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Bechtold811718_bindex.indd 656 25-03-2023 00:25:06
Handbook of Natural Colorants
Second Edition
Wiley Series
in
Renewable Resources
Series Editor:
Christian V. Stevens, Faculty of Bioscience Engineering, Ghent University, Belgium
Titles in the Series:

Wood Modification: Chemical, Thermal and Other Processes
Callum A. S. Hill
Renewables-Based Technology: Sustainability Assessment
Jo Dewulf, Herman Van Langenhove
Biofuels
Wim Soetaert, Erik Vandamme
Handbook of Natural Colorants
Thomas Bechtold, Avinash P. Manian, Tung Pham
Surfactants from Renewable Resources
Mikael Kjellin, Ingegärd Johansson
Industrial Applications of Natural Fibres: Structure, Properties and Technical Applications
Jörg Müssig
Thermochemical Processing of Biomass: Conversion into Fuels, Chemicals and Power
Robert C. Brown
Biorefinery Co-Products:
Phytochemicals, Primary Metabolites and Value-Added Biomass Processing
Chantal Bergeron, Danielle Julie Carrier, Shri Ramaswamy
Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and
Chemicals
Charles E. Wyman
Bio-Based
Plastics: Materials and Applications
Stephan Kabasci
Introduction to Wood and Natural Fiber Composites
Douglas D. Stokke, Qinglin Wu, Guangping Han
Cellulosic Energy Cropping Systems
Douglas L. Karlen
Introduction to Chemicals from Biomass, 2nd Edition
James H. Clark, Fabien Deswarte
Lignin and Lignans as Renewable Raw Materials: Chemistry, Technology and Applications
Francisco G. Calvo-Flores,
Jose A. Dobado, Joaquín Isac-García,
Francisco J. Martín-Martínez
Sustainability Assessment of Renewables-Based
Products: Methods and Case Studies
Jo Dewulf, Steven De Meester, Rodrigo A. F. Alvarenga
Cellulose Nanocrystals: Properties, Production and Applications
Wadood Hamad
Fuels, Chemicals and Materials from the Oceans and Aquatic Sources
Francesca M. Kerton, Ning Yan
Bio-Based Solvents
François Jérôme and Rafael Luque
Nanoporous Catalysts for Biomass Conversion
Feng-Shou
Xiao and Liang Wang
Thermochemical Processing of Biomass: Conversion into Fuels, Chemicals and Power
2nd Edition
Robert Brown
Chitin and Chitosan: Properties and Applications
Lambertus A.M. van den Broek and Carmen G. Boeriu
The Chemical Biology of Plant Biostimulants
Danny Geelen, Lin Xu
Biorefinery of Inorganics: Recovering Mineral Nutrients from Biomass and Organic Waste
Erik Meers, Evi Michels, René Rietra, Gerard Velthof
Process Systems Engineering for Biofuels Development
Adrián Bonilla-Petriciolet, Gade P. Rangaiah
Waste Valorisation: Waste Streams in a Circular Economy
Carol Sze Ki Lin, Chong Li, Guneet Kaur, Xiaofeng Yang
Bio-Based Packaging: Material, Environmental and Economic Aspects
Salit Mohd Sapuan, Rushdan Ahmad Ilyas
High-Performance Materials from Bio-based Feedstocks
Andrew J. Hunt, Nontipa Supanchaiyamat, Kaewta Jetsrisuparb, Jesper T. Knijnenburg
Forthcoming Titles:
Biogas Plants: Waste Management, Energy Production and Carbon Footprint Reduction
Wojciech Czekała
Handbook of Natural
Colorants
Second Edition
Edited by
THOMAS BECHTOLD
University of Innsbruck
Research Institute of Textile Chemistry and Textile Physics
Austria
AVINASH P. MANIAN
Austria
TUNG PHAM
Austria
This edition first published 2023
© 2023 John Wiley & Sons Ltd
All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means,
electronic, mechanical, photocopying, recording or otherwise, except as permitted by law. Advice on how to obtain permission to reuse
material from this title is available at http://www.wiley.com/go/permissions.
The right of Thomas Bechtold, Avinash P. Manian, and Tung Pham to be identified as the authors of the editorial material in this work has
been asserted in accordance with law.
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Library of Congress Cataloging-in-Publication Data applied for:
Hardback ISBN: 9781119811718
Cover image: © sagarmanis/Getty Images

Cover design: Wiley
Set in 9.5/12.5pt STIXTwoText by Straive, Chennai, India

Contents
List of Contributors xxi

Series Preface xxv
Preface xxvii
I Historical Development 1
1 History of Natural Dyes in the Ancient Mediterranean Civilization 3

Maria J. Melo
1.1 Introduction 3
1.1.1 Ancient Mediterranean World 3
1.1.2 Dyes from Antiquity 4
1.1.3 Unveiling the Secrets of Ancient Dyes with Modern Science 7
1.2 Ancient Reds 7
1.2.1 Anthraquinone Reds 7
1.2.2 Redwoods 10
1.2.3 Flavylium/Anthocyanin Reds 12
1.2.3.1 Equilibria in solution 13
1.3 Ancient Blues 14
1.3.1 Indigo Blues 14
1.3.2 Anthocyanin Blues 15
1.4 Ancient Purples 16
1.4.1 Tyrian Purple: Real Purple from Sea Snails 16
1.4.2 Orchil Purples 18
1.4.3 Folium 18
1.5 Ancient Yellows 20
1.5.1 Flavonoid Yellows 20
1.5.2 Carotenoid Yellows 21
1.5.3 Chalcone and Aurone Yellows 22
Acknowledgements 22
References 22
viii Contents
2 Colors in Civilizations of the World and Natural Colorants:

History under Tension 27
Dominique Cardon
2.1 Introduction 27
2.2 The Triumph of Mauveine: Synthetic Fulfillment of the Antique Purplemania 28
2.3 Blue: From Kingly Regional to Globally Democratic 29
2.4 Red and Yellow: From Micro to Macro Scales 29
2.5 What Is the Future for Natural Colorants in the Dawning Era
of Renewable Resources?30
Acknowledgement31
References31
3 History of Natural Dyes in North Africa_Egypt 33

Harby Ezzeldeen Ahmed
3.1 Introduction 33
3.2 Natural Dyes in Pharaonic Textiles 34
3.3 Dyeing Techniques 34
3.4 Dye Sources 34
3.4.1 Woad 35
3.4.2 Indigo 35
3.4.3 Red 35
3.4.4 Yellow 36
3.4.5 Black 36
3.4.6 Brown 36
3.4.7 Green 36
3.4.8 Purple 36
3.5 Dyeing in Coptic Textiles 36
3.6 Wool-Dyed Fabric with Natural Dye 38
3.7 Dyes in Islamic Textiles 38
3.8 Mordants 40
References40
II Natural Colorants in Different Regions of the World 43

4 Sources for Natural Colorants in Europe 45
Thomas Bechtold, Tung Pham and Avinash P. Manian
4.1 Introduction 45
4.2 Cultivation 46
4.2.1 Potential European Dye Plants Yesterday and Now 46
4.2.2 Modern Cultivation Methods—General Facts 47
4.2.3 Blue-Dye Plants 48
4.2.4 Red-Dye Plants 49
4.2.5 Yellow-Dye Plants 49
4.2.6 Brown-Dye Plants 52
4.2.7 Production of Dye Extracts 54
4.3 Natural Colorants from Agro-Food Residues 55
4.4 Natural Colorants from Forestry and Timber Industry 56
4.5 Relevant Examples for the Application 57
4.6 Conclusions, Discussion, and Summary 58
Contents ix
Acknowledgement58
References59
5 Dyes in South America 63

Veridiana Vera de Rosso and Adriana Zerlotti Mercadante
5.1 Introduction 63
5.2 Annatto 65
5.3 Turmeric 67
5.4 Marigold 68
5.5 Cochineal and Carmine 69
Acknowledgements71
References71
6 Natural Dyes in Eastern Asia (Vietnam and Neighboring Countries) 75

Tung Pham and Thomas Bechtold
6.1 Introduction 75
6.2 Annatto (Bixa orellana L., Family Bixaceae) 75
6.3 Tea (Camellia sinensis (L.) Kuntze, Family Theaceae) 77
6.4 Umbrella Tree (Terminalia catappa L., Family Combretaceae) 77
6.5 Mackloeur (Diospyros mollis L. Griff, Family Ebenaceae) 78
6.6 Indigo (Indigofera L., Family Fabaceae) 79
6.6.1 Indigofera tinctoria L. 79
6.6.2 Indigofera galegoides DC 80
6.6.3 Strobilanthes cusia (Baphicacanthus) 80
6.7 Henna (Kok Khan or Khao Youak in Laos) (Lawsonia spinosa L.,
Family Lythraceae) 80
6.8 Nacre (African Mahogany, Khaya senegalensis, Family Meliaceae) 81
6.9 Sappan Wood (Caesalpinia sappan L., Family Fabaceae) 81
6.10 Japanese Pagoda Tree Flowers (Sophora japonica L., Family Leguminosae) 82
6.11 Turmeric (Curcuma longa L., Family Zingiberaceae) 82
6.12 Sapodilla (Manilkara zapota L. or Achras zapota, Family Sapotaceae) 82
6.13 Betel (Piper betel L., Family Piperaceae) 83
6.14 Eucalyptus (Eucalyptus, Family Myrtaceae) 83
6.15 Caesalpinia Yellow (Caesalpinia pulcherrima L., Family Fabaceae) 83
6.16 Brow-Tuber; Yam (Dioscorea cirrhosa Lour, Family Dioscoreaceae) 83
6.17 Others 84
Acknowledgement84
References84
7 Sources for Natural Colorants in China 89

Ren-Cheng Tang
7.1 Introduction 89
7.2 Sophora japonica Yellow 92
7.3 Turmeric 93
7.4 Gardenia Yellow 93
7.5 Emodin 93
7.6 Baicalin 94
7.7 Berberine 94
7.8 Henna 94
x Contents
7.9 Monascus Red 95

7.10 Madder 95
7.11 Sorghum Red 95
7.12 Mulberry Red 96
7.13 Shikonin 96
7.14 Indigo 96
7.15 Condensed Tannins 97
7.16 Tea Polyphenols 98
7.17 Gallnut 99
References99
8 Sources, Application, and Analysis of Natural Colorants: An Indian Perspective 103

Prof. (Dr.) Ashis Kumar Samanta and Prof. (Dr.) Deepali Singhee
8.1 Introduction 103
8.2 Natural Dyes in India 104
8.2.1 History 104
8.2.2 Traditional Processes of Dyeing with Natural Dyes in Different Parts
of India 105
8.2.3 Sources of Natural Dyes in India 106
8.2.4 Use of Some Natural Dyes in Traditional Textiles of India 107
8.3 Details of Some Dye Sources and Their Application in India 109
8.3.1 Turmeric 109
8.3.2 Pomegranate 111
8.3.3 Flame of Forest 114
8.3.4 Marigold 116
8.3.5 Safflower 118
8.3.6 Annatto 120
8.3.7 Madder 123
8.3.8 Indian Mulberry 125
8.3.9 Arjuna 127
8.3.10 Sappanwood 130
8.3.11 Eucalyptus 132
8.3.12 Catechu 134
8.3.13 Gallnut 137
8.3.14 Myrobolan 140
8.3.15 Lac 142
8.3.16 Indigo 145
References147
9 Natural Dye Gardens in North America 161

Wendy Weiss and Thomas Bechtold
9.2 Participants 162
9.3 Education 163
9.4 Motivation to Work with Natural Dye 166
9.5 Plant List—Cultivated Plants 166
9.6 Chemical Background of Most Relevant Plants 168
9.7 Plant List—Foraged Plants 172
Contents xi
9.8 Plants with Indigotin 172

9.9 Importance of the Fibershed Movement 173
9.10 Educational and Community Gardens 174
9.11 Mexico 177
9.12 Canada 177
9.13 Future Research 178
References178
Notes179
III Colorant Production and Properties 181
10 Chlorophylls 183
María Roca
10.2 Chemical Structures and Physicochemical Properties 184
10.3 Chlorophylls as Colorants 187
10.4 New Trends in the Use of Chlorophylls as Colorants 189
10.5 Stability and Analysis 190
10.6 Toxicological and Safety Aspects 191
References192
11 Indigo—Production and Properties 195

Philip John and Luciana Gabriella Angelini
11.2 Agronomy 196
11.2.1 Isatis 196
11.2.1.1 Developmental Stages and Climate and Soil Crop
Requirements197
11.2.1.2 Rotation 201
11.2.1.3 Soil Tillage and Seed Sowing 202
11.2.1.4 Weeds, Pests, and Diseases 203
11.2.1.5 Fertilizers and Irrigation 204
11.2.1.6 Harvesting and Yields 205
11.2.1.7 Seed Production 207
11.2.1.8 Isatis indigotica Compared with Isatis tinctoria208
11.2.2 Persicaria 209
11.2.2.1 Introduction 209
11.2.2.2 Developmental Stages 211
11.2.2.3 Sowing, Harvesting, and Yield 211
11.2.2.4 Weeds, Pests, and Diseases 216
11.2.2.5 Fertilizer and Irrigation Requirement 216
11.2.2.6 Seed Production 217
11.2.3 Indigofera217
11.3 Methods of Determining Indigo 219
11.4 Precursors in the Plants 222
11.5 Direct Dyeing with Indican 227
11.6 Indigo Formation 227
xii Contents
11.7 Extraction Procedures 229

11.7.1 Traditional Process Using Crushed Leaf Material 229
11.7.1.1 Isatis 229
11.7.1.2 Persicaria 230
11.7.2 Steeping in Water 231
11.7.2.1 Indigofera 232
11.7.2.2 Isatis 234
11.7.2.3 Persicaria 239
11.8 Purity of Natural Indigo 240
11.8.1 Purification by Sublimation 241
11.8.2 Impurities in Natural Indigo 242
Acknowledgements245
References245
12 Anthocyanins: Revisiting Nature’s Glamorous Palette 251

Maria J. Melo, Fernando Pina, Natércia Teixeira and Claude Andary
12.1 Chemical Basis 251
12.1.1 Chemical Structures 251
12.1.2 Equilibria in Solution 253
12.1.3 Kinetics 254
12.1.4 Color and Color Stability 254
12.1.5 Anthocyanins as Antioxidants 258
12.2 Natural Sources and Applications for Anthocyanins 259
12.2.1 Plants Sources, Content, Influencing Parameters 259
12.2.2 Food Colorants 260
12.2.3 Other Uses 261
12.2.4 Examples of Commercial Products and Processing 262
References263
APPENDIX 1 267
A1.1 Multi-Equilibria in Acidic and Basic Media 267
A1.2 Measuring the Equilibria Constants 269
13 Natural Colorants—Quinoid, Naphthoquinoid, and Anthraquinoid Dyes 271

Goverdina C. H. Derksen and Thomas Bechtold
13.2 Benzoquinone Dyes 271
13.3 Diaryloylmethane Dyes 273
13.4 Naphthoquinone Dyes 273
13.4.1 Lawson (2-hydroxy-1,4-naphthoquinone, CI Natural Orange 6) 274
13.4.1.1 Properties and Use 274
13.4.1.2 Agricultural Aspects 276
13.4.2 Juglone (5-hydroxy-1,4-naphthoquinone, CI Natural Brown 7) 278
13.5 Anthraquinone Dyes 279
13.5.1 Main Components Emodin and Chrysophanol—Rheum and
Rumex Species 279
13.5.2 Main Components Alizarin and/or Pseudopurpurin/Purpurin 281
13.5.2.1 Plant Sources 281
13.5.2.2 Madder CI Natural Red 8 282
References294
Contents xiii
14 Natural Colorants from Lichens and Mushrooms 317

Riikka Räisänen
14.1 Use of Lichen and Mushroom Colorants in History 317
14.2 Cultivation of Lichens and Mushrooms 318
14.3 Colorant Structures in Lichens and Mushrooms 319
14.3.1 Lichen Dyes: Orchils and Litmus 321
14.3.2 Yellowish, Brownish, and Reddish Colorants from Lichen 322
14.3.3 Blue Terphenylquinones from Mushrooms 322
14.3.4 Anthraquinones 324
14.3.4.1 Bloodred Webcap (Cortinarius sanguineus) 324
14.3.5 Other Colorants of Fungi 326
14.3.5.1 Yellows from Grevillines 326
14.3.5.2 Yellow and Orange Colors from Pulvinic Acid Derivatives 326
14.3.5.3 Brown from Badiones 326
14.4 Stability of Lichen and Mushroom Colorants 326
14.5 New Approaches to Lichen and Fungal Colorants 327
References328
15 Focus on Tannins 333

Riitta Julkunen-Tiitto and Hely Häggman
15.2 Chemical Structure, Biosynthesis, and Degradation 335
15.3 Properties of Tannins 338
15.4 Chemical Activities of Tannins 340
15.5 Analysis of Tannins 340
15.5.1 Sample Preservation 340
15.5.2 Extraction and Purification 340
15.5.3 Quantification of Tannins 341
15.6 Use, Toxicology, and Safety Aspects of Tannins 342
References345
16 Carotenoid Dyes—Properties and Production 351

U. Gamage Chandrika
16.1.1 Occurrence of Carotenoids 351
16.1.2 Chemistry of Carotenoids 351
16.1.3 Chemical Characteristics of Natural Carotenoids 352
16.2 Properties and Functions of Carotenoids 354
16.2.1 Carotenoids’ Role as Pro-vitamin A 354
16.2.2 Use of Carotenoids as Markers of Dietary Practices 356
16.2.3 Carotenoids as Antioxidants 356
16.2.4 Carotenoids in the Macular Region of the Retina 357
16.2.5 Carotenoids as Anticancer Agents 357
16.2.6 Carotenoids as Natural Colorants 357
16.3 General Procedure for Carotenoid Analysis 357
16.3.1 Sampling 359
16.3.2 Extraction 359
16.3.3 Saponification of Carotenoids 359
16.3.4 Chromatographic Separation 359
xiv Contents
16.3.5 Chemical Tests 361

16.3.6 Detection and Identification of Carotenoids 361
16.3.7 Quantification of Carotenoids 362
16.4 Problems in Carotenoid Analysis 362
16.5 Factors Influencing Carotenoid Composition in Plant Sources 363
16.5.1 Stage of Maturity 363
16.5.2 Cultivar or Varietal Differences 363
16.5.3 Climatic or Geographic Effects 364
16.5.4 Post-Harvest Storage and Packing 364
16.5.5 Changes in Processing/Cooking 364
16.5.6 Effect of Agrochemicals 366
References366
17 Flavonoids as Natural Pigments 371

M. Monica Giusti, Gonzalo Miyagusuku-Cruzado and Taylor C. Wallace
17.2 Role of Localized Flavonoids in the Plant 372
17.3 General Flavonoid Chemical Structure 372
17.4 Biosynthesis of Flavonoids 373
17.5 Anthocyanins as Natural Colorants 373
17.5.1 Structure 375
17.5.2 Structural Transformation and pH 376
17.5.3 Temperature 377
17.5.4 Oxygen and Ascorbic Acid 377
17.5.5 Light 378
17.5.6 Enzymes and Sugars 379
17.5.7 Sulfur Dioxide 379
17.5.8 Co-Pigmentation and Metal Complexation 380
17.6 Other Flavonoids as Natural Colorants 381
17.6.1 Yellow Flavonoid Pigments 381
17.6.2 Tannins 381
17.6.3 Anthocyanin-Derived Pigments: Pyranoanthocyanins 382
17.7 Therapeutic Effects of Flavonoids in the Diet 382
17.8 The Use of Flavonoids as Food Colors in the US and EU 383
References384
18 Natural Colorants from Fungi 391

Cassamo U. Mussagy, Fernanda de Oliveira and Valeria C. Santos-Ebinuma
18.2 Types of Fungi Colorants 392
18.3 Fungal Producer of Colorants 394
18.4 Bioprocess 395
18.4.1 Biosynthesis Pathway 395
18.4.2 Production and Extraction Process 400
18.5 Toxicity 404
18.6 Industrial Application of Fungi Colorants 406
18.7 Conclusion 407
References407
Contents xv
19 Natural Colorants from Cyanobacteria and Algae 417

Laurent Dufossé
19.2 Phycobiliproteins from Cyanobacteria 418
19.2.1 Structural Characteristics of Phycobiliproteins 420
19.2.2 Food Grade Phycobiliproteins 422
19.2.3 Future Trends 422
19.3 Pigments from Microalgae 422
19.3.1 β-Carotene from the Microalga Dunaliella, Salty but Effective! 423
19.3.1.1 β-Carotene from Microalgae 423
19.3.1.2 Dunaliella Species for Carotenoids 424
19.3.2 Why Carotenoids from Dunaliella?424
19.3.2.1 Natural vs. Synthetic β-Carotene 424
19.3.2.2 Applications of β-Carotene 424
19.3.2.3 Advantages of Carotenoids Production from Dunaliella 425
19.3.2.4 Process for Production of β-Carotene from Dunaliella 425
19.3.2.5 Companies Producing Dunaliella 425
19.3.2.6 Marketed Products of β-Carotene 426
19.3.3 Haematococcus for Astaxanthin, the Red Gold Rush 426
19.3.3.1 Advantages of Astaxanthin over Other Carotenoids 427
19.3.3.2 Astaxanthin as Nutraceutical 427
19.3.3.3 Astaxanthin as Antioxidant 427
19.3.3.4 Astaxanthin for Health 428
19.3.3.5 Astaxanthin for Salmon and Trout Feeds 428
19.3.3.6 Astaxanthin for Humans 429
19.3.3.7 Production System for Haematococcus 429
19.3.3.8 Companies Producing Astaxanthin from Haematococcus 430
19.3.3.9 Astaxanthin-Containing Formulations 431
19.4 Natural Colorants from Macroalgae (e.g., Seaweeds) 431
19.4.1 Biodiversity of Seaweeds 431
19.4.2 Seasonal Variations and Environmental Threats 432
19.4.3 Major Classes of Seaweed Pigments 433
19.4.3.1 Chlorophylls 433
19.4.3.2 Carotenoids 433
19.4.3.3 Phycobiliproteins 434
19.5 Conclusion 434
References434
20 Biotechnological Production of Microbial Pigments: Recent Findings 439

Vivian Katherine Colorado Gómez, Juan Pablo Ruiz-Sánchez, Alejandro
Méndez-Zavala, Lourdes Morales-Oyervides and Julio Montañez
20.2 Microbial Pigments Market 440
20.3 Production Strategies 440
20.4 Novel Extraction Technologies for Pigments Recovery 441
20.5 Regulation and Biosynthesis of Microbial Pigments 443
20.6 Strain Engineering Strategies for Pigment Production 446
20.7 Trends in New Microbial Sources of Pigments 448
xvi Contents
20.8 Microbial Pigments Applications 449

20.8.1 Solar Cells 449
20.8.2 Therapeutic Application 450
20.8.3 Other Applications 450
20.9 Regulations on Microbial Pigments Use 451
20.10 Conclusions and Future Perspectives 452
References452
21 Analytical Methods for Characterization and Standardization of

Natural Dyes and Pigments 459
Tung Pham, Avinash Manian and Thomas Bechtold
21.2 Chemical Analysis—Identification 460
21.3 Quantification by Sum Parameters 463
21.4 Applicatory Tests 464
21.5 Product Performance 465
References466
22 Wood—From Natural Color Patterns Toward Naturally Altered

Color Impressions 469
Martin Weigl-Kuska, Andreas Kandelbauer, Christian Hansmann
and Ulrich Müller
22.1 The Color of Wood 469
22.1.1 Wood Chemical Composition 470
22.1.2 Wood Anatomical Appearance 471
22.1.3 Physical Properties of the Wood Surface 472
22.2 Coatings 473
22.3 Dyes 477
22.3.1 Impregnation 477
22.3.1.1 Technology 477
22.3.1.2 Color 479
22.3.1.3 Products 480
22.4 Color Modification 481
22.4.1 Drying 482
22.4.1.1 Basics 482
22.4.1.3 Color 484
22.4.2 Steaming 485
22.4.2.1 Basics 485
22.4.2.3 Color 486
22.4.3 Thermal Treatment 487
22.4.3.2 Color 487
22.4.4 Ammoniation 488
22.4.4.1 Basics 488
22.4.4.2 Color 489
Contents xvii
22.4.5 Bleaching 491

22.4.5.1 Basics 491
22.4.5.2 Color 491
22.4.6 Enzymatic Treatment 492
22.4.6.1 Basics 492
22.4.6.2 Laccases 493
22.4.7 Radiation 495
22.4.7.1 Basics 495
22.4.7.2 Color 495
22.5 Outlook 498
References498
23 The Role of Mordants in Fixation of Natural Dyes 507

Avinash P. Manian
23.2 Metal Salts 508
23.3 Biomordants 508
23.4 Substrate Pretreatments 508
23.5 No Mordant 509
References509
24 Textile Coloration with Natural Dyes and Pigments 517

Thomas Bechtold, Tung Pham and Avinash P. Manian
24.2 Reasons for Natural Coloration 518
24.3 The Dyestuff–Fiber Interaction 520
24.4 Design of a Dyeing Process 521
24.5 Transfer of a Dyeing Process into Technical Scale 523
24.6 Processes and Resources 524
24.7 Technical Requirements for a Natural Dyestuff 526
24.7.1 Gamut and Color Shade 526
24.7.2 Fastness Criteria 528
24.8 Handling of Natural Dyes in a Technical Dyehouse 530
24.9 Mordanting 531
24.10 Natural Dyes on an Industrial Scale 533
24.10.1 Dyeing Technology—Exhaust Process 533
24.10.2 Hank Dyeing of Woolen Yarn and Production of Woolen Caps 534
24.10.3 Dyeing of Cones in a Yarn Dyeing Machine 534
24.10.4 Dyeing of Cotton Fabric on a Jet Dyeing Machine 535
24.10.5 Fabric Dyeing on a Garment Dyeing Machine 536
24.10.6 Dyeing of Polyamide Tights in a Paddle Dyeing Machine 536
24.10.7 Dyeing Technology—Continuous Dyeing 536
24.11 Conclusion 537
Acknowledgement538
References538
xviii Contents
25 Hair Coloration with Natural Dyes and Pigments 543

Thomas Bechtold
25.2 Human Hair 544
25.3 General Requirements on Hair Dyeing Concepts 544
25.4 Chemical Principles of Dyestuff Binding 546
25.5 Relevant Natural Dyes for Hair Dyeing 546
25.5.1 Naphthoquinone Dyes—Henna and Walnut 546
25.5.1.1 Henna, CI (Color Index) Natural Orange 6 546
25.5.1.2 Juglon, CI Natural Brown 7 547
25.5.2 Indigo 548
25.5.3 Metal Complexes 548
25.5.4 Metal Reaction Dyes 550
25.5.5 Anthraquinoid Dyes 551
25.6 Specialties 551
25.7 Regulations 552
References552
26 Natural Colorants in the Mass Coloration of Plastics 557

Thomas Bechtold and Tung Pham
26.2 Representative Examples 559
Acknowledgement561
References561
27 Natural Colorants in Printing/Packaging 563

Thomas Bechtold and Tung Pham
27.2 Packaging Films 564
27.3 Film Coloration 567
27.4 Paper Dyeing 568
27.5 Paints 568
Acknowledgement569
References569
28 Technical Aspects and Requirements to Produce Natural Colorants—Processes

and Product Standardization 573
Thomas Bechtold and Avinash Manian
28.2 Sources of Plant Material—Product I 576
28.2.1 Organic Farming 576
28.2.2 Sustainable Farming 576
28.2.3 Native Species 577
28.2.4 Farming for Food or/and Natural Colorants 577
28.2.5 Residual Materials and By-Products 577
28.3 Processing to Dyestuff—Product II 579
28.4 Quality Control and Standardization of a Dye (Product II) 583
28.4.1 Anthocyanins 584
28.4.2 Flavonoids 584
28.4.3 Dye Lakes 585
Contents xix
28.5 Challenges for the Industrial Use of Natural Colorants 585

28.6 Dealing with Sustainability 586
28.7 Conclusions 587
References587
29 Environmental and Economic Position of Natural Colorants—Energy and

Resources Balances, Sustainability, Ecology, and Costs 591
Susanne Geissler and Thomas Bechtold
29.2 Dye Plant Production 592
29.3 Dye Extraction and Dyestuff Production 595
29.4 Transportation 596
29.5 Textile Dyeing 596
29.6 Commercial Aspects—Costs 597
29.6.1 Basic Requirements for the Industrial Use of Natural Colorants 598
29.6.1.1 Precondition 1: acceptable costs of natural colorants
and dyeing processes 599
29.6.1.2 Precondition 2: feasible cost of process engineering 599
29.6.1.3 Precondition 3: compliance with requested colorfastness
properties599
29.6.1.4 Precondition 4: competitive cost of naturally dyed products 600
29.6.1.5 Precondition 5: security of natural colorant supply 600
29.6.2 Consumer Expectations 600
29.6.3 Market Research for Naturally Dyed Products 601
29.7 Production Costs of Natural Colorant Products 602
29.7.1 Cost Categories 603
29.7.2 Aspects Influencing Production Costs 603
29.8 Prices of Synthetic Dyes—How Much Are Textile Companies Prepared
to Pay for Dyes? 605
29.9 Acceptable Production Costs through a Mixed Portfolio (Agricultural
Primary Production and Residues from Other Production Processes) 606
29.10 Closed-Loop Economy: Toward a Zero-Emission and Zero-Waste Society 607
29.11 Considerations Concerning the Life Cycle 609
29.12 Conclusion: Aspects Influencing Market Development for Natural Colorants 609
References610
30 Aspects of Human Toxicology and Consumer Safety 613

Judith Büttler, Thomas Bechtold and Tung Pham
30.2 Basic Aspects of Xenobiotic-Induced Toxicity 614
30.3 Toxicological Aspects of Natural Colorants in Food and Medical Applications 615
30.3.1 Risk Assessment 617
30.3.2 Therapeutic Effects (= Risk) 618
30.4 Toxicological Aspects of Natural Colorants in Cosmetics 618
30.4.1 Risk Assessment 619
30.5 Toxicological Aspects of Natural Colorants in Textile Dyeing 619
30.5.1 Plant Extracts 620
30.5.2 Pretreatment Agents and Mordants 621
30.5.3 Wastewater and Antimicrobial Compounds 621
30.5.4 Dyed Products 622
xx Contents
30.6 Test Methods for Toxicity Screening 622

30.6.1 Extract Preparation 624
30.6.2 Cytotoxicity 624
30.6.3 Mutagenicity and Carcinogenicity 625
30.6.4 Antimicrobial Activity 625
30.6.5 Metabolism and In Vivo Animal Bioassays 626
Acknowledgement626
References626
Index629
List of Contributors
Harby Ezzeldeen Ahmed Faculty of Archaeology, Cairo University, Giza, Egypt

Claude Andary Laboratory of Botany, Phytochemistry and Mycology, University of
Montpellier, Montpellier, France
Luciana Gabriella Angelini Department of Agriculture, Food and Environment, University of
Pisa, Pisa, Italy
Thomas Bechtold Research Institute of Textile Chemistry and Textile Physics, University of
Innsbruck, Dornbirn, Austria
Judith Büttler Research Institute of Textile Chemistry and Textile Physics, University of
Dominique Cardon Centre National de la Recherche Scientifique, France
U. Gamage Chandrika Department of Biochemistry, Faculty of Medical Sciences, University
of Sri Jayewardenepura, Gangodawila, Nugegoda, Sri Lanka
Fernanda de Oliveira Department of Bioprocess Engineering and Biotechnology, School of
Pharmaceutical Sciences, São Paulo State University (UNESP), São Paulo, Brazil; Department of
Biotechnology, Engineering School of Lorena, University of São Paulo, Lorena, São Paulo, Brazil
Veridiana Vera de Rosso Department of Health Science, Federal University of São Paulo
(UNIFESP), Santos, Brazil
Goverdina C. H. Derksen Natural Colour Research, Dorable Colours, Oud-Vossemeer, The
Netherlands
Laurent Dufossé Laboratoire de Chimie et Biotechnologie des Produits Naturels
(CHEMBIOPRO), ESIROI Département Agroalimentaire, Université de la Réunion, Ile de La
Réunion, Indian Ocean, France
Susanne Geissler SERA—Institute for Sustainable Energy and Resources Availability, Vienna,
Austria
M. Monica Giusti Parker Food Science and Technology, The Ohio State University, Columbus,
Ohio, USA
xxii List of Contributor
Vivian Katherine Colorado Gómez Department of Chemical Engineering, Universidad

Autónoma de Coahuila, Saltillo, Coahuila, México
Hely Häggman Department of Ecology and Genetics, University of Oulu, Oulu, Finland
Christian Hansmann Department of Material Science and Process Engineering, Institute of
Wood Technology and Renewable Materials, BOKU—University of Natural Resources and Life
Sciences, Tulln, Austria
Philip John School of Biological Sciences, University of Reading, Whiteknights, Reading, UK
Riitta Julkunen-Tiitto Department of Environmental and Biological Sciences, University of
Eastern Finland, Joensuu, Finland
Andreas Kandelbauer Reutlingen University, Reutlingen, Germany
Avinash P. Manian Research Institute of Textile Chemistry and Textile Physics, University of
Maria J. Melo LAQV/REQUIMTE, Department of Conservation and Restoration; Faculty of
Sciences and Technology, Universidade NOVA de Lisboa, Monte de Caparica, Portugal
Alejandro Méndez-Zavala Department of Chemical Engineering, Universidad Autónoma de
Coahuila, Saltillo, Coahuila, México
Adriana Zerlotti Mercadante Department of Food and Experimental Nutrition, Faculty of
Pharmaceutical Science, University of São Paulo, São Paulo, Brazil
Gonzalo Miyagusuku-Cruzado Parker Food Science and Technology, The Ohio State
University, Columbus, Ohio, USA
Julio Montañez Department of Chemical Engineering, Universidad Autónoma de Coahuila,
Saltillo, Coahuila, México
Lourdes Morales-Oyervides Department of Chemical Engineering, Universidad Autónoma de
Ulrich Müller Wood K plus-Competence Center for Wood Composites and Wood Chemistry,
Altenberger Straße, Linz, Austria
Cassamo U. Mussagy Escuela de Agronomia, Facultad de Ciencias Agronomicas y de Los
Alimentos Pontificia, Universidad Catolica de Valparaiso, Quillota, Chile
Tung Pham Research Institute of Textile Chemistry and Textile Physics, University of
Fernando Pina LAQV/REQUIMTE, Faculty of Sciences and Technology, Universidade NOVA
de Lisboa, Monte de Caparica, Portugal
Riikka Räisänen Craft Science, University of Helsinki, Finland
María Roca Spanish National Research Council (CSIC), Instituto de la Grasa, Department of
Food Biotechnology, Sevilla, Spain
Juan Pablo Ruiz-Sánchez Department of Chemical Engineering, Universidad Autónoma de
Ashis Kumar Samanta Department of Jute and Fibre Technology, Institute of Jute Technology,
University of Calcutta, Kolkata, West Bengal, India
List of Contributor xxiii
Valeria C. Santos-Ebinuma Department of Bioprocess Engineering and Biotechnology,

School of Pharmaceutical Sciences, São Paulo State University (UNESP), São Paulo, Brazil
Deepali Singhee JD Birla Institute (affiliated to Jadavpur University), Kolkata, West Bengal,
India
Reng-Cheng Tang College of Textile and Clothing Engineering; China National Textile and
Apparel Council Key Laboratory of Natural Dyes; Jiangsu Engineering Research Center of
Textile Dyeing and Printing for Energy Conservation, Discharge, Reduction and Cleaner
Production, Soochow University, China
Natércia Teixeira LAQV/REQUIMTE, Department of Chemistry and Biochemistry, Faculty of
Sciences, Universidade do Porto, Porto, Portugal
Taylor C. Wallace Think Healthy Group, Washington, DC, USA; Department of Nutrition and
Food Studies, George Mason University, Fairfax, Virginia, USA
Martin Weigl-Kuska Holzforschung Austria, Vienna, Austria
Wendy Weiss University of Nebraska–Lincoln, Lincoln, Nebraska, USA
Series Preface
Renewable resources, their use and modification, are involved in a multitude of important processes
with a major influence on our everyday lives. Applications can be found in the energy sector, paints
and coatings, and the chemical, pharmaceutical, and textile industries, to name but a few.
The area interconnects several scientific disciplines (agriculture, biochemistry, chemistry, tech-
nology, environmental sciences, forestry, etc.), which makes it very difficult to have an expert view
on the complicated interactions. Therefore, the idea to create a series of scientific books, focusing
on specific topics concerning renewable resources, has been very opportune and can help to clarify
some of the underlying connections in this area.
In a very fast-changing world, trends are not only characteristic of fashion and political stand-
points; science too is not free from hypes and buzzwords. The use of renewable resources is again
more important nowadays; however, it is not part of a hype or a fashion. As the lively discussions
among scientists continue about how many years we will still be able to use fossil fuels – opinions
ranging from 50 to 500 years – they do agree that the reserve is limited and that it is essential not
only to search for new energy carriers but also for new material sources.
In this respect, the field of renewable resources is a crucial area in the search for alternatives for
fossil-based raw materials and energy. In the field of energy supply, biomass-and renewables-based
resources will be part of the solution alongside other alternatives such as solar energy, wind energy,
hydraulic power, hydrogen technology, and nuclear energy. In the field of material sciences, the
impact of renewable resources will probably be even bigger. Integral utilization of crops and the use
of waste streams in certain industries will grow in importance, leading to a more sustainable way of
producing materials. Although our society was much more (almost exclusively) based on renewable
resources centuries ago, this disappeared in the Western world in the nineteenth century. Now it is
time to focus again on this field of research. However, it should not mean a “retour à la nature,” but
should be a multidisciplinary effort on a highly technological level to perform research towards new
opportunities, and to develop new crops and products from renewable resources. This will be essen-
tial to guarantee an acceptable level of comfort for the growing number of people living on our
planet. It is “the” challenge for the coming generations of scientists to develop more sustainable
ways to create prosperity and to fight poverty and hunger in the world. A global approach is c ertainly
favored.
This challenge can only be dealt with if scientists are attracted to this area and are recognized for
their efforts in this interdisciplinary field. It is, therefore, also essential that consumers recognize
the fate of renewable resources in a number of products. Furthermore, scientists do need to com-
municate and discuss the relevance of their work. The use and modification of renewable resources
xxvi Series Preface
may not follow the path of the genetic engineering concept in view of consumer acceptance in
Europe. Related to this aspect, the series will certainly help to increase the visibility of the impor-
tance of renewable resources. Being convinced of the value of the renewables approach for the
industrial world, as well as for developing countries, I was myself delighted to collaborate on this
series of books focusing on the different aspects of renewable resources. I hope that readers become
aware of the complexity, the interaction, and interconnections, and the challenges of this field, and
that they will help to communicate on the importance of renewable resources.
I certainly want to thank the people of Wiley’s Chichester office, especially David Hughes, Jenny
Cossham, and Lyn Roberts, in seeing the need for such a series of books on renewable resources,
for initiating and supporting it, and for helping to carry the project to the end.
Last, but not least, I want to thank my family, especially my wife Hilde and children Paulien and
Pieter-Jan, for their patience, and for giving me the time to work on the series when other activities
seemed to be more inviting.
Christian V. Stevens
Faculty of Bioscience Engineering, Ghent University, Belgium
Series Editor, “Renewable Resources”
June 2005
Preface
Nearly 15 years have passed between the release of the first edition of the Handbook of Natural
Colorants and this second edition. Things have changed a lot in this relatively short period.
In the 20th century, the dominance of the synthetic dyes restricted scientific and practical work
with natural colorants to a limited number of handicrafts, artists, as well as some researchers.
Activities were driven by creativity, tradition, curiosity, and scientific interests. Commercial suc-
cess and technical-scale work were limited due to the complications of the dye production and the
limited level of product quality, when compared to the big synthetic brothers.
With the first edition, aspects of sustainability, renewable resources, and bio-based economy
already were arguments for a more intensive consideration of natural colorants; however, cost
aspects and product economy still were in the central focus of industrial production.
The last 15 years brought a dramatic change. Public awareness about global warming and the
pressing need to transform industrial production toward higher sustainability using non-petrol-
based material also had an impact on the position of the natural colorants. The potential of complex
chemical molecules such as dyes provided as raw material by nature has been investigated by many
research groups around the world. Many authors of chapters were overwhelmed by the extremely
high research activity in their respective field, which could be recognized with the dramatic increase
in number of published scientific works about natural colorants.
This is a first point to thank all chapter authors for their high effort to review the numerous sci-
entific articles in the topics covered in their chapter.
Natural colorants have stepped outside the shadow of being forgotten as “old economy” or “tradi-
tional products” and now are part of the future game to transform industrial production and products
into more sustainable alternatives. The extraction of dyes and pigments from plant sources will be
central part of a bio-based economy, which utilizes products from nature at the highest possible stage.
The change in position of natural colorants also is reflected in the content of the book and in the
organization of chapters.
The first part of the book addresses historical uses and examples of natural colorants in different
civilizations. We have to understand history as part of the basis for future development and many
old recipes are highly valuable sources for interpretation of new concepts.
The second series of chapters highlights the different plants used in regions all over the world.
We can detect similarities between regions and can understand why climate-dependent growth of
plants will also determine the locally available color palette.
The third section organizes natural colorants with regard to their chemical structure and the
chemistry of the dye molecules. This will help to design appropriate extraction, handling, and appli-
cation procedures, as the chemistry of a dye is the key for an efficient application.
xxviii Preface
The fourth section includes dye production, analytics and standardization, and dye application.
New chapters address biotechnological production as well as dyes from algae and bacteria. Besides
technical examples for use of dyes in textile dyeing, also new applications, for example, mass col-
oration of plastics and use of natural colorants in paper and packing applications, are discussed.
In many publications, we find a generalized statement that all natural colorants are environmen-
tally friendly and non-toxic. A critical assessment of resources consumption during dye extraction
and application explains that a careful consideration of energy, solvents, chemical, and water con-
sumption is required and comparison to the best available technique must be undertaken to prove
the statement of environmental friendliness. A new chapter about toxicology and consumer safety
addresses the fact that dye extracted from natural sources also must be checked for adverse proper-
ties to demonstrate their non-toxicity.
The complexity of the field requires contribution from many co-authors which are experts in
their field. We would like to thank all the authors for their efforts and the energy contribution to
their chapters, and to allow us to benefit from their expertise.
We are convinced that the 2nd edition has been a step forward into the right direction; however,
we are aware that there are still many empty fields and gaps which we could not cover during the
revision.
We hope that the condensed form of the material and the high number of references will allow
researchers to gain a sound overview about a certain field in natural colorants in an efficient and
motivating way. We also hope that the revision and extension of the book will strengthen the future
development of natural colorants as bio-based raw material.
Thomas Bechtold, Avinash P. Manian, and Tung Pham

Dornbirn, 2023
I
Historical Development
1
History of Natural Dyes in the Ancient
Mediterranean Civilization
Maria J. Melo
LAQV/REQUIMTE, Department of Conservation and Restoration;

Faculty of Sciences and Technology, Universidade NOVA de Lisboa,
Monte de Caparica, Portugal
The colors used on textiles and artifacts, their social significance and the scope of their trade are
part and parcel of a people’s overall history.
Jenny Balfour-Paul, in Indigo
1.1 Introduction
1.1.1 Ancient Mediterranean World
The buildup of Mare Nostrum probably began much earlier than the 6th–5th millennium BC, and
there is material evidence pointing to such activity as early as the 12th–11th millennium BC [1].
Mare Nostrum, the Roman name for the Mediterranean Sea, was to become the home of a global
market that expanded beyond its natural borders in the first millennium BC. The Phoenicians, the
Etruscans, the Greeks and finally the Romans shaped Mare Nostrum; a geographic as well as a
cultural domain. It was also home to the first global dye, Tyrian purple, traded by the ingenious
and industrious Phoenicians. The purple of Tyre was famous, as were the luxury textiles dyed and
produced by the Phoenicians [2, 3]. It is said that the Greeks named the Phoenicians after phoini-
kes, the ancient Greek word for “red color,” probably as a result of their famous purple trade.
By the time of the founding of the Mediterranean civilizations, what we would consider the
classical palette for natural dyes had already been established, and the most valued colors were
indigo for the blues, anthraquinone-based chromophores for the reds and 6,6’-dibromoindigo for
purple. These colors were traded all over the Mediterranean, regardless of the distance to be
Handbook of Natural Colorants, Second Edition. Edited by Thomas Bechtold, Avinash P. Manian and Tung Pham.
© 2023 John Wiley & Sons Ltd. Published 2023 by John Wiley & Sons Ltd.
4 Handbook of Natural Colorants
traveled or the price to be paid. The natural sources for yellows were much more diverse, so yel-
lows could generally be obtained locally. For dyeing, with the exception of some browns, all
other colors and shades, including green and orange, could be obtained with these blue, red,
purple and yellow dyes. This classical palette was preserved over centuries, if not millennia. The
first adjustment resulted from the loss of Tyrian purple after the fall of Constantinople and the
subsequent collapse of the Roman social and commercial web. This was followed by a new entry,
cochineal red, brought by the Spanish from the New World [4]. However, even with the introduc-
tion of cochineal the chemical nature of the classical palette was maintained, as carminic acid is
still a substituted 1,2-dihydroxy anthraquinone. This classical palette was only challenged by
the audacity of chemists, who created new molecules, and colors never seen before, from the
mid-19th century on [5].
1.1.2 Dyes from Antiquity

Natural dyes, discovered through the ingenuity and persistence of our ancestors, can resist brightly for
centuries or millennia and may be found hidden in such diverse places as the roots of a plant, a para-
sitic insect and the secretions of a sea snail. By contrast, the bright colors that we see in the green of a
valley, the red of a poppy, the purple of mauve or the blue of cornflower are less stable. Natural dyes
were used to color a fiber or to paint. It is useful to distinguish between dyes and pigments based on
their solubility in the media used to apply the color; dyes are generally organic compounds that are
soluble in a solvent, whereas pigments, used in painting, are usually inorganic compounds or minerals
that are insoluble in the paint medium (oil, water, etc.), and are dispersed in the matrix. A pigment lake
is formed by precipitating a dye onto the surface of an inorganic substance, namely by complexation
with a metal ion.
Dyeing, in red, blue, purple or yellow, is a complex task that requires skill and knowledge [6];
this is true now and has been for several millennia. Color is obtained by a chemical compound
called a chromophore or chromogen—that which brings or creates color. To be used as a textile
dye, the chromophore must also be captured as strongly as possible into the fibers, that is, it must
be resistant to washing. Dyes can bind to the surface of the fiber or be trapped within. They are
often bound to textiles with the aid of metal ions known as mordants, which can also play a sig-
nificant role in the final color obtained (Box 1.1). As a source of aluminum ion, alum is an impor-
tant historical mordant and was widely used in the past. Other important mordants used in the
past were iron, copper and tin ions [6, 7]. Dyes, such as indigo, which are trapped in the fibers
due to an oxidation–reduction reaction, without the aid of a mordant, are known as vat dyes.
As pigments, natural dyes have been widely applied in painting. For example, anthraquinones
have been used as red dyes and pigment lakes from prehistoric times, and we can find written
accounts of the use of anthraquinone reds and purples as dyes in ancient Egypt [7, 8]; anthraqui-
none lake pigments (e.g., madder red) were also very popular with Impressionist painters, includ-
ing Vincent van Gogh [9b]. Red, purple and yellow lake pigments can be prepared by precipitating
the dye extract with aluminum or other inorganic salts, such as alum [9] (Box 1.1). Pure dyes
such as indigo have also been used as painting materials, for example, in medieval illuminations
(Figure 1.1).
These eternal colors will be described in more detail in the following sections, after a brief
account of the analytical techniques used to reveal the secrets of these ancient materials. The natural
colorants will be organized according to the color: first, the anthraquinone reds, followed by the
blues and purples, where indigo and its bromo derivatives play a major role. Yellows will close this
overview. More information about other important ancient dyes is provided in EuroWeb Digital
Atlas [10].
History of Natural Dyes in the Ancient Mediterranean Civilization 5
Figure 1.1 Medieval Portuguese illumination, dated from 12–13th-century, Lorvão 15 f. 50 (National Archive of
Torre do Tombo, ANTT, Lisbon, Portugal). Dark blues were painted with indigo, whereas the inorganic pigment lapis
lazuli was used for the background.
Box 1.1 Natural dyes as lake pigments

Sticklac Alkaline Al3+ Lac
solutions Lake
Extraction Filtration Precipitation Filtration
1st step 2nd step 3rd step 4th step 5th step
Figure 1 (Box 1.1) Preparing a lake pigment using lac dye as raw material. Design by Rita Carvalho.
A lake pigment is a metal complex, insoluble in water, prepared by adding a metal ion such
as Al3+ to an aqueous solution of a dye extracted from a natural source. The complex will
precipitate when a neutral molecule is formed, usually between a pH 6 and 7. In ancient
times, the dye was extracted in acidic media (in the presence of Al3+), in neutral (in urine) or
(Continued )
basic solutions (prepared with the ashes of plants, in which the oxides of alkaline metals are
transformed into the corresponding hydroxides by reaction with water). The main steps for
preparing a lac dye pigment are represented in Figure 1 (Box 1.1). Important lake pigments
Figure 2 (Box 1.1) Anthraquinone reds can resist for centuries or millennia, as shown in the precious Andean
textiles (embroidered mantle with shaman figures, mfa 31.501, 0-A.N.D. 100; Museum of Fine Arts, Boston,
USA). Lac dye, also based on alizarin core, was found on a Persian carpet (17th century, Museum of Fine Arts,
MNAA, Lisbon, Portugal) and applied as a lake pigment in manuscript illuminations dating from the 12th cen-
tury. As for any alizarin-based chromophore, it can take many shades of red, purple and pink, as on the
background used to highlight the dragon, symbol of the struggle between light and darkness, but also of
renaissance, painted in the monumental Bible Santa Cruz 1 (Municipal Library of Porto, BPMP, Porto, Portugal).
used in medieval manuscript illuminations were based on lac dye and brazilwood extracts,
Figure 2 (Box 1.1).
The same kind of metal complex was used to bind the dye to a textile fiber; again alu-
minum ion was one of the most important metal ions used in the past, as illustrated in the
following text. These metal ions, also known as mordants, were used to capture the dye to be
resistant to washing. Other important mordants were iron, copper and tin ions. The structures
of these dye–metal colors are complex, and there is still much we do not know about them.
However, we are getting closer to the answers with computational quantum mechanical mod-
eling (such as DFT, density functional theory).
1.1.3 Unveiling the Secrets of Ancient Dyes with Modern Science

Identifying the dyes and dye sources used in the past has only been possible with the development, in
the past two decades or so, of sensitive new microanalytical techniques [11–16]. Chromophores are
extracted, then separated chromatographically and characterized by UV–VIS spectrophotometry or
mass spectrometry; whenever possible, comparison with authentic references is performed. Currently,
the use of high-performance liquid chromatography with diode array detection (HPLC-DAD) enables
dyestuff characterization from as little as 0.1 mg of thread, by comparison with reference compounds.
For the identification of unknown components, analysis by high- resolution mass spectrometry
(HRMS/MS) is required, coupled to an HPLC or an ultra-high performance liquid chromatography
(UHPLC) system—HPLC–HRMS/MS or UHPLC–HRMS/MS [17–19]. Concomitantly, the devel-
opment of mild extraction methods as alternatives to extraction in strongly acidic media was essential
for the identification of the natural sources [13, 14, 20]. These new extraction procedures preserve the
integrity of the glycoside fingerprint, avoiding decomposition to their parent aglycons. The glycoside
fingerprint is particularly important for discussing the sources of yellow and red dyes. In 2011, within
the European project CHARISMA (Cultural Heritage Advanced Research Infrastructures), the litera-
ture on the extraction of organic colorants in cultural heritage objects for HPLC analysis was
reviewed [17]. The final aim was to propose the most appropriate extraction procedure for any kind
of sample.
Mordant analysis can also provide relevant information about the dyeing method or process used.
The metal ions can be quantified by inductively coupled plasma separation with atomic emission
spectrometric (ICP-AES) or mass spectrometric (ICP-MS) detection of samples (approximately
0.25 mg textile strands) previously digested with nitric acid solutions [15, 16, 21]. Before the sam-
ple analysis, calibration curves must be constructed using standards. Concentration linearity in the
range of ppb to ppm (or higher) can be achieved.
1.2 Ancient Reds

1.2.1 Anthraquinone Reds
The most stable reds used in antiquity are based on the 1,2-dihydroxy anthraquinone chromophore
(Figure 1.2), also known as alizarin. Dyes containing anthraquinone and its derivatives are among the
most resistant to light-induced fading [7]. These dyes were obtained from parasitic insects, such as the
famous Kermes vermilio, or from the roots of plants belonging to the Rubiaceae or madder family and
were among the reds that dominated the dye markets of Europe [6, 22]. Alizarin and purpurin are the
main chromophores in Rubia tinctorum, the most important species of the family Rubiaceae. In Persia
and India, other red dyes—of animal origin—were also used. These dyes were imported or sometimes
O OH
8 1
2 OH
7 9
6 10 3
5 4
O
Figure 1.2 Alizarin (1,2-dihydroxy anthraquinone).
found locally, and were considered luxury goods. Well-known examples are the reds based on the lac-
caic acids, kermesic acid and carminic acid (Table 1.1) from the scale insects, lac, kermes and cochi-
neal, respectively [6, 7, 23–24]. The female lac insect secretes a red resin, stick lac, from which both
lac dye and shellac resin are obtained. Common or Indian lac such as Kerria lacca (= Laccifer lacca,
Carteria lacca, Tachardia lacca and Lakshadia lacca) and Kerria chinensis are examples of species
that have been widely exploited [7]. In both cochineal (Dactylopius coccus) and kermes (K. vermilio),
the red dye is obtained from the eggs of the female insect, and therefore the harvest seasons corre-
sponded to the stage when the female was full of unlaid eggs. It was at this stage that the female
insects, alive or dead, were collected. K. vermilio is probably the most famous of the European insect
parasites and produced a dye “brighter than madder and faster than cochineal” [6, 9a], as already
described in the works of Theophrastus and Pliny. The word for worm in many Latin languages is
based on verme (or vermiculu, meaning “small worm”) and thus is the root of the word for red in
several modern European languages, namely, vermejo, vermelho, vermeil, and vermilion in Spanish,
Portuguese, French, and English, respectively [24].
Box 1.2: Armenian cochineal (Porphyrophora hamelii)

In the Armenian language, cochineal is known by the name vordan karmir ( ),
which literally means the worm’s red (vord = worm, karmir = red), and vordan can be broadly
applied to an insect or worm, red color or dyestuff. The etymology of karmir is explained by
an ancient root kirm (Pahlavi) or kr. mi (Sanskrit), meaning the worm [25].
P. hamelii species is endemic to the Ararat Valley, between Anatolia, the Armenian
Highlands and the Iranian Plateau. In Armenia, the semi-desert vegetation areas are their
habitats. Common host plants are coastal light-loving Aeluropus littoralis and common
water-loving Phragmites australis, named in Armenian sources as sēz (grass), vordnaxot
(worm’s grass) or ełeg (reed).
The females of this species are up to 12 mm long and 6 mm wide, oval-shaped, flat, with-
out wings, with six small legs, small eyes and antennae and dark red coloration, resembling
a worm. Males are smaller, with black body, transparent and purple-edged wings, big eyes,
long legs and long filiform tail, resembling a fly. They grow attached to the roots of the host
plant throughout a year. In August–September, both the females and males emerge from the
ground and seek mating. This period lasts about six weeks, but only one day for each insect.
Afterward, the males die, while the females bury themselves in the ground and snuggle up to
the roots of the host plant or nearby, preparing the waxy pockets for egg-laying. Later, the
females also die. In April–May, the newborn larvae go out from the egg pockets and move
10 mm
The field at the foot of Mount Ararat in the early morning. Aeluropus littoralis, the host plant of Armenian
cochineal and the emerging cochineal. Photography courtesy of Hermine Grigoryan, Universidade NOVA
de Lisboa.
toward the plant roots, if they are not already there. They feed on the roots and rhizomes of
the host plant until becoming mature in the next year [25].
Since ancient times, Armenian cochineal has been used as a dyestuff. According to Łazar
Pʽarpecʽi (5th century AD) “De même la gracieuse plaine d’Ararat produit. . .des cochenilles
pour la fabrication des couleurs vermeilles qui donnent du profit et du luxe aux gens intéres-
sés” [25]. This insect was profusely used in medieval Armenian workshops. From the 16th
century onward, Armenian cochineal was gradually replaced by the American s pecies [25].
In the words of a 19th-century traveler, Armenian cochineal was everywhere, “In some places
(Continued )
5 mm
5 mm
The female (left) and the male (right) of P. hamelii. Photography courtesy of Hermine Grigoryan, Universidade
NOVA de Lisboa.
it propagates in the quantities that the land seems a carpet with red ornaments. The animals
grazing here seem to have red-coloured legs, of having trampled the cochineal” [25].
From 1930s to 1970s, attempts were made to recover the cochineal production in Soviet
Armenia, but it remained at limited levels. In 1987, the natural state reserve Vordan Karmir
was established, to ensure the protection of the saline ecosystems of the Ararat Valley, and its
flora and fauna. However, in the following decades, the insect was endangered due to the
human factor. Agricultural interventions and animal pasture have reduced dramatically the
population. Nowadays, around 220, formerly 11 000, hectares of state reserve are protected
areas of P. hamelii, and the insect is included in the Red Book of endangered species of the
Republic of Armenia.
Other important historical insect sources of red or scarlet dyes derived from species of
Porphyrophora, for example, Polish cochineal (Porphyrophora polonica) and Armenian cochi-
neal (Porphyrophora hamelii). Know more about Armenian cochineal in Box 1.2 [25]. In Europe,
most of these sources were replaced in the 16th century by the American cochineal (D. coccus),
commercialized by the Spanish empire, which had earlier been carefully domesticated and culti-
vated by the New World’s indigenous peoples [4]. Although the various species of Porphyrophora
also contain carminic acid, dried specimens of D. coccus have a much higher content (15–20%)
of the dye, compared with only 0.8% and 0.6% for the Armenian and Polish specimens,
respectively [7].
1.2.2 Redwoods
Redwoods, also known in antiquity as brasil, were used as sources of dyes and pigment lakes [7, 9a].
It is said that the country Brazil was named after those redwoods, this possibly being the only country
in the world named after a tree. The name the Portuguese had in mind was Terra da Vera Cruz (land
of the Holy Cross). The reds obtained from the bark of the tree are not as stable as the previously
described anthraquinone reds, but they were important pigments in medieval miniature paintings,
particularly in books of hours produced in French and Flemish workshops [26a, 27, 28]. They were
also used in cosmetics [9a, 26a]. In his book, Cennino Cennini recommends the use of a good verzino
(brazilwood) to highlight the reddish-blue tone of purified lapis lazuli [26a]. This good verzino should
be obtained from a young lady, who, using it for lipstick and other cosmetics, would take care that she
had obtained a well-prepared product of a nice color.
Table 1.1 Chemical structures for anthraquinone reds, produced by scale insects.
Anthraquinone reds
Lac dye O
Kerria lacca
N CH3
H
HO O
O O OH
HO
OH
HO OH
O OH
Kermes O CH3 O OH
Kermes vermilio
HO
HO OH
O OH
Cochineals CH2OH
Dactylopius coccus O CH3 O OH

OH
O
Porphyrophora spp.
HO OH
OH
HO OH
O OH
8
HO O 2
3 OH
4 9
6' 1'
HO O
Figure 1.3 Brazilein; hematein is 8-hydroxy brazilein.
Since antiquity, brazilwood was used for pink and red colors in ancient Asian civilizations, and
in the early Middle Ages, it began to be imported into Europe from Sri Lanka, India, and Southeast
Asia [7, 29]. At that time, the Asian sappanwood, Caesalpinia sappan, was the only known brazil-
wood species. At the beginning of the 16th century, the Portuguese imported from Brazil to Europe
new redwoods belonging to different species, replacing to some extent the Asian sappanwood.
These new redwoods included Caesalpinia echinata, Caesalpinia brasiliensis, Caesalpinia viola-
cea, Caesalpinia crista, and Haematoxylum brasiletto [29]. Some are still important today, not so
much as a source of red dye, but for the medicinal properties of their components (C. sappan) or
because their wood is considered ideal for making violin bows (C. echinata) [29]. For dyeing, only
the colored heartwood of the trunk and larger branches of the trees were used, which could be cut
up into chips and ground into powder [7, 29].
The main dye in C. brasiliensis, C. echinate, C. sappan, C. violacea, and H. brasiletto is brazilin. In
Haematoxylum campechianum, the main dye is hematoxylin. Through oxidation, brazilin and hema-
toxylin are converted to the darker red compounds, brazilein and hematein, respectively (Figure 1.3) [30].
R'3
OH
B
HO 7 O
+ R'5
A
3 OGI
5
OGI
Figure 1.4 In the basic structure of anthocyanins, a hydroxyl group is present at positions 4’ and 7, and a sugar at
position 3 (monoglycoside) or positions 3 and 5 (diglycoside).
1.2.3 Flavylium/Anthocyanin Reds

Anthocyanins are ubiquitous colorants responsible for the impressive red and blue colors of flowers
and fruits (Figure 1.4). Natural flavylium reds can be considered their aglycone ancestors [31].
Anthocyanins have been found in a wide range of applications, from the millenary paints described by
the Roman architect Vitruvius to food additives, combining color and antioxidant effects, and even as
light absorbers in solar cells [31b,c, 32]. They were used as watercolors and textile dyes or as substi-
tutes for unavailable inorganic pigments. Vitruvius described a color for replacing Tyrian purple in
mural paintings; it was prepared by encapsulating the blueberry’s juice in a clay [31b, 32]. Watercolors
are described in written sources on illumination painting, including The Strasbourg Manuscript, De
Arte Illuminandi, the book on how to make all the color paints [33, 34]. Flavylium, as a textile dye,
was reported in Indian communities in Central and South America, and dragon’s blood resins were
found in artworks [31b, 35].
The color domain ranges from red to blue with anthocyanins, but with natural flavylium dyes it
is limited to yellow-red. One of the most famous examples of a natural flavylium red can be found
in dragon’s blood resins. Dragon’s blood is a natural resin with a deep, rich red color obtained from
various trees, namely, Dracaena draco and Dracaena cinnabari, which belong to the Liliaceae
family. The resin appears in injured areas of the plant, and it has been used for centuries for diverse
medical and artistic purposes [36]. These resins contain not only the red chromophores but also
additional flavonoids and steroids; dragon’s blood resins have been used in traditional Chinese
medicine. The molecules responsible for the red color of the resin obtained from the palm tree
Daemonorops draco (Calamus draco was used in the past) have been characterized by Brockmann
et al. and named dracorubin and dracorhodin (Table 1.2) [37]. Brockman et al. concluded that dra-
corhodin is a natural flavylium chromophore belonging to the anthocyanin family. More recently,
Table 1.2 Chemical structures responsible for the red color in dragon’s blood resins. The structures correspond
to the quinoid bases (A).
dracorhodin nordracorhodin dracorubin dracoflavylium
OH
O O O O O O
O O
OMe OMe O O
OMe
OMe
other natural flavylium chromophores, such as dracoflavylium, have been identified in D. draco,
D. cinnabari and other Dracaenaceae (Table 1.2) [36].
1.2.3.1 Equilibria in solution

As stated in the earlier text, dracorhodin and dracoflavylium are natural flavylium reds related to
anthocyanins. Anthocyanins are characterized by a hydroxyl group in positions 4’ and 7, and a sugar
in position 3 (monoglycosides) or 3 and 5 (diglycosides). On the other hand, in anthocyanidins, the
hydroxyl groups take the positions of the glycosides, leading to unstable structures in solution. By
contrast, the so-called deoxyanthocyanidins correspond to “anthocyanidins” lacking the hydroxyl in
position 3 (but bearing a hydroxyl in position 5) and are quite stable in solution [31, 32].
In the 1970s, it was established by Dubois and Brouillard (anthocyanins) [38a] and McClelland
(synthetic flavylium salts) [38b] that both families of compounds undergo multiple structural trans-
formations in aqueous solution following the same basic mechanisms [31, 39] (Figure 1.5). The
flavylium cation (AH+) is the dominant species in very acidic solutions, but with increasing pH a
series of more or less reversible chemical reactions take place: (i) proton transfer leading to the
quinoidal base (A), (ii) hydration of the flavylium cation giving rise to the colorless hemicetal (B),
(iii) a tautomerization reaction responsible for ring opening to give the pale yellow Z-chalcone,
form (Cc), and finally, (iv) cis–trans isomerization to form the pale yellow E-chalcone (Ct).
Furthermore, at higher pH, and depending on the number of hydroxyl groups, further deprotonated
species are found, such as Ctn‒ and An‒. The relevant contributors to color are AH+ and the quinoid
bases A and A‒. The red color of dragon’s blood resin was found to be due mainly to the red quinoid
base A [36].
4 OH OH O–
O O O O O
HO 7
+ + H+ + H+
3
5 Ka1 Ka2
OCH3 OCH3 OCH3
AH+ A A–
Kh
OH OH
HO OH
HO O Kt HO O
+ H+
OCH3 OCH3
Ki
B Cc
OH OH –O
OH
HO –O
O KCt1 O KCt2 O
+ H+ + H+
OCH3 OCH3 OCH3
OH OH O–
Ct Ct – Ct2–
Figure 1.5 Scheme of chemical reactions for dracoflavylium. Reprinted with permission from [36], Melo, M. J. et al.,
Chem. Eur. J., 13, 1417–1422 (2007) © 2007, Wiley-VCH.
1.3 Ancient Blues

1.3.1 Indigo Blues
Indigo blue was one of the earliest and most popular dyestuffs known to man (Figure 1.6). It is
still a universally used color, as the worldwide use of indigo-dyed blue jeans can attest. Indigo,
as the name implies, has its origins in ancient India. In the great civilizations of Egypt, Greece
and Rome, it was prized for its quality as a dye even though transportation costs meant it was
very expensive [40]. Indigo sources are found all over the world, and several plants were most
likely used in antiquity. In his Commentarii de Bello Gallico, Julius Caesar describes the warrior
skin paintings of his Gaulish adversaries, as being obtained from a blue juice; the warriors’ faces
were frightening, and they believed that dyeing the skin would protect them, making them
invulnerable.
Isatis tinctoria was grown in Europe, but it is known that indigo from Indigofera tinctoria was
traded to Europeans, namely from Persia to Muslim Spain, and from there distributed to other
European countries [41]. Species of Indigofera produced high-quality indigo.
Indigo is also one of the most light-stable organic dyes, a characteristic that explains not only its
wide use in antiquity and the premodern era, but also its longevity as a colorant [42–44].
The stability of indigo is also the reason why it was used in medieval illuminations and by the
great masters of the 17th and 18th centuries, such as Rubens [42, 44, 45] (Figure 1.1). Usually, with
the exception of some necessary and almost irreplaceable color lakes, organic compounds were
avoided in oil painting, as it was known that they were less stable to light than the inorganic avail-
able pigments. Highly pure indigo was the exception.
In 1865, Bayer started his work on indigo, and some years later, he proposed the chemical struc-
ture and a possible synthesis of indigo. At the time, indigo was an important molecule due to its
commercial value as a dye; synthetic indigo paved the way not only for the development of the
“big” German chemical and pharmaceutical industries but also helped to end the colonial produc-
tion of indigo, which until then had come from natural sources in British, French and Iberian colo-
nies. This particularly affected the British Indian colony, which was the major producer at that time.
Even at the beginning of the 21st century, indigo is still a surprisingly important dye. Since indigo
can be obtained from natural sources using microbial fermentation, its production using “green”
chemistry is of considerable interest [46].
The precursors of indigo (= indigotin) can be extracted entirely from plants. The extract, a solu-
tion of the water-soluble indoxyl glucoside, indican, is hydrolyzed via fermentation to give indoxyl,
which will further react with another indoxyl molecule producing indigo or with isatin, resulting in
indirubin, a reddish dye [7, 46] (Figure 1.7). The indigo derivatives are generally known as vat dyes
and, in their oxidized forms, are insoluble in water [7].
A common characteristic of vat dyes is the presence of one or more carbonyl groups, which,
when treated with a reducing agent in the presence of an alkali, form a water-soluble dye known as
O
H
N
N
H
O
Figure 1.6 Indigo (= indigotin).

indigo
O
O
H
N
N
H N
H
H O
N
H
N
O NH
indoxyl
NH O O
O
indirubin
O
isatin
Figure 1.7 Indigo dye bath: colorless precursors and pigments formed—indigo blue and indirubin red.
the leuco species. The process of dyeing a textile with these species involves the use of the vat dye
in a reducing media leading to its leuco form [7, 47]. The explanation of the blue color of indigo
and its derivatives has also been an intriguing and fascinating subject, and was explored in great
detail and ingenuity during the 1970s and 1980s [48]. It has been discovered that the fundamental
chromophore of the indigo dyes includes the central double bond (connecting the two rings)
together with the nitrogen and carbonyl groups [44, 48a–c]. Substitution in different ring positions
of indigo is likely to promote significant shifts in both the visible long-wavelength and UV
bands [48d].
Indirubin can be formed during the dyeing with indigo, namely in the interface where more oxy-
gen is available, which is the reason why it is also known as the red shade of indigo [49]; as was
previously mentioned, indirubin is formed through the reaction of indoxyl anion with isatin, a side
reaction in the reaction of indoxyl anion with itself to give indigo (Figure 1.7). It can also be present
in the Muricidae (see Section 1.4.1—Tyrian Purple: Real Purple from Sea Snails). Indirubin was
identified in the blues used in pre-Columbian textiles, such as the magnificent Andean textiles from
the Museum of Fine Arts (MFA, Boston) collection [43b] (Box 1.1). For dragon’s blood, its renais-
sance has been a consequence of its pharmaceutical activity [49].
1.3.2 Anthocyanin Blues

As reported in Section 1.2.3, there are several ancient references to the use of anthocyanin watercolors
for painting, particularly for illuminations, for example, as described in the Strasbourg Manuscript
[33a]. More recently, the use of Commelina communis for blue in Aztec manuscripts was
proposed [50].
In the past, extracting and capturing an anthocyanin blue were not the easy tasks; these blues are
complex, self-assembled, supramolecular structures, bound by noncovalent interactions. The
overall supramolecular complex must be preserved, not just the monomeric subunits; otherwise,
the color is lost. For example, to obtain a “cornflower” blue, the supramolecular assembly must be
maintained within a certain pH range. Apparently, this was achieved by following the recipes
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Handbook of Natural Colorants 2nd

Edition Thomas Bechtold

Textile Chemistry 2nd Edition Thomas Bechtold

Textile Chemistry Second Edition Thomas Bechtold

Handbook of Natural Polymers Volume 1 1st Edition M S

Springer Handbook of Atmospheric Measurements Thomas

The Handbook of Natural Resources Second Edition Six

The Routledge Handbook of Parliamentary Administrations

The Routledge Handbook of Civil Military Relations 2nd

Natural History 2nd Edition Dk

Titles in the Series:

© 2023 John Wiley & Sons Ltd

Limit of Liability/Disclaimer of Warranty

Library of Congress Cataloging-­in-­Publication Data applied for:

Hardback ISBN: 9781119811718

Cover image: © sagarmanis/Getty Images

Set in 9.5/12.5pt STIXTwoText by Straive, Chennai, India

List of Contributors xxi

1 History of Natural Dyes in the Ancient Mediterranean Civilization 3

2 Colors in Civilizations of the World and Natural Colorants:

3 History of Natural Dyes in North Africa_Egypt 33

II Natural Colorants in Different Regions of the World 43

5 Dyes in South America 63

6 Natural Dyes in Eastern Asia (Vietnam and Neighboring Countries) 75

7 Sources for Natural Colorants in China 89

7.9 Monascus Red 95

8 Sources, Application, and Analysis of Natural Colorants: An Indian Perspective 103

9 Natural Dye Gardens in North America 161

9.8 Plants with Indigotin 172

III Colorant Production and Properties 181

11 Indigo—­Production and Properties 195

11.7 Extraction Procedures 229

12 Anthocyanins: Revisiting Nature’s Glamorous Palette 251

13 Natural Colorants—­Quinoid, Naphthoquinoid, and Anthraquinoid Dyes 271

14 Natural Colorants from Lichens and Mushrooms 317

15 Focus on Tannins 333

16 Carotenoid Dyes—­Properties and Production 351

16.3.5 Chemical Tests 361

17 Flavonoids as Natural Pigments 371

18 Natural Colorants from Fungi 391

19 Natural Colorants from Cyanobacteria and Algae 417

20 Biotechnological Production of Microbial Pigments: Recent Findings 439

20.8 Microbial Pigments Applications 449

21 Analytical Methods for Characterization and Standardization of

22 Wood—­From Natural Color Patterns Toward Naturally Altered

22.4.5 Bleaching 491

23 The Role of Mordants in Fixation of Natural Dyes 507

24 Textile Coloration with Natural Dyes and Pigments 517

25 Hair Coloration with Natural Dyes and Pigments 543

26 Natural Colorants in the Mass Coloration of Plastics 557

27 Natural Colorants in Printing/Packaging 563

28 Technical Aspects and Requirements to Produce Natural Colorants—­Processes

28.5 Challenges for the Industrial Use of Natural Colorants 585

29 Environmental and Economic Position of Natural Colorants—­Energy and

30 Aspects of Human Toxicology and Consumer Safety 613

30.6 Test Methods for Toxicity Screening 622

Harby Ezzeldeen Ahmed Faculty of Archaeology, Cairo University, Giza, Egypt

Vivian Katherine Colorado Gómez Department of Chemical Engineering, Universidad

Valeria C. Santos-­Ebinuma Department of Bioprocess Engineering and Biotechnology,

Thomas Bechtold, Avinash P. Manian, and Tung Pham

LAQV/REQUIMTE, Department of Conservation and Restoration;

1.1.2 Dyes from Antiquity

Box 1.1 Natural dyes as lake pigments

Library of Congress Cataloging-in-Publication Data applied for:

List of Contributors xxi

1 History of Natural Dyes in the Ancient Mediterranean Civilization 3

3 History of Natural Dyes in North Africa_Egypt 33

II Natural Colorants in Different Regions of the World 43

5 Dyes in South America 63

6 Natural Dyes in Eastern Asia (Vietnam and Neighboring Countries) 75

7 Sources for Natural Colorants in China 89

7.9 Monascus Red 95

8 Sources, Application, and Analysis of Natural Colorants: An Indian Perspective 103

9 Natural Dye Gardens in North America 161

9.8 Plants with Indigotin 172

III Colorant Production and Properties 181

11 Indigo—Production and Properties 195

11.7 Extraction Procedures 229

12 Anthocyanins: Revisiting Nature’s Glamorous Palette 251

13 Natural Colorants—Quinoid, Naphthoquinoid, and Anthraquinoid Dyes 271

14 Natural Colorants from Lichens and Mushrooms 317

15 Focus on Tannins 333

16 Carotenoid Dyes—Properties and Production 351

16.3.5 Chemical Tests 361

17 Flavonoids as Natural Pigments 371

18 Natural Colorants from Fungi 391

19 Natural Colorants from Cyanobacteria and Algae 417

20 Biotechnological Production of Microbial Pigments: Recent Findings 439

20.8 Microbial Pigments Applications 449

22 Wood—From Natural Color Patterns Toward Naturally Altered

22.4.5 Bleaching 491

23 The Role of Mordants in Fixation of Natural Dyes 507

24 Textile Coloration with Natural Dyes and Pigments 517

25 Hair Coloration with Natural Dyes and Pigments 543

26 Natural Colorants in the Mass Coloration of Plastics 557

27 Natural Colorants in Printing/Packaging 563

28 Technical Aspects and Requirements to Produce Natural Colorants—Processes

28.5 Challenges for the Industrial Use of Natural Colorants 585

29 Environmental and Economic Position of Natural Colorants—Energy and

30 Aspects of Human Toxicology and Consumer Safety 613

30.6 Test Methods for Toxicity Screening 622

Valeria C. Santos-Ebinuma Department of Bioprocess Engineering and Biotechnology,

Figure 1.2 Alizarin (1,2-dihydroxy anthraquinone).

Figure 1.3 Brazilein; hematein is 8-hydroxy brazilein.