PREFACE About the Author

Contents / vii CONTENTS PREFACE About the Author CONTENTS v vi vii INTRODUCTION Sorption and Biosorption Share the Methodology 1 1. POTENTIAL OF BIOSORPTION 5 1.1 METALS: ENVIRONMENTAL THREAT 5 1.2 BIOSORPTION TECHNOLOGY 7 1.3 BIOSORPTION ENTERPRISE 9 Techno-Economic Basis 11 Identification of Potential Synergies and Partners 11 1.4 CONCLUSION 12 2. BIOSORPTION R&D 13 2.1 Biomass Screening where to look and why? 14 What are Biosorbents? 16 Biosorption Performance 17 Biosorbent Metal Selectivity 18 Review of Biosorption Performance 19 REFERENCES 23 2.2 Adsorption - Uptake 25 2.3 Desorption 27 2.4 Mechanism of metal biosorption 29 2.5 Modeling 30 2.6 Granulation 31 Biosorption Process operation 32 2.7 Project disciplines and Tasks 33 3. THE MECHANISM OF METAL BIOSORPTION 35 3.1 BIOSORPTION AND BIOACCUMULATION 35 3.2 CHEMICAL BINDING 36 Complexation, Coordination, Chelation of Metals 36 Ion Exchange, Adsorption 39 Inorganic Microprecipitation 40 3.3 THE MECHANISM OF BIOSORPTION 41 Temperature Effect 41 Influence of ph 42 Ionic Strength Effect 43 Presence of Other Anions 43 Overall Mechanisms: Ion Exchange, Adsorption, Microprecipitation 44 Contribution of Electrostatic Attraction and Complexation 45 Binding Sites 46

viii / SORPTION & BIOSORPTION 3.4 INSTRUMENTAL ANALYSES 48 FTIR Analysis Cation Deposition 49 FTIR Analysis Anion Deposition 52 Chromate Biosorption 52 Vanadate Biosorption 53 Gold-Cyanide Biosorption 54 Determination of Electrostatic Attraction 54 Combination Mechanisms 54 3.5 REFERENCES 57-58 4. METALS IN BIOSORPTION 59 4.1 THE CHOICE OF METALS 59 4.1-1 Removal of Toxic Heavy Metals 60 The Big Three 60 Second-Tier Toxic Heavies 60 Radionuclides 60 4.2 INDUSTRIAL ENVIRONMENTAL THREATS 61 4.2-1 Electroplating Operations 61 4.2-2 Mining Industry Effluents 63 Acid Mine Drainage 63 4.2-3 Power-Generating Stations 65 4.3 RECOVERY OF METALS 67 4.3-1 Precious Metals 67 4.3-2 Strategic Metals 67 4.3-3 Rare Earth Elements 68 Chemical Properties of REE 69 4.3-4 Metal Removal/Recovery Priorities 71 4.4 METAL BEHAVIOR IN SOLUTION 72 4.4-1 Chromate in Solution 73 4.4-2 Vanadate in Solution 73 4.4-3 Gold-Cyanide in Solution 74 4.4-4 Example of Uranium speciation in solution 75 4.4-5 MINEQL+ 78 4.5 REFERENCES 80 5. SORPTION BY BIOMASS 81 5.1 BIOMASS TYPES 81 5.1-1 References 83-84 5.2 SORPTION BY CHITINOUS BIOMASS 85 5.2-1 Properties and Composition of Crab Shells 85 5.2-2 Main Biomolecules in Crab Shells 86 Chitin 86 Protein 87 Chitin-Protein Complex 87 5.3 BIOSORPTION BY ALGAL BIOMASS 88 5.3-1 Seaweed Cell walls 89 5.3-2 Main Biomolecules in Seaweeds 91 Cellulose 91 Alginic Acid 92 Fucoidan 93

Contents / ix 5.3-3 Sulfated Galactans of Red Algae 93 Agar 93 Porphyran 94 Carrageenan 94 5.3-4 The mechanism of biosorption by marine algae 94 Importance of ion exchange Relevance of complexation and electrostatic attraction 95 5.4 SORPTION BY MICROBIAL BIOMASS 95 5.4-1 Biosorption by Bacteria 95 5.4-2 Biosorption by Fungi 97 5.5 REFERENCES 100-102 6. EQUILIBRIUM BIOSORPTION PERFORMANCE 103 6.1 SORPTION EQUILIBRIUM 103 6.1-1 Single-Sorbate Isotherms 105 Simple Sorption Models 105 Langmuir model 105 Freundlich model 106 Other sorption isotherm relationships 107 6.1-2 Comparison of Sorption Performance 108 6.1-3 Equilibrium Constants 110 6.1-4 Experimental Sorption Isotherm 112 The tea-bag experiment 114 Sorbent Comparison Based on % Removal 114 6.1-5 REFERENCES 116 6.1-6 Ion Exchange Isotherms and Separation Factors 117 Ion Exchange Equilibrium Relationships 118 Example of Biosorbent Ion Exchange 120 REFERENCES 120 6.2 MULTI-SORBATE SORPTION EQUILIBRIUM (3-D) 121 6.2-1 Sorption Isotherms with a Parameter 121 6.2-2 Sorption Isotherm Plots 123 6.2-3 Cutting of Sorption Isotherm 123 6.2-4 Example of the Fe-Cd Sorption System 125 6.2-5 BIBLIOGRAPHY 126 6.3 MODELING OF EQUILIBRIUM BIOSORPTION 127 6.3-1 Types of Sorption Models 129 Models Considering Ideality 130 6.3-2 Sorption Reactions and Modeling 132 Multi-Component Langmuirian Models 133 Symbols 134 Langmuirian Models with Equilibrium Constants 135 Considering also the electrostatic binding 136 Considering the effect of ph 137 Models Considering Non-Ideality 138 i) In the Liquid Phase Only 138

x / SORPTION & BIOSORPTION ii) In the Solid Phase 139 Surface Complex Model 139 Donnan Model 140 Wilson Model for Ion Exchange 140 6.3-3 Two Binding Sites 142 6.3-4 Considering the effect of Ionic Strength: Donnan Model 144 Incorporating sorption particle swelling 145 6.3-5 Combination of the Isotherm and Donnan Models 146 Calculation Without Iterations 146 6.3-6 Summary 148 6.3-7 REFERENCES 149-150 6.4 EQUILIBRIUM MODEL WITH SOLUTION CHEMISTRY 151 6.4-1 HIEM model for Uranium Biosorption Isotherm 151 6.4-2 Determination of HIEM model parameters and modeling of experimental data 159 6.4-3 Comparison of experimental uranium isotherms and HIEM calculations at different solution ph values 162 6.4-5 Summary 163 6.4-6 REFERENCES 164 6.5 BIOSORPTION BATCH DYNAMICS 165 6.5-1 End-Point Titration Curves 166 6.5-2 Eliminating External Mass Transfer 166 6.5-3 Biosorbent Particle Size and Sorption Rate 167 6.5-4 Rate of Uptake and Proton Release 169 6.5-5 Mass Transfer Model for Biosorption Rate 170 6.5-6 Numerical Solution of the Model Equations 172 6.5-7 Regression of Model Parameters 174 6.5-8 Desorption Rate 176 6.5-9 REFERENCES 178 7. BIOSORPTION PROCESS PRINCIPLES 179 CONTINUOUS-FLOW REACTOR/CONTACTOR SYSTEMS 179 7.1 The Fixed-Bed Column Sorption System 180 7.2 The Fluidized Bed Column Sorption System 181 7.3 The Completely Mixed Solid-Liquid Sorption System 181 7.4 Fundamental Aspects of the Continuous-Flow Fixed-Bed Column 183 The Breakthrough Curve and its Interpretation 183 The link between equilibrium and column breakthrough 184 Ion Exchange with Mixed Sorbates 185 Sorption Process Optimization Challenge 186 7.5 Process Example 187 Specifications 187 Mass Balances 188 Sizing 189 8. MODELING OF COLUMN PERFORMANCE 191 8.1 REVIEW: CFFB Sorption Column Performance Modeling 191 REFERENCES 196

Contents / xi 8.2 (ECM) EQUILIBRIUM COLUMN MODEL 197 Symbols 198 Equilibrium Considerations 198 Defining Characteristics of the ECM 199 8.2-1 Basic concepts of ECM and symbol conventions 199 ECM Equations for Transitions 201 8.2-2 Calculation of Concentration Histories for Column Effluent 203 Effects of Competitive Ion Exchange on the Performance of sorption Columns 203 8.2-3 Case Study 204 a) Theory of overshoots in ternary systems 204 b) Agreement between overshoots predicted by the ECM and experiments 205 c) Assessment of overshoots in a biosorption process removing Cu from wastewater containing traces of Cd or Zn 207 The Use of ECM to Determine the Elution Order of Metals and the Column Service Time for Multi-Metal Mixtures 208 8.2-4 Conclusions on the ECM Concept 210 8.2-5 REFERENCES 212 8.3 (MTM) COLUMN SORPTION MODEL WITH MASS TRANSFER 213 Symbols 214 8.3-1 Connection between Equilibrium and Dynamic Sorption 215 Start with Equilibrium Considerations 215 8.3-2 Fitting the Equilibrium Model and Ion Exchange Isotherms 219 8.3-3 Fitting and Use of the Sorption Column Model 219 8.3-4 Example of the MTM Use 220 8.3-5 Conclusions on the MTM concept 221 8.3-6 REFERENCES 222 8.4 DERIVATION OF MASS TRANSFER MODEL FOR SORPTION COLUMS 223 8.4-1 Axial Dispersion Experimental Evaluation 223 8.4-2 Model Derivation 224 8.4-3 Numerical Solution of the Model Equations 227 8.4-4 Determination of Model Parameters and Data Modeling 229 8.4-5 REFERENCES 232 9. BIOSORBENT MATERIAL PREPARATION 233 9.1 Biomass Sources 233 Industrial Biomass 234 Seaweeds 234 9.2 Characterization of Biosorbent Particles 235 Particle Size 235 Particle Shape 236 Porosity 236 Mechanical Strength 237 Density and Swelling 237

xii / SORPTION & BIOSORPTION 9.3 Biosorbent Material Formulation 238 9.3-1 Biomass Reinforcement 238 9.3-2 Crosslinking Procedures 240 Formaldehyde and Urea Formaldehyde Crosslinking 242 Experimental Crosslinking Examples 243 9.3-3 Granulation Techniques 244 Extrusion 244 Fluidized Bed Granulation 244 Spray Drying 245 9.4 Column Pressure Drop 246 9.5 Conclusion to Processing 247 9.6 Desorption 248 9.6-1 Choice of Ionic Form of Sorbent 250 9.6-2 Pre-treatment of Sargassum biomass 251 Leaching of organic material and active sites 251 Biosorbent Stability and Metal Affinities 252 9.7 REFERENCES 253-254 10. MONOCLONAL ANTIBODIES BIOSORPTION 255 10.1 Silver Bullet Biosorption 255 10.2 Production of Monoclonal Antibodies 257 In vitro Production Methods 259 10.3 Purification and Application of mabs 260 Ion Exchange Chromatography 261 Hydrophobic Interaction Chromatography 261 Gel Filtration Chromatography 262 Affinity Chromatography 262 Large Scale Purification 265 10.4 The Future: Monoclonal vs. Single Domain Antibodies 267 10.5 Summary of mabs Work Cited (Table 10-3) 268 10.6 REFERENCES 270-273 11. BIOSORPTION PUBLICATIONS McGill University Research Group 275 12. APPENDICES 279 Appendix A Matlab Code for HIEM Model 279 Appendix B Fortran Code for Galerkin Finite Element Method 281 Appendix C Fortran Code for Orthogonal Collocation Method 285 Appendix D Matlab Subroutines for Column Concentration Profiles 293-299 13. LIST OF FIGURES and TABLES 301-312 14. INDEX 313-316