Department of Earth Sciences, University of Bristol
Advanced Aqueous Geochemistry
Prof. D.M. Sherman

Overview

The goal of this course is provide a more advanced treatment of thermodynamics of minerals and solutions and introduce the applications of thermodynamics and kinetics to model geochemical process in aquatic geochemistry using computer codes (e.g., PHREEQC). In addition, we will introduce theoretical and experimental techniques that allow us to obtain a molecular-level understanding of minerals and aqueous solutions.

Lecture Notes (in PDF)

1a. Overview and Review of Chemical Equilibrium
2. Aqueous Solutions I 3. Solubility Equilibria and Solid Solutions
4. Reaction Paths, Irreversible Reactions 5. Kinetics of Mineral-Solution Reactions
6. Advection and Diffusion
7. Redox Equilibria and Electrochemistry 8. Sorption on Mineral Surfaces I 9. Sorption on Mineral Surfaces II
10.Ion Exchange Reactions 11. Aqueous Solutions II: Pitzer model, Brines and Evaporites 12. Hydrothermal Solutions
13.Inverse Models 14.Reliability of Thermodynamic Data: application to Mine Pit Lakes 15.Speciation from Spectroscopy and Atomistic Simulations
16.Reactions at High Pressure

Practicals and Homework Assignments (PDF)



Introduction to Geochemical Modelling (Lecture)

Practical 1: Mineral Solubilities
Practical 2: Feldspar Weathering, Reaction Progress and Kinetics
PHREEQC Input File for part I
PHREEQC Input File for part II
PHREEQC Input File for part III
PHREEQC Input File for part IV
Practical 3: Uranium Sorption on FeOOH
PHREEQC Input File to generate sorption edges
PHREEQC Input File for U advection
Practical 4: Inverse Modelling Practical 5: CO2 Sequestration
PHREEQC Input file example


PHREEQC resources

Reading List

Books (available in Wills Memorial Library):

  • Appelo, C.A.J. and Postma D. (2005) Geochemistry, groundwater and pollution (2nd ed.) Leiden, London.
  • Langmuir, D. (1997) Aqueous Environmental Geochemistry. Prentice Hall, New York.
  • Zhu, C. and G. Anderson (2002) Environmental Applications of Geochemical Modeling. Cambridge University Press.

Papers:

  • Helgeson HC, DH Kirkham and GC Flowers (1981) Theoretical prediction of the thermodynamic behavior of aqueous electrolytes at high pressures and temperatures: IV. Calculation of activity coefficients, osmotic coefficients, and apparent molal and standard and relative partial molal properties to 600°C and 5 kb Am. J. Sci. 281:1249-1516.

  • Sverjensky DA, Shock EL, Helgeson HC (1997) Prediction of the thermodynamic properties of aqueous metal complexes to 1000 degrees C and 5 kb Geochimica et Cosmochimica Acta 61: 1359-1412.

  • Shock EL, Helgeson HC (1989) Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures--correlation algorithms for ionic species and equation of state predictions to 5 kb and 1000 C. Geochimica et Cosmochimica Acta 52: 2009-2036.

  • Helgeson HC, Garrels RM, Mackenzie FT (1968) Evalulation of irreversible reactions in geochemical processes involving minerals and aqueous solutions 2. Applications. Geochimica et Cosmochimica Acta 33:455.

  • Garrels RM, and Mackenzie FT (1967) Origin of the chemical composition of springs and lakes, in Equilibrium concepts in natural water systems: American Chemical Society, Advances in Chemistry Series 67:222-242.

Recent Applications of Geochemical Modelling

  • Brown JG, Glynn PD (2003) Kinetic dissolution of carbonates and Mn oxides in acidic water: measurement of in situ field rates and reactive transport modeling Applied Geochemistry 18,1225-1239. (Get article)

  • Tonkin, JW, Balistrieri LS, and Murray JW (2002) Modeling Metal Removal onto Natural Particles Formed during Mixing of Acid Rock Drainage with Ambient Surface Water Environ. Sci. Technol., 36, 484-492. (Get article)

  • Timms WA, Hendry MJ (2007) Quantifying the impact of cation exchange on long-term solute transport in a clay-rich aquitard, Journal of Hydrology 332, 110-122. (Get article)

  • Raffensperger JP, Garven G (1995) The formation of unconformity-type uranium ore-deposits. 2. Coupled hydrochemical modeling. American Journal of Science 295 (6): 639-696.

  • Steefel CI, DePaulo DJ, and PC Lichtner (2005) Reactive transport modeling: An essential tool and a new research approach for the Earth sciences Earth and Planetary Science Letters, 240, 539-558. (Get article)