Volume 91A: Surface Complexation Models

Piotr Zarzycki, Johannes Lützenkirchen, Benjamin Gilbert, editors

2025, i-xiv + 456 pages. ISSN 1529-6466

Description

From the Preface to the volume:

Chemical reactions at aqueous interfaces play major roles in Earth terrestrial and subsurface cycles of most reactive elements, trace elements, heavy/radioactive ions, and environmental pollutants. Understanding these interfacial geochemical reactions requires identifying the products that may occur and form. Predicting them requires the reactions to be quantitatively defined through the reaction stoichiometries and associated equilibrium constants. These descriptions are the basis of thermodynamic models, known as Surface Complexation Models (SCMs), which aim to predict the chemical equilibrium state of a given (charged) interface in contact with solution. SCMs appear to be one of the most successful models in geochemistry. SCMs have provided the ability to understand, predict, and explain the sorption of protons, aqueous ions, and molecules to hydrated mineral surfaces using physical models for interfacial processes and energies.

SCMs are, however, often challenging to construct and apply realistically. First, the identity and the stoichiometries of the reactants and products are not easily determined. They must be inferred from bulk measurements, partially glimpsed through molecular probes, or predicted using state-of-the-art simulation methods. Second, the equilibrium constants are influenced by local mesoscale chemical phenomena that alter interfacial free energies while they are, in turn, coupled to changes in speciation at the interface and in the solution. In particular, the distribution of the charges close to the interface—the electric double layer—and the structuring of interfacial water directly influence energetics in a dynamical system. While some aspects of the molecular and mesoscale interactions and energetics remain enigmatic at the fundamental level, SCMs can deliver self-consistent thermodynamic descriptions that can predict interfacial effects in natural systems at scale.

The short course is devoted to the foundational science, illustrates the state-of-the-art experimental and molecular modeling methods for determining structural and energetic data, and demonstrates how these thermodynamic models may be developed for increasingly complex systems such as nanoscale confinement. The volume is intended to provide instruction and guidance to new scientists, suggest new problems and methods for experienced practitioners, and identify opportunities for new collaborations between fields.

Read more in the Preface

Piotr Zarzycki (Lawrence Berkeley National Laboratory, CA, USA)
Piotr Zarzycki (Lawrence Berkeley National Laboratory, CA, USA)
Johannes Lützenkirchen (Karlsruhe Institute of Technology, Germany)
Benjamin Gilbert (Lawrence Berkeley National Laboratory, CA, USA,
University of California, Berkeley, CA, USA

Table of Contents

Chapter 1. Solution and Surface Complexation: The European Perspective
Staffan Sjöberg, p. 1-12.

Chapter 2. Development and Modus Operandi relating Surface Structure and Ion Complexation Modeling for Important Metal (Hydr)oxides
Tjisse Hiemstra, Johannes Lützenkirchen, p. 13-94

Chapter 3. Impedance Spectroscopy of the Mineral–Electrolyte Interfaces
Youzheng Qi, Yuxin Wu, p. 85-104

Chapter 4. Molecular Controls on Complexation Reactions and Electrostatic Potential Development at Mineral Surfaces
Jean-François Boily, p. 105-148

Chapter 5. Surface Complexation at Charged Organic Surfaces
Maryam Salehi, p. 149-174

Chapter 6. Surface Complexation and Reactivity of Ferrihydrite in Relation to its Surface and Mineral Structure, with Applications to Natural Systems
Tjisse Hiemstra, Annette Hofmann, Juan C. Mendez, Yilina Bai, p. 175-228

Chapter 7. Ligand and Charge Distribution Modeling of Natural Organic Matter Adsorption on Metal (Hydr)oxides: State-of-the-art
Yun Xu, Yilina Bai, Tjisse Hiemstra, Liping Weng, p. 229-250

Chapter 8. Ion-Dependent Calcium Carbonate Cohesion: Insights from Surface Forces Measured between Calcite Surfaces
Joanna Dziadkowiec, Anja Røyne, p. 251-294

Chapter 9. Measurements of the Electrostatic Potential at the Mineral/Electrolyte Interface
Tin Klačić, Jozefina Katić, Davor Kovačević, Danijel Namjesnik, Ahmed Abdelmonem, Tajana Begović, p. 295-336

Chapter 10. Surface Complexation Reactions in Oxide Nanopores
Anastasia G. Ilgen, 337-352

Chapter 11. Transport and Surface Complexation in Subsurface Flow-through Systems
Massimo Rolle, Lucien Stolze, Jacopo Cogorno, Muhammad Muniruzzaman, p. 353-382

Chapter 12. History, Algorithms, Model Uncertainty, and Common Pitfalls of Traditional SCM Fitting Procedures
Norbert Jordan, Frank Heberling, Jeffrey Kelling, Johannes Lützenkirchen, p. 383-412

Chapter 13. Practical Application of Surface Complexation Models: Evolution, Approaches, and Examples
David A. Dzombak, Jerry D. Allison, Ted P. Lillys, Jason Mills, p. 413-456