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Activated Carbon for Water and Wastewater Treatment

Integration of Adsorption and Biological Treatment

- ec- en and Özgür Aktas-


Ferhan C

ffirs 7 July 2011; 12:8:13


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ffirs 7 July 2011; 12:8:13


- ec- en and Özgür Aktas-
Ferhan C

Activated Carbon for Water and Wastewater


Treatment

Integration of Adsorption and Biological Treatment

WILEY-VCH Verlag GmbH & Co. KGaA

ffirs 7 July 2011; 12:8:13


The Authors & All books published by Wiley-VCH are carefully
produced. Nevertheless, authors, editors, and
Prof. Ferhan C- ec- en publisher do not warrant the information
Bogazici University contained in these books, including this book, to
Inst. of Environmental Sciences be free of errors. Readers are advised to keep in
34342 Istanbul mind that statements, data, illustrations,
Turkey procedural details or other items may
inadvertently be inaccurate.
Dr. Özgür Aktas-
TUBITAK-MRC Library of Congress Card No.: applied for
Environment Institute
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ffirs 7 July 2011; 12:8:13


|V

Contents

Preface xvii
List of Abbreviations xxi
Acknowledgement xxvii

1 Water and Wastewater Treatment: Historical Perspective of


Activated Carbon Adsorption and its Integration with
Biological Processes 1
- ec- en
Ferhan C
1.1 Historical Appraisal of Activated Carbon 1
1.2 General Use of Activated Carbon 3
1.3 Application of Activated Carbon in Environmental
Pollution 4
1.3.1 Activated Carbon in Drinking Water Treatment 4
1.3.2 Activated Carbon in Wastewater Treatment 5
1.3.2.1 Municipal Wastewater Treatment 6
1.3.2.2 Industrial Wastewater Treatment 6
1.3.3 Applications of Activated Carbon in Other
Environmental Media 7
1.3.3.1 Remediation of Contaminated Groundwater and Soil 7
1.3.3.2 Treatment of Flue Gases 7
1.3.3.3 Water Preparation for Industrial Purposes 7
1.3.4 Integration of Activated Carbon Adsorption with
Biological Processes in Wastewater and Water
Treatment 7
1.3.4.1 Wastewater Treatment 7
1.3.4.2 Water Treatment 8
1.3.5 Improved Control of Pollutants through Integrated
Adsorption and Biological Treatment 8

Activated Carbon for Water and Wastewater Treatment: Integration of Adsorption and Biological Treatment.
First Edition. Ferhan Çeçen and Özgür Aktas-
r 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Published 2011 by WILEY-VCH Verlag GmbH & Co. KGaA

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vi
| Contents
2 Fundamentals of Adsorption onto Activated Carbon in Water
and Wastewater Treatment 13
Özgür Aktas- and Ferhan C
- ec- en
2.1 Activated Carbon 13
2.1.1 Preparation of Activated Carbons 13
2.1.2 Characteristics of Activated Carbon 14
2.1.3 Activated Carbon Types 15
2.1.3.1 Powdered Activated Carbon (PAC) 15
2.1.3.2 Granular Activated Carbon (GAC) 16
2.2 Adsorption 16
2.2.1 Types of Adsorption 16
2.2.2 Factors Influencing Adsorption 18
2.2.2.1 Surface Area of Adsorbent 18
2.2.2.2 Physical and Chemical Characteristics of the Adsorbate 18
2.2.2.3 pH 19
2.2.2.4 Temperature 20
2.2.2.5 Porosity of the Adsorbent 20
2.2.2.6 Chemical Surface Characteristics 21
2.2.3 Kinetics of Adsorption 22
2.2.3.1 Transport Mechanisms 22
2.2.4 Adsorption Equilibrium and Isotherms 24
2.2.5 Single- and Multisolute Adsorption 27
2.2.5.1 Single Solute Adsorption 27
2.2.5.2 Multisolute Adsorption 28
2.3 Activated Carbon Reactors in Water and Wastewater
Treatment 30
2.3.1 PAC Adsorbers 30
2.3.2 GAC Adsorbers 30
2.3.2.1 Purpose of Use 30
2.3.2.2 Types of GAC Adsorbers 30
2.3.2.3 Operation of GAC Adsorbers 31
2.3.2.4 Breakthrough Curves 34
2.4 Activated Carbon Regeneration and Reactivation 37

3 Integration of Activated Carbon Adsorption and Biological


Processes in Wastewater Treatment 43
- ec- en and Özgür Aktas-
Ferhan C
3.1 Secondary and Tertiary Treatment: Progression from
Separate Biological Removal and Adsorption to Integrated
Systems 43
3.1.1 Activated Carbon in Secondary Treatment 46
3.1.1.1 PAC 46
3.1.1.2 GAC 46
3.1.2 Activated Carbon in Tertiary Treatment 46

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Contents | vii
3.1.2.1 PAC 46
3.1.2.2 GAC 47
3.2 Fundamental Mechanisms in Integrated Adsorption and
Biological Removal 47
3.2.1 Main Removal Mechanisms for Organic Substrates 47
3.2.1.1 Biodegradation/Biotransformation 48
3.2.1.2 Sorption onto Sludge 52
3.2.1.3 Sorption onto Activated Carbon 53
3.2.1.4 Abiotic Degradation/Removal 53
3.2.2 Main Interactions between Organic Substrates, Biomass, and
Activated Carbon 54
3.2.2.1 Retention of Slowly Biodegradable and Nonbiodegradable
Organics on the Surface of Activated Carbon 56
3.2.2.2 Retention of Toxic and Inhibitory Substances on the Surface
of Activated Carbon 56
3.2.2.3 Concentration of Substrates on the Surface of Activated
Carbon 58
3.2.2.4 Retention of Volatile Organic Compounds (VOCs) on the
Surface of Activated Carbon 58
3.2.2.5 Attachment and Growth of Microorganisms on the Surface
of Activated Carbon 59
3.2.2.6 Biological Regeneration (Bioregeneration) of Activated
Carbon 59
3.2.3 Behavior and Removal of Substrates in Dependence of their
Properties 59
3.3 Integration of Granular Activated Carbon (GAC) into
Biological Wastewater Treatment 59
3.3.1 Positioning of GAC Reactors in Wastewater Treatment 59
3.3.2 Recognition of Biological Activity in GAC Reactors 63
3.3.3 Conversion of GAC into Biological Activated Carbon (BAC) 64
3.3.3.1 Removal Mechanisms and Biofilm Formation in BAC
Operation 65
3.3.3.2 Advantages of BAC Over GAC Operation 66
3.3.3.3 Advantages of the BAC Process Compared to Other
Attached-Growth Processes 66
3.3.4 Main Processes in BAC Reactors 66
3.3.5 Types of GAC Reactors with Biological Activity (BAC
Reactors) 67
3.3.5.1 Fixed-Bed BAC Reactors 67
3.3.5.2 Expanded- and Fluidized-Bed BAC Reactors 68
3.4 Integration of Powdered Activated Carbon (PAC) into
Biological Wastewater Treatment 69
3.4.1 Single-Stage Continuous-Flow Aerobic PACTs Process 70
3.4.1.1 Development of the PACT Process 70
3.4.1.2 Basic Features of the Activated Sludge Process 70

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viii
| Contents
3.4.1.3 Characteristics of the PACT Process 71
3.4.1.4 Process Parameters in PACT Operation 72
3.4.2 Sequencing Batch PACT Reactors 73
3.4.3 Anaerobic PACT Process 74
3.5 Biomembrane Operation Assisted by PAC and GAC 74
3.5.1 Membrane Bioreactors (MBRs) 74
3.5.2 The PAC-MBR Process 75
3.5.3 Membrane-Assisted Biological GAC Filtration – the BioMAC
Process 76
3.6 Observed Benefits of Integrated Systems 76
3.6.1 Enhancement of Organic Carbon Removal by Activated
Carbon 78
3.6.2 Enhancement of Nitrification by Activated Carbon 78
3.6.2.1 Inhibition of Nitrification 79
3.6.2.2 Nitrification in the Presence of PAC 79
3.6.3 Enhancement of Denitrification by Activated Carbon 80
3.6.4 Effect of Activated Carbon Addition on Inorganic Species 80
3.6.5 Enhancing Effects of Activated Carbon in Anaerobic
Treatment 81
3.6.6 Properties of Biological Sludge in the Presence of Activated
Carbon 81
3.6.6.1 Improvement of Sludge Settling and Thickening 81
3.6.6.2 Improvement in the Dewaterability of Sludge 82
3.6.7 Effect of PAC on Membrane Bioreactors (MBRs) 82
3.6.7.1 Importance of Microbial Products 82
3.6.7.2 Effect of Activated Carbon on Microbial Products 83
3.6.7.3 Effect of Activated Carbon on Membrane Filtration 85
3.7 Regeneration of PACT and BAC Sludges 86

4 Effect of Activated Carbon on Biological Treatment of


Specific Pollutants and Wastewaters: Laboratory- and
Pilot-Scale Studies 95
Özgür Aktas- and Ferhan C
- ec- en
4.1 Treatment of Industrial Wastewaters 95
4.1.1 Pharmaceutical Wastewaters 95
4.1.2 Paper and Pulp Wastewaters 97
4.1.3 Petroleum Refinery and Petrochemical Wastewaters 98
4.1.4 Textile Wastewaters 99
4.1.5 Other Industrial Wastewaters 100
4.2 Removal of Specific Chemicals 104
4.2.1 Volatile Organic Compounds (VOCs) 104
4.2.2 Phenols 106
4.2.3 Pharmaceuticals and Endocrine Disrupting Compounds
(EDCs) 109
4.2.4 Pesticides and Polychlorinated Biphenyls (PCBs) 109

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Contents | ix
4.2.5 Priority Pollutants 109
4.2.6 Dyes 110
4.2.7 Organic Pollutants in Secondary Sewage Effluents 111
4.2.8 Other Chemicals 112
4.3 Landfill Leachate Treatment 113
4.3.1 Leachate Treatment in PAC-added Activated Sludge
Systems 114
4.3.2 Leachate Treatment Using the PAC-MBR Process 118
4.3.3 Leachate Treatment in Biological Activated Carbon (BAC)
Media 118

5 Combination of Activated Carbon with Biological


Wastewater Treatment at Full Scale 127
Özgür Aktas- and Ferhan C
- ec- en
5.1 Full-Scale PACT Systems 127
5.1.1 Full-Scale PACT for Industrial Effluents 128
5.1.1.1 Organic Chemicals Production Industry 128
5.1.1.2 Synthetic Fiber Manufacturing Industry 130
5.1.1.3 Propylene Oxide/Styrene Monomer (PO/SM) Production
Wastewater 130
5.1.1.4 Refinery and Petrochemical Wastewaters 131
5.1.1.5 Treatment of Priority Pollutants 134
5.1.1.6 Treatment of Pharmaceutical Wastewaters 135
5.1.2 PACT for Co-treatment of Domestic and Industrial
Wastewaters 136
5.1.3 PACT for Landfill Leachates 136
5.1.4 PACT for Contaminated Groundwaters 138
5.1.5 PACT for Reuse of Domestic Wastewaters 139
5.1.6 PACT for Contaminated Surface Runoff Waters 139
5.2 Biological Activated Carbon (BAC) Filtration at Full
Scale 140
5.2.1 BAC Filtration for Reuse Purposes 140
5.2.1.1 Treatment of Sewage for Reuse in Agriculture 140
5.2.1.2 Reclamation of Domestic Wastewater for Drinking
Purposes 140
5.2.1.3 Reclamation of Domestic and Industrial Wastewaters for
Nonpotable Uses 141

6 Modeling the Integration of Adsorption with Biological


Processes in Wastewater Treatment 145
- ec- en
Ferhan C
6.1 Modeling of GAC Adsorbers with Biological Activity 145
6.1.1 Introduction 145
6.1.2 Fundamental Processes around a Carbon Particle
Surrounded by a Biofilm 146

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x
| Contents
6.1.3 Benefits of Integrated Adsorption and Biological Removal:
Link to Fundamental Processes 155
6.1.4 Modeling Approaches in GAC/BAC Reactors 158
6.1.4.1 Mass Balances in GAC/BAC Reactors 158
6.1.4.2 Characterization of BAC Reactors by Dimensionless
Numbers 164
6.1.5 Prevalent Models in BAC Reactors Involving Adsorption and
Biodegradation 173
6.1.5.1 Initial Steps in Modeling: Recognizing the Benefits of
Integrated Systems 173
6.1.5.2 Consideration of Substrate Removal and Biofilm Formation 173
6.1.5.3 Integration of Adsorption into Models 174
6.1.5.4 Modeling in the Case of High Substrate Concentrations 175
6.1.5.5 Modeling the Case of Very Low Substrate (Fasting)
Conditions 176
6.1.5.6 Modeling the Step Input of Substrate in a Three-Phase
Fluidized-Bed Reactor 177
6.1.5.7 Consideration of Carbon Properties in Modeling 177
6.2 Modeling of the PACT Process 178
6.2.1 Mass Balances in the PACT Process 178
6.2.2 Mass Balance for PAC in the PACT Process 178
6.2.2.1 Determination of Biomass or Carbon Concentration in a
PACT Sludge 180
6.2.3 Models Describing Substrate Removal in the PACT Process 181

7 Bioregeneration of Activated Carbon in Biological


Treatment 189
Özgür Aktas- and Ferhan C
- ec- en
7.1 Mechanisms of Bioregeneration 189
7.1.1 Bioregeneration Due to Concentration Gradient 189
7.1.2 Bioregeneration Due to Exoenzymatic Reactions 191
7.1.3 Bioregeneration Due to Acclimation of Biomass 193
7.2 Offline Bioregeneration 194
7.3 Concurrent (Simultaneous) Bioregeneration in PACT and
BAC Systems 195
7.4 Dependence of Bioregeneration on the Reversibility of
Adsorption 195
7.5 Other Factors Affecting Bioregeneration 198
7.5.1 Biodegradability 199
7.5.2 Chemical Properties of Substrate 200
7.5.3 Carbon Particle Size 200
7.5.4 Carbon Porosity 201
7.5.5 Carbon Activation Type 202
7.5.6 Physical Surface Properties of Carbon 202

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Contents | xi
7.5.7 Desorption Kinetics 203
7.5.8 Substrate–Carbon Contact Time 203
7.5.9 Concentration Gradient and Carbon Saturation 204
7.5.10 Biomass Concentration 205
7.5.11 Dissolved Oxygen Concentration 206
7.5.12 Microorganism Type 206
7.5.13 Substrate and Biomass Associated Products of
Biodegradation 207
7.5.14 Presence of Multiple Substrates 208
7.6 Determination of Bioregeneration 209
7.6.1 Investigation of the Extent of Reversible Adsorption 211
7.6.2 Use of Adsorption Isotherms 211
7.6.3 Direct Measurement by Using Adsorption Capacities 213
7.6.4 Direct Measurement by Solvent Extraction 213
7.6.5 Quantification of Bioregeneration in Simultaneous Adsorption–
Biodegradation 213
7.6.6 Measurement of Biodegradation Products 214
7.6.7 Use of Respirometry in Aerobic Systems 215
7.6.8 Investigation by Scanning Electron Microscopy (SEM) 216
7.7 Bioregeneration in Anaerobic/Anoxic Systems 216
7.8 Models Involving Bioregeneration of Activated
Carbon 217
7.8.1 Modeling of Bioregeneration in Concurrent Adsorption and
Biodegradation 218
7.8.2 Modeling of Bioregeneration in Single Solute Systems 220
7.8.3 Modeling of Bioregeneration in Multicomponent Systems 225
7.8.4 Modeling of Offline Bioregeneration 228
7.8.5 Modeling the Kinetics of Bioregeneration 228

8 Combination of Activated Carbon Adsorption and Biological


Processes in Drinking Water Treatment 237
- ec- en
Ferhan C
8.1 Introduction 237
8.2 Rationale for Introduction of Biological Processes in Water
Treatment 238
8.3 Significance of Organic Matter in Water Treatment 238
8.3.1 Expression and Fractionation of Organic Matter 239
8.3.1.1 Expression of Organic Matter in Terms of Organic Carbon 239
8.3.1.2 Measurement of the Biodegradable Fraction in NOM 239
8.3.1.3 Nonbiodegradable Dissolved Organic Carbon (non-BDOC or
NBDOC) 243
8.3.1.4 Fractionation of NOM in Terms of Molecular Size and Chemical
Behavior 243
8.4 Removal of NOM in Conventional Water Treatment 244

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xii
| Contents
8.4.1 Rationale for NOM Removal 244
8.4.2 Extent of NOM Removal 245
8.5 Use of Activated Carbon in Water Treatment 246
8.5.1 Powdered Activated Carbon (PAC) Addition 246
8.5.2 Granular Activated Carbon (GAC) Filtration 247
8.6 Biological Activated Carbon (BAC) Filtration 247
8.6.1 History of BAC Filtration in Water Treatment 247
8.6.2 Combination of Ozonation and BAC Filtration 249
8.6.3 Current Use of BAC Filtration in Water Treatment 249
8.7 Adsorption and Biodegradation Characteristics of
Water 250
8.7.1 Raw Water NOM 250
8.7.2 Impact of Ozonation on NOM Characteristics 250
8.7.2.1 Increase in the Biodegradability of NOM 251
8.7.2.2 Change in the Adsorbability of NOM 255
8.7.3 Determination of Adsorption and Biodegradation
Characteristics of Water 255

9 Removal of NOM, Nutrients, and Micropollutants in


BAC Filtration 265
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Ferhan C
9.1 Removal of Organic Matter 265
9.1.1 Main Mechanisms 265
9.1.2 Breakthrough Curves 265
9.1.2.1 Initial Stage of Operation: Removal by Adsorption 265
9.1.2.2 Intermediate and Later Stages of Operation 266
9.1.3 Bioregeneration of BAC Filters 272
9.2 Factors Affecting the Performance of BAC Filtration 273
9.2.1 Comparison of GAC with Other Media 273
9.2.1.1 Biomass Attachment 273
9.2.1.2 Removal Performance 273
9.2.2 Importance of GAC Grade 274
9.2.2.1 Coal- and Wood-Based GAC 274
9.2.2.2 GAC Activation 274
9.2.3 Empty Bed Contact Time (EBCT) and Hydraulic Loading Rate
(HLR) 274
9.2.4 Filter Backwashing 276
9.2.5 Effect of Temperature 276
9.2.6 Effect of Oxidant Residuals 277
9.3 Performance of BAC Filters: Organics Removal 277
9.4 Performance of BAC Filters: Nutrient Removal 285
9.4.1 Nitrification in BAC Filters 285
9.4.1.1 Importance of Ammonia Removal 285

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Contents | xiii
9.4.1.2 Factors Affecting Nitrification in BAC Filters 285
9.4.2 Denitrification in BAC Filters 286
9.5 Removal of Micropollutants from Drinking Water in BAC
Systems 288
9.5.1 Occurrence of Organic Micropollutants in Water 288
9.5.2 Competition Between Background NOM and Organic
Micropollutants 288
9.5.3 Adsorption of Organic Micropollutants onto Preloaded
GAC 290
9.5.4 Effect of GAC Characteristics on Adsorption 290
9.5.5 Adsorption and Biological Removal of Organic Micropollutant
Groups in BAC Filtration 291
9.5.5.1 Pesticides 291
9.5.5.2 Pharmaceuticals and Endocrine Disrupting Compounds
(EDCs) 291
9.5.5.3 Geosmin and MIB 292
9.5.5.4 Microcystins (Toxic Algal Metabolites) 293
9.5.5.5 Other Organic Micropollutants 294
9.5.6 Removal of Precursors and Disinfection By-Products (DBPs) in
BAC Filtration 294
9.5.6.1 Removal of DBP Precurcors in BAC Filters 295
9.5.6.2 Removal of Trihalomethanes (THMs) and Haloacetic Acids
(HAAs) in BAC Filters 297
9.6 Removal of Ionic Pollutants in BAC Filtration 298
9.6.1 Nitrate Removal 298
9.6.2 Bromate Removal 298
9.6.3 Perchlorate Removal 301
9.7 Integration of PAC and GAC into Biological Membrane
Operations 302
9.7.1 Effect of PAC on Membrane Bioreactors 302
9.7.2 BAC Filtration Preceding Membrane Bioreactor
Operation 303
9.8 Integration of GAC into Groundwater Bioremediation 303
9.9 Biomass Characteristics in BAC Filtration 304
9.9.1 Microbial Ecology of BAC Filters 304
9.9.2 Control of Biofilm Growth in BAC Filters 305
9.9.3 Determination of Biomass and Microbial Activity in BAC
Filters 305
9.9.4 Determination of Microorganisms by Classical and Molecular
Microbiology Methods 306
9.9.4.1 Heterotrophic Biomass and Activity in BAC Filters 306
9.9.4.2 Nitrifying Biomass and Activity in BAC Filters 308
9.9.5 Microbiological Safety of Finished Water 309

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xiv
| Contents
10 BAC Filtration Examples in Full-Scale Drinking Water
Treatment Plants 319
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Ferhan C
10.1 Limits for BDOC and AOC as Indicators of Re-growth
Potential in Water Distribution 319
10.2 BAC Filtration Experiences in Full-Scale Surface Water
Treatment 320
10.2.1 Mülheim Plants, Germany 320
10.2.2 Leiden Plant, Amsterdam, the Netherlands 320
10.2.3 Plants in the Suburbs of Paris, France 322
10.2.4 Ste Rose Plant in Quebec, Canada 323
10.2.5 Plant in Zürich-Lengg, Switzerland 323
10.2.6 Weesperkarspel Plant, Amsterdam, the Netherlands 324
10.2.7 Drinking Water Treatment Plants, Bendigo, Castlemaine, and
Kyneton, Victoria, Australia 326
10.3 New Approaches in the Evaluation of Ozonation and BAC
Filtration 327
10.4 BAC Filtration Experiences in Full-Scale Groundwater
Treatment 327

11 Review of BAC Filtration Modeling in Drinking Water


Treatment 331
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Ferhan C
11.1 Substrate Removal and Biofilm Formation 331
11.2 Modeling of BAC Filtration 333
11.2.1 Models Emphasizing Biological Processes in Biofilters 334
11.2.1.1 Initial Models in Biofiltration 334
11.2.1.2 The CHABROL Model 335
11.2.1.3 Uhl’s Model 335
11.2.1.4 The Model of Wang and Summers 337
11.2.1.5 The Dimensionless Empty-Bed Contact Time
Concept 338
11.2.1.6 The BIOFILT Model 339
11.2.1.7 Consideration of Multiple Species Inside Drinking Water
Biofilters 341
11.2.2 Models Integrating Adsorption and Biological Processes 342
11.2.2.1 Initial Models 342
11.2.2.2 Models Involving Adsorption, Biomass Development, and
Biodegradation 343
11.2.3 Models Describing the Removal of Micropollutants 346
11.2.3.1 Pesticides/Herbicides Removal 346
11.2.3.2 Perchlorate Removal 347

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Contents | xv
11.2.3.3 Microcystin Removal 348
11.2.3.4 THM Removal 348

12 Concluding Remarks and Future Outlook 353


- ec- en and Özgür Aktas-
Ferhan C
12.1 Overview of Applications in Wastewater and Water
Treatment: PACT and BAC Systems 353
12.2 Further Research on Removal Mechanisms and
Micropollutant Elimination 355
12.2.1 Wastewater Treatment 355
12.2.2 Drinking Water Treatment 358
12.3 Further Research on Regeneration of Activated
Carbon 360
12.3.1 Importance of Activated Carbon Grade 360
12.3.2 Bioregeneration of Activated Carbon 361
12.3.2.1 Discussion of the Term ‘Bioregeneration’ and Hypotheses 361
12.3.2.2 Bioregeneration of Activated Carbon in the Case of
Micropollutants 362
12.3.2.3 Bioregeneration Conditions 362
12.3.2.4 Bioregeneration of Activated Carbon in Drinking Water
Treatment 363
12.3.3 Physicochemical Regeneration of Biological Activated
Carbon 363

Index 365

FTOC 8 July 2011; 15:29:49

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