Environmental and Low Temperature Geochemistry

Cover
Title Page
Copyright
Contents
Preface
Acknowledgements
Chapter 1 Background and Basic Chemical Principles: Elements, Ions, Bonding, Reactions
	1.1 An Overview Of Environmental Geochemistry – History, Scope, Questions, Approaches, Challenges for the Future
	1.2 The Naturally Occurring Elements – Origins and Abundances
		1.2.1 Origin of the light elements H and He (and Li)
		1.2.2 Formation of heavier elements
		1.2.3 Formation of planets and compositional differentiation
	1.3 Atoms, Isotopes, and Valence Electrons
		1.3.1 Atoms: protons, neutrons, electrons, isotopes
		1.3.2 Electrons and bonding
	1.4 Measuring Concentrations
		1.4.1 Mass‐based concentrations
		1.4.2 Molar concentrations
		1.4.3 Concentrations of gases
		1.4.4 Notes on precision and accuracy, significant figures, and scientific notation
	1.5 Periodic Table
		1.5.1 Predicting behavior of elements using the periodic table
		1.5.2 The earth scientist\'s periodic table
	1.6 Ions, Molecules, Valence, Bonding, Chemical Reactions
		1.6.1 Ionic bonding
		1.6.2 Determining ionic bond strength
		1.6.3 Covalent bonding
		1.6.4 Electronegativity and predicting bond type
		1.6.5 Metallic bonds, hydrogen bonds, and van der Waals forces
	1.7 Acid–Base Equilibria, PH, K Values
		1.7.1 Definitions of acids and bases
		1.7.2 The law of mass action and quantifying acid dissociation
	1.8 Fundamentals of Redox Chemistry
		1.8.1 Defining oxidation and reduction
		1.8.2 Redox reactions
	1.9 Chemical Reactions
	1.10 Equilibrium, Thermodynamics, and Driving Forces for Reactions: Systems, Gibbs Energies, Enthalpy and Heat Capacity, Entropy, Volume
		1.10.1 Pyrite oxidation as an introductory example
		1.10.2 Systems, species, phases, and components
		1.10.3 First law of thermodynamics
		1.10.4 Second law of thermodynamics
		1.10.5 Enthalpy
		1.10.6 Heat capacity
		1.10.7 Gibbs free energy and predicting stability
		1.10.8 The Van\'t Hoff equation: relating gibbs free energy to the equilibrium constant (Keq)
	1.11 Kinetics and Reaction Rates
		1.11.1 Factors controlling reaction rate
		1.11.2 Reaction rate, reaction order
			1.11.2.1 Zero‐order reactions
			1.11.2.2 First‐order reactions
			1.11.2.3 Second‐order reactions
		1.11.3 Temperature and the Arrhenius equation
	Questions
	References
Chapter 2 Surficial and Environmental Mineralogy
	2.1 Introduction to Minerals and Unit Cells
	2.2 Ion Coordination, Pauling\'s Rules, and Ionic Substitution
		2.2.1 Coordination and radius ratio
		2.2.2 Bond strength considerations
		2.2.3 Pauling and goldschmidt rules of ionic solids
			2.2.3.1 Rule 1: the coordination principle
			2.2.3.2 Rule 2: the principle of local charge balance
			2.2.3.3 Rule 3: sharing of polyhedral edges and faces
			2.2.3.4 Rule 4: valency and sharing of polyhedral components
			2.2.3.5 Rule 5: the principle of parsimony
	2.3 Silicates
		2.3.1 Nesosilicates
		2.3.2 Inosilicates
		2.3.3 Phyllosilicates
			2.3.3.1 The 2 : 1 phyllosilicates
			2.3.3.2 The 1 : 1 phyllosilicates
		2.3.4 Tectosilicates
	2.4 Clay Minerals (1 : 1 and 2 : 1 Minerals, Interstratified Clays)
		2.4.1 Smectite
			2.4.1.1 Smectites with tetrahedrally derived layer charge
			2.4.1.2 Smectites with octahedrally derived layer charge
		2.4.2 Vermiculite
		2.4.3 Illite
		2.4.4 Chlorite and berthierine
		2.4.5 Kaolin group (kaolinite and halloysite)
		2.4.6 Interstratified clay minerals
		2.4.7 Trace metals and metalloids in clay minerals
	2.5 Crystal Chemistry of Adsorption and Cation Exchange
		2.5.1 Cation exchange
			2.5.1.1 Mechanisms by which cations are attracted to surfaces
			2.5.1.2 Particle attributes that influence ion exchange
			2.5.1.3 Point of zero charge and isoelectric point
			2.5.1.4 Double‐layer complexes
			2.5.1.5 Units of concentration and measurement of CEC
	2.6 Low‐Temperature Non‐Silicate Minerals: Carbonates, Oxides and Hydroxides, Sulfides, Sulfates, Salts
		2.6.1 Carbonates
		2.6.2 Oxides and hydroxides
		2.6.3 Sulfides and sulfates
			2.6.3.1 Halide and nitrate salts
	2.7 Mineral Growth and Dissolution
	2.8 Biomineralization
	Questions
	References
Chapter 3 Organic Compounds in the Environment
	3.1 Introduction to Organic Chemistry: Chains and Rings, Single, Double, and Triple Bonds, Functional Groups, Classes of Organic Compounds, Organic Nomenclature
		3.1.1 Definition of organic compounds
		3.1.2 Hybridization of carbon atoms in organic compounds
		3.1.3 Alkanes
		3.1.4 Alkenes
		3.1.5 Functional groups
		3.1.6 Aromatic hydrocarbons and related compounds
		3.1.7 Nitrogen, phosphorus, and sulfur in organic compounds
		3.1.8 Pharmaceutical compounds
		3.1.9 Emerging contaminants – PFCs
	3.2 Natural Organic Compounds at the Earth Surface
		3.2.1 Humic and fulvic material
		3.2.2 Origins and compositions of fossil fuels
	3.3 Fate and Transport of Organic Pollutants, Controls on Bioavailability, Behavior of DNAPLS and LNAPLS, Biodegradation, Remediation
		3.3.1 Solid–liquid–gas phase considerations
		3.3.2 Solubility considerations
		3.3.3 Interactions of organic compounds and organisms
		3.3.4 Adsorption of organic compounds
			3.3.4.1 Adsorbates
			3.3.4.2 Adsorbents
		3.3.5 Non‐aqueous phase liquids (NAPLs) in the environment
		3.3.6 Biodegradation
		3.3.7 Remediation
	3.4 Summary
	Questions
	References
Chapter 4 Aqueous Systems and Water Chemistry
	4.1 Introduction to the Geochemistry of Natural Waters
		4.1.1 Geochemistry and the hydrologic cycle
			4.1.1.1 Evaporation and precipitation
			4.1.1.2 Infiltration, soils, chemical weathering
			4.1.1.3 Surface water and groundwater
			4.1.1.4 Graphical analysis of climate and surface water composition
	4.2 The Structure of Water – Implications of Geometry and Polarity
	4.3 Dissolved versus Particulate, Solutions, and Suspensions
		4.3.1 Dissolved constituents and the nature of solutions
		4.3.2 Particulate (suspended) fraction
		4.3.3 Immiscible liquids
		4.3.4 Dissolved vs. particulate vs. colloidal
	4.4 Speciation: Simple Ions, Polyatomic Ions, and Aqueous Complexes
	4.5 Controls on the Solubility of Inorganic Elements and Ions
		4.5.1 Role of temperature
		4.5.2 Residence time
		4.5.3 The ratio of ionic charge : ionic radius and its effect on solubility
		4.5.4 Reduction–oxidation reactions
			4.5.4.1 Half‐cell reactions
			4.5.4.2 Redox reactions in the environment
		4.5.5 Acid–base considerations and pH
		4.5.6 Ligands and elemental mobility
	4.6 Ion Activities, Ionic Strength, TDS
		4.6.1 Ion activity coefficients
		4.6.2 Ion activity product
		4.6.3 Ionic strength
		4.6.4 Total dissolved solids
	4.7 Solubility Products, Saturation
	4.8 Coprecipitation
	4.9 Behavior of Selected Elements in Aqueous Systems
		4.9.1 Examples of heavy metals and metalloids
			4.9.1.1 Heavy metals
			4.9.1.2 Metalloids
	4.10 Eh–pH Diagrams
		4.10.1 Principles of Eh–pH
		4.10.2 Eh–pH diagrams for Cu, Pb, As, U, Fe, Al
	4.11 Silicon in Solution
	4.12 Effect of Adsorption and Ion Exchange on Water Chemistry
		4.12.1 Ionic potential, hydration radius, and adsorption
		4.12.2 Law of mass action and adsorption
		4.12.3 Adsorption edges
		4.12.4 Adsorption isotherms
	4.13 Other Graphical Representations of Aqueous Systems: Piper and Stiff Diagrams
	4.14 Summary
	Questions
	References
Chapter 5 Carbonate Geochemistry and the Carbon Cycle
	5.1 Inorganic Carbon in the Atmosphere and Hydrosphere
		5.1.1 Atmospheric CO2, carbonate species, and the pH of rain
		5.1.2 Speciation in the carbonate system as a function of pH
		5.1.3 Alkalinity
		5.1.4 Carbonate solubility and saturation
		5.1.5 The effect of CO2 partial pressure on stability of carbonate minerals
		5.1.6 The effect of mineral composition on stability of carbonate minerals
	5.2 The Carbon Cycle
		5.2.1 Oxidation states of carbon
		5.2.2 Global‐scale reservoirs and fluxes of carbon
		5.2.3 Processes that transfer carbon into the crust
			5.2.3.1 Carbonate rocks
			5.2.3.2 Fixation of organic carbon into organisms
			5.2.3.3 Formation of hydrocarbons
			5.2.3.4 Formation of coal
		5.2.4 Rates of organic carbon flux to and from the crust
		5.2.5 The ocean reservoir
			5.2.5.1 Fixation of C into oceans
			5.2.5.2 Ocean acidification
			5.2.5.3 Long‐term viability of oceans as C sink
			5.2.5.4 Methane hydrates
		5.2.6 Carbon in cold region soils
		5.2.7 The atmospheric reservoir
			5.2.7.1 Changes to atmospheric carbon over geological time
			5.2.7.2 Feedback loops
			5.2.7.3 Anthropogenic C and the atmosphere
		5.2.8 Carbon sequestration
	Questions
	References
Chapter 6 Biogeochemical Systems and Cycles (N, P, S)
	6.1 Systems and Elemental Cycles
		6.1.1 Reservoirs, fluxes, and systems
		6.1.2 The concept of steady state vs. dynamic equilibrium
	6.2 Elemental Cycles
		6.2.1 The nitrogen cycle
			6.2.1.1 Nitrogen oxidation states, nitrogen species
			6.2.1.2 Processes operating within the nitrogen cycle
			6.2.1.3 Global‐scale reservoirs and fluxes of nitrogen
			6.2.1.4 Human perturbation of the nitrogen cycle and resulting environmental impacts
		6.2.2 The phosphorus cycle
			6.2.2.1 P cycling in soils
			6.2.2.2 The global phosphorus cycle
			6.2.2.3 Phosphorus and eutrophication
		6.2.3 Comparison of N and P
		6.2.4 The sulfur cycle
			6.2.4.1 Sulfur oxidation states, sulfur species
			6.2.4.2 The global S cycle
			6.2.4.3 The marine S cycle
			6.2.4.4 Sulfur, soils, and biota
			6.2.4.5 Sulfur and the atmosphere
			6.2.4.6 Sulfur and river flux
		6.2.5 Integrating the C, N, P, and S cycles
	Questions
	References
Chapter 7 The Global Atmosphere: Composition, Evolution, and Anthropogenic Change
	7.1 Atmospheric Structure, Circulation, and Composition
		7.1.1 Structure and layering of the atmosphere
		7.1.2 Geological record of atmospheric composition
		7.1.3 Climate proxies
		7.1.4 Orbital control on C
		7.1.5 Composition of the current atmosphere
		7.1.6 Air circulation
	7.2 Evaporation, Distillation, CO2 Dissolution, and the Composition of Natural Precipitation
	7.3 The Electromagnetic Spectrum, Greenhouse Gases, and Climate
		7.3.1 Electromagnetic spectrum
		7.3.2 Reradiation from earth\'s surface
		7.3.3 Greenhouse effect and heat trapping
	7.4 Greenhouse Gases: Structures, Sources, Sinks, and Effects on Climate
		7.4.1 Molecular structures and vibrations of greenhouse gases
		7.4.2 Greenhouse gases, radiative forcing, GWPs
		7.4.3 Global warming
	Questions
	References
Chapter 8 Air Quality: Urban and Regional Pollutants
	8.1 Air Pollution: Definitions and Scope
	8.2 Oxygen and its Impact on Atmospheric Chemistry
	8.3 Free Radicals
	8.4 Sulfur Dioxide
	8.5 Nitrogen Oxides
	8.6 Carbon Monoxide
	8.7 Particulate Matter
	8.8 Lead (Pb)
	8.9 Hydrocarbons and Air Quality: Tropospheric Ozone and Photochemical Smog
	8.10 Stratospheric Ozone Chemistry
	8.11 Sulfur and Nitrogen and Acid Deposition
	8.12 Organochlorine Pesticides, Mercury, and Other Trace Constituents in the Atmosphere
		8.12.1 Pesticides in air
		8.12.2 Mercury in air
		8.12.3 As, Cd, and Ni
	Questions
	References
Chapter 9 Chemical Weathering, Soils, and Hydrology
	9.1 Chemical Weathering of Primary Minerals in Soils
		9.1.1 Thermodynamic vs. kinetic considerations
		9.1.2 Predicting weathering rates: Goldich stability sequence
		9.1.3 Laboratory determinations of primary mineral weathering rates
		9.1.4 Chemical weathering reactions
			9.1.4.1 Hydrolysis
			9.1.4.2 Dissolution of ionic solids
			9.1.4.3 Reduction–oxidation
			9.1.4.4 Hydration
	9.2 Products and Consequences of Chemical Weathering
		9.2.1 Congruous vs. incongruous weathering: dissolved vs. solid products
		9.2.2 Geochemical quantification of elemental mobility in soil
		9.2.3 Quantifying chemical weathering: CIA
		9.2.4 Secondary minerals: controls on formation, mineral stability diagrams
			9.2.4.1 Factors controlling soil mineralogy
			9.2.4.2 Mineral stability diagrams
	9.3 Soil Profiles, Nomenclature, Soil‐Forming Factors
		9.3.1 The concept of the soil profile
		9.3.2 Soil‐forming factors
			9.3.2.1 Climate
			9.3.2.2 Organisms
			9.3.2.3 Relief (topography)
			9.3.2.4 Parent material
			9.3.2.5 Time
			9.3.2.6 Anthropogenic factors
		9.3.3 Soil classification – soil orders and geochemical controls
	9.4 Soils and the Geochemistry of Paleoclimate Analysis
	9.5 Effects of Acid Deposition on Soils and Aquatic Ecosystems
		9.5.1 Increased solubility of Al in acidic soil solution
		9.5.2 Displacement of adsorbed nutrient cations
		9.5.3 Leaching of base cations enhanced by increased NO3 and SO4
		9.5.4 Decrease of soil buffering capacity and base saturation
		9.5.5 Acid deposition and heavy metals
	9.6 Soils and Plant Nutrients
	9.7 Saline and Sodic Soils
	9.8 Toxic Metals and Metalloids
	9.9 Organic Soil Pollutants and Remediation (Fuels, Insecticides, Solvents)
	Questions
	References
Chapter 10 Stable Isotope Geochemistry
	10.1 Stable Isotopes – Mass Differences and the Concept of Fractionation
	10.2 Delta (