9781405186124

Environmental and Low-Temperature Geochemistry presents conceptual and quantitative principles of geochemistry in order to foster understanding of natural processes at and near the earth’s surface, as well as anthropogenic impacts on the natural environment. It provides the reader with the essentials of concentration, speciation and reactivity of elements in soils, waters, sediments and air, drawing attention to both thermodynamic and kinetic controls. Specific features include:

• An introductory chapter that reviews basic chemical principles applied to environmental and low-temperature geochemistry
• Explanation and analysis of the importance of minerals in the environment
• Principles of aqueous geochemistry
• Organic compounds in the environment
• The role of microbes in processes such as biomineralization, elemental speciation and reduction-oxidation reactions
• Thorough coverage of the fundamentals of important geochemical cycles (C, N, P, S)
• Atmospheric chemistry
• Soil geochemistry
• The roles of stable isotopes in environmental analysis
• Radioactive and radiogenic isotopes as environmental tracers and environmental contaminants
• Principles and examples of instrumental analysis in environmental geochemistry

The text concludes with a case study of surface water and groundwater contamination that includes interactions and reactions of naturally-derived inorganic substances and introduced organic compounds (fuels and solvents), and illustrates the importance of interdisciplinary analysis in environmental geochemistry.

Readership: Advanced undergraduate and graduate students studying environmental/low T geochemistry as part of an earth science, environmental science or related program.

Additional resources for this book can be found at: www.wiley.com/go/ryan/geochemistry.

Peter Crowley Ryan is Professor of Geology and Environmental Studies at Middlebury College where he teaches courses in environmental geochemistry, hydrology, sedimentary geology and interdisciplinary environmental science. He received a Ph.D. in geology at Dartmouth College, an M.S. in geology from the University of Montana and a B.A. in earth sciences from Dartmouth College. He has served as Director of the Program in Environmental Studies and as Chair of the Department of Geology at Middlebury College. His research interests fall into two main areas: (1) understanding the geological and mineralogical controls on trace element speciation, particularly the occurrence and mobility of arsenic and uranium in bedrock aquifers; and (2) the temporal evolution of marine terrace soils in the tropics, with emphasis on mechanisms and rates of mineralogical reactions, nutrient cycling and application of soil geochemical analysis to correlation and geological interpretation.

Outline for Geochemistry of Environmental Systems.

PART I: FUNDAMENTAL PRINCIPLES AND EARTH MATERIALS.

Chapter 1. Basic chemical principles: elements, ions, bonding, reactions.

1.1 The naturally occurring elements—origins and abundances.

1.2 Atoms, ions, molecules, valence and bonding.

1.3 Isotopes.

1.4 Fundamentals of redox chemistry.

1.5 Valence, ions and bonding.

1.6 Acid-base equilibria.

1.7 Thermodynamics and driving forces for reactions: Gibbs energies, enthalpy and heat capacity, entropy, volume, equilibrium.

1.8 Kinetics and reaction rates: distance from equilibrium, activation energy, metastability..

Chapter 2. Surficial and environmental mineralogy.

2.1 Minerals, unit cells, crystallinity.

2.2 Overview of relevant mineral classes: silicates, oxides and hydroxides, sulfides, sulfates, carbonates, salts.

2.3 Layer silicates / clay minerals (T-O minerals, T-O-T minerals, interstratified clays).

2.4 Instrumental Analysis by X-ray diffraction.

2.5 Cation exchange and adsorption (as controlled by layer charge, crystal size, surface charges, aqueous geochemistry).

2.6 Environments of formation of sulfides, sulfates, carbonates, oxides and hydroxides.

2.7 Trace elements in minerals: Instrumental Analysis by Ion Microprobe.

2.8 Diffusion and advection.

2.9 Crystal nucleation, growth, and dissolution,Ostwald ripening.

Chapter 3. Biomineralization.

3.1 Basic principles of biomineralization.

3.2 Biologically induced mineralization.

3.3 Boundary organized (biologically controlled) biomineralization.

3.4 Examples and consequences of biomineralization: biogenic silica, sulfides, carbonates, iron hydroxides and oxides.

Chapter 4. Organic Geochemistry..

4.1 Basic organic chemistry: chains and rings, single, double, and triple bonds, functional groups, classes of organic compounds, organic nomenclature.

4.2 Natural and anthropogenic organic compounds at the earth surface.

4.3 The complex chemistry of petroleum.

4.4 Chlorinated hydrocarbons and organophosphates.

4.5 Instrumental analysis: chromatography.

4.6 Fate and transport of organic pollutants: structures, controls on bioavailability, behaviour of DNAPLs and LNAPLs, biodegradation, remediation schemes.

Chapter 5. Aqueous Systems.

5.1 Dissolved versus particulate: Examples of solutions and suspensions.

5.2 Speciation: ions, complexes and coordination.

5.3 Controls on solubility.

Reduction-oxidation potential (pe or Eh), redox pairs, redox equilibria.

Acidity and alkalinity.

Dissolved oxygen (DO).

Saturation relative to minerals and amorphous solids.

Concentration of total dissolved solids (TDS).

Co-precipitation and concentrations of specific solutes.

5.4 Ion Activities.

5.5 Solubility products.

5.6 Instrumental analysis by GFAA & ICP-AES.

5.7 Graphical representations of aqueous systems: Eh-pH (pe-pH), Piper, Stiff diagrams..

Chapter 6: The Carbonate system: Inorganic carbon in the atmosphere, solutions, and minerals.

6.1 Atmospheric CO2 and carbonic acid.

6.2 Speciation in the carbonate system and pH.

6.3 Alkalinity.

6.4 Carbonate solubility, partial pressure and precipitation/dissolution of carbonate minerals.

Chapter 7. Isotope Geochemistry.

7.1 Stable isotopes – Mass differences and fractionation: e.g. evaporation, mineral crystallization, nutrient uptake. Equilibrium versus nonequilibrium processes.

7.2 Stable isotopes – Delta (d) notation.

7.3 Stable isotopes – Common isotopic systems and applications in earth surface geochemistry.

Oxygen.

Hydrogen.

Carbon.

Nitrogen.

Sulfur.

7.4 Radioactive Isotopes – Radioactive decay, Arrhenius equation.

7.5 Common radioactive isotopes in earth surface systems and their applications, including geochronologic and tracer studies.

3H.

14C.

10Be and 36Cl.

87Sr.

222Rn.

226Ra and 228Ra.

235U and 238U.

.

PART II: EARTH-SURFACE SYSTEMS.

Chapter 8. The Atmosphere, Climate and Precipitation.

8.1 Atmospheric structure, composition and the electromagnetic spectrum.

8.2 Evaporation, distillation, CO2 dissolution and the composition of natural precipitation.

8.3 IR radiation and CO2, CH4, H2O and N2O as greenhouse gases: sources, sinks, effects, geological records and predictions of future global climate.

8.4 Stratospheric ozone chemistry.

8.5 Tropospheric ozone, NOx, hydrocarbons and photochemical smog.

8.6 Sulfur and nitrogen gases and acid deposition.

Sources of atmospheric S and N.

Chemical reactions, equilibrium and kinetics, atmospheric transport.

Spatial and temporal distribution of acid deposition.

8.7 Trace elements in atmospheric deposition and environmental health: mercury, lead.

Chapter 9. Weathering, Soils and the Vadose Zone.

9.1 Primaryminerals, chemical disequilibrium, chemical weathering reactions, and products of chemical weathering.

9.2 Mineral stability diagrams.

9.3 Soil development and controls on natural soil formation.

Climatic controls on soil mineralogy and composition.

Organisms (effects of flora and fauna) and geomicrobiology.

Relief (topographic controls on soil mineralogy and composition).

Parent material and the role of rock type on soil development.

Time— the role of kinetic factors in weathering and soil formation.

The concept of steady state with respect to soil development.

9.4 Isotopic tracers in studies of chemical weathering.

9.5 Soils and paleoclimate analysis.

9.6 Neutralization of acid deposition, effect of acid deposition on soil composition (particularly pH and exchangeable ion pools).

9.7 Soils and agriculture.

9.8 Vadose zone geochemistry – reactions at the interface of soil, surface water and ground water.

9.9 Inorganic soil pollutants and remediation (trace metals, nutrients).

9.10 Organic soil pollutants and remediation (fuels, insecticides, solvents).

Chapter 10. Streams and Lakes.

10.1 Controls on the natural composition of surface water – major and trace element geochemistry, including sources of cations and anions.

10.2 The role of evaporative concentration in arid regions and soil salinization.

10.3 Acid deposition, from soil to vadose zone to stream to lake.

Temporal records of acidification of precipitation, soils and surface water.

Effects of pH on aluminium solubility.

Impacts to forest and aquatic ecosystems.

Remediation and environmental policy.

10.4Sulphide weathering and acid-mine drainage: causes, effects, remediation.

10.5 Excess N and P and eutrophication of lakes and estuaries.

Chapter 11. The Oceans .

11.1 Chemical composition of seawater.

11.2 Ocean circulation.

11.3 Evaporation and salinity.

11.4 Mixing of marine water and fresh water: estuary geochemistry.

11.5 The carbonate compensation depth.

11.6 Ocean nutrients, productivity and C cycling.

11.7 High standing islands and elemental fluxes.

11.8 Sea floor hydrothermal systems: biotic and ore-forming implications.

11.9 Isotopic records of seawater evolution through geological time.

Chapter 12. Aquifer Geochemistry.

12.1 Recharge, ground water flow and residence time.

12.2 Natural controls on ground water chemistry (major and trace elements).

12.3 Variation in pH, TDS and dissolved oxygen (redox conditions).

12.4 Equilibration with minerals.

12.5 Case studies of common inorganic ground water pollutants and remediation schemes.

Radionuclides.

Arsenic.

Nitrate.

12.6 N isotopes as geochemical tracers in groundwater systems.

12.7 Case studies of common organic ground water pollutants and remediation schemes.

Fuels, solvents and pesticides.

Non-aqueous and dissolved behaviour of organic fluids: fate and transport of.

DNAPLs and LNAPLs.

Adsorption-desorption, microbes and biodegradation.

Engineered remediation (pump-and-treat, land farming, air sparging, microbial.

schemes).

12.8Karst: a unique weathering and hydrogeological environment.

Chapter 13. Sediments, Diagenesis and Deep Ground Water.

13.1 Diagenesis of mudstones: dissolution of feldspar, illitization of smectite and production of quartz.

13.2 Petroleum origins, maturation and migration.

13.3 Diagenesis of carbonate sediments and rocks.

13.4 Diagenesis of sands and sandstone.

13.5 Oxygen isotope analysis of diagenesis.

13.6 Origin and geochemistry of deep basin brines.

13.7 Carbon sequestration by injection of CO2 into aquifers.

13.8 Geological disposal of radioactive waste.

Chapter 14. Global Geochemical Cycles and Anthropogenic Impacts.

14.1 The carbon cycle.

14.2 The nitrogen cycle.

14.3 The sulphur cycle.

14.4 Linkage of atmospheric, hydrologic and tectonic cycles

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Environmental and Low Temperature Geochemistry

Environmental and Low Temperature Geochemistry

1405186127

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