THANATIAThe Destiny of the Earth's

Mineral Resources

A Cradle-to-Cradle Thermodynamic Assessment

Antonio Valero CapillaAlicia Valero Delgado

CIRCE - Universidad de Zaragoza, Spain

World Scientific

NEW JERSEY • LONDON • SINGAPORE • BEIJING • SHANGHAI • HONG KONG • TAIPEI • CHENNAI

Contents

Preface vii

Acknowledgments xv

List of Figures xxxi

List of Tables xxxvii

The Threads: Minerals, Economy and Thermodynamics 1

1. The Depletion of Non-Renewable Abiotic Resources 3

1.1 Introduction 3

1.2 The demand for minerals 3

1.3 Energy and environment 7

1.4 Materials demand for the new Green Economy 9

1.4.1 Bioenergy 10

1.4.2 Solar photovoltaics 12

1.4.3 Wind energy 13

1.5 The shortage of strategic elements. An international problem ... 15

1.6 The implications of mineral scarcity 20

1.7 Thanatia: the destiny of mineral resources? 21

1.8 Summary of the chapter 24

2. Economic versus Thermodynamic: Accounting 27

2.1 Introduction 27

2.2 Natural capital concept 27

2.3 Cost, price and value 29

2.4 The economists' view 30

2.4.1 The neoclassical approach 31

2.4.2 A discussion on the Hotelling and Barnct and Morse

approaches 32

xix

xx Thanaiia: The Destiny of Ike Earth's Mineral Resources

2.4.3 The environmental economists' approach 33

2.4.4 The ecological economists' approach 34

2.4.5 How is economic thinking related to the Entropy Law and

its recent developments? 38

2.5 The accountants' view 40

2.5.1 The SNA and the U.N. System of Environmental-Economic

Accounts (SEEA) 40

2.5.2 The net price and the user cost methods 43

2.5.3 The Hueting approach: environmental functions 46

2.5.4 Weak and strong sustainability 49

2.5.5 Mineral capital or mineral endowment? 50

2.6 The natural scientists' view 52

2.6.1 Material input per unit of service 53

2.6.2 Ecological footprint 54

2.6.3 Energy/exergy indicators 54

2.6.4 Energy, land and time indicators: a relationship? 57

2.6.5 Thermoeconomics 59

2.7 Summary of the chapter 59

3. From Thermodynamics to Economics and Ecology 63

3.1 Introduction 63

3.2 Second Law: the link between Physics and Economics 63

3.2.1 The First Law 63

3.2.2 The Second Law 65

3.2.3 Exergy and the Snow White myth 67

3.2.4 The nature of irreversibility 70

3.3 From Thermodynamics to Economics: Thermoeconomics 71

3.3.1 Basics of Thermoeconomics 72

3.3.2 The exergy cost 74

3.3.3 Success and shortcomings of Thermoeconomics 78

3.3.4 Thermoeconomics a new vision of saving natural resources 79

3.4 From Thermoeconomics to Ecology: Exergoeeology and

Physical Geonomics 80

3.5 Philosophical afterthoughts and warnings 82

3.6 Summary of the chapter 85

4. Physical Geonomics: A Cradle-Grave-Cradle Approach for

Mineral Depletion Assessment 87

4.1 Introduction 87

4.2 Material cycles and the dispersion problem 87

4.3 The view over the rainbow: cradle to grave 90

4.4 The view down the rainbow: grave to cradle 92

Contents xxi

4.5 Thermodynamic rarity 96

4.6 Summary of the chapter 100

Over the Rainbow: From Nature to Industry 103

5. The Geochemistry of the Earth 105

5.1 Introduction 105

5.2 The bulk Earth 105

5.2.1 The composition of the Earth 105

5.3 The atmosphere 107

5.3.1 The chemical composition of the atmosphere 108

5.4 The hydrosphere 108

5.4.1 Seawater 110

5.4.2 Renewable water resources: surface and groundwaters . . .115

5.4.3 Ice caps, ice sheets and glaciers 117

5.5 The continental crust 119

5.5.1 The chemical composition of the upper continental crust.

121

5.6 The mineralogical composition of the upper continental crust. . .

124

5.6.1 Early models of the mineralogical composition of the crust 125

5.7 Summary of the chapter 131

6. The Resources of the Earth 133

6.1 Introduction 133

6.2 Natural resources: definition, classification and early assessments.

133

6.3 The energy balance 134

6.4 Energy from the solid Earth 135

6.4.1 Geothennal energy 136

6.4.2 Nuclear energy 137

6.5 Tidal energy 139

6.6 Energy from the sun 140

6.6.1 Solar power 140

6.6.2 Hydroelectricity 141

6.6.3 Wind energy 142

6.6.4 Ocean energy 143

6.6.5 Biomass 145

6.6.6 Fossil fuels 146

6.7 Energy resources summary 155

6.8 Non-fuel mineral resources 156

6.8.1 The economic classification of minerals 158

6.8.2 Average mineral ore grades 159

6.8.3 Mineral abundance 161

xxii ThanaLia: The Destiny of the liarlh's Mineral Resources

6.9 Summary of the chapter 164

7. An Introduction to Mining and Metallurgy 165

7.1 Introduction 165

7.2 Exploration 165

7.3 Mining 167

7.4 Reclamation, rehabilitation and post-closure 169

7.5 Smelting and refining 169

7.5.1 Pyrometallurgy 170

7.5.2 Hydrometallurgy 171

7.6 General environmental issues 173

7.6.1 The environmental impact of mining 173

7.6.2 The environmental impact of smelting 176

7.7 Summary of the chapter 177

8. Metallurgy of Key Minerals 179

8.1 Introduction 179

8.2 Iron and steel 180

8.2.1 Process 180

8.2.2 Energy and environmental issues 181

8.3 Aluminium 183

8.3.1 Process 183

8.3.2 Energy and environmental issues 184

8.4 Copper 187

8.4.1 Process 187

8.4.2 Energy and environmental issues 188

8.5 Copper related metals: Selenium and Tellurium 190

8.6 Tin 191

8.6.1 Process 191

8.6.2 Energy and environmental issues 191

8.7 Nickel and Cobalt 192

8.7.1 Nickel sulphides process 192

8.7.2 Nickel laterites process 194

8.7.3 Energy and environmental issues 195

8.8 Lead, Zinc, Cadmium and related ore metals 197

8.8.1 Lead process 198

8.8.2 Zinc process 199

8.8.3 Energy and environmental issues of lead and zinc

production 201

8.8.4 Cadmium 203

8.8.5 Indium, Germanium and other co-products 203

8.9 Precious metals 204

Contents xxiii

8.9.1 Silver process 205

8.9.2 Gold process 206

8.9.3 Platinum Group Metals process 207

8.9.4 Energy and environmental issues of precious metals....

208

8.10 Mercury 210

8.11 Refractory metals 211

8.11.1 Chromium 212

8.11.2 Manganese 213

8.11.3 Tungsten (Wolfram) 214

8.11.4 Vanadium 215

8.11.5 Molybdenum 216

8.11.6 Titanium 217

8.11.7 Niobium and Tantalum 219

8.11.8 Rhenium 221

8.11.9 Zirconium and Hafnium 222

8.12 Lithium and Magnesium 223

8.12.1 Lithium 223

8.12.2 Magnesium 225

8.13 Rare Earth Metals 226

8.13.1 Main uses of REE 227

8.13.2 Geochemistry of REE 228

8.13.3 Main REE deposits 230

8.13.4 Extraction and physical bcneficiation of REO 231

8.13.5 Chemical upgrading of REO 232

8.13.6 Isolation of RE Elements 232

8.13.7 From REO to RE metals 235

8.13.8 Purification of RE metals 237

8.13.9 REE alloys 239

8.13.10 Energy and environmental issues of REE 240

8.14 Summary of the chapter 244

Down the Rainbow: From Grave to Cradle 251

9. Thermodynamics of Mineral Resources 253

9.1 Introduction 253

9.2 Thermodynamic analysis of mineral formation and its industrial

treatment 253

9.2.1 Stage I: molecular formation 254

9.2.2 Stage II: solidification 255

9.2.3 Stage III: mineralisation and rock formation 256

9.2.4 Stage IV: formation of a mineral deposit 256

xxiv Thanatia: The Destiny of the liarlh'« Mineral Resources

9.2.5 Stage Va and Vb: mining and beneficiation 257

9.2.6 Stage Via and Vlb: smelting and refining 257

9.3 Entropic analysis 257

9.3.1 Entropy of mixing, pollution, separation and purification . 258

9.3.2 Entropy, probability and information 261

9.4 An entropic vision of mining and smelting 263

9.4.1 Mining exploration 263

9.4.2 Mining exploitation: declining ore grades and scarcity . . . 264

9.4.3 Separation processes in beneficiation, smelting and refining 264

9.5 The exergy of non-fuel mineral resources 272

9.5.1 General definition 273

9.5.2 The exergy of non-fuel mineral resources 275

9.5.3 The chemical exergy of fossil fuels 281

9.6 Exergy costs 281

9.7 Thermoeconomics in the mining and metallurgical industry .... 283

9.7.1 Cost of input mineral resources 284

9.7.2 Allocation 285

9.7.3 The importance of disaggregation 286

9.7.4 Thermoeconomics and LCA 287

9.8 Summary of the chapter 288

10. Thanatia and the Crepuscular Earth Model 291

10.1 Introduction 291

10.2 Thanatia: the baseline for the exergy assessment of mineral

resources 291

10.2.1 Entropic versus commercial death of the planet 292

10.2.2 Thanatia compared with Gaia and Medea 294

10.3 The Crepuscular Earth Model 296

10.3.1 The crepuscular atmosphere 296

10.3.2 The crepuscular hydrosphere 301

10.3.3 The crepuscular continental crust 302

10.4 The difference between Thanatia and the reference environment. .

312

10.5 Summary of the chapter 315

11. The Exergy of the Earth and its Mineral Resources 317

11.1 Introduction 317

11.2 The properties of the Earth 317

11.2.1 The thermodynamic properties of the atmosphere 318

11.2.2 The thermodynamic properties of the hydrosphere 319

11.2.3 The thermodynamic properties of the upper continental crust324

11.2.4 The chemical exergy of the Earth 332

11.3 The exergy of mineral resources 332

Contents xxv

11.3.1 The exergy contained in fossil fuels 333

11.3.2 The exergy of non-fuel minerals 343

11.3.3 The exergy of natural resources on Earth 346

11.4 Summary of the chapter 349

12. The Exergy Replacement Costs of Mineral Wealth 351

12.1 Introduction 351

12.2 Formulas for assessing the exergy replacement costs of minerals. .

351

12.3 Technological development and the theory of learning curves. . .

356

12.4 Energy consumption as a function of ore grade for some import ant

commodities 357

12.4.1 Gold 357

12.4.2 Copper 358

12.5 The exergy replacement costs of the minerals on Earth 359

12.6 The decrease of mineral endowment due to raw material

production 363

12.7 The mineral exergy replacement costs of world mineral reserves. . 366

12.8 Summary of the chapter 370

13. The Exergy Evolution of Mineral Wealth 371

13.1 Introduction 371

13.2 The Hubbert Peak Model applied to exergy 371

13.3 The depletion of the exergy reservoir for the principal minerals in

Australia 376

13.3.1 Gold 377

13.3.2 Copper 378

13.3.3 Nickel 379

13.3.4 Silver 380

13.3.5 Lead 382

13.3.6 Zinc 384

13.3.7 Iron 385

13.3.8 Coal 387

13.3.9 Oil 388

13.3.10 Summary and discussion of the results 391

13.3.11 The exergy countdown 396

13.4 Conversion of exergy costs into monetary costs 399

13.5 The depletion of the exergy reservoir of the Earth's principal

minerals in the 20th century 401

13.5.1 Non-fuel minerals 401

13.5.2 Fuel minerals 411

13.6 Summary of the chapter 425

xxvi Thanatia: The Destiny of the liarth's Mineral Resources

Tying the Rainbows: Towards a Rational Management of

Resources 429

14. Recycling Solutions 431

14.1 Introduction 431

14.2 Levels of criticality 431

14.3 Materials recycling: A global view 432

14.4 Urban mining 436

14.5 EoL technologies 438

14.6 Minor metals recovery 440

14.6.1 Minor metals recovery from BoL 440

14.6.2 Minor metals recovery from EoL 442

14.7 Entropic backfire: reagents and recyclate entropy generation .... 444

14.8 Conventional vs urban mining 445

14.9 Summary of the chapter 448

15. The Challenge of Resource Depletion 451

15.1 Introduction 451

15.2 Geological scarcity or commercial shortage? 451

15.3 Putting the brake on Gaia's evolution towards Thanatia 455

15.4 Meeting the challenge 457

15.4.1 The Earth cannot be subject to the economics of Man. . 458

15.4.2 Understanding the complexity of the natural web 461

15.4.3 Maintenance as the key to resource preservation 464

15.5 A Third Industrial Revolution? 467

15.6 Summary of the chapter 468

16. The Principles of Resource Efficiency 471

16.1 Introduction 471

16.2 The necessity for a rational management of resources 471

16.3 The principles 473

16.4 Summary of the chapter 493

17. Epilogue 495

17.1 Introduction 495

17.2 Thermodynamics and the global view of resources 496

17.2.1 Exergy is a universal measure for resource accounting . . . 496

17.2.2 Abiotic resources are not well denned thermodynamic

systems 497

17.2.3 Thanatia is a coherent baseline for mineral exergy

calculations 498

Contents xxvii

17.2.4 Exergy costs inform as to the physical irreversibility of pro¬

duction processes 499

17.2.5 Cradle-to-grave technologies constitute only half of a ma¬

terial cycle 500

17.2.6 Depletion should be measured on a grave-to-cradle basis

through exergy replacement costs 501

17.2.7 The thermodynamic rarity of minerals indicate the hidden

and real costs associated with production 502

17.2.8 Replacement costs, technology and conservation of

resources 504

17.2.9 Exergy replacement cost: a good environmental indicator? 50G

17.3 Main outcomes of the thermodynamic assessment of the mineral

endowment 507

17.3.1 Mineral endowment exergy 507

17.3.2 Mineral endowment exergy replacement costs 508

17.3.3 The exergy evolution of mineral endowment 509

17.4 The spiraling tree of the elements 511

17.5 A way to cross over from the theoretical to the practical 513

17.5.1 From SEEA to a global system of environmental-

thermo-economic accounts 514

17.5.2 Appeal to the UN and the EU by thermodynamic

researchers 515

Appendix A Materials in "Green" Technologies 517

A.l Mobile phones and ICTs 517

A.2 Electric and hybrid vehicles 518

A.3 Energy saving in lighting 521

Appendix B Geochemistry and Main Uses of Minerals 523

B.l Main groups of minerals found in Nature 523

B.l.l The silica minerals 523

B.l.2 The feldspar group 523

B.l.3 The pyroxene group 523

B.l.4 The amphibole group 524

B.l.5 The olivine group 524

B.l.6 The mica group 524

B.l.7 The chlorite group525

B.2 Main uses and geochemistry of the most commonly produced

minerals 525

B.2.1 Aluminium 525

B.2.2 Antimony 526

B.2.3 Arsenic 526

Thanatia: The Destiny of the liarlh's Mineral Resources

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Contents xxix

B.2.46 Phosphorous 540

B.2.47 Platinum 541

B.2.48 Potassium 541

B.2.49 Praseodymium 541

B.2.50 Rare Earth Elements: Praseodymium, Samarium,

Europium, Gadolinium. Terbium, Dysprosium, Holmimn,Erbium, Thulium and Lutetimn 542

B.2.51 Rhenium 542

B.2.52 Rhodium 542

B.2.53 Rubidium 543

B.2.54 Ruthenium 543

B.2.55 Samarium 543

B.2.56 Scandium 543

B.2.57 Selenium 544

B.2.58 Silicon 544

B.2.59 Silver 545

B.2.60 Sodium 545

B.2.61 Strontium 545

B.2.62 Sulphur 545

B.2.63 Tantalum 54C

B.2.64 Tellurium 54G

B.2.65 Terbium 540

B.2.66 Thallium 547

B.2.67 Thorium 547

B.2.68 Thulium 547

B.2.69 Tin 548

B.2.70 Titanium 548

B.2.71 Uranium 548

B.2.72 Vanadium 548

B.2.73 Wolfram (Tungsten) 549

B.2.74 Ytterbium 549

B.2.75 Yttrium 549

B.2.76 Zinc 550

B.2.77 Zirconium 550

Appendix C The System of Environmental-Economic Accounts 553

C. l Asset accounts for mineral and energy resources in the SEEA. . .

553

Appendix D Additional Data and Calculation Procedures 559

D.l Standard redox potentials 559

D.2 Data required for calculating the comminution exergy 5G0

D.3 Calculation of the chemical exergy of fuels 5G3

XXX Thanalia: The Destiny of the Earth's Mineral Resources

D.4 Comparisons between the upper crust models of Grigor'ev (2007)and Rudnick and Gao (2004) 569

D.5 Australian fossil fuel production 571

D.5.1 Coal 571

D.5.2 Oil 571

D.5.3 Natural gas 572

D.6 World's fuel production 573

D.6.1 Uranium 573

D.6.2 Coal 574

D.6.3 Oil 575

D.6.4 Natural gas 576

Appendix E An Interview with Nicholas Georgescu-Roegen 579

Bibliography 589

Index 625