3.6 Instrumental neutron activation analysis of uranium 3.7 Applications of instrumental neutron activation analysis with an isotopic neutron source and a 14.5 MeV neutron generator 3.7.1 Survey 3.7.2 INAA with isotopic neutron sources in the radiochemical laboratory 3.7.3 INAA with the neutron generator in the radiochemical laboratory 3.7.4. Conclusion 3.8 Applications of IPAA to silicates 3.9 Applications of IPAA to silicates 3.10 Applications of prompt techniques 3.10.1 Applications of PGAA and PIGE 3.10.2 Applications of PIXE References 4 NEUTRON ACTIVATION ANALYSIS INCLUDING CHEMICAL SEPARATION OF GEOLOGICAL SAMPLES 4.1 Introduction 4.2 Dissolution procedures and separation schemes 4.3 Lanthanides 4.3.1 General 4.3.2 Present procedures 4.4 Noble metals 4.4.1 General 4.4.2 Separation schemes 4.4.3 Single element determinations 4.5 Uranium and thorium 4.5.1 General 4.5.2 Procedures 4.5.2.1 Uranium 4.5.2.2 Thorium 4.6 Other elements 4.6.1 General 4.6.2 Alkali metals 4.6.3 Earth alkali metals 4.6.4 Copper and zinc 4.6.5 Mercury 4.6.6 Indium 4.6.7 Thallium 4.6.8 Tin 4.6.9 Elements with volatile halides and hydrides: Ga, Ge, As, Se, Sb, Te 4.6.9.1 Survey 4.6.9.2 Procedures 4.6.10 Vanadium and tantalum 4.6.11 Chromium 4.6.12 Molybdenum andtungsten 4.6.13 Halogens References 5 RADIOANALYSIS OF WATER 5.1 Survey 5.2 Elemental analysis of fresh water 5.2.1 Survey 5.2.2 Routine elemental analysis of rainwater 5.2.2.1 Sampling and sample treatment 5.2.2.2 Irradiation and processing of aliquots 5.2.2.3 Results 5.2.3 Special elemental analysis of rainwater 5.2.3.1 Bromine and iodine by isotopic exchange 5.2.3.2 Iodate by anion-exchange 5,2.3.3 Silver by cation-exchange and subsequent INAA 5.2.4 Routine elemental analysis of surface and ground water 5.2.4,1 General 5.2.4.2 Routine procedures 5.3 Elemental analysis of seawater 5.3.1 Survey 5.3.2 Routine elemental analysis of seawater by preconcentration on a "Chelex"-column and INAA 5.3.3 Routine elemental analysis of seawater by preconcentration on active carbon 5.3.3,1 General 5.3.3.2 Arsenic and antimony 5,3.3.3 Vanadium, iodine, tellurium and uranium 5.3.3.4 Total antimony, molybdenum and tungsten 5,3.3.5 Chromate, cobalt, nickel and tetravalent selenium 5.3.3,6 Mercury 5.3.4 Special elemental analysis of seawater 5.3.4.1 General 5.3.4.2 Rubidium and cesium 5.3.4.3 Strontium 5.3.4.4 Manganese and zinc 5,3,4.5 Tin 5.3.4.6 Nickel 5.3.4.7 Noble metals 5.3.4.8 Mercury References 6 RADIOTRACER EXPERIMENTS IN THE LABORATORY 6.1 Survey 6.2 Basic equations of radiotracer experiments in closed systems 6.3 Isotopic exchange in solution 6.4 Isotopic exchange between a solution and a solid 6.5 Reactions in solution 6.6 Reaction between a solution and a solid 6.6.1 Dissolution 6.6. 2 Leaching 6.6.3 Diffusion from solids 6.6.4 Sorption 6.7 Migration studies in solid-liquid systems 6.7.1 General 6.7.2 The determina tion of distribution coefficients in seawater 6.7.3 Radioecological column experiments in the laboratory 6.7.4 Laboratory experiments on very slow migration; the case of the actinides References 7 RADIOTRACER EXPERIMENTS IN THE FIELD 7.1 Survey 7.2 Principles of (radio)tracer experiments in open systems with flow in one direction 7.2.1 Basic concepts 7.2.2 Measurement of linear velocity and flow rate 7.2.3 Measurement of axial dispersion 7.2.4 Measurement of sedimentation rates 7.2.4.1 General 7.2.4.2 Lead-210 7.2.4.3 Cesium-137 7.2.5 Measurement of the degree of sediment mixing 7.2.6 Measurement of filtration velocity in case of horizontal groundwater flow 7.2.7 Measurement of groundwater flow in the unsaturated zone by radiocarbon 7.3 Principles of (radio)tracer experiments in open systems with flow in various directions 7.3.1 Survey 7.3.2 Measurement of sand or silt flow rates on the sea floor 7.3.3 Radiotracer measurements in water movement in the saturated zone 7.3.4 Radiotracer measurement on water movement in the unsaturated zone 7.4 Practical aspects of radiotracer experiments in the field 7.4.1 Preparation 7.4.2 Performance 7.4.3 Calculations References 8 MEASUREMENT OF NATURAL RADIOACTIVITY 8.1 General 8.1.1 Survey 8.1.2 Concentrations 8.1.3 Detection by direct measurement ofradiation 8.1.3.1 In situ measurements of uranium and thorium 8.1.3.2 Laboratory measurements 8.1.4 Detection by secundary effects 8.2 Measurement of low-level gamma-activities 8.2.1 General 8.2.2 A low background system (LBS) 8.2.2.1 Set-up 8.2.2.2 Limits of detection and determination 8.2.2.3 Processing of data 8.2.3. Anti-coincidence (AC)-counting 8.3 Measurements in rocks and sediments 8.3.1 General 8.3.2 Radon measurements (emanometry) 8.3.3 Age dating by measurement of disequilibrium in the natural decay-series 8.3.3.1 General 8.3.3.2 234U-230Th 8.3.3.3 235U-231Pa 8.3.3.4 232Th-230Th 8.3.3.5 230Th-231Pa 8.3.4 Environmental laboratory measurements on naturally occurring radionucl

Note: TABLE OF CONTENTS Preface Chapter 1. The CO2-Carbonic Acid System and Solution Chemistry Basic Concepts Activity Coefficients in Solutions Influences of Temperature and Pressure The Carbonic Acid System in Seawater Calculation of the Saturation State of Seawater with Respect to Carbonate Minerals Concluding Remarks Chapter 2. Interactions Between Carbonate Minerals and Solutions Sedimentary Carbonate Minerals Basic Concepts Characteristics of Sedimentary Carbonate Minerals Solubility Behavior of Carbonate Minerals General Considerations Calcite and Aragonite Solubility Methods for the Calculation of Equilibrium Solution Composition Under Different Conditions Surface Chemistry of Carbonate Minerals Basic Principles Adsorption of Ions on Carbonate Surfaces Carbonate Dissolution and Precipitation Kinetics Basic Principles Reaction Kinetics in Simple Solutions Reaction Kinetics in Complex Solutions Concluding Remarks Chapter 3. Coprecipitation Reactions and Solid Solutions of Carbonate Minerals General Concepts Background Information Basic Chemical Considerations Coprecipitation of "Foreign" Ions in Carbonate Minerals Examples of Coprecipitation Reactions General Models for Partition Coefficients in Carbonates Magnesian Calcite General Considerations The Fundamental Problems Experimental Observations Hypothesis of a Hydrated Magnesian Calcite Stable Isotope Chemistry General Considerations Oxygen Isotopes Carbon Stable Isotopes Concluding Remarks Chapter 4. The Oceanic Carbonate System and Calcium Carbonate Accumulation in Deep Sea Sediments An Overview of Major Processes The CO2 System in Oceanic Waters The Upper Ocean The Deep Sea Saturation State of Deep Seawater with Respect to CaCO3 Sources and Sedimentation of Deep Sea Carbonates Sources Sedimentation The Distribution of CaCO3 in Deep Sea Sediments and Carbonate Lithofacies General Considerations The Distribution of CaCO3 in Surface Sediments Factors Controlling the Accumulation of Calcium Carbonate in Deep Sea Sediments General Relations Factors Leading to Variability Near Interfacial Processes Variability of Calcium Carbonate Deposition in Deep Sea Sediments with Time Influence of Glacial Times The Impact of Fossil Fuel CO2 on the Ocean-Carbonate System Concluding Remarks Chapter 5. Composition and Source of Shoal-Water Carbonate Sediments Introduction Shoal-Water Carbonates in Space and Time Carbonate Grains and Skeletal Parts Overview and Examples Sediment Classification Depositional Environments Concluding Statement Biomineralization General Aspects Environmental Controls on Mineralogy Stable Isotopes Coprecipitation Precipitation of Carbonates from Seawater Carbonate Chemistry of Shallow Seawater Abiotic Precipitation of CaCO3 from Seawater Sources of Aragonite Needle Muds Formation of Oöids Concluding Remarks 238 Chapter 6. Early Marine Diagenesis of Shoal-Water Carbonate Sediments Introduction Some Preliminary Thermodynamic and Kinetic Considerations Very Early Diagenesis Major Diagenetic Processes Pore Water Chemistry Precipitation of Early Carbonate Cements Dissolution of Carbonates Concluding Remarks Chapter 7. Early Non-Marine Diagenesis of Sedimentary Carbonates Introduction Plate-Tectonic Controls on Diagenesis General Considerations for Early Non-Marine Diagenesis Major Types of Non-Marine Environments Water Chemistry Reactivity of Sedimentary Carbonates Major Phase Transformations The Transformation of Aragonite to Calcite Dolomite Formation Summary Remarks Mass Transfer During Diagenesis General Considerations Geochemical Constraints on Mass Transfer Beachrock Formation Lithification in the Meteoric Environment Introduction The Meteoric Environment and Cement Precipitates Bermuda: A Case Study of a Meteoric Diagenetic Environment Introduction Geological Framework Limestone Chemistry and Isotopic Composition Water Chemistry Carbonate Mass Transfer A Brief Synthesis of Meteoric Diagenesis Diagenetic Stages Effect of Original Mineralogy Climatic Effects Rock-Water Relationships Mixed Meteoric-Marine Regime Concluding Remarks Chapter 8. Carbonates as Sedimentary Rocks in Subsurface Processes Introduction P,T, and X and Carbonate Mineral Stability Subsurface Water Chemistry in Sedimentary Basins Continuous Processes Pressure Solution Dolomitization Mud to Spar Neomorphism Secondary Porosity Cementation in the Subsurface Examples of "Models" of Long-Term Diagenesis The Present Ocean Setting The Present Continental Setting Concluding Remarks Chapter 9. The Current Carbon Cycle and Human Impact Introduction Modern Biogeochemical Cycle of Carbon A Model for the Cycle of Carbon Methane and Carbon Monoxide Fluxes CO2 Fluxes Human Impact on Carbon Fluxes The Fossil Fuel and Land Use Fluxes Observed Atmospheric CO2 Concentration Increase Future'Atmospheric CO2 Concentration Trends Consequences of Increased Atmospheric CO2 Levels The Oceanic System Sources of Calcium, Magnesium, and Carbon for Modern Oceans Mass Balance of Ca, Mg, and C in Present Oceans Oceanic Mass Balance of Elements Interactive with Ca, Mg, and C Concluding Remarks Chapter 10. Sedimentary Carbonates in the Evolution of Earth's Surface Environment Introduction Sedimentary Rock Mass-Age Distributions Secular Trends in Sedimentary Rock Properties Lithologic Types Chemistry and Mineralogy Carbon Cycling Modeling Introduction and Development of a Global Model Glacial-Interglacial Changes of Carbon Dioxide Long-Term Changes of Atmospheric CO2 Phanerozoic Cycling of Sedimentary Carbonates Synopsis of the Origin and Evolution of the Hydrosphere-Atmosphere-Sedimentary Lithosphere Origin of the Hydrosphere The Early Stages The Transitional Stage Modern Conditions Concluding Remarks Epilogue Introduction The Road Traveled The State of the Art Ever Onward References Index